Polyamic acid, polyamideimide and use thereof

Abstract

Disclosed in the present application are a polyamic acid, a polyamideimide and the use thereof. The polyamideimide has a repeating unit structure as represented by formula (II), wherein Ra represents an aromatic diacyl chloride component residue; Rb represents a tetracarboxylic acid component residue and / or a dianhydride component residue; and Rc represents an aromatic diamine component residue. A thin film prepared from the polyamideimide provided in the present application has a relatively high light transmittance and a relatively low yellowness index, and also has an excellent thermal stability, a relatively high glass transition temperature and excellent mechanical properties.

Description

Polyamic acid, polyamide-imide and their applications

[0001] This application is based on and claims priority from the Chinese patent application filed on July 16, 2024 with application number 202410953880.8 and invention name “Polyamic acid, polyamideimide and their applications”. Technical Field

[0002] The present application relates to the field of polymer technology, and in particular to polyamic acid, polyamide-imide and their applications. Background Art

[0003] Materials used in electronics face relatively stringent requirements, including structural, optical, thermal, electronic, and other properties. The rapid growth of the commercial electronics market has placed even more stringent demands on materials. Among these, polyamide-imide, with its high modulus and flexibility, can replace glass in traditional electronic display devices and enable the fabrication of flexible electronic devices.

[0004] Polymer-based materials are used for displays, and the required main physical properties are optical properties and mechanical properties. In order to prepare the polyamide-imide with excellent optical properties and mechanical properties, the reported method has, for example, copolymerization of a monomer with high transparency advantage and a monomer with strong linearity and rigidity, and improving the copolymerization ratio of strong linearity or rigid monomers to improve the mechanical strength of the polyamide-imide, but when the introduction ratio of monomers with strong linearity and rigidity is high, the handling property of the solution deteriorates, so there is a problem that the processing difficulty increases or cannot be realized. Moreover, because the intermolecular spacing becomes dense, the charge transfer complex formed in the polyamide-imide increases, and these charge transfer complexes are colored brown or yellow, causing the optical properties of the material to deteriorate, and the transmittance in the visible light region decreases, so it is difficult to be applied to display materials. In addition, the introduction of monomers with strong rigidity can accelerate white turbidity in the high-temperature drying process, causing the optical physical properties to deteriorate, which needs to reduce the process temperature of drying, but so just can't ensure sufficient productivity, increases the difficulty of process application.

[0005] Another method for rendering polyamide-imide colorless and transparent is to use alicyclic diamines or aliphatic diamines as components to suppress the formation of intramolecular charge transfer complexes. However, while these non-aromatic polyamide-imides have high transparency, they suffer from poor mechanical properties. Furthermore, various functional monomers have been tried in the prior art to transform the yellow color of polyamide-imide into colorless and transparent. However, these methods are difficult to implement due to difficulties in the synthesis of functional monomers and control of polymer viscosity, and are insufficient to address the problem of reducing the inherently excellent mechanical properties of polyamide-imide while ensuring transparency.

[0006] Therefore, it is necessary to develop a technology for polyamide-imide, which has good optical properties and excellent mechanical and physical properties, especially high modulus, and can be used in various display material fields including replacing modified glass materials. Summary of the Invention

[0007] To solve all or part of the above technical problems, this application provides the following technical solutions:

[0008] One of the purposes of the present application is to provide a polyamic acid having a repeating unit structure shown in Formula I:

[0009] Among them, R a Represents the residue of aromatic diacyl chloride component; R b represents a tetracarboxylic acid component residue and / or a dianhydride component residue; R c represents an aromatic diamine component residue.

[0010] The polyamide-imide formed from the polyamic acid having the repeating unit structure has the advantages of high modulus, high light transmittance, low yellowness index, good thermal stability, and exhibits a high glass transition temperature.

[0011] In some embodiments, the molar ratio of the total molar amount of Ra and Rb to Rc in the polyamic acid is 1:1. a With R b The molar ratio is 5~100:5~100.

[0012] In some embodiments, R a The aromatic dicarboxylic acid chloride monomers include one or more of terephthaloyl chloride (TPC), isophthaloyl chloride (IPC), 4,4′-biphenyl dicarboxylic acid chloride (BPC), 1,4-naphthaloyl dicarboxylic acid chloride (NPC), 2,6-naphthaloyl dicarboxylic acid chloride (NTC), 1,5-naphthaloyl dicarboxylic acid chloride (NEC), 4,4′-oxybis(benzoyl chloride) (DEDC), and / or derivatives thereof. When the aromatic dicarboxylic acid chlorides form an amide structure in the polymer chain, the optical and physical properties of the polyamide-imide can be improved, particularly the mechanical strength such as the modulus.

[0013] In some preferred embodiments, the aromatic diacid chloride monomer forming Ra includes terephthaloyl chloride (TPC). The modulus of the polyamide-imide film containing structural units derived from terephthaloyl chloride is further improved; furthermore, the resulting polyamide-imide film can reduce thickness-direction retardation and suppress degradation of optical properties. Therefore, the resulting polyamide-imide film can be used in display devices to reduce image distortion.

[0014] In some embodiments, the component residue formed by one or more of terephthaloyl chloride (TPC), isophthaloyl chloride (IPC), 4,4′-biphenyl dichloride (BPC), 1,4-naphthalene dichloride (NPC), 2,6-naphthalene dichloride (NTC), 1,5-naphthalene dichloride (NEC), 4,4′-oxybis(benzoyl chloride) (DEDC) and / or their derivatives is 5-100 mol% of the total amount of Ra.

[0015] In some embodiments, R b The monomer includes an aromatic dianhydride, and the aromatic dianhydride includes one or more of 1,2,4,5-pyromellitic dianhydride (PMDA), 3,3′,4,4′-diphenyl ether tetracarboxylic dianhydride (ODPA), 2,3,3′,4′-biphenyltetracarboxylic dianhydride (α-BPDA), 2,2′,3,3′-biphenyltetracarboxylic dianhydride (i-BPDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (s-BPDA), 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF) and / or their derivatives.

[0016] In some embodiments, the component residue formed by the aromatic dianhydride is R b 5-100 mol% of the total amount.

[0017] In some embodiments, R b The monomer further comprises alicyclic dianhydride. When the alicyclic dianhydride forms a non-conjugated structure in the polymer chain, it can effectively reduce the formation of charge transfer complexes, thereby improving the optical and physical properties of the polyamide-imide.

[0018] In some embodiments, the alicyclic dianhydride includes one or more of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,3,4-cyclohexanetetracarboxylic dianhydride (HPMDA), 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride (DMCBDA), norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride (CpODA) and / or their derivatives.

[0019] In some embodiments, the monomer forming Rc includes a compound represented by Formula III:

[0020] wherein R1, R2, and R3 are independently selected from hydrogen, hydroxy, cyano, halogen, alkyl, heteroalkyl, alkoxy, heteroalkoxy, haloalkyl, haloalkoxy, silyl, siloxy, hydrocarbon aryl, substituted or unsubstituted hydrocarbon aryl, or substituted or unsubstituted heteroaryl.

[0021] In some embodiments, the component residue formed by the compound represented by formula III is R c 5-100 mol% of the total amount.

[0022] In some embodiments, the compound represented by formula III includes one or more of the following compounds:

[0023] In some preferred embodiments, the compound represented by formula III includes compounds represented by formula III-1 and / or formula III-2:

[0024] In some embodiments, the monomer forming Rc also includes a second aromatic diamine different from the compound represented by Formula III, wherein the second aromatic diamine includes 2,2′-bis(trifluoromethyl)benzidine (TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (4BDAF), 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (FA), 4,4′-diaminodiphenyl ether (4,4′-ODA), p-phenylenediamine (PDA), 1,4-bis(4-aminophenoxy)benzene (144APB), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (6HMDA) and / or one or more of their derivatives.

[0025] The second object of this application is to provide a method for preparing the above-mentioned polyamic acid, comprising:

[0026] A mixed reaction system containing aromatic diacyl chloride monomer, dianhydride monomer, aromatic diamine monomer and solvent is polymerized at a temperature of -20 to 80° C. to obtain polyamic acid.

