JP2009052042A - Precursor for polyimide and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a precursor for polyimide which has a structure of following formula (1) and to provide polyimide prepared from the precursor. <P>SOLUTION: The precursor for the polyimide has the structure of formula (1) (in the formula, R represents a 1-14C linear or branched alkyl, a 6-14C aryl or aralkyl or an ethylenically unsaturated group, R<SB>x</SB>each independently represents H or an ethylenically unsaturated group, G each independently represents a tetravalent organic group and P each independently represents a bivalent organic group and (m) is an integer of 0-100). The polyimide exhibits excellent operation characteristics and physical properties. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel precursor of polyimide. The present invention also relates to the use of novel precursors in the preparation of polyimide (PI).

  Polyimide has been used as a high performance polymer because it has excellent thermal stability and good mechanical, electrical, and chemical properties. Furthermore, the use of conventional inorganic materials has become a problem and limited in many applications, raising the requirements for semiconductors. The properties of polyimide can compensate for the shortcomings of conventional materials in some embodiments. Therefore, since E.I.Du Pont Company has developed aromatic polyimide technology, polyimide has been in widespread use and various applications have been developed.

  In the semiconductor industry, polyimide is widely used in passivation coatings, stress buffer coatings, α-particle shielding, dry etch masks, micromachines and interlayer dielectrics. Still being developed for other uses. Polyimide is primarily used as a coating to protect integrated circuit elements, since polyimide materials can pass reliability tests performed on integrated circuit elements. However, polyimide is used not only in the integrated circuit industry, but also in electronic component mounting, enameled wires, printed circuit boards, sensor elements, separation membranes, and structural materials.

  Polyimide is usually synthesized by a two-stage polymerization and condensation reaction. Usually, in the first step, a diamine monomer is added to a polar aprotic solvent such as N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMAC), dimethylformamide (DMF), or dimethylsulfoxide (DMSO). Dissolve. An equivalent amount of dianhydride monomer is then added. The condensation reaction is then carried out at low or room temperature to form a polyimide precursor, ie poly (amic acid) (PAA).

  In the second stage, thermal imidization or chemical imidization is performed to achieve condensation, dehydration, and cyclization reactions so that the poly (amic acid) is converted to polyimide.

  Currently, the reaction scheme for preparing polyimide is as follows:

It can be described briefly as follows.

  In the above preparation method, when the molecular weight of the poly (amic acid) obtained in the first stage does not reach a certain standard (that is, it is excessively low), a polyimide film having good physical properties after imidization is obtained. I can't. However, if the poly (amic acid) obtained in the first stage has an excessively high molecular weight, its viscosity will be too high and operability will be insufficient. In addition, leveling tends to be insufficient in the coating step. For example, an insufficient leveling phenomenon is likely to occur during spin coating where the central portion is convex and the end is thick. Furthermore, if the poly (amic acid) is too high in molecular weight, very strong internal stresses are caused due to intermolecular interactions and molecular chain shortening in the second stage imidization. The strong internal stress bends and deforms the coated substrate. To address these issues, many literatures have submitted various discussions on the relationship between heating curve gradient control and internal stress in the second-stage imidization to reduce internal stress. Various methods have also been developed. Nevertheless, leveling problems and internal stresses are caused by the excessively high molecular weight of the poly (amic acid) obtained in the first stage. In other words, if the molecular weight of poly (amic acid) can be appropriately controlled, a polyimide film having excellent physical properties can be obtained.

  In addition, poly (amic acid) is highly hygroscopic, so poly (amic acid) reacts rapidly with water molecules and then decomposes. As a result, storage of poly (amic acid) is not easy.

  Despite the great desire for useful polyimides in this field, there is a conflict between material properties and operability. Accordingly, an object of the present invention is to solve the above-mentioned problems. In particular, a polyimide film having desirable physical properties and operability is provided by some kind of synthesis to meet industrial needs.

  One object of the present invention is to provide a novel precursor of polyimide.

  Another object of the present invention is to provide a composition comprising the precursor described above.

  Yet another object of the present invention is to provide a method for preparing polyimides.

  The polyimide precursor according to the present invention has the following formula (1):

(Where
R represents straight-chain or branched alkyl having 1 to 14 carbon atoms, aryl or aralkyl having 6 to 14 carbon atoms, or an ethylenically unsaturated group;
R _x each independently represents H or a photopolymerizable group;
G each independently represents a tetravalent organic group,
Each P independently represents a divalent organic group,
m is an integer from 0 to 100)
An amic acid ester oligomer having the structure:

  According to an embodiment of the present invention, in the above formula (1), R represents a linear or branched alkyl having 1 to 14 carbon atoms. For example, a straight chain or branched alkyl having 1 to 14 carbon atoms is

It may be.

