JP2023035862A - Diamine derivative having cyclobutane ring, and salt thereof - Google Patents

Abstract

To provide a compound which can be used as a raw material monomer for producing a polyimide having high light transmissivity, excellent solubility in a solvent, and sufficiently high heat resistance.SOLUTION: There are provided: diamine derivatives represented by the following formula; or salts formed from the diamine derivatives and acids. A1, A2, A3 and A4 are each independently hydrogen, a C3-10 cycloalkyl, a C3-10 cycloalkenyl, phenyl, naphthyl, fluorenyl or pyridyl; and Z1, Z2, Z3 and Z4 are each independently a single bond, a C1-20 alkylene, a C2-20 alkenediyl or a C2-20 alkynediyl.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a diamine having a cyclobutane ring and a salt thereof, particularly a salt formed from a diamine and a derivative thereof as raw materials for polymers used in flexible substrates, films, electrical insulating materials, and varnishes for forming liquid crystal alignment films.

In general, diamines are useful as raw materials for producing polyimide resins, epoxy curing agents, and the like. Among such diamines, for example, aromatic diamine compounds such as 4,4'-diaminophenyl ether have been mainly used as raw materials for polyimide resins used in the field of electronic devices. However, such aromatic tetracarboxylic dianhydrides are used as raw materials for polyimide resins used in applications such as the optical field, since the resulting polyimide resins are colored due to their aromaticity. was not good enough. In addition, polyimide resins obtained using such aromatic diamines have low solubility in solvents and are not satisfactory in terms of workability.

On the other hand, although 1,4-cyclohexanediamine and the like have been reported as cycloaliphatic diamines (Patent Document 1), aliphatic amines are more basic than aromatic amines, and production methods are limited. Therefore, it has not been considered as much. Also, 1,3-diamine having a cyclobutane skeleton is known to have four methyl-substituted diamines at the 2- and 4-positions, but there are almost no reports of 1,3-diamines having other substituents. (Patent Documents 2 to 4, Non-Patent Document 1) Therefore, in order to produce a polyimide resin having high light transmittance and excellent solubility in solvents, aliphatic tetracarboxylic dianhydrides are used instead of amines. has been considered.

Furthermore, wholly aromatic polyimides (for example, trade name "Kapton") have been known as materials indispensable for advanced industries such as space and aviation applications.
Wholly aromatic polyimide is synthesized by combining aromatic tetracarboxylic dianhydride and aromatic diamine, and exhibits the highest class of heat resistance (glass transition temperature (Tg): 410°C) among heat-resistant polymers. It is known that there is (Non-Patent Document 2). However, such a wholly aromatic polyimide exhibits a brown color and is transparent because intramolecular charge transfer (CT) occurs between the aromatic tetracarboxylic dianhydride unit and the aromatic diamine unit. However, it could not be used for optical applications where . Therefore, in order to produce a polyimide that can be used for optical applications, research has been conducted on alicyclic polyimides that do not cause intramolecular CT and have high light transmittance.

Publication No. 2004-149609 International Publication No. 2014-202827 WO2019-147458 U.S. Pat. No. 3,287,390

J. Org. Chem. 1964, 29, 11, 3139 Engineering Plastics, Kyoritsu Shuppan, 1987, p88

In order to solve the problems of the above-described conventional technology, the present invention uses as a raw material monomer for producing a polyimide having high light transmittance, sufficiently excellent solubility in solvents, and sufficiently high heat resistance. To provide 2,2,4,4-tetrasubstituted-1,3-diaminocyclobutanes and salts of 2,2,4,4-tetrasubstituted-1,3-diaminocyclobutanes capable of and In addition, the present invention provides a polyimide that can have high optical transparency and sufficiently high physical stability when processed into a molded body including a film, and the polyimide efficiently and reliably. An object of the present invention is to provide a method for producing a polyimide that can be produced.