[0027] In some embodiments, the molar ratio of the aromatic diacyl chloride monomer to the dianhydride monomer is 5-100:5-100, and the total molar amount of the aromatic diacyl chloride monomer and the dianhydride monomer is equal to the total molar amount of the aromatic diamine monomer.

[0028] In some embodiments, the solvent includes one or more of N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, ethyl cellosolve, methyl cellosolve, acetone, ethyl acetate, m-cresol, γ-butyrolactone and / or their derivatives.

[0029] The specific selection of the aromatic diacid chloride monomer, dianhydride monomer, aromatic diamine monomer, and other monomers that may be added during the preparation process have been described in detail in one of the objectives of this application and will not be repeated here.

[0030] The third object of the present application is to provide a polyamide-imide having a repeating unit structure shown in Formula II:

[0031] Among them, R a Represents the residue of aromatic diacyl chloride component; R b represents a tetracarboxylic acid component residue and / or a dianhydride component residue; R c represents an aromatic diamine component residue.

[0032] In the polyamide-imide, R a and R b The total molar amount of R c The molar ratio is 1:1, R a With R b The molar ratio is 5~100:5~100.

[0033] In some embodiments, R a The aromatic dicarboxylic acid chloride monomer includes one or more of terephthaloyl chloride (TPC), isophthaloyl chloride (IPC), 4,4′-biphenyl dicarboxylic acid chloride (BPC), 1,4-naphthalene dicarboxylic acid chloride (NPC), 2,6-naphthalene dicarboxylic acid chloride (NTC), 1,5-naphthalene dicarboxylic acid chloride (NEC), 4,4′-oxybis(benzoyl chloride) (DEDC) and / or derivatives thereof.

[0034] In some embodiments, the component residue formed by one or more of terephthaloyl chloride (TPC), isophthaloyl chloride (IPC), 4,4′-biphenyl dichloride (BPC), 1,4-naphthalene dichloride (NPC), 2,6-naphthalene dichloride (NTC), 1,5-naphthalene dichloride (NEC), 4,4′-oxybis(benzoyl chloride) (DEDC) and / or their derivatives is 5-100 mol% of the total amount of Ra.

[0035] In some embodiments, R b The monomer includes an aromatic dianhydride, and the aromatic dianhydride includes one or more of 1,2,4,5-pyromellitic dianhydride (PMDA), 3,3′,4,4′-diphenyl ether tetracarboxylic dianhydride (ODPA), 2,3,3′,4′-biphenyltetracarboxylic dianhydride (3,4-BPDA), 2,2′,3,3′-biphenyltetracarboxylic dianhydride (3,3-BPDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (4,4-BPDA), 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF) and / or their derivatives.

[0036] In some embodiments, the component residue formed by the aromatic dianhydride is Rb 5-100 mol% of the total amount.

[0037] In some embodiments, R b Monomers also include alicyclic dianhydrides.

[0038] In some embodiments, the alicyclic dianhydride includes one or more of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,3,4-cyclohexanetetracarboxylic dianhydride (HPMDA), 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride (DMCBDA), norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride (CpODA) and / or their derivatives.

[0039] In some embodiments, R c The monomers include compounds represented by formula III:

[0040] wherein R1, R2, and R3 are independently selected from hydrogen, hydroxy, cyano, halogen, alkyl, heteroalkyl, alkoxy, heteroalkoxy, haloalkyl, haloalkoxy, silyl, siloxy, substituted or unsubstituted hydrocarbon aryl, or substituted or unsubstituted heteroaryl.

[0041] In some embodiments, the component residue formed by the compound represented by formula III is R c 5-100 mol% of the total amount.

[0042] In some embodiments, the compound represented by formula III includes one or more of the following compounds:

[0043] In some preferred embodiments, the compound represented by formula III includes compounds represented by formula III-1 and / or formula III-2:

[0044] In some embodiments, the monomer forming Rc also includes a second aromatic diamine different from the compound represented by Formula III, wherein the second aromatic diamine includes 2,2′-bis(trifluoromethyl)benzidine (TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (4BDAF), 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (FA), 4,4′-diaminodiphenyl ether (4,4′-ODA), p-phenylenediamine (PDA), 1,4-bis(4-aminophenoxy)benzene (144APB), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (6HMDA) and / or one or more of their derivatives.

[0045] In some embodiments, the glass transition temperature of the polyamide-imide is g Greater than 300℃.

[0046] In some embodiments, the yellowness index (YI) value of the polyamide-imide is less than 7.0.

[0047] A fourth object of the present application is to provide a method for preparing the polyamide-imide, comprising: imidizing the polyamic acid to obtain the polyamide-imide.

[0048] A fifth object of the present application is to provide a composition comprising:

[0049] The polyamic acid described in any one of the above technical solutions and / or the polyamide-imide described in any one of the above technical solutions;

[0050] At least one aprotic solvent.

[0051] In some embodiments, the aprotic solvent includes one or more of N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, ethyl cellosolve, methyl cellosolve, acetone, ethyl acetate, m-cresol, γ-butyrolactone and / or their derivatives.

[0052] The sixth object of the present application is to provide a polyamide-imide film, which comprises the polyamide-imide described in any one of the technical solutions, or the polyamide-imide film is obtained by curing the composition described in any one of the technical solutions.

[0053] In some embodiments, the total light transmittance of the polyamide-imide film in the wavelength range of 380-800 nm is greater than 87.0%.

[0054] In some embodiments, the haze of the polyamide-imide film is less than 2.0%.

[0055] In some embodiments, the polyamide-imide film has a yellowness index of 7.0 or less.

[0056] In some embodiments, the modulus of the polyamide-imide film is greater than 4.0 GPa.

[0057] Since the polyamide-imide film has high modulus, high light transmittance and low yellowness index, the polyamide-imide film can be used as a substitute for glass, for example, as a flexible substitute for glass in electronic devices.

[0058] The seventh object of the present application is to provide a transparent structure, which comprises the polyamide-imide film described in any one of the technical solutions.

[0059] An eighth object of the present application is to provide a device having a transparent component, wherein the device includes the transparent structure.

[0060] In some embodiments, the transparent structure may be applied to one or more of a device substrate, a color filter substrate, a cover film, a cover layer, an active display, a TFT layer, and a touch screen panel of a device.

[0061] Compared with the prior art, this application has at least the following beneficial effects:

[0062] (1) The polyamic acid and polyamide-imide provided in the present application contain structural units derived from aromatic diacyl chlorides. When the aromatic diacyl chlorides form amide structures in the polymer chain, the optical physical properties and mechanical strength of the polyamide-imide can be improved, especially the polyamide-imide of the present application exhibits a high modulus. In addition, the polyamide-imide based on the repeating unit structure described in the present application also has a high light transmittance, a low yellowness index, and a high glass transition temperature.

[0063] (2) Furthermore, the present applicant has found that when the aromatic dicarboxylic acid chloride contains TPC, the modulus and other mechanical properties of the polyamide-imide film can be further improved; and when the polyamide-imide film is applied to a display device, the delay in the thickness direction of the film can be reduced, the degradation of the optical physical properties can be suppressed, and the image distortion of the device can be significantly reduced;

[0064] (3) Furthermore, the present application found that when R b When the dianhydride includes alicyclic dianhydride, the non-conjugated structure formed in the polymer chain can effectively reduce the formation of charge transfer complexes, thereby improving the optical and physical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] Embodiments are illustrated in the accompanying drawings to improve understanding of the concepts as presented herein.