  In the above formula, n is an integer of 0 to 0. Examples of straight chain or branched alkyl having 1 to 14 carbon atoms include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, 1-methylpropyl, 2-methylpropyl, n-butyl, isobutyl Tert-butyl, 1-methylbutyl, 2-methylbutyl, amyl, hexyl, heptyl, and octyl.

  Aryl or aralkyl having 6 to 14 carbon atoms is preferably the following group:

Selected from the group consisting of

  The ethylenically unsaturated group is not particularly limited, and examples thereof include, but are not limited to, vinyl, propenyl, methylpropenyl, n-butenyl, isobutenyl, vinylphenyl, propenylphenyl, propenyloxymethyl, propenyloxyethyl, propenyloxy Propyl, propenyloxybutyl, propenyloxyamyl, propenyloxyhexyl, methylpropenyloxymethyl, methylpropenyloxyethyl, methylpropenyloxypropyl, methylpropenyloxybutyl, methylpropenyloxyamyl, and methylpropenyloxyhexyl, and the following formula ( 2):

Wherein R ₁ is phenylene, linear or branched C1-C8 alkylene, linear or branched C2-C8 alkenylene, C3-C8 cycloalkylene, or linear or branched C1-C8 hydroxyalkylene. And R ₂ is H or C1-C4 alkyl)
The group of is mentioned. Preferred groups of formula (2) are

It is.

In the formula (1) of the present invention, each R _x independently represents H or any photopolymerizable group. Preferably, the photopolymerizable group is a group having an ethylenically unsaturated group as defined above. According to the present invention, each R _x independently represents H, 2-hydroxypropyl methacrylate group, ethyl methacrylate group, ethyl acrylate group, propenyl, methylpropenyl, n-butenyl, or isobutenyl. More preferably, each R _x is independently H or 2-hydroxypropyl methacrylate group:

Represents.

  The tetravalent organic group G of the amic acid ester oligomer in the formula (1) of the present invention is not particularly limited. For example, it may be a tetravalent aromatic group or a tetravalent aliphatic group. The aromatic group may be a monocyclic or polycyclic group, preferably:

Selected from the group consisting of

In the formula, each Y independently represents H, a halo group, C1-C4 perfluoroalkyl, or C1-C4 alkyl, and B represents —CH ₂ —, —O—, —S—, —CO—, — SO ₂ —, —C (CH ₃ ) ₂ —, or —C (CF ₃ ) ₂ — is represented. More preferably, the aromatic group is:

Selected from the group consisting of

  In addition, the tetravalent aliphatic groups are:

Can be selected from the group consisting of

  The divalent organic group P of the amic acid ester oligomer in the formula (1) of the present invention is not particularly limited. Usually, the divalent organic group P is an aromatic group, preferably each independently:

Represents.

In the above formula, each X independently represents H, a halo group, C1-C4 alkyl, or C1-C4 perfluoroalkyl, and A represents —O—, —S—, —CO—, —CH ₂ —, -OC (O)-or -CONH- is represented. More preferably, each divalent organic group P is independently:

Represents.

  In one embodiment, the divalent organic group P is

It is.

  The divalent organic group P is similarly

(Wherein X has the meaning defined above, and each of w and z independently represents an integer of 1 to 3)
Non-aromatic groups such as

  Preferably, the divalent organic group P is

It is.

  Inventors of the present invention, unlike conventional poly (amic acid) precursors for preparing polyimides, the amic acid ester oligomers of formula (1) according to the present invention have fewer acidic groups and are therefore more hygroscopic. I found it low. Even if the amidate oligomers of formula (1) may be hydrated, they are more stable and do not need to be stored at lower temperatures (eg, -20 ° C.) and can be stored at room temperature.

The amic acid ester oligomer of the present invention comprises the following procedure:
(a) reacting a dianhydride of formula (3) with a compound having a hydroxyl group (R-OH) to form a compound of formula (4):

and
(b) adding a diamine compound of formula H ₂ NP-NH ₂ to the product obtained from step (a) to form an amic acid ester oligomer of formula (5):

  (c) Equation (6):

(Wherein R, G and P are as defined above, a, b and f are each an integer from 0 to 100 and a + b ≦ 100)
Optionally adding a monomer with a photopolymerizable group (R *), e.g., epoxy acrylate, to carry out the reaction to form an amidate oligomer of
Can be produced by any one of the conventional polymerization methods known to those skilled in the art, such as methods comprising

