KR102397948B1 - Polyamic Acid Composition - Google Patents

Abstract

The present application relates to a polyamic acid composition, a polyimide solution, a manufacturing method thereof, a polyimide including the same, and a semiconductor device including the same, and has excellent dielectric properties such as low dielectric constant and low dielectric loss tangent in a high frequency band, and is easy to process Provided is a polyamic acid composition that is excellent, has hygroscopicity and heat resistance of a certain level or more, and can implement adhesive strength of a certain level or more.

Description

Polyamic Acid Composition

The present application relates to a polyamic acid composition, a polyimide solution, a manufacturing method thereof, a polyimide including the same, and a semiconductor device including the same.

Recently, the mobile communication industry market has entered the 5th generation mobile communication era. If network connectivity through smartphones was the main focus in the existing 4G LTE market, 5G mobile communication services can provide large capacity, low latency, and fast transmission speed characteristics. Data utilization-based systems can be expanded to include Internet (IOT) devices, automobiles, robots, factories, and smart cities. Accordingly, the unprecedented data explosion and the semiconductor market for accommodating it are also expected to inevitably expand.

Accordingly, there is a need for a semiconductor device that stably implements 5G mobile communication performance. In particular, 5G mobile communication technology transmits and receives signals in a high frequency band compared to the existing 4G mobile communication technology, A characteristic for suppressing a decrease in transmission speed or loss of an electrical signal is required at a high level. That is, in order to obtain high reliability in a high-frequency band of gigahertz (GHz), the information processing capability of the semiconductor device should be improved without adversely affecting the transmission of electrical signals.

Accordingly, it is necessary to develop an adhesive material for forming an insulating layer having excellent processability due to excellent dielectric properties such as low dielectric constant and low dielectric loss tangent in a high frequency band, as well as excellent solubility in organic solvents.

The present application provides a polyamic acid composition having excellent dielectric properties, such as exhibiting a low dielectric constant and low dielectric loss tangent in a high frequency band, excellent processing, hygroscopicity and heat resistance of a certain level or more, and capable of implementing an adhesive force of a certain level or more.

This application relates to a polyamic acid composition. The polyamic acid may include a dianhydride monomer component and a diamine monomer component as polymerization units. The present application also provides a polyimide, which is a cured product of the polyamic acid. The polyimide may be mixed with an organic solvent to provide a polyimide solution, but is not limited thereto. The polyimide may be a photosensitive polyimide, and may be applied to a semiconductor device for 5G mobile communication. In addition, the present application may provide an adhesive including the polyimide, and the adhesive may be applied to a semiconductor device for 5G mobile communication. The polyamic acid composition of the present application has excellent dielectric properties, such as exhibiting a low dielectric constant and particularly low dielectric loss tangent in a high frequency band, has excellent processing, and has hygroscopicity and heat resistance of a certain level or more, and can implement adhesive strength of a certain level or more.

As described above, the polyamic acid composition of the present application may include a dianhydride monomer component and a diamine monomer component as polymerization units. The diamine monomer may include a dimer diamine and a diamine monomer of Formula 2 below.

[Formula 2]

In Formula 2, R is oxygen, a carbonyl group, an alkylcarbonyl group, a single bond, an alkylene group or an alkylidene group, A ₁ and A ₂ are each independently oxygen, a carbonyl group, an alkylcarbonyl group, a single bond, an alkylene group or an alkylidene group.

In one example, the dimer diamine monomer may be a compound derived from a dimer acid, which is a dimer of an unsaturated fatty acid. The dimer diamine monomer may have a linear, branched or cyclic aliphatic structure. In addition, the linear, branched or cyclic aliphatic structure may have 5 to 60 carbon atoms. The range of the number of carbon atoms may be, for example, a lower limit of 8, 10, 13, 15, 18, 20, 23, 25, 28, 30, 33, 35, 38, 40, 43, 45, 48, 50 or 53 or more. and the upper limit may be, for example, 58, 55, 52, 47, 45, 42, 40, 37, 35, 32, 30, 27, 25, 22, or 17 or less. The dimer diamine monomer of the present application may not include an aromatic structure, but is not limited thereto. The present application may also include the diamine diamine monomer in a ratio of 3 mol% to 40 mol% of the total diamine monomer component. The lower limit of the content is, for example, 3.5 mol%, 4 mol%, 4.3 mol%, 4.5 mol%, 4.8 mol%, 5 mol%, 8 mol%, 8.5 mol%, 10 mol%, 15 mol%, 20 mol%, 23 mol%, 28 mol%, or 30 mol% or more, the upper limit being, for example, 35 mol%, 33 mol%, 28 mol%, 25 mol%, 23 mol%, 18 mol%, 15 mol% %, 13 mol%, 10 mol%, 9.9 mol%, 9.5 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5.8 mol%, 5.5 mol%, or 5.3 mol% . By including the dimer diamine compound as a polymerization unit, the present application can be made relatively hydrophobic and have a relatively long hydrocarbon chain, thereby simultaneously realizing a low dielectric constant, processability, heat resistance and adhesive strength along with a desired low dielectric loss tangent property. can