[0066] FIG1 is a DMA test curve of the polyamide-imide film prepared in Example 5 of the present application;

[0067] FIG2 is a TGA test curve of the polyamide-imide film prepared in Example 5 of the present application;

[0068] FIG3 is a DMA test curve of the polyamide-imide film prepared in Example 7 of the present application;

[0069] FIG4 is a DMA test curve of the polyamide-imide film prepared in Example 8 of the present application;

[0070] FIG5 is a DMA test curve of the polyamide-imide film prepared in Example 38 of the present application. DETAILED DESCRIPTION

[0071] The embodiments described in this specification may be modified into various other forms. What is described in this specification is merely exemplary and non-restrictive. After reading this specification, technicians will understand that other aspects and embodiments are possible without departing from the scope of this application.

[0072] In addition, unless otherwise defined, technical and scientific terms used in the present specification may have meanings that are commonly understood by those skilled in the art in the technical fields disclosed in the present specification.

[0073] Other features and benefits of any one or more embodiments will be apparent from the following detailed description and from the claims.The detailed description first presents definitions of terms, followed by polyamic acid, polyamideimide, methods for making polyamideimide films, and finally examples.

[0074] 1. Definition of terms

[0075] Before presenting details of the following embodiments, some terms are defined or clarified.

[0076] Throughout the specification, unless otherwise specifically stated, the description "comprising" or "including" a certain component means that other components may also be included, rather than excluding other components. For example, condition A or B is satisfied by any of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0077] Moreover, the use of "a / an" to describe the elements and components described herein is only for convenience and to give a general sense of the scope of the application. This description should be read to include one / an or at least one / an, and the singular also includes the plural unless it is obvious that it is meant otherwise.

[0078] The numerical ranges used in this specification include the lower and upper limits and all values ​​within the range, increments logically derived from the form and width of the defined range, all values ​​defined therein, and all possible combinations of upper and lower limits of numerical ranges defined in different forms. As an example, when the content of a component is defined as 10-80% or 20-50%, it should be interpreted that the numerical range of 10-50% or 50-80% is also recorded in this specification. Unless otherwise specifically defined in this specification, values ​​outside the numerical range that may appear due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0079] Hereinafter, unless otherwise specifically defined in the present specification, "a combination thereof" may refer to a mixture or copolymerization of the components.

[0080] Hereinafter, unless otherwise specifically defined in this specification, "A and / or B" may refer to a case where both A and B are included, or may refer to a case where only one of A and B is selected.

[0081] Hereinafter, unless otherwise specifically defined in this specification, "polymer" refers to a relatively high molecular weight molecule whose structure may include multiple repetitions of units derived from low molecular weight molecules. In one embodiment, the polymer may be an alternating copolymer, a block copolymer, a random copolymer, a graft copolymer, a gradient copolymer, a branched copolymer, a crosslinked copolymer, or a copolymer comprising all of them (e.g., a polymer comprising more than one monomer). In another embodiment, the polymer may be a homopolymer (e.g., a polymer comprising one monomer).

[0082] Hereinafter, unless otherwise specifically defined in the present specification, "polyamic acid" refers to a polymer including a structural unit having an amic acid portion, and "polyamideimide" may refer to a polymer including a structural unit having an amide portion and an imide portion.

[0083] Hereinafter, unless otherwise specifically defined in the present specification, the polyamideimide film may be a film comprising polyamideimide, specifically a high heat-resistant film prepared by solution polymerization of a diamine compound solution with a dianhydride compound and a diacid chloride to prepare polyamic acid followed by imidization.

[0084] Hereinafter, unless otherwise specifically defined in this specification, when describing a layer, membrane, film, region, plate or the like as being "on" or "over" another part, this includes not only the case where it is "directly" "on" another part, but also the case where there are other parts in between.

[0085] As used in the “Definition and Clarification of Terms”, R a 、R b 、R c , R1, R2, R3 and any other variables are generic names and may be the same as or different from those defined in the formula.

[0086] As used herein, the term "alicyclic" refers to a cyclic group that is not aromatic. The group may be saturated or unsaturated.

[0087] The term "alkyl" includes branched and straight chain saturated aliphatic hydrocarbon groups. Unless otherwise indicated, the term is also intended to include cyclic groups.

[0088] In certain embodiments, unless otherwise specifically defined herein, “substituted” refers to a hydrogen atom in a compound being replaced by a substituent.

[0089] The term "alkyl" further includes both substituted and unsubstituted hydrocarbon groups. In some embodiments, the alkyl group can be mono-, di- and tri-substituted. An example of a substituted alkyl group is trifluoromethyl. Other substituted alkyl groups are formed by one or more of the substituents described herein. For example, the substituent can be selected from deuterium, a halogen atom (F, Br, Cl or I), a hydroxyl, a nitro, a cyano, an amino, an azido, an amidino, a hydrazine, a hydrazide, a carbonyl, a carbamoyl, a thiol, an ester, a carboxyl or a salt thereof, a sulfonic acid or a salt thereof, a phosphoric acid or a salt thereof, a C 1-30 Alkyl, C 2-30 Alkenyl, C 2-30 Alkynyl, C 6-30 Aryl, C 7-30 Arylalkyl, C 1-3 Alkoxy, C 1-20 Heteroalkyl, C 3-20 Heteroarylalkyl, C 3-30 Cycloalkyl, C 3-15 Cycloalkenyl. C 6-15 Cycloalkynyl, C 2-20 heterocyclic groups and combinations thereof.

[0090] The term "aprotic" refers to a class of solvents that lack acidic hydrogen atoms and therefore cannot act as hydrogen donors. Common aprotic solvents include alkanes, carbon tetrachloride (CCl4), benzene, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAC), γ-butyrolactone, etc.

[0091] The term "aromatic compound" is intended to mean an organic compound containing at least one unsaturated cyclic group having 4n+2 delocalized π electrons. The term is intended to encompass both aromatic compounds having only carbon and hydrogen atoms, and heteroaromatic compounds in which one or more carbon atoms within the cyclic group has been replaced by another atom, such as nitrogen, oxygen, sulfur, etc.

[0092] The term "aryl" or "aryl group" is intended to mean a moiety formed by removing one or more hydrogen ("H") or deuterium ("D") from an aromatic compound. An aryl group can be a single ring (monocyclic) or have multiple rings (bicyclic or higher) that are fused together or covalently linked. A "hydrocarbyl" has only carbon atoms in one or more aromatic rings. A "heteroaryl" has one or more heteroatoms in at least one aromatic ring. In some embodiments, a hydrocarbyl group has from 6 to 60 ring carbon atoms; in some embodiments, from 6 to 30 ring carbon atoms. In some embodiments, a heteroaryl group has from 4 to 50 ring carbon atoms; in some embodiments, from 4 to 30 ring carbon atoms.

[0093] The term "alkoxy" is intended to mean the group -OR, where R is alkyl.

[0094] The term "aryloxy" is intended to mean the group -OR, where R is aryl.

[0095] Unless otherwise indicated, all groups may be substituted or unsubstituted. Optionally substituted groups, such as, but not limited to, alkyl or aryl, may be substituted by one or more substituents which may be the same or different. Suitable substituents include deuterium, alkyl, aryl, nitro, cyano, N(R′)(R″), halogen, hydroxy, carboxyl, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy, arylalkyl, silyl, siloxy, siloxane, thioalkoxy, -SO2, -CO-N(R′)(R″), (R′)(R″)N-alkyl, (R′)(R″)N-alkoxyalkyl, (R′)(R″)N-alkylaryloxyalkyl, -SO-aryl, -SO2-aryl, -SO-heteroaryl, -SO2-heteroaryl. Each R′ and R″ is independently an optionally substituted alkyl, cycloalkyl or aryl group. R' and R", together with the nitrogen atom to which they are attached, can form a ring system in certain embodiments. The substituent can also be a cross-linking group.

[0096] The term "amine" is intended to refer to a compound containing a basic nitrogen atom having a lone pair of electrons, where a lone pair refers to a set of two valence electrons not shared with another atom.

[0097] The term "amino" refers to the functional group -NH2, -NHR or -NR2, where R at each occurrence is the same or different and can be an alkyl group or an aryl group.

[0098] The term "diamine" is intended to mean a compound containing two basic nitrogen atoms with associated lone pairs of electrons.

[0099] The term "polyamine" is intended to mean a compound containing two or more basic nitrogen atoms with associated lone pairs of electrons.