  In the above method for preparing the amic acid ester oligomer of formula (1), the dianhydride used in step (a) may be aliphatic or aromatic, preferably aromatic. Examples of aromatic dianhydrides include, but are not limited to, pyromellitic dianhydride (PMDA), 4,4'-biphthalic dianhydride (BPDA), 4,4'-hexafluoroisopropylidenediphthalic acid Dianhydride (6FDA), 1- (trifluoromethyl) -2,3,5,6-benzenetetracarboxylic dianhydride (P3FDA), benzophenone-tetracarboxylic dianhydride (BTDA), 3,3 ′ , 4,4'-Oxydiphthalic dianhydride (ODPA), 1,4-bis (trifluoromethyl) -2,3,5,6-benzenetetracarboxylic dianhydride (P6FDA), 1- (3 ' , 4'-dicarboxyphenyl) -1,3,3-trimethylindane-5,6-dicarboxylic dianhydride, 1- (3 ', 4'-dicarboxyphenyl) -1,3,3-trimethylindane -6,7-dicarboxylic dianhydride, 1- (3 ', 4'-dicarboxyphenyl) -3-methylindan-5,6-dicarboxylic dianhydride, 1- (3', 4'-di Carboxyphenyl) -3-methylindane-6,7-dicarboxylic dianhydride 2,3,9,10-perylenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-2,4,5,8-tetracarboxylic acid Anhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 1,2', 3,3'-benzophenone tetra Carboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-Biphenyltetracarboxylic dianhydride, 4,4'-isopropylidenediphthalic anhydride, 3,3'-isopropylidenediphthalic anhydride, 4,4'-oxydiphthalic anhydride, 4,4' -Sulphonyldiphthalic anhydride, 3,3'-oxydiph Luric anhydride, 4,4'-methylenediphthalic anhydride, 4,4'-thiodiphthalic anhydride, 4,4'-ethylidene diphthalic anhydride, 2,3,6,7-naphthalenetetracarboxylic Acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic acid And dianhydrides, pyridine-2,3,5,6-tetracarboxylic dianhydrides, and mixtures thereof.

  Preferably, the aromatic dianhydride used in step (a) is pyromellitic dianhydride (PMDA), 4,4′-biphthalic anhydride (BPDA), 4,4′-hexafluoroisopropylidene diene. Phthalic dianhydride (6FDA), 1- (trifluoromethyl) -2,3,5,6-benzenetetracarboxylic dianhydride (P3FDA), 1,4-bis (trifluoromethyl) -2,3 , 5,6-benzenetetracarboxylic dianhydride (P6FDA), benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4'-oxydiphthalic anhydride (ODPA), and mixtures thereof Selected from the group consisting of In one embodiment, pyromellitic dianhydride (PMDA) is used.

  The compound having a hydroxyl group used in the method of the present invention for preparing the amic acid ester oligomer of formula (1) may be an alcohol such as monool, diol, or polyol, preferably monool. is there. Monools useful in the present invention are not particularly limited and may be alkanols, aralkanols, or arylols. Monool has (but is not limited to) the following structure:

(Where n is an integer from 0 to 10)
Or a straight-chain or branched alkanol having 1 to 14 carbon atoms, such as a straight-chain or branched alkanol. In this case, examples of linear or branched alkanols having 1 to 14 carbon atoms include, but are not limited to, methanol, ethanol, n-propanol, isopropanol, 1-methylpropanol, n-butanol, isobutanol, Neobutanol, 1-methylbutanol, 2-methylbutanol, pentanol, hexanol, heptanol, and octanol. Monools useful in the present invention are also the following structures:

Or an aralkanol or arylol having 6 to 14 carbon atoms, such as aralkanol or arylol.

  The compound having a hydroxyl group used in the method of the present invention may have a photopolymerizable group such as an ethylenically unsaturated group. Preferably, this compound has the following formula (7):

Wherein R ₁ is phenylene, C3-C8 cycloalkylene, linear or branched C1-C8 alkylene, linear or branched C1-C8 alkenylene, or linear or branched C1-C8 hydroxyalkylene, R ₂ is H or C1-C4 alkyl)
Have Preferably, the compound of formula (7) is selected from the group consisting of 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), glycidyl methacrylate (GMA), glycidyl acrylate, and mixtures thereof.