In addition, the polyamic acid composition of the present application may include the diamine monomer of Formula 2 in a ratio of 40 mol% or more of the total diamine monomer component. The lower limit of the ratio is, for example, 45 mol%, 48 mol%, 55 mol%, 60 mol%, 65 mol%, 68 mol%, 73 mol%, 78 mol%, 83 mol%, 88 mol%, 93 mol% may be greater than or equal to mol% or 98 mol%, with an upper limit of, for example, 100 mol%, 99 mol%, 98 mol%, 97 mol%, 96 mol%, 95 mol%, 93 mol%, 90 mol%, or 88 mol% It may be less than or equal to mole %. The present application includes 40 mol% or more of a diamine monomer having a specific structure represented by the following formula (2), which in particular realizes a low dielectric constant value compared to the prior art, enables polyimide solution, improves solubility in organic solvents, and provides excellent heat resistance after curing It is possible to realize the desired physical properties.

[Formula 2]

In Formula 2, R is oxygen, a carbonyl group, an alkylcarbonyl group, a single bond, an alkylene group or an alkylidene group, A ₁ and A ₂ are each independently oxygen, a carbonyl group, an alkylcarbonyl group, a single bond, an alkylene group or an alkylidene group. The alkylene group or alkylidene group may be unsubstituted or substituted with at least one substituent. The substituent may be an alkyl group, an alkenyl group, or an alkynyl group, and in one example, the substituent may be an alkyl group substituted with at least one fluorine, and may be a perfluoroalkyl group in which all hydrogens are substituted with fluorine.

Formula 2 may be represented by, for example, Formula 4 below.

[Formula 4]

In Formula 4, Q is -C _a (CH ₃ ) _2a -, -C _b (CF ₃ ) _2b -, -(CH ₂ ) _c -, or -O(CH ₂ ) _d O-, and a to d is each independently an integer of 1 to 4. The Q may be substituted with at least one fluorine. Further, in another example, the diamine monomer component may include two kinds of diamine monomers, and each monomer may be unsubstituted or substituted with highly polar fluorine. In addition, at least one of the two diamine monomers may include a compound represented by Formula 4, wherein R may be -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ - .

In addition, the present application may include two different types of diamine monomers of Chemical Formula 2 . That is, in the present application, two types of the diamine monomer of Formula 2 may be used, and the two types may be different compounds. At least one of the diamine monomers of Formula 2 may have an alkyl group substituted with fluorine, and among the two types of diamine monomers of Formula 2, the diamine monomer having an alkyl group substituted with fluorine has a higher content than the monomers of Formula 2 otherwise. may be included. In addition, the polyamic acid composition according to the present application may not include, but is not limited to, diamine monomers other than the dimer diamine and the diamine monomer of Formula 2 described above.

As used herein, the term "alkyl group", unless otherwise specified, has 1 to 30 carbon atoms, 1 to 25 carbon atoms, 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. may mean an alkyl group of The alkyl group may have a straight-chain, branched-chain or cyclic structure, and may be optionally substituted by one or more substituents. The substituent may be, for example, a polar functional group.

As used herein, the term "alkenyl group", unless otherwise specified, has 1 to 30 carbon atoms, 1 to 25 carbon atoms, 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to carbon atoms. It may mean an alkenyl group of 4. The alkenyl group may have a linear, branched or cyclic structure, and may be optionally substituted by one or more substituents. The substituent may be, for example, a polar functional group.

As used herein, the term "alkynyl group", unless otherwise specified, has 1 to 30 carbon atoms, 1 to 25 carbon atoms, 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to carbon atoms. It may mean an alkynyl group of 4. The alkynyl group may have a linear, branched or cyclic structure, and may be optionally substituted with one or more substituents. The substituent may be, for example, a polar functional group.

As used herein, the term "alkylene group", unless otherwise specified, has 2 to 30 carbon atoms, 2 to 25 carbon atoms, 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 10 carbon atoms, or carbon atoms. It may mean an alkylene group of 2 to 8. The alkylene group may have a linear, branched or cyclic structure, and may be optionally substituted by one or more substituents. The substituent may be, for example, a polar functional group.

In the present specification, the term "alkylidene group", unless otherwise specified, has 2 to 30 carbon atoms, 2 to 25 carbon atoms, 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 10 carbon atoms, or It may mean an alkylidene group having 2 to 8 carbon atoms. The alkylidene group may have a linear, branched or cyclic structure, and may be optionally substituted by one or more substituents. The substituent may be, for example, a polar functional group.

As used herein, the term “single bond” may refer to a bond connecting both atoms without any atoms. For example, when R in Formula 2 is a single bond, both aromatic rings may be directly connected to each other.