式（１）において、
Ａ^１、Ａ^２、Ａ^３、およびＡ^４は独立して、水素、炭素数３～１０のシクロアルキル、炭素数３～１０のシクロアルケニル、フェニル、ナフチル、フルオレニル、またはピリジルであり、これらの環の少なくとも１つの水素は、ハロゲン、炭素数１～１２のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１～１２のアルキルで置き換えられてもよく；
Ｚ^１、Ｚ^２、Ｚ^３、およびＺ^４は独立して、単結合、炭素数１～２０のアルキレン、炭素数２～２０のアルケンジイル、または炭素数２～２０のアルキンジイルであり、これらの基の少なくとも１つの水素はハロゲンで置き換えられてもよく；
－Ｚ^１－Ａ^１と－Ｚ^２－Ａ^２、または－Ｚ^３－Ａ^３と－Ｚ^４－Ａ^４は、互いに結合して環構造を形成してもよく；
Ａ^１、Ａ^２、Ａ^３、およびＡ^４が同時に水素である場合、Ｚ^１、Ｚ^２、Ｚ^３、およびＺ^４のうちの少なくとも１つは、単結合またはメチレンではない。 As means for solving the above problems, the present invention has the following configurations.
[1] A diamine derivative represented by formula (1).

In formula (1),
A ¹ , A ² , A ³ , and A ⁴ are independently hydrogen, cycloalkyl having 3 to 10 carbon atoms, cycloalkenyl having 3 to 10 carbon atoms, phenyl, naphthyl, fluorenyl, or pyridyl, and at least one hydrogen of the ring may be replaced by halogen, alkyl of 1 to 12 carbon atoms, or alkyl of 1 to 12 carbon atoms in which at least one hydrogen is replaced by halogen;
Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently a single bond, alkylene having 1 to 20 carbon atoms, alkenediyl having 2 to 20 carbon atoms, or alkynediyl having 2 to 20 carbon atoms, and these groups at least one hydrogen of may be replaced with a halogen;
-Z ¹ -A ¹ and -Z ² -A ² , or -Z ³ -A ³ and -Z ⁴ -A ⁴ may combine with each other to form a ring structure;
When A ¹ , A ² , A ³ and A ⁴ are simultaneously hydrogen, at least one of Z ¹ , Z ² , Z ³ and Z ⁴ is not a single bond or methylene.

[2] The diamine derivative according to item [1], wherein in formula (1), Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a single bond or an alkylene having 1 to 20 carbon atoms.

[3] In formula (1), A ¹ , A ² , A ³ and A ⁴ are each independently hydrogen, cycloalkyl having 3 to 10 carbon atoms, cycloalkenyl having 3 to 10 carbon atoms, phenyl or fluorenyl The diamine derivative according to item [1] or [2].

[4] Any one of items [1] to [3], wherein in formula (1), Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently a single bond, methylene, or ethylene Diamine derivatives as described.

[5] In formula (1), A ¹ , A ² , A ³ and A ⁴ are each independently cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, dicyclo[2.2.2]octyl , or phenyl, the diamine derivative according to any one of items [1] to [4].

式（１）において、
Ａ^１、Ａ^２、Ａ^３、およびＡ^４は独立して、水素、炭素数３～１０のシクロアルキル、炭素数３～１０のシクロアルケニル、フェニル、ナフチル、フルオレニル、またはピリジルであり、これらの環の少なくとも１つの水素は、ハロゲン、炭素数１～１２のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１～１２のアルキルで置き換えられてもよく；
Ｚ^１、Ｚ^２、Ｚ^３、およびＺ^４は独立して、単結合、炭素数１～２０のアルキレン、炭素数２～２０のアルケンジイル、または炭素数２～２０のアルキンジイルであり、これらの基の少なくとも１つの水素はハロゲンで置き換えられてもよく；
－Ｚ^１－Ａ^１と－Ｚ^２－Ａ^２、または－Ｚ^３－Ａ^３と－Ｚ^４－Ａ^４は互いに結合して環構造を形成してもよい。 [6] A salt formed from a diamine derivative represented by formula (1) and an acid,
The acid is at least one salt selected from carbonic acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, methanesulfonic acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, acetic acid, and propionic acid.

In formula (1),
A ¹ , A ² , A ³ , and A ⁴ are independently hydrogen, cycloalkyl having 3 to 10 carbon atoms, cycloalkenyl having 3 to 10 carbon atoms, phenyl, naphthyl, fluorenyl, or pyridyl, and at least one hydrogen of the ring may be replaced by halogen, alkyl of 1 to 12 carbon atoms, or alkyl of 1 to 12 carbon atoms in which at least one hydrogen is replaced by halogen;
Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a single bond, alkylene having 1 to 20 carbon atoms, alkenediyl having 2 to 20 carbon atoms or alkynediyl having 2 to 20 carbon atoms, and these groups at least one hydrogen of may be replaced with a halogen;
-Z ¹ -A ¹ and -Z ² -A ² , or -Z ³ -A ³ and -Z ⁴ -A ⁴ may combine with each other to form a ring structure.