  In the above method for preparing the amic acid ester oligomer of formula (1), the diamine used in step (b) is not particularly limited, and may be an aromatic diamine. Aromatic diamines useful in the process of the present invention are known to those skilled in the art. For example, aromatic diamines include, but are not limited to, the following groups: 4,4'-oxy-dianiline (ODA), para-phenylenediamine (pPDA), 2,2-dimethyl-4,4-diamino-biphenyl ( DMDB), 2,2'-bis (trifluoromethyl) benzidine (TFMB), o-tolidine (oTLD), 4,4'-octafluorobenzidine (OFB), tetrafluorophenylenediamine (TFPD), 2,2 ' , 5,5'-tetrachlorobenzidine (TCB), 3,3'-dichlorobenzidine (DCB), 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (4-amino) Phenyl) hexafluoropropane, 4,4'-oxo-bis (3-trifluoromethyl) aniline, 3,5-diaminobenzotrifluoride, tetrafluorophenylenediamine, tetrafluoro-m-phenylenediamine, 1,4-bis (4-Aminophenoxy-2-tert-butylbenzene (BATB), 2,2'-dimethyl-4,4'-bis (4-amino Enoxy) biphenyl (DBAPB), 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane (BAPPH), 2,2'-bis [4- (4-aminophenoxy) phenyl] norborane (BAPN ), 5-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 4, 4'-methylenebis (o-chloroaniline), 3,3'-dichlorobenzidine (DCB), 3,3'-sulfonyldianiline, 4,4'-diaminobenzophenone, 1,5-diaminonaphthalene, bis (4- Aminophenyl) diethylsilane, bis (4-aminophenyl) diphenylsilane, bis (4-aminophenyl) ethylphosphine oxide, N- (bis (4-aminophenyl) -N-methylamine, N- (bis (4- Aminophenyl))-N-phenylamine, 4,4'-methylenebis (2-methylaniline), 4,4'-methylenebis (2-methoxyaniline), 5,5'-methylene (2-aminophenol), 4,4'-methylenebis (2-methylaniline), 4,4'-oxybis (2-methoxyaniline), 4,4'-oxybis (2-chloroaniline), 2,2 '-Bis (4-aminophenol), 5,5'-oxybis (2-aminophenol), 4,4'-thiobis (2-methylaniline), 4,4'-thiobis (2-methoxyaniline), 4 , 4'-thiobis (2-chloroaniline), 4,4'-sulfonylbis (2-methylaniline), 4,4'-sulfonylbis (2-ethoxyaniline), 4,4'-sulfonylbis (2- Chloroaniline), 5,5′-sulfonylbis (2-aminophenol), 3,3′-dimethyl-4,4′-diaminobenzophenone, 3,3′-dimethoxy-4,4′-diaminobenzophenone, 3, 3'-dichloro-4,4'-diaminobenzophenone, 4,4'-diaminobiphenyl, m-phenylenediamine, 4,4'-methylenedianiline (MDA), 4,4'-thiodianiline, 4,4'- Sulfonyl dianiline, 4,4'- Sopropylidenedianiline, 3,3'-dimethoxybenzidine, 3,3'-dicarboxybenzidine, 2,4-tolyl-diamine, 2,5-tolyl-diamine, 2,6-tolyl-diamine, m-key It can be selected from silyl diamine, 2,4-diamino-5-chloro-toluene, 2,4-diamino-6-chloro-toluene, and mixtures thereof. Preferably, the diamine is 4,4'-oxy-dianiline (ODA), para-phenylenediamine (pPDA), 2,2-dimethyl-4,4-diamino-biphenyl (DMDB), 2,2'-bis (tri Fluoromethyl) benzidine (TFMB), o-tolidine (oTLD), 4,4′-methylenedianiline (MDA), or mixtures thereof.

  Preferably, the diamine used in step (b) is

Selected from the group consisting of

  As mentioned above, a monomer having a photopolymerizable group can optionally be added to step (c) to give the photopolymerizable group to the amic acid ester oligomer.

Specifically, when a monomer having a photopolymerizable group is not added, R _x of the amidate ester oligomer of the formula (1) represents H. When a monomer having a photopolymerizable group is added, _Rx of the amic acid ester oligomer of the formula (1) represents a photopolymerizable group. When R _x represents a photopolymerizable group, the molecules of the amic acid ester oligomer will chemically bond with each other during the next step to synthesize the polyimide to form a crosslink.

  The present invention further provides a precursor composition for preparing a polyimide comprising the amidate ester oligomer of formula (1) described above and a solvent.

  The solvent used in the composition of the present invention is preferably a polar aprotic solvent. For example, polar aprotic solvents include, but are not limited to, N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMAC), N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), toluene, It can be selected from the group consisting of xylene and mixtures thereof.

  In the composition of the present invention, the amount of amidate ester oligomer ranges from 15% to 70%, preferably from 30% to 60%, and the amount of solvent ranges from 20% to 80%, based on the total weight of the composition. %, Preferably ranging from 45% to 75%.