[0100] The term "aromatic diamine" is intended to mean an aromatic compound having two amino groups.

[0101] The term "aromatic polyamine" is intended to mean an aromatic compound having two or more amino groups.

[0102] The term "isomeric diamine" is intended to mean a diamine in which the two basic nitrogen atoms and the associated lone electron pairs are positioned asymmetrically about the center of symmetry of the respective compound or functional group, for example, meta-phenylenediamine:

[0103] The term "residue of an aromatic diamine" is intended to mean a portion bonded to two amino groups in the aromatic diamine.

[0104] The term "residue of an aromatic polyamine" is intended to mean a moiety bonded to two or more amino groups in the aromatic polyamine.

[0105] The term "residue of an aromatic diisocyanate" is intended to mean a portion bonded to two isocyanate groups in an aromatic diisocyanate compound.

[0106] The term "residue of an aromatic polyisocyanate" is intended to mean a portion that is bonded to two or more isocyanate groups in an aromatic polyisocyanate compound. This is further explained below.

[0107] The terms "diamine residue" and "diisocyanate residue" are intended to mean a moiety bonded to two amino groups or two isocyanate groups, respectively, wherein the moiety is aliphatic or aromatic. The terms "polyamine residue" and "polyisocyanate residue" are intended to mean a moiety bonded to two or more amino groups or two or more isocyanate groups, respectively, wherein the moiety is aliphatic or aromatic.

[0108] The term "compound" is intended to mean an uncharged substance composed of molecules further comprising atoms, wherein an atom cannot be separated from its corresponding molecule by physical means without breaking the chemical bonds. The term is intended to include oligomers and polymers.

[0109] The term "coefficient of linear thermal expansion (CTE)" is intended to refer to a parameter that defines the amount a material expands or contracts with temperature. It is expressed as the change in length per degree Celsius and is typically expressed in units of ppm / K.

[0110] The measured CTE values ​​disclosed herein are generated via known methods during the first or second heating scan.Understanding the relative expansion / contraction characteristics of materials can be an important consideration in the manufacture and / or reliability of electronic devices.

[0111] The term "dopant" is intended to mean a material within a layer comprising a host material that changes one or more electronic properties or one or more target wavelengths of radiation emission, reception, or filtering of the layer as compared to the one or more electronic properties or one or more wavelengths of radiation emission, reception, or filtering of the layer in the absence of such material.

[0112] The term "elongation at break" or "tensile strain" is intended to mean the percentage increase in length that occurs in a material before the material breaks under an applied tensile stress.

[0113] The prefix "fluoro" is intended to indicate that one or more hydrogens in the group have been replaced by fluorine.

[0114] The term "glass transition temperature (or T g ) is intended to mean the temperature at which a reversible change occurs in an amorphous polymer, or in the amorphous regions of a semicrystalline polymer, in which the material suddenly changes from a hard, glassy, ​​or brittle state to a flexible or elastic state. Microscopically, the glass transition occurs when normally coiled, stationary polymer chains become free to rotate and can move past each other. T can be measured using differential scanning calorimetry (DSC), thermomechanical analysis (TMA), dynamic mechanical analysis (DMA), or other methods. g .

[0115] The term "haloalkyl" is intended to mean an alkyl group having one or more hydrogen atoms replaced by a halogen atom.

[0116] The term "haloalkoxy" is intended to mean an alkoxy group having one or more hydrogen atoms replaced by a halogen atom.

[0117] The prefix "hetero" indicates that one or more carbon atoms have been replaced by a different atom. In some embodiments, the heteroatom is O, N, S, or a combination thereof.

[0118] The term "high boiling point" is intended to mean a boiling point above 100°C.

[0119] The term "host material" is intended to refer to a material to which a dopant is added. The host material may or may not have one or more electronic properties or capabilities to emit, receive, or filter radiation. In some embodiments, the host material is present in a relatively high concentration.

[0120] The term "liquid composition" is intended to mean a liquid medium in which a material is dissolved to form a solution, a liquid medium in which a material is dispersed to form a dispersion, or a liquid medium in which a material is suspended to form a suspension or emulsion.

[0121] The term "5% weight loss" is intended to mean the temperature at which 5% of the original polymer weight is lost due to decomposition (excluding absorbed water).

[0122] The term "polyamic acid solution" refers to a solution of a polymer containing an amic acid unit having intramolecular cyclization capability to form an imide group.

[0123] The term "polyanhydride" refers to a compound having two or more anhydride groups. The term "polyanhydride residue" is intended to mean a moiety bonded to two or more anhydride groups. This is further explained below.

[0124] The term "polyamideimide" refers to a polymer having an amide bond (-NH-CO-) and an imide bond (-CO-NH-CO-) in its main chain.

[0125] The term "satisfactory" when referring to a material property or characteristic is intended to mean that the property or characteristic meets all requirements / demands for the material in use.

[0126] The term "soft bake" station refers to a process commonly used in electronics manufacturing where a coated material is heated to drive off solvents and cure the film. Soft baking is typically performed at temperatures between 60°C and 110°C on a hot plate or in an exhaust oven as a preparatory step for subsequent thermal treatment of the coated layer or film.

[0127] The term "substrate" refers to a base material that may be rigid or flexible and may include one or more layers of one or more materials, including but not limited to glass, polymers, metals, or ceramic materials, or combinations thereof. The substrate may or may not include electronic components, circuits, or conductive members.

[0128] The term "tensile modulus" is intended to mean a measure of the stiffness of a solid material that defines the initial relationship between stress (force per unit area) and strain (proportional deformation) in a material such as a film. The commonly used unit is GPa.

[0129] The term "tetracarboxylic acid component" is intended to mean any one or more of a tetracarboxylic acid, a tetracarboxylic acid monoanhydride, a tetracarboxylic acid dianhydride, a tetracarboxylic acid monoester, and a tetracarboxylic acid diester.

[0130] The term "tetracarboxylic acid component residue" is intended to mean a moiety bonded to four carboxyl groups in a tetracarboxylic acid component, which is further described below.

[0131] The term "transmittance" refers to the percentage of light of a given wavelength impinging on a film that passes through the film so as to be detectable on the other side. Measurements of light transmittance in the visible region (380 nm to 800 nm) are particularly useful for characterizing the film color characteristics that are most important for understanding the in-use properties of the polyamideimide films disclosed herein.

[0132] The term "yellowness index (or YI)" refers to the magnitude of yellowness relative to a standard. Positive values ​​of YI indicate the presence and magnitude of yellow. Materials with negative YI appear bluish, particularly for polymerized and / or cured materials run at high temperatures.

[0133] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present application, suitable methods and materials are described below. Unless a specific passage is cited, all publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and are not intended to be limiting.

[0134] To the extent not described herein, many details regarding specific materials, processing activities, and circuits are conventional and can be found in books, articles, and other sources in the fields of organic light emitting diode displays, photodetectors, photovoltaics, and semiconductor components.

[0135] Hereinafter, a composition according to a specific embodiment will be described.

[0136] According to a specific embodiment, a polyamic acid is provided, comprising units derived from aromatic diamines, units derived from aromatic dianhydrides, and units derived from aromatic diacid chlorides. The polyamic acid can form polyamide-imides having good mechanical and optical properties.

[0137] According to a specific embodiment, a polyamide-imide is provided, comprising units derived from an aromatic diamine, units derived from an aromatic dianhydride, and units derived from an aromatic diacid chloride. Compared with existing polyamide-imides, the polyamide-imide has good mechanical and optical properties.

[0138] The aromatic diamine may include the compound represented by formula III-1 and / or the compound represented by formula III-2, the aromatic dianhydride may include 4,4-hexafluoroisopropylphthalic anhydride (6FDA), and the aromatic diacid chloride may include terephthaloyl chloride (TPC).

[0139] As an example, by using the III-1 compound as an aromatic diamine, TPC as an aromatic diacid chloride, and 6FDA as an aromatic dianhydride in combination, a polyamide-imide film having excellent mechanical and optical properties can be provided.