The polyamic acid composition of the present application may include the dianhydride monomer of Formula 1 below in a ratio of 30 mol% or more of the total dianhydride monomer component. The lower limit of the ratio is, for example, 32 mol%, 35 mol%, 38 mol%, 40 mol%, 43 mol%, 45 mol%, 48 mol%, 55 mol%, 60 mol%, 65 mol%, 68 mol% mol%, 73 mol%, 78 mol%, 83 mol%, 88 mol%, or 93 mol% or more, the upper limit being, for example, 100 mol%, 95 mol%, 90 mol%, 85 mol%, 80 mol% mol%, 75 mol%, 73 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 48 mol%, 45 mol%, 43 mol%, or 40 mol%. The present application includes 30 mol% or more of a dianhydride monomer having a specific structure of the following formula (1), particularly to realize a low dielectric loss tangent value compared to the prior art, to make polyimide solution possible, to improve solubility in organic solvents, and to cure Afterwards, desired physical properties such as excellent heat resistance can be realized. Therefore, the polyimide according to the present application is used as a molded article such as a photosensitive layer and is suitable for use in a semiconductor device using a high frequency band for mobile communication.

[Formula 1]

In Formula 1, R may be oxygen, a carbonyl group, an alkylcarbonyl group, a single bond, an alkylene group, or an alkylidene group. In addition, A ₁ and A ₂ may each independently be oxygen, a carbonyl group, an alkylcarbonyl group, a single bond, an alkylene group, or an alkylidene group. The A ₁ and A ₂ may be connected to any one carbon of an anhydride group present at both terminals. The alkylene group or alkylidene group may be unsubstituted or substituted with at least one substituent. The functional group may be, for example, an alkyl group, an alkenyl group, or an alkynyl group, but is not limited thereto. The alkyl group, alkenyl group, or alkynyl group may be linear, branched or cyclic, and may have 1 to 30 carbon atoms or 1 to 10 carbon atoms. The lower limit of the number of carbon atoms may be 1, 2, 3, or 4, and the upper limit may be 30, 25, 20, 15, 10 or 8 or less.

In addition, in an embodiment of the present application, the dianhydride monomer component may include at least one compound represented by the following formula (3).

[Formula 3]

Wherein M includes at least one or more from the group comprising an alkylene group, an alkylidene group, a carbonyl group, an alkylcarbonyl group, an alkoxy group, and a sulfonyl group, and M is at least one or more from the group comprising a fluorine and an alkyl group. substituted or unsubstituted. M in Formula 3 may be an alkylene group having as a substituent an alkyl group substituted with at least one fluorine. As an example, the alkyl group having 1 to 6 carbon atoms substituted with at least one fluorine may be a perfluoroalkyl group, specifically, a perfluoromethyl group. In another example, the dianhydride monomer component may include at least one dianhydride monomer substituted with at least one fluorine.

The dianhydride monomer of Formula 3 may be included, for example, in a ratio of 70 mol% or less of the total dianhydride monomer component. The lower limit of the ratio is, for example, 0 mol%, 5 mol%, 10 mol%, 15 mol%, 18 mol%, 23 mol%, 25 mol%, 30 mol%, 35 mol%, 40 mol%, or 55 mol% or more, and the upper limit is, for example, 70 mol%, 68 mol%, 65 mol%, 63 mol%, 60 mol%, 55 mol%, 53 mol%, 50 mol%, 45 mol%, 40 mol% mole %, 35 mole %, or 33 mole % or less.

The dianhydride monomer that can be used in the preparation of the polyamic acid of the present application may be exemplified by a monomer having the above-described chemical structure or other additionally possible monomers. Specific examples of the monomers may be exemplified as follows. The monomer may be an aromatic tetracarboxylic dianhydride, and the aromatic tetracarboxylic dianhydride is pyromellitic dianhydride (or PMDA), 3,3',4,4'-biphenyltetracar Voxylic dianhydride (or BPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (or a-BPDA), oxydiphthalic dianhydride (or ODPA), diphenylsulfone -3,4,3',4'-tetracarboxylic dianhydride (or DSDA), bis (3,4-dicarboxyphenyl) sulfide dianhydride, 2,2-bis (3,4-dicarboxy Phenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4 ,4'-benzophenonetetracarboxylic dianhydride (or BTDA), bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane Dianhydride, p-phenylenebis(trimellitic monoester acid anhydride), p-biphenylenebis(trimellitic monoester acid anhydride), m-terphenyl-3,4,3' ,4'-tetracarboxylic dianhydride, p-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, 1,3-bis(3,4-dicarboxyphenoxy) Benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, 2,2- Bis[(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA), 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxyl ric dianhydride, 4,4'-(2,2-hexafluoroisopropylidene)diphthalic acid dianhydride, and the like.

In addition, the diamine monomer that can be used in the preparation of the polyamic acid is an aromatic diamine, and the monomers of the above formula or additional monomers may be classified as follows.

1) 1,4-diaminobenzene (or paraphenylenediamine, PDA), 1,3-diaminobenzene, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobenzo A diamine having a single benzene nucleus in structure, such as acid acid (or DABA), and a diamine having a relatively rigid structure;

2) 4,4'-diaminodiphenyl ether (or oxydianiline, ODA), diaminodiphenyl ether such as 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane (methylenediamine), 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl ) -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane , 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis(4-aminophenyl)sulfide, 4,4'-diaminobenzanilide, 3,3' -dichlorobenzidine, 3,3'-dimethylbenzidine (or o-tolidine), 2,2'-dimethylbenzidine (or m-tolidine), 3,3'-dimethoxybenzidine, 2,2'-dimethoxy Benzidine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4' -diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone , 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diamino-4,4'-dichlorobenzophenone, 3,3'-diamino-4,4' -dimethoxybenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis (3- aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane; 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenylsulfoxide, 3,4'-diaminodi diamines having two benzene nuclei in structure, such as phenylsulfoxide and 4,4'-diaminodiphenylsulfoxide;