  The compositions of the present invention can optionally include additives known to those skilled in the art, such as photoinitiators, silane coupling agents, leveling agents, stabilizers, catalysts, and / or antifoaming agents.

  When the above-mentioned amic acid ester oligomer of formula (1) has a photopolymerizable group, a photoinitiator can optionally be added. Photoinitiators suitable for the present invention are not particularly limited, but include benzophenone, benzoin, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane- 1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, N-phenylglycine, 9-phenylacridine, benzyldimethyl ketal, 4,4'-bis (diethylamino) diphenyl ketone, 2 1,4,5-triarylimidazole dimer, and mixtures thereof, of which benzophenone is preferred. Specifically, the amount of photoinitiator ranges from 0.01 to 20% by weight, preferably from 0.1 to 5% by weight, based on the total weight of the precursor composition of the present invention.

  Common silane coupling agents include (but are not limited to) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and these Selected from the group consisting of mixtures.

  The present invention also provides a polyimide prepared by polymerization of an amic acid ester oligomer of formula (1). For example, the polyimide according to the present invention has the following scheme:

It can produce | generate by the polymerization method shown by these.

  Conventional methods for synthesizing polyimides required that a poly (amidic acid) having a higher molecular weight be synthesized first as a precursor. However, the molecular weight is excessively high, resulting in an excessively high viscosity, resulting in poor precursor handling and poor leveling during coating. Furthermore, the excessively high molecular weight of poly (amic acid) causes extreme internal stress due to intermolecular interactions and molecular chain shortening during precursor imidization. Extreme internal stress causes distortion and deformation of the substrate being coated. Also, in the conventional method for synthesizing polyimide, the solid content of poly (amic acid) formed by polymerization is about 10% to about 30%, so that the volume shrinkage after cyclization is more high. As a result, the coating procedure must be repeated many times to achieve the desired thickness of the product, thereby making the process more complex.

Amide ester oligomers according to the present invention are characterized by having both ester (-C (O) OR) and carboxyl (-C (O) OH) end groups, are in a metastable state and have their own amino groups Does not react with (-H ₂ N). Since the amidate oligomers have a low molecular weight, their operability is better during coating and a leveling effect can be achieved. In the next cure, after raising the temperature above 100 ° C., the ester and carboxyl end groups are anhydrided with amino groups and then reacted to form an amic acid ester oligomer. The oligomer is then further polymerized to form molecules with higher molecular weights for subsequent condensation to yield polyimides with excellent thermal, mechanical and tensile properties. Compared to the prior art where higher viscosity poly (amidic acid) was used, the present invention provides a lower viscosity amidic acid ester oligomer that exhibits better leveling and operability when coated. Use.

  Furthermore, the polyimides of the present invention are characterized in that during imidation of the precursor composition, the amic acid ester oligomer is cyclized intramolecularly prior to intermolecular polymerization and cyclization. This reaction sequence effectively reduces the internal stress remaining in the polyimide. Compared to the prior art, the polyimide obtained by cyclization of the precursor composition of the present invention will not distort.

  Since the polyimide precursor composition of the present invention has a high solid content, the amount of solvent used can be reduced, resulting in a shortened firing time, lower firing temperature, and volatilization of a large amount of solvent. This prevents the volume shrinkage phenomenon caused by the phenomenon. Also, the drying and film formation rates are faster and the number of coatings to achieve the desired product thickness can be reduced.

  In a further embodiment, the cyclization temperature for preparing the polyimide was generally from 300 ° C to 350 ° C in the prior art. However, the precursor composition of the present invention can be cyclized at temperatures in the range of about 200 ° C. to 250 ° C., further reducing operating costs.

  In addition, in general polymerization reactions, several monomers or short-chain oligomers are usually added so as to crosslink between molecules. However, since the precursor of the present invention contains a photopolymerizable group, it can self-crosslink during the curing step. Thus, the precursor composition of the present invention does not require additional unsaturated monomers or oligomers, which can reduce process complexity and cost.

  The invention will be described in greater detail by the following examples, which are used only to illustrate the invention, not to limit the scope of the invention. All modifications or equivalents readily achievable by those skilled in the art are within the scope of the disclosure herein and the appended claims.

(Example)
Examples 1-20 describe the steps and conditions for preparing compositions for producing the polyimides of the present invention. Comparative Example 1 relates to a prior art composition for producing polyimide.