[0140] The reaction between the III-1 compound and TPC generates an amide group. Therefore, the prepared polyamide-imide film resin contains multiple amide bonds, which increases the intramolecular and / or intermolecular interactions of the amide bonds, thereby significantly improving the mechanical and physical properties.

[0141] While not intending to be bound by any particular theory, III-1, TPC, and 6FDA all contain aromatic rings, thereby increasing the carbon content of the polyamide-imide resin. This allows for the provision of a film having both superior mechanical properties and sufficient optical properties.

[0142] In addition to the compounds of formula III-1 and formula III-2, the aromatic diamine may be mixed with aromatic diamines commonly used in the art as needed. For example, in addition to the compounds of formula III-1 and formula III-2, a second aromatic diamine different from III-1 and III-2 may be included. The second aromatic diamine may include, for example, substituted or unsubstituted C 6-30 Aromatic ring, wherein the aromatic ring can be a single ring; or a condensed ring of two or more aromatic rings; or two or more aromatic rings can be connected by a single bond, C 1-5 Alkylene, O, or C=O connected non-condensed ring. Alternatively, the second aromatic diamine may be introduced with a fluorine substituent, and the use of an aromatic diamine introduced with a fluorine substituent can help improve the optical properties of the polyamide-imide. Specifically, the second aromatic diamine may include an aromatic ring substituted with one or more trifluoroalkyl groups, and the aromatic ring substituted with a trifluoroalkyl group may be further substituted with other substituents other than trifluoroalkyl groups or may be unsubstituted.

[0143] Specifically, the second aromatic diamine may include, for example, 2,2′-bis(trifluoromethyl)benzidine (TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (4BDAF), 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (FA), 4,4′-diaminodiphenyl ether (4,4′-ODA), p-phenylenediamine (PDA), 1,4-bis(4-aminophenoxy)benzene (144APB), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (6HMDA), and / or a mixture of more than one of these derivatives, but is not limited thereto. More specifically, the second aromatic diamine may include 2,2′-bis(trifluoromethyl)benzidine (TFMB).

[0144] The aromatic diamine may be composed solely of compounds III-1 and / or III-2, or a second aromatic diamine may be mixed in. When the second aromatic diamine is mixed in, the mixing ratio is not limited. However, the content of III-1 may be, for example, 1 mol% or more, 2 mol% or more, 5 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 55 mol% or more, 60 mol% or more, or 70 mol% or more, and may be, for example, 99 mol% or less, 98 mol% or less, 95 mol% or less, 90 mol% or less, 80 mol% or less, 75 mol% or less, 70 mol% or less, 65 mol% or less, 60 mol% or less, or 50 mol% or less, based on the total molar number of the aromatic diamine (units derived from the aromatic diamine), but is not necessarily limited thereto.

[0145] The aromatic dianhydride can be 6FDA alone, or other dianhydrides commonly used in the art can be mixed as needed. For example, other aromatic dianhydrides can be selected as the second dianhydride. The aromatic dianhydride refers to a dianhydride containing at least one aromatic ring, which can be a monocyclic ring, or a condensed ring formed by condensing two or more aromatic rings, or two or more aromatic rings connected by a single bond, a substituted or unsubstituted C 1-5 Alkylene, O or C = O connected non-condensed ring. For example, other aromatic dianhydrides can include 1,2,4,5-pyromellitic dianhydride (PMDA), 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (3,4-BPDA), 2,2',3,3'-biphenyltetracarboxylic dianhydride (3,3-BPDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (4,4-BPDA), 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride (BPAF) and / or a mixture of one or more of their derivatives.

[0146] Other dianhydrides may also include alicyclic dianhydrides, and the alicyclic dianhydrides may be dianhydrides containing alicyclic rings commonly used in the art, and the type is not limited. The alicyclic dianhydride refers to a dianhydride containing at least one alicyclic ring, and the alicyclic ring may be a single ring, or two or more alicyclic condensed rings, or two or more alicyclic rings connected by a single bond, a substituted or unsubstituted C1-5 alkylene group, O, or C=O.

[0147] Specifically, the alicyclic dianhydride may include, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,3,4-cyclohexanetetracarboxylic dianhydride (HPMDA), 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride (DMCBDA), norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride (CpODA) and / or a mixture of one or more of their derivatives. More specifically, the alicyclic dianhydride may include 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA).

[0148] When a non-conjugated structure is formed in the polymer chain by the alicyclic dianhydride, the formation of charge transfer complexes can be effectively reduced, and the optical physical properties can be improved.

[0149] When further comprising alicyclic dianhydride, its mixing ratio is unrestricted.For example, the total mole number of the aromatic dichloride (derived from the unit of aromatic dichloride), aromatic dianhydride (derived from the unit of aromatic dianhydride) and alicyclic dianhydride (derived from the unit of the dianhydride containing alicyclic) contained with described polyamic acid, polyamide-imide is benchmark, the content of alicyclic dianhydride (derived from the unit of the dianhydride containing alicyclic) can be more than 1 mol %, more than 2 mol %, more than 5 mol %, more than 10 mol %, more than 20 mol %, more than 30 mol %, more than 40 mol %, more than 50 mol %, more than 55 mol %, more than 60 mol % or more than 70 mol %, and can be below 99 mol %, below 98 mol %, below 95 mol %, below 90 mol %, below 80 mol %, below 75 mol %, below 70 mol %, below 65 mol %, below 60 mol % or below 50 mol %.But, be not limited to above-mentioned scope.

[0150] The aromatic diacyl chloride may be TPC alone, or may be a mixture of TPC and other aromatic diacyl chlorides commonly used in the art. For example, the other aromatic diacyl chlorides may include isophthaloyl chloride (IPC), 4,4′-biphenyl dicarboxylic acid chloride (BPC), 1,4-naphthalene dicarboxylic acid chloride (NPC), 2,6-naphthalene dicarboxylic acid chloride (NTC), 1,5-naphthalene dicarboxylic acid chloride (NEC), 4,4′-oxybis(benzoyl chloride) (DEDC), and / or a mixture of one or more of these derivatives, but the present invention is not limited thereto.

[0151] When an amide structure is formed in the polymer chain by the aromatic diacid chloride, the optical physical properties can be improved, and in particular, the mechanical strength such as the modulus can be further improved.

[0152] In a composition according to a specific embodiment, the content of TPC (units derived from TPC) can be, for example, 1 mol% or more, 2 mol% or more, 5 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 55 mol% or more, 60 mol% or more, or 70 mol% or more, and can be, for example, 99 mol% or less, 95 mol% or less, 90 mol% or less, 80 mol% or less, 75 mol% or less, or 70 mol% or less, based on the total molar amount of the dianhydride (units derived from the dianhydride) and the aromatic diacid chloride (units derived from the aromatic diacid chloride), but is not necessarily limited thereto. A composition according to a specific embodiment includes TPC, thereby further improving the mechanical properties of the polyamide-imide film, such as the modulus; and reducing the increase in thickness-direction retardation and the deterioration of optical properties. Therefore, the polyamide-imide film can be used in display devices to reduce image distortion.

[0153] The above content range is an example given to satisfy desired physical properties and can be changed according to the composition of the monomers, and is not limited thereto.

[0154] According to a specific embodiment, a composition is provided, which includes the polyamic acid and / or polyimide, and a solvent.

[0155] The solvent may be an organic solvent, specifically a polar solvent, and more specifically may include any one or more of N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ethyl cellosolve, methyl cellosolve, acetone, ethyl acetate, m-cresol, γ-butyrolactone (GBL) and / or their derivatives, but is not limited thereto.

[0156] In addition to the above components, the composition may further include additives as needed. The additives may be additives for improving film formation, adhesion, optical physical properties, mechanical physical properties, flame retardancy, etc., and may include, but are not limited to, flame retardants, tackifiers, inorganic particles, antioxidants, UV inhibitors, and / or plasticizers.