[7] in formula (1), Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a single bond or an alkylene having 1 to 20 carbon atoms;
The salt according to item [6], wherein the acid is carbonic acid.

[8] In formula (1), A ¹ , A ² , A ³ and A ⁴ are each independently hydrogen, cycloalkyl having 3 to 10 carbon atoms, cycloalkenyl having 3 to 10 carbon atoms, phenyl or fluorenyl; can be;
The salt according to item [6] or [7], wherein the acid is carbonic acid.

[9] in formula (1), Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently a single bond, methylene, or ethylene;
The salt according to any one of items [6] to [8], wherein the acid is carbonic acid.

[10] In formula (1), A ¹ , A ² , A ³ , and A ⁴ are independently hydrogen, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, dicyclo[2.2.2 ] octyl, or phenyl;
The salt according to any one of items [6] to [9], wherein the acid is carbonic acid.

[11] in formula (1), Z ¹ , Z ² , Z ³ and Z ⁴ are methylene, and A ¹ , A ² , A ³ and A ⁴ are hydrogen;
The salt according to item [6], wherein the acid is carbonic acid.

[12] A polymer obtained by using the diamine derivative according to any one of items [1] to [5] or the salt according to any one of items [6] to [11].

[13] The polymer according to item [12], wherein the polymer is polyamic acid, polyimide, polyamide, polyamideimide, polyurethane, or epoxy resin.

[14] A varnish containing the polymer according to item [13].

[15] A molded article produced using the varnish according to item [14].

When the diamine derivatives of the present invention having a cyclobutane ring and diamines containing diamine salts formed therefrom are used as raw materials for polymers such as polyimides and polyamides, compared with the case of using conventional aromatic diamines, The light transmittance of the polymer can be maintained high up to the shorter wavelength region. As a result, molded articles, including films using these polymers, have high transparency and high physical stability, and thus have high transparency in a wide wavelength range, including flexible displays. It is suitable as a required substrate material.

2 shows the results of transmission light spectrum measurement of varnishes in Example 2 of the present invention and Comparative Example 1. FIG.

In the following description, the diamine derivative represented by formula (1) may be represented by compound (1). A salt of the diamine derivative represented by formula (1) may be represented by compound (2). The term "arbitrary" as used herein to designate atoms or groups in a chemical structure means that not only the bonding positions but also the number thereof can be freely selected. In addition, "at least one" means that not only the number but also the bonding position can be freely selected.

式（１）における、Ａ^１、Ａ^２、Ａ^３および、Ａ^４は独立して、水素、炭素数３～１０のシクロアルキル、炭素数３～１０のシクロアルケニル、フェニル、ナフチル、フルオレニル、またはピリジルであり、これらの環の少なくとも１つの水素は、ハロゲン、炭素数１～１２のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１～１２のアルキルで置き換えられてもよい。 The diamine derivative of the present invention is represented by Formula (1).

In formula (1), A ¹ , A ² , A ³ and A ⁴ are independently hydrogen, cycloalkyl having 3 to 10 carbon atoms, cycloalkenyl having 3 to 10 carbon atoms, phenyl, naphthyl, fluorenyl, or pyridyl, and at least one hydrogen of these rings may be replaced by halogen, alkyl of 1 to 12 carbon atoms, or alkyl of 1 to 12 carbon atoms in which at least one hydrogen is replaced by halogen.

Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently a single bond, alkylene having 1 to 20 carbon atoms, alkenediyl having 2 to 20 carbon atoms, or alkynediyl having 2 to 20 carbon atoms, and these groups may be replaced with halogen.
-Z ¹ -A ¹ and -Z ² -A ² or -Z ³ -A ³ and -Z ⁴ -A ⁴ may combine with each other to form a ring structure.
When A ¹ , A ² , A ³ and A ⁴ are simultaneously hydrogen, at least one of Z ¹ , Z ² , Z ³ and Z ⁴ is not a single bond or methylene.