(Example 1)
21.81 g (0.1 mol) of pyromellitic dianhydride (PMDA) was dissolved in 200 g of N-methyl-2-pyrrolidinone (NMP). The mixture was heated to 50 ° C. and stirred for 2 hours. 1.161 g (0.01 mol) of 2-hydroxyethyl acrylate (HEA) was slowly added dropwise to the mixture and stirred at 50 ° C. for 2 hours. Then 20.024 g (0.1 mol) of 4,4′-oxy-dianiline (ODA) was added to the solution. After complete dissolution, the solution was further stirred at 50 ° C. for 6 hours.

(Comparative Example 1)
20.024 g (0.1 mol) of ODA was dissolved in 200 g of NMP, then the mixture was placed in a 0 ° C. ice bath with stirring for 1 hour. Then 0.29 g (0.002 mol) of phthalic anhydride was added and the reaction was stirred for 1 hour. Then 21.59 g (0.099 mol) PMDA was slowly added and stirred for 12 hours.

(Example 2)
21.81 g (0.1 mol) PMDA was dissolved in 200 g NMP. The mixture was heated to 50 ° C. and stirred for 2 hours. 13.01 g (0.01 mol) of 2-hydroxyethyl methacrylate (HEMA) was slowly added dropwise to the mixture and stirred at 50 ° C. for 2 hours. Then 20.024 g (0.1 mol) of ODA was added to the solution. After complete dissolution, the solution was further stirred at 50 ° C. for 6 hours.

(Example 3)
21.81 g (0.1 mol) PMDA was dissolved in 200 g NMP. The mixture was heated to 50 ° C. and stirred for 2 hours. 1.161 g (0.01 mol) of HEA was slowly added dropwise to the mixture and stirred at 50 ° C. for 2 hours. Then 10.814 g (0.1 mol) of para-phenylenediamine (pPDA) was added to the solution. After complete dissolution, the solution was further stirred at 50 ° C. for 6 hours.

(Example 4)
21.81 g (0.1 mol) PMDA was dissolved in 200 g NMP. The mixture was heated to 50 ° C. and stirred for 2 hours. 13.01 g (0.01 mol) of HEMA was slowly added dropwise to the mixture and stirred at 50 ° C. for 2 hours. Then 10.814 g (0.1 mol) of pPDA was added to the solution. After complete dissolution, the solution was further stirred at 50 ° C. for 6 hours.

(Example 5)
21.81 g (0.1 mol) PMDA was dissolved in 200 g NMP. The mixture was heated to 50 ° C. and stirred for 2 hours. 1.161 g (0.01 mol) of HEA was slowly added dropwise to the mixture and stirred at 50 ° C. for 2 hours. 21.23 g (0.1 mol) of 2,2-dimethyl-4,4-diamino-biphenyl (DMDB) was then added to the solution. After complete dissolution, the solution was further stirred at 50 ° C. for 6 hours.

(Example 6)
21.81 g (0.1 mol) PMDA was dissolved in 200 g NMP. The mixture was heated to 50 ° C. and stirred for 2 hours. 13.01 g (0.01 mol) of HEMA was slowly added dropwise to the mixture and stirred at 50 ° C. for 2 hours. Then 21.23 g (0.1 mol) DMDB was added to the solution. After complete dissolution, the solution was further stirred at 50 ° C. for 6 hours.

(Example 7)
21.81 g (0.1 mol) PMDA was dissolved in 200 g NMP. The mixture was heated to 50 ° C. and stirred for 2 hours. 1.161 g (0.01 mol) of HEA was slowly added dropwise to the mixture and stirred at 50 ° C. for 2 hours. 21.23 g (0.1 mol) of o-tolidine (oTLD) was then added to the solution. After complete dissolution, the solution was further stirred at 50 ° C. for 6 hours.

(Example 8)
21.81 g (0.1 mol) PMDA was dissolved in 200 g NMP. The mixture was heated to 50 ° C. and stirred for 2 hours. 13.01 g (0.01 mol) of HEMA was slowly added dropwise to the mixture and stirred at 50 ° C. for 2 hours. 21.23 g (0.1 mol) oTLD was then added to the solution. After complete dissolution, the solution was further stirred at 50 ° C. for 6 hours.

(Example 9)
21.81 g (0.1 mol) PMDA was dissolved in 200 g NMP. The mixture was heated to 50 ° C. and stirred for 2 hours. 1.161 g (0.01 mol) of HEA was slowly added dropwise to the mixture and stirred at 50 ° C. for 2 hours. 32.02 g (0.1 mol) of 2,2′-bis (trifluoromethyl) benzidine (TFMB) was then added to the solution. After complete dissolution, the solution was further stirred at 50 ° C. for 6 hours.