[0157] The composition can be prepared by precipitating after adding all monomers including aromatic diamine, dianhydride and aromatic diacid chloride, or by mixing aromatic diamine and aromatic diacid chloride, followed by precipitation and then mixing with the remaining monomers.

[0158] Another specific embodiment provides a polyamideimide film, wherein the polyamideimide film is obtained by curing the composition, or the polyamideimide film comprises the polyamideimide described above.

[0159] According to a specific embodiment of the polyamide-imide film, the total light transmittance measured at 380-800 nm according to the ASTM D1003 standard can be 87.0% or more, 87.5% or more, 88.0% or more, 88.3% or more, 88.5% or more, 89.0% or more, 89.5% or more, or 90.0% or more, but is not necessarily limited thereto.

[0160] According to a specific embodiment of the polyamide-imide film, the haze measured according to the ASTM D1003 standard may be 2.0% or less, 1.5% or less, 1.3% or less, 1.2% or less, 1.0% or less, 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.5% or less, or 0.4% or less, but is not necessarily limited thereto.

[0161] According to a specific embodiment of the polyamide-imide film, the yellowness index measured according to ASTM E313 may be 7.0 or less, 6.5 or less, 6.0 or less, 5.8 or less, 5.5 or less, 5.0 or less, 4.5 or less, or 4.0 or less, but is not necessarily limited thereto.

[0162] The polyamideimide film according to a specific embodiment may have a modulus measured according to ASTM D882 of 4.0 GPa or more, 4.5 GPa or more, 5.0 GPa or more, 5.5 GPa or more, 6.0 GPa or more, 6.5 GPa or more, 6.8 GPa or more, 7.0 GPa or more, 7.5 GPa or more, 8.0 GPa or more, or 9.5 GPa or more.

[0163] The physical property values ​​of the polyamideimide may be values ​​obtained by measuring a polyamideimide film subjected to a drying process at 80-100° C., 85-95° C., or about 90° C., or may be values ​​obtained by measuring a polyamideimide film subjected to a drying process at a high temperature of 110-160° C., 120-160° C., 130-150° C., or about 140° C.

[0164] According to a specific embodiment, the polyamide-imide film is prepared by utilizing a liquid composition of polyamic acid and / or polyamide-imide included in one embodiment, wherein the polyamic acid and / or polyamide-imide includes a unit derived from a III-1 compound, a unit derived from 6FDA, and a unit derived from TPC, thereby providing a film that simultaneously satisfies the desired physical properties of a transmittance of 85.0% or more, a haze of 2.0% or less, a yellowness index of 7.0 or less, and a modulus of 4.0 GPa or more.

[0165] The thickness of the polyamide-imide film may be 1-500 μm, 10-250 μm, 10-100 μm, 20-100 μm, or 20-80 μm, but is not necessarily limited thereto.

[0166] The polyamide-imide film according to one embodiment can be prepared by coating the composition comprising polyamic acid and / or polyamide-imide and a solvent according to one embodiment on a substrate, followed by drying and / or stretching, or can be prepared by a solution casting method.

[0167] More specifically, the preparation may include the following steps: imidizing the polyamic acid of the above embodiment and a solvent to prepare a polyamide-imide resin; dissolving the polyamide-imide resin in an organic solvent to obtain a resin composition; and coating the resin composition to form a film.

[0168] The organic solvent may include, for example, dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ethyl cellosolve, methyl cellosolve, acetone, ethyl acetate, m-cresol, γ-butyrolactone (GBL) and / or a combination of one or more of their derivatives, but is not necessarily limited thereto.

[0169] The imidization can be carried out by chemical imidization using any one or more selected from an imidization catalyst and a dehydrating agent. The imidization catalyst can be used to be selected from any one or more selected from pyridine, isoquinoline, and β-quinoline, etc. In addition, the dehydrating agent can be used to be selected from any one or more selected from acetic anhydride, phthalic anhydride, and maleic anhydride, etc. The imidization catalyst and the dehydrating agent can be used with commonly used imidization catalysts and dehydrating agents, and are not necessarily limited to the above-mentioned types.

[0170] In addition, in the step of preparing the polyamide-imide resin, additives such as flame retardant, tackifier, inorganic particles, antioxidant, UV inhibitor and plasticizer can be mixed in the polyamic acid solution to prepare the polyamide-imide resin. In addition, after imidization, solvent is utilized to refine resin to obtain solid compound, and the solid compound is dissolved in a solvent, thereby polyamide-imide resin composition can be obtained. At this moment, solvent, for example, can comprise DMAc etc., but is not limited thereto.

[0171] The film forming step is a step of coating the polyamide-imide resin composition on a substrate and then heat-treating it to form a film. The substrate can be, for example, glass, stainless steel, or a film, and the coating can be performed by a die coater, air knife coating, reverse roll coating, spray coating, blade coating, casting, gravure coating, spin coating, or the like.

[0172] The heat treatment can be carried out in steps. For example, a primary drying can be carried out at 70-160°C for a drying time of 1 minute to 2 hours, and a secondary drying can be carried out at 150-450°C for a drying time of 1 minute to 2 hours. However, it is not necessary to be limited to the above temperature and time conditions. For example, the primary drying can be carried out at 25-220°C, 80-150°C, 70-110°C, 130-150°C, 90°C, 120°C or 140°C for 1-300 minutes, 10-150 minutes, 10-90 minutes, 20-60 minutes or 30 minutes, and the secondary drying can be carried out at 200-500°C, 200-300°C, 220-300°C or 250-300°C for 1-300 minutes, 10-150 minutes, 10-90 minutes, 30-90 minutes or 40-80 minutes. In addition, when heat treatment is performed in steps, the heating rate may be 1-20°C / min. In addition, the heat treatment may be performed in a separate vacuum oven or an oven filled with an inert gas, etc., and is not necessarily limited thereto. In addition, the coating may be formed into a film on a support using an applicator.

[0173] According to a specific embodiment of the polyamide-imide film, the drying process is performed at a high temperature of about 140° C. during the primary drying, which can achieve the effect of suppressing optical degradation (clouding), thereby ensuring the feasibility of mass production.

[0174] The following examples and experimental examples are specifically illustrated and described. However, the following examples and experimental examples are only used to illustrate a part of a specific embodiment and should not be interpreted as limiting the technology described in this specification.

[0175] Measurement method

[0176] 1. Light transmittance (total light transmittance)

[0177] For the films prepared in this specification, the total light transmittance (%) was measured over the entire wavelength range of 360-780 nm using an UltraScan VIS spectrophotometer (Hunter Lab, USA) using CIE standard illuminant D65.

[0178] 2.Haze

[0179] For the films prepared in the present description, the haze value (%) was measured using an UltraScan VIS spectrophotometer (Hunter Lab, USA) using CIE standard illuminant D65.

[0180] 3. Yellowness Index (YI)

[0181] For the films prepared in the description herein, the yellowness index was measured using CIE standard illuminant D65 with an UltraScan VIS spectrophotometer (Hunter Lab, USA).

[0182] 4. Modulus

[0183] For the polyamide-imide films having a length of 50 mm and a width of 10 mm prepared in Examples and Comparative Examples, the modulus (GPa) was measured under the condition of stretching at 25° C. and 2 mm / min.

[0184] Example 1

[0185] This example illustrates the preparation of polyamic acid using compound III-1, as follows:

[0186] Under nitrogen atmosphere, N,N-dimethylacetamide (DMAc) and the compound of formula III-1 are added to a reactor equipped with a mechanical stirrer and stirred thoroughly, and then 4,4-hexafluoroisopropylphthalic anhydride (6FDA) is added and stirred thoroughly until dissolved; terephthaloyl chloride (TPC) is then added and stirred for 24 hours to dissolve to obtain a mixed reaction system, and the temperature of the mixed reaction system is maintained below 50°C for polymerization reaction to prepare a polyamic acid resin composition, wherein the molar ratio of the added TPC, 6FDA, and the compound III-1 is 5:95:100; during the polymerization reaction, the content of the polyamic acid resin is adjusted by adding an appropriate amount of DMAc so that the reaction product always maintains a uniform solution viscosity without foaming, and finally the polyamic acid resin is controlled to be 10.0% by weight.