That is, any hydrogen in cycloalkyl, cycloalkenyl, phenyl, naphthyl, fluorenyl, or pyridyl may be replaced by halogen, alkyl having 1 to 12 carbon atoms, or halogenated alkyl having 1 to 12 carbon atoms. Become. Here, multiple hydrogens may be replaced with a group selected from the group consisting of halogen, alkyl having 1 to 12 carbon atoms, and halogenated alkyl having 1 to 12 carbon atoms. The substituents in this case may be the same group or different groups. For example, at least two hydrogens may each be replaced with the same alkyl halide. Three or four hydrogens may be replaced with alkyl halides having different carbon numbers, respectively. Preferred halogens are fluorine and chlorine. Halogenated alkyls are alkyls in which at least one hydrogen has been replaced with fluorine or chlorine. Preferred alkyl halides are perfluoroalkyls.

A polymer having a diamine having fluoro or perfluoroalkyl as one of raw materials tends to act to reduce the surface energy of a liquid crystal alignment film or a molded article obtained by using the polymer, for example.

Preferred examples of the diamine derivative of the present invention are shown below.

Next, a method for producing compound (1) will be described. The ring structure represented by formula (1) can be produced using acid halides compound (a) and compound (b) as starting materials. Hal in the formula represents a halide (chlorine, bromine, etc.). That is, compound (c) is obtained by subjecting compound (a) and compound (b) to a cyclization reaction in the presence of a base such as a trialkylamine such as triethylamine or an aromatic nitrogen base such as pyridine. By reacting hydroxylamine sulfate and other hydroxylamines on compound (c), compound (d) converted to an oxime can be synthesized. Furthermore, compound (1) can be synthesized by reducing compound (d). As the reduction method, catalytic hydrogenation using a catalyst such as Pd/C or sponge-Ni under a hydrogen atmosphere, or a method using a reducing agent such as sodium borohydride can be used.

これらの式におけるＡ^１、Ａ^２、Ａ^３、Ａ^４、Ｚ^１、Ｚ^２、Ｚ^３、およびＺ^４は、式（１）におけるこれらの記号と同一の定義である。

A ¹ , A ² , A ³ , A ⁴ , Z ¹ , Z ² , Z ³ and Z ⁴ in these formulas have the same definitions as those symbols in formula (1).

Other methods for introducing desired terminal groups, rings and linking groups into starting materials are described in Houben-Wyle, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, Organic Syntheses, John Wily & Sons, Inc.), Organic Reactions (John Wily & Sons Inc.), Comprehensive Organic Synthesis (Pergamon Press), New Experimental Chemistry Course (Maruzen), etc. ing.

An example of a method for producing the bonding groups (Z ¹ to Z ⁴ ) will be described. In the schemes shown below, both MSG ¹ and MSG ² are monovalent organic groups having at least one ring. Multiple MSG ¹ (or MSG ² ) shown in the scheme may be the same or different. Tf is _{CF3SO2 .}

(I) Formation of single bond

Arylboric acid derivative (21) is reacted with compound (22) synthesized by a known method in the presence of an aqueous carbonate solution and a catalyst such as tetrakistriphenylphosphine palladium (Pd( _PPh3 ) ₄ ). , to synthesize compound (1a). This compound (1a) is prepared by reacting n-butyllithium (n-BuLi) with compound (23) synthesized by a known method to produce zinc chloride and dichlorobistriphenylphosphinepalladium (PdCl ₂ (PPh ₃ ) ₂ ). It can also be synthesized by sequentially reacting such a catalyst and compound (22).

(II) Generation of —CH ₂ —

After the compound (23) is reacted with butyllithium to induce a lithiated product, carbon dioxide is reacted to obtain a carboxylic acid (24). This is reacted with thionyl chloride to give an acid chloride (25). A compound (27) is obtained by reacting an organocopper reagent (26) synthesized by a known method. Then, compound (1b) is synthesized by reducing the carbonyl of compound (27) with a trialkylsilane such as triethylsilane.

(III) Formation of -CH=CH-

Compound (28) synthesized by a known method is reacted with a base such as potassium t-butoxide (t-BuOK) to generate phosphorus ylide. On the other hand, compound (29) is reacted with butyl lithium to induce a lithiated product, and then reacted with formamide such as N,N-dimethylformamide to obtain aldehyde (30). This is reacted with phosphorus ylide to synthesize compound (1c). Depending on the reaction conditions, the cis isomer is produced, so it is isomerized to the trans isomer by a known method.

Generation of (IV)-(CH ₂ ) _2-

Compound (1d) is synthesized by catalytically hydrogenating compound (1c) in the presence of a catalyst such as palladium on carbon (Pd—C).