3) 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 1,4-bis(4-amino) Phenyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene (or TPE-Q), 1,4-bis(4-aminophenoxy) Benzene (or TPE-Q), 1,3-bis (3-aminophenoxy) -4-trifluoromethylbenzene, 3,3'-diamino-4- (4-phenyl) phenoxybenzophenone, 3 ,3'-diamino-4,4'-di(4-phenylphenoxy)benzophenone, 1,3-bis(3-aminophenylsulfide)benzene, 1,3-bis(4-aminophenylsulfide)benzene , 1,4-bis(4-aminophenylsulfide)benzene, 1,3-bis(3-aminophenylsulfone)benzene, 1,3-bis(4-aminophenylsulfone)benzene, 1,4-bis(4 -Aminophenylsulfone)benzene, 1,3-bis[2-(4-aminophenyl)isopropyl]benzene, 1,4-bis[2-(3-aminophenyl)isopropyl]benzene, 1,4-bis diamines having three benzene nuclei in the structure, such as [2-(4-aminophenyl)isopropyl]benzene;

4) 3,3'-bis(3-aminophenoxy)biphenyl, 3,3'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[3-(3-aminophenoxy)phenyl]ether, bis[3-(4-aminophenoxy)phenyl]ether, bis[4- (3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, bis[3-(3-aminophenoxy)phenyl]ketone, bis[3-(4-aminophenoxy) cy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]ketone, bis[3-(3-aminophenoxy)phenyl]sulfide , bis[3-(4-aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[3- (3-aminophenoxy)phenyl]sulfone, bis[3-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy) cy)phenyl]sulfone, bis[3-(3-aminophenoxy)phenyl]methane, bis[3-(4-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl ]methane, bis[4-(4-aminophenoxy)phenyl]methane, 2,2-bis[3-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(4 -aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane ( BAPP), 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3- (4- Aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3 structure, such as ,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, etc. Diamine with 4 phase benzene nuclei.

Since one of the main characteristics of polyimide resins in terms of molecular structure is rigidity, it has been generally used for devices requiring rigidity. In contrast, the polyamic acid composition according to the present invention has a flexible molecular structure compared to the prior art by including the monomer component of the specific compound, thereby improving solubility in organic solvents, and significantly reducing the dielectric loss tangent value compared to the prior art and polyimide based thereon may be suitable for implementation in a solution state.

In one example, the weight average molecular weight of the polyamic acid resin of the present invention may be 10,000 g/mol to 100,000 g/mol. The lower limit of the weight average molecular weight may be 15,000 g/mol, 20,000 g/mol, 25,000 g/mol, or 28,000 g/mol or more, and the upper limit of the weight average molecular weight is 90,000 g/mol, 80,000 g/mol, 70,000 g/mol , 60,000 g/mol, 50,000 g/mol, 30,000 g/mol, 29,000 g/mol, or 28,500 g/mol or less. Here, the weight average molecular weight means a value converted to standard polystyrene measured by gel permeation chromatograph (GPC). By adjusting the weight average molecular weight within the above range, the polyamic acid composition according to the present invention has excellent processability and thus a desired photosensitive polyimide composition can be formed.

In one example, the polyamic acid composition of the present invention may have a solid content of 5 to 70% by weight. The lower limit of the weight percent solids content is 5, 8, 9, 10, 15, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, or 34 weight percent or more. and the upper limit of the weight% of the solid content may be 70, 65, 60, 55, 50, 45, 40, or 37% by weight or less. By adjusting the solid content of the polyamic acid composition, it is possible to control the increase in viscosity and shorten the process time during the curing process.

In one example, the polyamic acid composition of the present invention may have a viscosity in the range of 1,000 to 50,000 cP measured at a temperature of 23° C. and a shear rate of 1s ⁻¹ . Specifically, the lower limit of the viscosity of the polyamic acid composition is 1,200 cP or more, 1,500 cP or more, 1,600 cP or more, 1,700 cP or more, 2,000 cP or more, 2,200 cP or more, 2,500 cP or more, 2,600 cP or more, 2,700 cP or more, 2,900 cP or more or more, 3,000 cP or more, 3,050 cP or more, 3,150 cP or more, 3,250 cP or more, or 3,300 cP or more, and the upper limit thereof is 49,000 cP or less, 45,000 cP or less, 40,000 cP or less, 30,000 cP or less, 25,000 cP or less, 20,000 or more cP or less, 18,000 cP or less, 16,000 cP or less, 15,500 cP or less, 15,000 cP or less, 14,500 cP or less, 8,000 cP or less, 5,000 cP or less, 3,500 cP or less, 2,900 cP or less, 2,800 cP or less, 2,750 cP or less, 2,650 cP or less or 2,500 cP or less. In the present application, by controlling the viscosity range of the polyamic acid composition, it is possible to form a polyimide having excellent processability and desired physical properties.

In the present application, the polyamic acid composition may include an organic solvent.