[0187] The polyamic acid resin composition prepared above was filtered and coated onto a clean glass substrate. The mixture was then soft-dried on a hot plate at 90°C and heated in stages to the highest curing temperature in a vacuum drying oven. The glass substrate was then removed from the oven, immersed in water, and manually delaminated to obtain a polyamide-imide film sample. The curing temperature and performance parameters of the polyamide-imide film are listed in Table 2.

[0188] Example 2

[0189] The only difference between Example 2 and Example 1 is that, as shown in Table 1, the molar ratio of TPC, 6FDA, and III-1 compound used is 10:90:100, and the rest is the same as in Example 1.

[0190] Example 3

[0191] The only difference between Example 3 and Example 1 is that, as shown in Table 1, the molar ratio of TPC, 6FDA, and III-1 compound used is 30:70:100, and the rest is the same as Example 1.

[0192] Example 4

[0193] The only difference between Example 4 and Example 1 is that, as shown in Table 1, the molar ratio of TPC, 6FDA, and III-1 compound used is 50:50:100, and the rest is the same as in Example 1.

[0194] Example 5

[0195] The only difference between Example 5 and Example 1 is that, as shown in Table 1, the molar ratio of TPC, 6FDA, and III-1 compound used is 70:30:100, and the rest is the same as in Example 1.

[0196] Example 6

[0197] The only difference between Example 6 and Example 1 is that, as shown in Table 1, the molar ratio of TPC, 6FDA, and III-1 compound used is 95:5:100, and the rest is the same as in Example 1.

[0198] Example 7

[0199] This example illustrates the chemical preparation of polyamide-imide as follows:

[0200] Under nitrogen atmosphere, DMAc, III-1, and TFMB were added to a reactor equipped with a mechanical stirrer and stirred thoroughly, and then 6FDA was added and stirred thoroughly until dissolved; TPC was then added and stirred for 24 hours to dissolve to obtain a mixed reaction system, and the temperature of the mixed reaction system was maintained below 50° C. to carry out a polymerization reaction to prepare a polyamic acid resin composition, wherein the molar ratio of the added formula III-1, TFMB, TPC, and 6FDA was 95:5:50:50; during the polymerization reaction, the content of the polyamic acid resin was adjusted by adding an appropriate amount of DMAc so that the viscosity of the reaction product was kept uniform and non-foaming, and finally the polyamic acid resin was controlled to be 10.0% by weight;

[0201] Acetic anhydride (the amount of acetic anhydride added is 2-3 times the amount of theoretical amic acid functional groups in polyamic acid) and pyridine (the amount of pyridine added is 2-3 times the amount of theoretical amic acid functional groups in polyamic acid) are added to the polyamic acid resin prepared above, and stirred for 24 hours to react to prepare a transparent polyamide-imide solution.

[0202] The polyamide-imide solution was added dropwise to 5 times the amount of ethanol to obtain white fibrous polyamide-imide. The polyamide-imide was purified and then dissolved in DMAc to obtain a 10.0 wt% polyamide-imide solution.

[0203] The polyamide-imide solution prepared above was filtered and coated onto a clean glass substrate. The product was then soft-dried on a hot plate at 90°C and heated in stages to the highest curing temperature in a vacuum drying oven. The glass substrate was then removed from the oven, immersed in water, and manually delaminated to obtain a polyamide-imide film sample. The curing temperatures and performance parameters of the polyamide-imide film are listed in Table 2.

[0204] Examples 8 to 11

[0205] The only difference between Examples 8 to 11 and Example 7 is that the TPC, 6FDA, III-1 and TFMB monomers and their contents are changed as shown in Table 1, and the rest are carried out in the same manner as Example 7.

[0206] Examples 12-39

[0207] The only difference between Examples 12-39 and Example 1 is that the selection and amount of monomers are changed as described in Table 1, and the preparation method is the same as that of Example 1.

[0208] Comparative Example 1

[0209] Comparative Example 1 differs from Example 7 only in that no TPC is added during the preparation process, meaning the resulting polymer contains no TPC-derived structural units. 6FDA and III-1 monomers, as shown in Table 1, and their contents are used, with the remainder of the process being the same as in Example 7.

[0210] Comparative Example 2

[0211] Comparative Example 2 differs from Example 1 only in that no dianhydride is added during the preparation process, i.e., the resulting polymer does not have an imide structural unit. TPC and TFMB monomers and their contents are as shown in Table 1, and the remaining steps are the same as in Example 1.

[0212] Comparative Example 3

[0213] Comparative Example 3 differs from Example 1 only in that TPC is omitted during the preparation process, meaning the resulting polymer lacks imide structural units. Furthermore, only 3 mol% of the compound of Formula III-1 is added. The monomers 6FDA, III-1, and TFMB, and their contents, are used as shown in Table 1. The remainder of the preparation is identical to Example 1.

[0214] Comparative Example 4

[0215] Comparative Example 4 differs from Example 1 only in that TPC is not added during the preparation process, i.e., the resulting polymer does not have an amide structural unit. BPDA and III-1 monomers and their contents are as shown in Table 1, and the remaining steps are the same as in Example 1.

[0216] Comparative Example 5

[0217] Comparative Example 5 differs from Example 7 only in that TPC is not added during the preparation process, i.e., the resulting polymer does not contain structural units derived from TPC. 6FDA and III-2 monomers and their contents are as shown in Table 1, and the remainder of the process is the same as in Example 7.

[0218] Comparative Example 6

[0219] The only difference between Comparative Example 6 and Example 1 is that no dianhydride 6FDA is added during the preparation process, TPC and III-1 compound monomers and their contents are used as shown in Table 1, and the rest of the process is the same as Example 1.

[0220] Figure 1 is a DMA test curve of the polyamide-imide film prepared in Example 5; Figure 2 is a TGA test curve of the polyamide-imide film prepared in Example 5; Figure 3 is a DMA test curve of the polyamide-imide film prepared in Example 7; Figure 4 is a DMA test curve of the polyamide-imide film prepared in Example 8; Figure 5 is a DMA test curve of the polyamide-imide film prepared in Example 38.

[0221] Table 1 Diacyl chloride, dianhydride and diamine monomers used in the examples and comparative examples of this application and their contents

[0222] Table 2 Curing temperature and related properties of polyamide-imide films in the examples and comparative examples of the present application

[0223] By comparing Examples 1 to 6 and Comparative Example 1, it can be seen that Examples 1 to 6 have aromatic diacid chloride structures derived from TPC, and the tensile properties of the polyamide-imide films formed in Examples 1 to 6 are improved to a certain extent, which is caused by the hydrogen bond interaction between the amide structures.

[0224] By comparing Examples 7 to 11 with Comparative Examples 2 and 3, it can be seen that Examples 7 to 11 have both an aromatic diacid chloride structure derived from TPC and an aromatic diamine structure derived from III-1. The tensile properties of the polyamide-imide films formed in Examples 7 to 11 are balanced, which is caused by the amide structure and the polyphenyl structure.

[0225] By comparing Example 39 with Comparative Examples 4, 5 and 6, it can be seen that the mechanical properties of the polyamide-imide film of Example 39 are improved to a certain extent, which is caused by the combined effect of the amide and imide groups.

[0226] It should be noted that not all of the operations described in the general description or examples above are necessary, a portion of a specific operation may not be necessary, and one or more other operations may be performed in addition to those described. In addition, the order of operations listed is not necessarily the order in which they are implemented.

[0227] It will be appreciated by those skilled in the art that various modifications and variations may be made without departing from the scope of the present application as set forth in the claims. Therefore, the specification and drawings should be considered in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of the present application.

[0228] Benefits, other advantages, and solutions to problems have been described above with respect to specific embodiments. However, any benefit, advantage, solution to a problem, and any one or more features that may cause any benefit, advantage, or solution to occur or make it more apparent, are not to be construed as key, required, or essential features of any or all claims.