Generation of (V)-C≡C-

Using amines such as diethylamine as a solvent, compound (31) is reacted with 1-trimethylsilylethyne in the presence of a catalyst of dichlorobistriphenylphosphine palladium and copper halide to obtain compound (32). The protecting group is then removed using tetrabutylammonium fluoride (TBAF) to give compound (33). Compound (1e) is synthesized by reacting this with compound (22) under the same conditions as in the first step of this method.

Generation of (VI)-(CH ₂ ) ₄ -

Compound (1f) is synthesized by using compound (34) in place of compound (28), producing -CH=CH- according to method (III), and further catalytically hydrogenating according to method (IV).

式（１）における、Ａ^１、Ａ^２、Ａ^３、およびＡ^４は独立して、水素、炭素数３～１０のシクロアルキル、炭素数３～１０のシクロアルケニル、フェニル、ナフチル、フルオレニル、またはピリジルであり、これらの環の少なくとも１つの水素は、ハロゲン、炭素数１～１２のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１～１２のアルキルで置き換えられてもよい。
Ｚ^１、Ｚ^２、Ｚ^３、およびＺ^４は独立して、単結合、炭素数１～２０のアルキレン、炭素数２～２０のアルケンジイル、または炭素数２～２０のアルキンジイルであり、これらの基の少なくとも１つの水素はハロゲンで置き換えられてもよい。
－Ｚ^１－Ａ^１と－Ｚ^２－Ａ^２、または－Ｚ^３－Ａ^３と－Ｚ^４－Ａ^４は互いに結合して環構造を形成してもよい。
カウンター種となる酸は、炭酸、塩酸、臭化水素酸、硫酸、硝酸、トリフルオロメタンスルホン酸、リン酸、ギ酸、または酢酸である。 The salt of the present invention is formed from a diamine derivative represented by formula (1) and an acid.

In formula (1), A ¹ , A ² , A ³ , and A ⁴ are independently hydrogen, cycloalkyl having 3 to 10 carbon atoms, cycloalkenyl having 3 to 10 carbon atoms, phenyl, naphthyl, fluorenyl, or pyridyl, and at least one hydrogen of these rings may be replaced by halogen, alkyl of 1 to 12 carbon atoms, or alkyl of 1 to 12 carbon atoms in which at least one hydrogen is replaced by halogen.
Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently a single bond, alkylene having 1 to 20 carbon atoms, alkenediyl having 2 to 20 carbon atoms, or alkynediyl having 2 to 20 carbon atoms, and these groups may be replaced with halogen.
-Z ¹ -A ¹ and -Z ² -A ² , or -Z ³ -A ³ and -Z ⁴ -A ⁴ may combine with each other to form a ring structure.
Counterspecies acids are carbonic acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, or acetic acid.

Preferred examples of the salt formed from the diamine derivative of the present invention and an acid are shown below.

Next, a polymer obtained by using the diamine derivative of the present invention as one of raw materials and a varnish containing the same will be described as an example. Polyamic acid is obtained by reacting at least one compound (1) or compound (2) with a tetracarboxylic dianhydride in a solvent, which can be led to a polyimide. Furthermore, at least one compound (1) or compound (2) and other diamines or diamine salts may be used in combination. The varnish of the present invention is a composition containing this polyamic acid or polyimide and a solvent.

A polyamide is obtained by reacting at least one compound (1) with a dicarboxylic acid. A polyamideimide is obtained by reacting at least one compound (1) with a tricarboxylic acid. Polyamideimide can also be derived by reacting a mixture of at least two of dicarboxylic acids, tricarboxylic acids and tetracarboxylic acids with at least one compound (1). Furthermore, at least one compound (1) and other diamines may be used in combination. The varnish of the present invention may contain this polyamide or polyamideimide in order to further improve the properties of the varnish described above. Furthermore, the varnish of the present invention may contain known polymer compounds such as polyamides and polyamideimides that do not use compound (1). When these polyamides, polyamideimides or known polymeric compounds are added, their proportion is 0.01 to 30% by weight based on the total weight of the polymer in the varnish. A preferred proportion thereof is 0.01 to 10% by weight, and a more preferred proportion is 0.1 to 5% by weight. By using the component such as the above polyamide in such a ratio, the above effects can be exhibited without reducing the effects of the polymer of the present invention.