The organic solvent is not particularly limited as long as it is an organic solvent in which the polyamic acid can be dissolved, but may be an aprotic polar solvent as an example.

The aprotic polar solvent is, for example, N,N'-dimethylformamide (DMF), N,N'-diethylformamide (DEF), N,N'-dimethylacetamide (DMAc), dimethylpropane Amide solvents such as amide (DMPA), phenolic solvents such as p-chlorophenol and o-chlorophenol, N-methyl-pyrrolidone (NMP), gamma butyrolactone (GBL) and Diglyme, etc. and these may be used alone or in combination of two or more.

In the present application, the solubility of the polyamic acid may be controlled by using an auxiliary solvent such as toluene, tetrahydrofuran, acetone, methyl ethyl ketone, methanol, ethanol, and water in some cases.

In one example, the polyamic acid composition may have a dielectric constant (Dk) of 3.5 or less after curing at any one point in a frequency band of 3.4 to 10 GHz. The lower limit of the dielectric constant after curing is not particularly limited, but may be, for example, 1.0 or more, and the upper limit may be 3.4, 3.3, 3.2, 3.1, 3.0, 2.95, or 2.9 or less. In addition, the polyamic acid composition may have a dielectric loss tangent (Df) of less than 0.0033 after curing at any one point in a frequency band of 3.4 to 10 GHz. The lower limit of the dielectric loss tangent after curing is also not particularly limited, but may be, for example, 0.001 or more, and the upper limit may be less than 0.0032, 0.0031, 0.00305, 0.003, 0.0029, 0.0028, 0.0027 or 0.0026. Since the polyimide resin obtained by curing the polyamic acid composition of the present application has both low dielectric constant and dielectric loss tangent, particularly in a high frequency band, it may have excellent dielectric properties.

In particular, the frequency bands of 3.4 to 10 GHz, 4.0 to 10 GHz, 5.0 to 10 GHz, or 8.0 to 10 GHz are used in 5G mobile communication technology, which is a higher frequency band compared to the existing 4G mobile communication technology. That is, the polyamic acid composition of the present application may sufficiently exhibit a characteristic of suppressing a decrease in a transmission speed of an electrical signal or a loss of an electrical signal in a circuit in a semiconductor device when transmitting and receiving a signal in the specific high-frequency band. Accordingly, high reliability can be obtained by improving the information processing capability of the semiconductor device without adversely affecting the transmission of electrical signals.

In one example, the polyamic acid composition according to the present application may have a glass transition temperature after curing in the range of 100°C to 300°C. In particular, the upper limit of the glass transition temperature after curing may be 295 ℃, 290 ℃, 285 ℃, 280 ℃, 275 ℃, 270 ℃, 265 ℃, 260 ℃, 255 ℃, 250 ℃, 245 ℃, 240 ℃ or 210 ℃ or less. and the lower limit thereof may be at least 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 195°C, 198°C, or 200°C. Since the polyimide resin according to the present invention has a relatively flexible molecular structure, the glass transition temperature after curing may have a particularly low value compared to other polyimide resins. Accordingly, the polyimide of the present invention is prepared in a solution state can be

The present application also relates to polyimides. The polyimide may be a cured product of the above-described polyamic acid composition. In addition, the present application may provide a polyimide solution including the polyimide and an organic solvent. In general, the polyamic acid exists in a solution state, and unlike a solid polyimide is formed after curing, the present application may be in the form of a solution in a polyimide state.

Another embodiment of the present invention provides a method for preparing a polyimide. The manufacturing method may be the manufacturing method of the above-described polyimide solution.

First, the method for preparing a polyimide may include a step (step 1) of preparing a polyamic acid precursor solution by polymerizing a diamine monomer and a dianhydride monomer. The polyamic acid precursor solution may be prepared by one of the following methods, and the scope of the present invention is not limited thereto, and any known method may be used.

1) The whole amount of the diamine-based monomer is put in an organic solvent, and then the dianhydride-based monomer can be added so as to be substantially equimolar with the diamine monomer.

2) The whole amount of the dianhydride-based monomer may be put in an organic solvent, and then the diamine-based monomer may be added so as to be substantially equimolar with the dianhydride-based monomer.

3) After putting some components of the diamine-based monomer in the organic solvent, some components of the dianhydride-based monomer are mixed in a ratio of about 95 mol% to 105 mol% with respect to the reaction component, and then the remaining diamine-based monomer components are added and the remaining dianhydride-based monomer components may be continuously added thereto so that the diamine-based monomer and the dianhydride-based monomer are substantially equimolar.

4) After the dianhydride-based monomer is put in the organic solvent, some components of the diamine compound are mixed in a ratio of 95 mol% to 105 mol with respect to the reaction component, then another dianhydride-based monomer component is added and the remaining By adding the diamine-based monomer component, it may be added so that the diamine-based monomer and the dianhydride-based monomer are substantially equimolar.