[0229] It is to be understood that, for the sake of clarity, certain features described herein in the context of separate embodiments may also be provided in a single embodiment in combination. Conversely, for the sake of brevity, the various features described in the context of a single embodiment may also be provided individually or in any sub-combination. The use of numerical values ​​within the various ranges specified herein is described as approximate, just as the minimum and maximum values ​​within the ranges are both preceded by the expression "about". In this way, slight variations above and below the ranges achieved may be used to achieve substantially the same results as the values ​​within these ranges. Moreover, the disclosure of these ranges is intended to be a continuous range of each value included between the minimum and maximum averages, including fractional values ​​that may be generated when some components of a value are mixed with components of different values. In addition, when disclosing wider and narrower ranges, it is within the expectations of the present application to match the minimum value from one range with the maximum value from another range, and vice versa.

Claims

1. A polyamic acid, characterized in that: The polyamic acid has a repeating unit structure shown in Formula I: Among them, R a Represents the residue of aromatic diacyl chloride component; R b represents a tetracarboxylic acid component residue and / or a dianhydride component residue; R c represents an aromatic diamine component residue.

2. The polyamic acid according to claim 1, wherein: Form R a The aromatic dicarboxylic acid chloride monomer includes one or more of terephthaloyl chloride, isophthaloyl chloride, 4,4′-biphenyl dicarboxylic acid chloride, 1,4-naphthalene dicarboxylic acid chloride, 2,6-naphthalene dicarboxylic acid chloride, 1,5-naphthalene dicarboxylic acid chloride, 4,4′-oxybis(benzoyl chloride) and / or derivatives thereof; and / or, forming R b The monomer includes an aromatic dianhydride, and the aromatic dianhydride includes one or more of 1,2,4,5-pyromellitic dianhydride, 3,3′,4,4′-diphenyl ether tetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 2,2′,3,3′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride and / or derivatives thereof; and / or, forming R c The monomers include compounds represented by formula III: wherein R1, R2, and R3 are independently selected from hydrogen, hydroxy, cyano, halogen, alkyl, heteroalkyl, alkoxy, heteroalkoxy, haloalkyl, haloalkoxy, silyl, siloxy, substituted or unsubstituted hydrocarbon aryl, or substituted or unsubstituted heteroaryl; And / or, in the polyamic acid, R a and R b The total molar amount of R c The molar ratio is 1:1, R a With R b The molar ratio is 5-100:5-100; And / or, the preparation method of the polyamic acid comprises: subjecting a mixed reaction system containing an aromatic diacid chloride monomer, a dianhydride monomer, an aromatic diamine monomer and a solvent to polymerization reaction at a temperature of -20 to 80° C. to obtain the polyamic acid.

3. The polyamic acid according to claim 2, wherein: The component residue formed by one or more of terephthaloyl chloride, isophthaloyl chloride, 4,4'-biphenyl dicarboxylic acid chloride, 1,4-naphthalene dicarboxylic acid chloride, 2,6-naphthalene dicarboxylic acid chloride, 1,5-naphthalene dicarboxylic acid chloride, 4,4'-oxybis(benzoyl chloride) and / or their derivatives is R a 5-100 mol% of the total amount; And / or, the component residue formed by the aromatic dianhydride is R b 5-100 mol% of the total amount; and / or, forming R b The monomer further comprises an alicyclic dianhydride, preferably, the alicyclic dianhydride comprises one or more combinations of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride and / or derivatives thereof; And / or, the component residue formed by the compound represented by formula III is R c 5-100 mol% of the total amount; And / or, the compound represented by formula III includes one or more of the following compounds: and / or, forming R c The monomer further includes a second aromatic diamine different from the compound represented by formula III, wherein the second aromatic diamine includes one or more of 2,2′-bis(trifluoromethyl)benzidine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, 4,4′-diaminodiphenyl ether, p-phenylenediamine, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane and / or derivatives thereof.

4. A polyamide-imide, characterized in that The polyamide-imide has a repeating unit structure shown in Formula II: Among them, R a Represents the residue of aromatic diacyl chloride component; R b represents a tetracarboxylic acid component residue and / or a dianhydride component residue; R c represents an aromatic diamine component residue.

5. The polyamide-imide according to claim 4, characterized in that: Form R a The aromatic dicarboxylic acid chloride monomer includes one or more of terephthaloyl chloride, isophthaloyl chloride, 4,4′-biphenyl dicarboxylic acid chloride, 1,4-naphthalene dicarboxylic acid chloride, 2,6-naphthalene dicarboxylic acid chloride, 1,5-naphthalene dicarboxylic acid chloride, 4,4′-oxybis(benzoyl chloride) and / or derivatives thereof; and / or, forming R b The monomer includes an aromatic dianhydride, and the aromatic dianhydride includes one or more of 1,2,4,5-pyromellitic dianhydride, 3,3′,4,4′-diphenyl ether tetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 2,2′,3,3′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride and / or derivatives thereof; and / or, forming R c The monomers include compounds represented by formula III: wherein R1, R2, and R3 are independently selected from hydrogen, hydroxy, cyano, halogen, alkyl, heteroalkyl, alkoxy, heteroalkoxy, haloalkyl, haloalkoxy, silyl, siloxy, substituted or unsubstituted hydrocarbon aryl, or substituted or unsubstituted heteroaryl; And / or, in the polyamide-imide, R a and R b The total molar amount of R c The molar ratio is 1:1, R a With R b The molar ratio is 5-100:5-100.

6. The polyamide-imide according to claim 5, characterized in that: The component residue formed by one or more of terephthaloyl chloride, isophthaloyl chloride, 4,4'-biphenyl dicarboxylic acid chloride, 1,4-naphthalene dicarboxylic acid chloride, 2,6-naphthalene dicarboxylic acid chloride, 1,5-naphthalene dicarboxylic acid chloride, 4,4'-oxybis(benzoyl chloride) and / or their derivatives is R a 5-100 mol% of the total amount; And / or, the component residue formed by the aromatic dianhydride is R b 5-100 mol% of the total amount; and / or, forming R b The monomer further comprises an alicyclic dianhydride, preferably, the alicyclic dianhydride comprises one or more combinations of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride and / or derivatives thereof; And / or, the component residue formed by the compound represented by formula III is R c 5-100 mol% of the total amount; And / or, the compound represented by formula III includes one or more of the following compounds: and / or, forming R c The monomer further includes a second aromatic diamine different from the compound represented by formula III, wherein the second aromatic diamine includes one or more of 2,2′-bis(trifluoromethyl)benzidine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, 4,4′-diaminodiphenyl ether, p-phenylenediamine, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane and / or derivatives thereof; And / or, the glass transition temperature T g Greater than 300℃; And / or, the yellowness index YI value of the polyamide-imide is 7.0 or less.

7. A composition, characterized in that include: The polyamic acid according to any one of claims 1 to 3 and / or the polyamide-imide according to any one of claims 4 to 6; At least one aprotic solvent.

8. The composition according to claim 7, characterized in that: The aprotic solvent includes one or more of N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, ethyl cellosolve, methyl cellosolve, acetone, ethyl acetate, m-cresol, γ-butyrolactone and / or their derivatives.

9. A polyamide-imide film, characterized in that: The polyamide-imide film comprises the polyamide-imide according to any one of claims 4 to 6, or the polyamide-imide film is obtained by curing the composition according to any one of claims 7 to 8.

10. The polyamide-imide film according to claim 9, characterized in that: The total light transmittance of the polyamide-imide film in the wavelength range of 380-800 nm is greater than 87.0%; and / or, the haze of the polyamide-imide film is 2.0% or less; and / or, the yellowness index of the polyamide-imide film is 7.0 or less; And / or, the modulus of the polyamide-imide film is 4.0 GPa or greater.

11. A transparent structure, characterized in that: The transparent structure comprises the polyamide-imide film according to claim 9 or 10.

12. A device having a transparent component, characterized in that: The device comprises the transparent structure according to claim 11.

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