Examples of preferred tetracarboxylic dianhydrides used to prepare the polymers of the present invention are shown below. Some of these compounds have isomers, and mixtures containing these isomers are also acceptable. A mixture of at least two of these compounds, or a mixture containing at least one of these compounds and a tetracarboxylic dianhydride other than these compounds, is used as a raw material for producing the polymer of the present invention. may

Next, examples of other diamines (diamines other than compound (1)) are shown below. However, these exemplifications are not meant to limit the diamines that can be used in combination with compound (1).

式（３）において、Ｒ^１およびＲ^２は独立して、炭素数１～３のアルキルまたはフェニルである。Ａ^６は炭素数１～６のアルキレンであり、このアルキレン中の任意の－ＣＨ_２－は、－ＮＨ－、フェニレン、またはアルキル置換フェニレンで置き換えられてもよい。そして、ｐは１～１０の整数である。Ｈ_２Ｎ－Ａ^６－の例は、アミノメチル、２－アミノエチル、３－アミノプロピル、４－アミノブチル、５－アミノペンチル、６－アミノヘキシル、Ｎ－（２－アミノエチル）アミノメチル、Ｎ－（２－アミノエチル）－３－アミノプロピル、４－アミノフェニル、３－アミノフェニル、２－メチル－４－アミノフェニル、４－アミノフェニルエチル、４－アミノフェニルプロピルなどである。
このようなシロキサン結合を有するジアミンのワニスへの添加量は、ワニスに含有される固形分の重量に基づいて０．０１～５重量％、好ましくは０．１～３重量％である。 A diamine having a siloxane bond can be used together with the compound (1) for the purpose of adjusting the adhesion to the glass substrate and the hardness of the alignment film. A preferred diamine having a siloxane bond is the compound represented by formula (3).

In formula (3), R ¹ and R ² are independently alkyl having 1 to 3 carbon atoms or phenyl. A ⁶ is an alkylene having 1 to 6 carbon atoms, and any —CH ₂ — in this alkylene may be replaced with —NH—, phenylene, or alkyl-substituted phenylene. and p is an integer of 1-10. Examples of H ₂ NA ⁶ - are aminomethyl, 2-aminoethyl, 3-aminopropyl, 4-aminobutyl, 5-aminopentyl, 6-aminohexyl, N-(2-aminoethyl)aminomethyl, N-(2-aminoethyl)-3-aminopropyl, 4-aminophenyl, 3-aminophenyl, 2-methyl-4-aminophenyl, 4-aminophenylethyl, 4-aminophenylpropyl and the like.
The amount of such a diamine having a siloxane bond added to the varnish is 0.01 to 5% by weight, preferably 0.1 to 3% by weight, based on the weight of the solid content contained in the varnish.

A silane coupling agent or an organic silicon compound such as silicone oil can be added to the varnish of the present invention for the purpose of improving adhesion to a glass substrate and adjusting hardness. Examples of silane coupling agents are aminopropyltrimethoxysilane, aminopropyltriethoxysilane, vinyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl) -3-aminopropyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4- epoxycyclohexyl)ethyltrimethoxysilane and the like. Examples of silicone oils are dimethylpolysiloxane, polydimethylsiloxane, polydiphenylsiloxane, and the like. The amount of such organosilicon compound added to the varnish is 0.01 to 5% by weight, preferably 0.1 to 3% by weight, based on the weight of the solid content contained in the varnish.

Examples of solvents used in varnish preparation are N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), ethylene glycol monobutyl ether (BC), ethylene glycol monoethyl ether, γ-butyrolactone, and the like. The varnish of the present invention is a mixture in which the polymer of the present invention and other ingredients are dissolved in at least one of these solvents. The non-volatile content in this varnish is 0.1-30% by weight, preferably 1-10% by weight, based on the total weight of the varnish.

This varnish is applied onto the substrate by a brush coating method, dipping method, spinner method, spray method, printing method, or the like, and then the solvent is evaporated at 50 to 150°C, preferably 80 to 120°C. C., preferably 180 to 280.degree. If the surface of the substrate is treated with a silane coupling agent before coating and a film is formed thereon, the adhesion between the film and the substrate can be improved. Thereafter, the surface of this film is rubbed in one direction with a cloth or the like to obtain the alignment film of the present invention.