5) A first polymer is formed by reacting a part of a diamine-based monomer component and a part of a dianhydride-based monomer component in an organic solvent in an excessive amount, and a part of a diamine-based monomer component and a part of a dianhydride in another organic solvent A method for forming a second polymer by reacting a monomer component in excess of any one, mixing the first and second polymers, and completing polymerization, wherein the diamine-based monomer component is formed when the first polymer is formed. In the case of excess, the dianhydride-based monomer component is excessive in the second polymer, and when the dianhydride-based monomer component is in excess in the first polymer, the diamine-based monomer component is in excess in the second polymer, The second polymers may be mixed and added so that the total diamine-based monomer component and the dianhydride-based monomer component used in these reactions are substantially equimolar.

Meanwhile, when preparing the polyamic acid precursor solution, the dianhydride monomer may be added in substantially equimolar amount with the diamine monomer, or may be added in an excess of the diamine monomer.

Next, it may include a step of stirring the polyamic acid precursor solution, through this, it is possible to obtain a polyamic acid solution (step 2).

In one example, separate heating may be performed in the stirring step, and heating may be performed within a temperature range of 20°C to 70°C. The temperature range is not particularly limited, but the lower limit of the heating temperature may be 22°C, 24°C, 25°C, 26°C, 28°C, 30°C, 32°C, 34°C, 36°C, or 38°C, and the upper limit thereof may be 65°C, 58°C, 56°C, 54°C, 52°C, 50°C, 48°C, 46°C, 44°C, or 42°C.

In one example, the heating step may be performed for 30 minutes to 5 hours. The heating time is not particularly limited, but the lower limit of the heating time may be 40 minutes, 45 minutes, 50 minutes, 55 minutes or 90 minutes, and the upper limit thereof is, for example, 4 hours, 3 hours, 150 minutes or 100 minutes. can In the present application, within the heating time range, unreacted substances can be minimized and storage stability of the polyamic acid solution can be secured.

Next, it may include a step of forming a polyimide solution (step 3). This is a step of imidizing polyamic acid to obtain a polyimide resin, and the imidization method may be a known method such as thermal imidization method of thermal dehydration and ring closure, chemical imidization method using a dehydrating agent, etc. Complex imidization may also be used.

In particular, it may be preferable to imidize under mild conditions such as chemical imidization that does not require high-temperature heat treatment, and in this case, pyridine, 2-methylpyridine, 3-methylpyridine, triethylamine, isoquinoline as a catalyst A tertiary amine such as these can be used as a catalyst, and acetic anhydride or the like can be used as a dehydrating agent. The tertiary amine may be included, for example, in the range of 0.8 to 2.0 equivalents relative to the number of moles of polyamic acid. In addition, the acetic anhydride may be included, for example, in the range of 2.5 to 4.0 equivalents relative to the number of moles of the polyamic acid.

Meanwhile, the polyimide resin obtained according to the present invention may be provided in the form of a solution, as described above.

The present application relates to a method for producing polyimide.

A polyimide can be formed by forming into a film by a well-known method using the obtained polyimide solution, drying and hardening. For example, the polyimide solution is cast on a support such as a glass substrate using a doctor blade or the like, and is usually 40° C. to 400° C. using a hot air dryer, an infrared dryer, a vacuum dryer, an inert oven, or the like. The polyimide can be formed by drying and curing in a temperature range of °C. The lower limit of the temperature may be 45 °C, 50 °C, 55 °C, or 60 °C, and the upper limit may be 350 °C, 300 °C, or 250 °C.

The present application provides a polyimide, which is a cured product of the above-described polyimide solution. The polyimide may be a photosensitive polyimide, and the above-described polyimide solution may be a photosensitive polyimide solution. In addition, without being limited thereto, the present application provides an adhesive including the polyimide. The adhesive may include an organic solvent and a known crosslinking agent.

The photosensitive polyimide composition includes the above-described polyimide, and since the polyimide according to the present invention has excellent solubility in a solvent, it can be provided as a solution. There is no need, therefore, a separate solvent may not be required, and it may be used as a molded article such as a photosensitive layer due to excellent processability.

The photosensitive polyimide composition may include a photoactive compound, and the photoactive compound may be used without limitation as long as it exhibits photosensitivity. In one example, the photoactive compound may be included in an amount of 1 to 50 parts by weight based on 100 parts by weight of the polyimide solution. If necessary, a sensitizer such as perylene, anthracene, thioxanthone, Michler ketone, benzophenone, or fluorene may be used in combination with the photoactive compound.

The photosensitive polyimide resin composition may further include additives such as a dissolution rate control agent, a sensitizer, an adhesion enhancer, or a surfactant in addition to the above components.

The photosensitive polyimide composition of the present invention is applied on a substrate such as a glass substrate using a conventional method such as spin coating, slit spin coating, roll coating, die coating, and curtain coating, through the application process, exposure process, and development process steps. , can be used as a photosensitive layer. In the exposure process, the light source irradiated from the light irradiation means is not particularly limited, and examples of the light source include electromagnetic waves, visible light from ultraviolet rays, electron beams, X-rays, and laser light. The method of irradiating light by the light irradiation means is not particularly limited, and methods of irradiating with known light sources such as high-pressure mercury lamps, xenon lamps, carbon arc lamps, halogen lamps, cold cathode tubes for copiers, LEDs, and semiconductor lasers are exemplified. there is. The developing process may be a process of exposing the photosensitive layer by the exposure process, curing the exposed region of the photosensitive layer, and then developing by removing the uncured region to form a pattern. The developer is not particularly limited, and examples thereof include an aqueous solution of an alkali metal or alkaline earth metal hydroxide or carbonate, hydrogen carbonate, aqueous ammonia, and a quaternary ammonium salt. The thickness of the photosensitive layer thus obtained may vary depending on the purpose, and may be, for example, 1 μm to 20 μm, but is not limited thereto.