(Example 10)
21.81 g (0.1 mol) PMDA was dissolved in 200 g NMP. The mixture was heated to 50 ° C. and stirred for 2 hours. 13.01 g (0.01 mol) of HEMA was slowly added dropwise to the mixture and stirred at 50 ° C. for 2 hours. Then 32.02 g (0.1 mol) TFMB was added to the solution. After complete dissolution, the solution was further stirred at 50 ° C. for 6 hours.

(Example 11)
21.81 g (0.1 mol) PMDA was dissolved in 200 g NMP. The mixture was heated to 50 ° C. and stirred for 2 hours. 0.32 g (0.01 mol) of methanol was slowly added dropwise to the mixture and stirred at 50 ° C. for 2 hours. Then 20.024 g (0.1 mol) of ODA was added to the solution. After complete dissolution, the solution was further stirred at 50 ° C. for 6 hours.

(Example 12)
21.81 g (0.1 mol) PMDA was dissolved in 200 g NMP. The mixture was heated to 50 ° C. and stirred for 2 hours. 0.601 g (0.01 mol) of isopropanol was slowly added dropwise to the mixture and stirred at 50 ° C. for 2 hours. Then 20.024 g (0.1 mol) of ODA was added to the solution. After complete dissolution, the solution was further stirred at 50 ° C. for 6 hours.

(Example 13)
21.81 g (0.1 mol) PMDA was dissolved in 200 g NMP. The mixture was heated to 50 ° C. and stirred for 2 hours. 0.32 g (0.01 mol) of methanol was slowly added dropwise to the mixture and stirred at 50 ° C. for 2 hours. Then 10.814 g (0.1 mol) of pPDA was added to the solution. After complete dissolution, the solution was further stirred at 50 ° C. for 6 hours.

(Example 14)
21.81 g (0.1 mol) PMDA was dissolved in 200 g NMP. The mixture was heated to 50 ° C. and stirred for 2 hours. 0.601 g (0.01 mol) of isopropanol was slowly added dropwise to the mixture and stirred at 50 ° C. for 2 hours. Then 10.814 g (0.1 mol) of pPDA was added to the solution. After complete dissolution, the solution was further stirred at 50 ° C. for 6 hours.

(Example 15)
21.81 g (0.1 mol) PMDA was dissolved in 200 g NMP. The mixture was heated to 50 ° C. and stirred for 2 hours. 0.32 g (0.01 mol) of methanol was slowly added dropwise to the mixture and stirred at 50 ° C. for 2 hours. Then 21.23 g (0.1 mol) DMDB was added to the solution. After complete dissolution, the solution was further stirred at 50 ° C. for 6 hours.

(Example 16)
21.81 g (0.1 mol) PMDA was dissolved in 200 g NMP. The mixture was heated to 50 ° C. and stirred for 2 hours. 0.601 g (0.01 mol) of isopropanol was slowly added dropwise to the mixture and stirred at 50 ° C. for 2 hours. 21.23 g (0.1 mol) of DBDB was then added to the solution. After complete dissolution, the solution was further stirred at 50 ° C. for 6 hours.

(Example 17)
21.81 g (0.1 mol) PMDA was dissolved in 200 g NMP. The mixture was heated to 50 ° C. and stirred for 2 hours. 0.32 g (0.01 mol) of methanol was slowly added dropwise to the mixture and stirred at 50 ° C. for 2 hours. 21.23 g (0.1 mol) oTLD was then added to the solution. After complete dissolution, the solution was further stirred at 50 ° C. for 6 hours.

(Example 18)
21.81 g (0.1 mol) PMDA was dissolved in 200 g NMP. The mixture was heated to 50 ° C. and stirred for 2 hours. 0.601 g (0.01 mol) of isopropanol was slowly added dropwise to the mixture and stirred at 50 ° C. for 2 hours. 21.23 g (0.1 mol) oTLD was then added to the solution. After complete dissolution, the solution was further stirred at 50 ° C. for 6 hours.

(Example 19)
21.81 g (0.1 mol) PMDA was dissolved in 200 g NMP. The mixture was heated to 50 ° C. and stirred for 2 hours. 0.32 g (0.01 mol) of methanol was slowly added dropwise to the mixture and stirred at 50 ° C. for 2 hours. Then 32.02 g (0.1 mol) TFMB was added to the solution. After complete dissolution, the solution was further stirred at 50 ° C. for 6 hours.

(Example 20)
21.81 g (0.1 mol) PMDA was dissolved in 200 g NMP. The mixture was heated to 50 ° C. and stirred for 2 hours. 0.601 g (0.01 mol) of isopropanol was slowly added dropwise to the mixture and stirred at 50 ° C. for 2 hours. Then 32.02 g (0.1 mol) of TFBM was added to the solution. After complete dissolution, the solution was further stirred at 50 ° C. for 6 hours.