The polymer of the present invention can be used for various polyimide coating agents, polyimide resin moldings, films, or fiber moldings, in addition to liquid crystal alignment film applications. The diamine derivative of the present invention can also be used as a raw material for polyamide resins, polyamideimide resins and polyurea resins, or as a curing agent for epoxy resins.

The diamine derivative of the present invention and the polyimide resin obtained by using this compound are shown in Examples. All NMR data in Examples are values measured in deuterated chloroform. The molecular weight of the polymer was measured using GPC using polystyrene as a standard solution. The equipment used was LC-9A manufactured by Shimadzu Corporation, the column was Shodex GF-7M manufactured by Showa Denko, the column temperature was 40° C., the eluent was DMF (dimethylformamide), and the flow rate was 0.5 mL/mL. min. is. However, the present invention is not limited to these examples.

Evaluation methods for polyimide resins used in Examples are shown below.
The evaluation was performed using a polyimide resin as a coating film.
(1) Transmission spectrum measurement Measurement was performed using an ultraviolet-visible-near-infrared photometer V-660 manufactured by JASCO Corporation. At that time, a glass substrate not coated with resin is used as a blank.
The method for preparing the polyimide resin sample applied to the glass substrate is as follows.
i) A resin varnish is applied to a glass substrate (EAGLE XG; manufactured by Corning) using a spin coater so as to have a film thickness of 100 nm to form a coating film.
ii) Dry the coated glass substrate for 80 seconds on a hot plate heated to 60°C.
iii) Baking the coating film formed on the glass substrate for 30 minutes in a hot air oven heated to 230° C. for imidization.

(2) Pencil hardness Measured according to JIS standard; JIS K5600-5-4 (ISO/DIN 15184) scratch hardness (pencil method). The coating film used was prepared in the same manner as the sample preparation method described in (1) Transmission spectrum measurement method.

（第１段）
塩酸ヒドロキシルアミン（５９．５ｇ：８５６．３ｍｍｏｌ）のピリジン（１５０ｍｌ）溶液を０℃に冷却し、そこに文献記載の方法に準拠して得た２，２，４，４－テトラメチルシクロブタン－１，３－ジオン（３０ｇ：２１４．０ｍｍｏｌ）を少量ずつ加え、０℃で５分間撹拌した。更に室温で２４時間撹拌した後、得られた反応混合物に蒸留水を加えて析出した固体をろ過し、更に固体を水洗後、６０℃にて真空乾燥を行い、２，２，４，４－テトラメチルシクロブタン－１，３－ジオン ジオキシム（３５．８ｇ：２１０．３ｍｍｏｌ）収率９８．３％を得た。これを化合物（２－１－１－１ａ）とする。 [Example 1]
(Synthesis of 2,2,4,4-tetramethylcyclobutanediamine carbonate (Compound No. 2-1-1-1))

(first stage)
A solution of hydroxylamine hydrochloride (59.5 g: 856.3 mmol) in pyridine (150 ml) was cooled to 0° C., whereupon 2,2,4,4-tetramethylcyclobutane-1 obtained according to the method described in the literature was added. ,3-dione (30 g: 214.0 mmol) was added portionwise and stirred at 0° C. for 5 minutes. After further stirring at room temperature for 24 hours, distilled water was added to the resulting reaction mixture, the precipitated solid was filtered, and the solid was washed with water and vacuum-dried at 60° C. Tetramethylcyclobutane-1,3-dione dioxime (35.8 g: 210.3 mmol) was obtained with a yield of 98.3%. This is designated as compound (2-1-1-1a).

(second stage)
In an autoclave reactor, compound (2-1-1-1a) (20.0 g: 117.5 mmol) was dissolved in 200 mL of tetrahydrofuran (THF), sponge-Ni (4.0 g) was added, and under a hydrogen atmosphere, The mixture was stirred at 80° C. until no more hydrogen was absorbed. After the completion of the reaction, the sponge-Ni was filtered off, a bubbler was introduced into the obtained reaction solution, carbon dioxide was blown thereinto, and the obtained solid was filtered off. Thereafter, the solid was washed with ethyl acetate and diethyl ether and dried under reduced pressure to obtain 2,2,4,4-tetramethylcyclobutanediamine carbonate (Compound No. 2-1-1-1) (23. 7 g: 116.3 mmol).
¹ H-NMR (CDCl ₃ ) δ: 2.66 (d, 2H), 1.01 (t, 12H).