The present application also provides a semiconductor device for 5G mobile communication. Here, 5G mobile communication may mean using a frequency band of 3.4 to 10 GHz. In the high frequency band, the photosensitive layer using the polyimide according to the present invention exhibits a low dielectric constant and a low dielectric loss tangent, and thus has excellent dielectric properties, and thus can greatly suppress the loss of electrical signals. can have high reliability.

In addition, the photosensitive layer made of the photosensitive polyimide composition according to the present invention is an interlayer insulating film, a passivation film, a buffer coating film, an insulating film for multilayer printed circuit boards, an OLED insulating film, as well as a thin film of a liquid crystal display device in a semiconductor device for 5th generation mobile communication. It can be used as a protective film of a transistor, an electrode protective film of an organic EL device, a semiconductor protective film, and the like.

The present application provides a polyamic acid composition having excellent dielectric properties, such as exhibiting a low dielectric constant and low dielectric loss tangent in a high frequency band, excellent processing, hygroscopicity and heat resistance of a certain level or more, and capable of implementing an adhesive force of a certain level or more.

Hereinafter, the present invention will be described in more detail through Examples according to the present invention and Comparative Examples not according to the present invention, but the scope of the present invention is not limited by the Examples presented below.

<Preparation of polyamic acid solution>

Example 1

Methylpyrrolidone (NMP) was introduced while nitrogen was injected into a 500ml reactor equipped with a stirrer and a nitrogen injection/discharge tube, and the temperature of the reactor was set to 40°C. First, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP, 2,2-Bis [4- (4-aminophenoxy) phenyl] propane) monomer and Priamine (CRODA) were added to proceed with dissolution, and 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and are added and sufficiently stirred for at least 6 hours at 40°C. After stirring, 4,4'-bisphenol A dianhydride (BPADA, 4,4'-Bisphenol A dianhydride) was added and stirred for at least 6 hours to react until there was no change in viscosity to obtain a polyamic acid solution.

Examples 2 to 8

In Example 1, polyamic acid solutions of Examples 2 to 8 were prepared in the same manner as in Example 1, except that the monomer and its molar ratio were changed as shown in Table 1 below.

Comparative Examples 1 to 2

Polyamic acid solutions of Comparative Examples 1 to 4 were prepared in the same manner as in Example 1, except for the monomers and contents according to Table 1 below.

Dianhydride (mol%) Diamine (mol%) Example 1 BPDA(60) + BPADA(40) BAPP(95) + PA(5) Example 2 BPDA(60) + BPADA(40) BAPP(55) + m-Tolidine(40) + PA(5) Example 3 BPDA(60) + BPADA(40) BAPP(45) + HFBAPP(50) + PA(5) Example 4 BPDA(60) + BPADA(40) BAPP(90) + PA(10) Example 5 BPDA(75) + BTDA(25) BAPP(95) + PA(5) Example 6 BPDA(60) + BPADA(40) BAPP(40) + HFBAPP(50) + PA(10) Example 7 BPDA(60) + BPADA(40) HFBAPP(95) + PA(5) Example 8 BPDA(100) BAPP(70) + PA(30) Comparative Example 1 BPADA(100) ODA(70) + PA(30) Comparative Example 2 BPADA(100) ODA(80) + PA(20) BPDA: 4,4'-Bisphenol A dianhydride
BPADA: 4,4'-Bisphenol A dianhydride
BTDA: Benzophenonetetracarboxylic dianhydride
BAPP: 2,2-Bis [4- (4-aminophenoxy) phenyl] propane
HFBAPP: 2,2-Bis [4- (4-aminophenoxy phenyl)] hexafluoropropane
m-Tolidine: 2,2'-Tolidine
PA: Priamine (CRODA)
ODA: 4,4'-oxydianiline

Experimental Example - Viscosity Measurement

Viscosity of the polyamic acid solutions prepared by the Examples and Comparative Examples was measured using HAKKE Viscotester at a shear rate of 1s ⁻¹ , a temperature of 23° C., and a plate gap of 1 mm.

Table 3 below shows the viscosity (cP @23 ℃) ALC solid content (%) of the polyamic acid solution.

solid content
(%) Viscosity
(cP @23℃) Example 1 10 2,700 Example 2 10 2,900 Example 3 10 1,300 Example 4 10 2,600 Example 5 10 3,200 Example 6 15 3,500 Example 7 10 3,100 Example 8 10 4,000 Comparative Example 1 10 3,700 Comparative Example 2 10 5,700

<Preparation of polyimide solution>

Examples 1 to 8, and Comparative Examples 1 to 2

In the polyamic acid solutions prepared in Examples 1 to 8 and Comparative Examples 1 to 2, 1.0 equivalent of 3-methylpyridine (BP) relative to the number of moles of polyamic acid, and acetic anhydride, respectively After adding 3.0 equivalents, the temperature was raised to 70° C. and stirred for about 1 hour. Then, it was cooled to room temperature. Impurities such as acetic acid were removed with a vacuum pump to obtain polyimide solutions according to Examples 1 to 8 and Comparative Examples 1 to 2.