Physical property test of polyimide Relevant data on the molecular weight of the produced polyimide was tested with HT-GPC equipment (Waters 2010 type) and listed in Table 1.

  From the data in Table 1, it can be seen that the present invention has a lower dispersibility, i.e. a narrower molecular weight distribution and a smaller difference between high and low molecular weights, which can result in polyimides that exhibit better quality. Recognize.

  A film was formed by spin coating with the composition of Example 1 and Comparative Example 1. The film was then baked in an oven at 150 ° C./60 minutes, 250 ° C./60 minutes, and 350 ° C./60 minutes with a three stage heating curve control, ie at a heating rate of 2 ° C./min, and then cooled. The physical properties of this film were tested.

  The mechanical properties of the polyimide film were tested with a universal testing machine (Hungta Instrument, high temperature bending tester 9102 type). The polyimide film was cut into test samples having dimensions of 12 cm × 10 cm × 0.25 mm and then attached to a universal testing machine. The test was carried out at a temperature of 23 ° C. and a speed of 10 mm / min. Polyimide films prepared from the compositions of Example 1 and Comparative Example 1 were tested separately and their tensile strength was measured. The results are shown in Table 2.

  From the results in Table 2, it is clear that the polyimide film of the present invention exhibits better tensile strength and elongation.

Claims (14)

The following formula (1):

(Where
R represents straight-chain or branched alkyl having 1 to 14 carbon atoms, aryl or aralkyl having 6 to 14 carbon atoms, or an ethylenically unsaturated group;
R _x each independently represents H or an ethylenically unsaturated group;
G each independently represents a tetravalent organic group,
Each P independently represents a divalent organic group,
m is an integer from 0 to 100)
Precursor of polyimide having the structure: The ethylenically unsaturated group is vinyl, propenyl, methylpropenyl, n-butenyl, isobutenyl, vinylphenyl, propenylphenyl, propenyloxymethyl, propenyloxyethyl, propenyloxypropyl, propenyloxybutyl, propenyloxyamyl, propenyloxyhexyl , Methylpropenyloxymethyl, methylpropenyloxyethyl, methylpropenyloxypropyl, methylpropenyloxybutyl, methylpropenyloxyamyl, and methylpropenyloxyhexyl, and the following formula (2):

Wherein R ₁ is phenylene, C3-C8 cycloalkylene, linear or branched C1-C8 alkylene, linear or branched C2-C8 alkenylene, or linear or branched C1-C8 hydroxyalkylene. And R ₂ is H or C1-C4 alkyl)
The precursor of claim 1, selected from the group consisting of: The precursor according to claim 1, wherein each R _x independently represents H, 2-hydroxypropyl methacrylate group, ethyl methacrylate group, ethyl acrylate group, propenyl, methylpropenyl, n-butenyl, or isobutenyl. The precursor according to claim 1, wherein R _x each independently represents H or 2-hydroxypropyl methacrylate. The tetravalent organic group is

(In the formula, each Y independently represents H, a halo group, C1-C4 perfluoroalkyl, or C1-C4 alkyl, and B represents —CH ₂ —, —O—, —S—, —CO—, (Represents -SO _2- , -C (CH ₃ ) _2- , or -C (CF ₃ ) _2- )
The precursor of claim 1, wherein the precursor is selected from the group consisting of: The tetravalent organic group is

6. The precursor according to claim 5, wherein the precursor is selected from the group consisting of: The divalent organic group is

(In the formula, each X independently represents H, a halo group, C1-C4 alkyl, or C1-C4 perfluoroalkyl, and A represents —O—, —S—, —CO—, —CH ₂ —, -OC (O)-, or -CONH-, and w and z each represent an integer of 1 to 3)
The precursor of claim 1, wherein the precursor is selected from the group consisting of: The divalent organic group is

The precursor of claim 7, selected from the group consisting of:   The precursor according to claim 1, wherein m is an integer of 5 to 25. R is

(Where n is an integer from 0 to 10)
The precursor of claim 1, wherein the precursor is selected from the group consisting of:   A polyimide precursor composition comprising the precursor according to claim 1 and a solvent.   12. The composition of claim 11, wherein the solvent is selected from the group consisting of N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, toluene, xylene, and mixtures thereof. .   Benzophenone, benzoin, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, N-phenylglycine, 9-phenylacridine, benzyldimethyl ketal, 4,4'-bis (diethylamino) diphenyl ketone, 2,4,5-triarylimidazole dimer, and these 12. The composition of claim 11, further comprising a photoinitiator selected from the group consisting of a mixture.   A polyimide prepared by polymerization of the precursor according to claim 1.