<Production of polyimide>

Examples 1 to 8, and Comparative Examples 1 to 2

Coating the polyimide solutions according to Examples 1 to 8 and Comparative Examples 1 to 2, and under a nitrogen atmosphere, at 110 ° C. for 20 minutes, 180 ° C. for 20 minutes, and 300 ° C. for 1 hour at 4 ° C./min. A polyimide in the form of a film was obtained.

Experimental Example - Thickness

The thickness of the polyimide prepared in Examples and Comparative Examples was measured using an Electric Film thickness tester manufactured by Anritsu Corporation.

Experimental example - dielectric constant and dielectric loss tangent measurement

The dielectric constant and dielectric loss tangent at 10 GHz of the polyimides manufactured by the Examples and Comparative Examples were measured at 23° C. and 50% RH using a Network Analyzer EVA Vector Network Analyzer (E5063A, Keysight Corporation).

Table 3 below shows the values of physical properties measured according to the experimental examples of the polyimide.

thickness
(μm) Permittivity (@10GHz) Dielectric loss tangent (@10GHz) Example 1 10 3.42 0.00293 Example 2 10 3.36 0.00306 Example 3 10 3.40 0.00262 Example 4 10 3.32 0.00281 Example 5 10 3.35 0.00291 Example 6 48 3.30 0.00279 Example 7 48 2.95 0.00285 Example 8 10 2.57 0.00301 Comparative Example 1 10 3.10 0.00330 Comparative Example 2 10 3.21 0.00365

Claims (20)

A dianhydride monomer component and a diamine monomer component are included as polymerized units,
The dianhydride monomer includes compounds represented by the following Chemical Formulas 1 and 3,
The diamine monomer is a polyamic acid composition comprising a dimer diamine and a diamine monomer of Formula 2 below:
[Formula 1]

[Formula 2]

[Formula 3]

In Formula 1, R is oxygen, a carbonyl group, an alkylcarbonyl group, a single bond, an alkylene group or an alkylidene group, A ₁ and A ₂ are each independently oxygen, a carbonyl group, an alkylcarbonyl group, a single bond, an alkylene group or an alkylidene group,
In Formula 2, R is oxygen, a carbonyl group, an alkylcarbonyl group, a single bond, an alkylene group or an alkylidene group, A ₁ and A ₂ are each independently oxygen, a carbonyl group, an alkylcarbonyl group, a single bond, an alkylene group or an alkylidene group,
M is an alkylene group, an alkylidene group, a carbonyl group, an alkylcarbonyl group, an alkoxy group, and at least one including at least one of the group comprising a sulfonyl group, wherein M is at least one or more from the group comprising a fluorine and an alkyl group substituted or unsubstituted. The polyamic acid composition according to claim 1, wherein the diamine monomer of Formula 2 is included in a ratio of 40 mol% or more of the total diamine monomer component. The polyamic acid composition according to claim 1, wherein the dimer diamine monomer is derived from a dimer acid that is a dimer of an unsaturated fatty acid. The polyamic acid composition according to claim 1, wherein the dimer diamine monomer has a linear, branched or cyclic aliphatic structure. The polyamic acid composition according to claim 4, wherein the linear, branched or cyclic aliphatic structure has 5 to 60 carbon atoms. The polyamic acid composition according to claim 1, wherein the dimer diamine monomer is included in a ratio of 3 mol% to 40 mol% of the total diamine monomer component. [Claim 2] The polyamic acid composition according to claim 1, comprising two different types of diamine monomers of formula (2). The polyamic acid composition according to claim 7, wherein at least one of the diamine monomers of Formula 2 has an alkyl group substituted with fluorine. delete The polyamic acid composition of claim 1, wherein the dianhydride monomer of Formula 1 comprises 30 mol% or more of the total dianhydride monomer component. delete The polyamic acid composition according to claim 1, wherein the weight average molecular weight is in the range of 10,000 g/mol to 100,000 g/mol. The polyamic acid composition according to claim 1, wherein the solid content is 5 to 70 wt%. The polyamic acid composition according to claim 1, wherein the viscosity measured at a temperature of 23°C and a shear rate of 1s ^-1 is in the range of 1,000 to 50,000 cP. The polyamic acid composition according to claim 1, further comprising an organic solvent. The polyamic acid composition according to claim 1, wherein the dielectric constant (Dk) after curing at any one point in the frequency band of 3.4 to 10 GHz is 3.5 or less. The polyamic acid composition according to claim 1, wherein the dielectric loss tangent (Df) after curing at any one point in the frequency band of 3.4 to 10 GHz is 0.0035 or less. A polyimide comprising a cured product of the polyamic acid composition according to claim 1 . A polyimide solution comprising the polyimide according to claim 18 and an organic solvent. A semiconductor device for 5th generation mobile communication comprising the polyimide according to claim 18.