[Example 2]
(Synthesis of polyamic acid)
(Compound No. 2-1-1-1) (1.50 g) synthesized in exactly the same manner as in Example 1 was placed in a 200 ml four-necked flask and dissolved in NMP (27 mL). Pyromellitic dianhydride (PMDA) (0.80 g) and cyclobutanetetracarboxylic dianhydride (MMDA) (0.72 g) were added to the solution and stirred for 12 hours. By diluting the resulting solution with a mixed solvent of NMP (18 mL) and BC (5 mL), a transparent liquid having a polyamic acid concentration of 6% by weight was obtained. The viscosity of this solution at 25° C. was 15 mPa·s, and the weight average molecular weight of the polymer contained in this solution was 20,000. This solution is called Varnish A.

[Example 3]
(Synthesis of polyimide)
Acetic anhydride (3.76 g) and pyridine (2.91 g) were added to the varnish A obtained in Example 2, and the mixture was heated to reflux at 100° C. for 3 hours. After cooling, the reaction mixture was poured into methanol to reprecipitate the polymer and filtered to obtain a crude product. This crude product was boiled and washed twice with pure water (500 ml) and once with methanol (500 ml) for about 30 minutes each. Then, it was dried under reduced pressure at 120° C. for 8 hours to obtain polyimide (3.6 g). The weight average molecular weight of this polyimide was 25,000.

（第１段）
塩酸ヒドロキシルアミン（５９．５ｇ：８５６．３ｍｍｏｌ）のピリジン（１５０ｍｌ）溶液を０℃に冷却し、そこに文献記載の方法に準拠して得た２，４－ジエチル－２，４－ジシクロヘキシルシクロブタン－１，３－ジオン（６５．２ｇ：２１４．０ｍｍｏｌ）を少量ずつ加え、０℃で５分間撹拌した。更に室温で２４時間撹拌した後、得られた反応混合物に蒸留水を加えて析出した固体をろ過し、更に固体を水洗後、６０℃にて真空乾燥を行い、２，４－ジエチル－２，４－ジシクロヘキシルシクロブタン－１，３－ジオン ジオキシム（６８．０ｇ：３０３．３ｍｍｏｌ）収率９５．０％を得た。これを化合物（２－２－１－２７ａ）とする。 [Example 4]
(Synthesis of 2,4-diethyl-2,4-dicyclohexylcyclobutanediamine (Compound No. 1-2-1-14))

(first stage)
A solution of hydroxylamine hydrochloride (59.5 g: 856.3 mmol) in pyridine (150 ml) was cooled to 0° C., and 2,4-diethyl-2,4-dicyclohexylcyclobutane- 1,3-dione (65.2 g: 214.0 mmol) was added portionwise and stirred at 0° C. for 5 minutes. After further stirring at room temperature for 24 hours, distilled water was added to the resulting reaction mixture, the precipitated solid was filtered, and the solid was washed with water and vacuum-dried at 60°C. 4-Dicyclohexylcyclobutane-1,3-dione dioxime (68.0 g: 303.3 mmol) yield 95.0%. This is designated as compound (2-2-1-27a).

(second stage)
In an autoclave reactor, compound (2-2-1-27a) (39.3 g: 117.5 mmol) was dissolved in 200 mL of tetrahydrofuran (THF), sponge-Ni (4.0 g) was added, and under a hydrogen atmosphere, The mixture was stirred at 80° C. until no more hydrogen was absorbed.
After the completion of the reaction, sponge-Ni was filtered off, the solvent was distilled off under reduced pressure, and 2,2,4,4-diethyl-2,4-dicyclohexylcyclobutanediamine (compound No. 1-2-1 -14) (35.6 g: 116.3 mmol) was obtained.

実施例４で得られた化合物（１－２－１－１４）３０ｇ（９７．９ｍｍｏｌ）をテトラヒドロフラン（ＴＨＦ）２００ｍＬへ溶解させ、バブラーを導入後、二酸化炭素を吹き込み得られた固体を濾別した。その後固体を酢酸エチル、ジエチルエーテルで洗浄し減圧下乾燥し、収率９９％で２，２，４，４－ジエチル－２，４－ジシクロヘキシルシクロブタンジアミン炭酸塩（化合物Ｎｏ．２－２－１－２７）（３６．１ｇ：１１６．３ｍｍｏｌ）を得た。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）δ：２．６５（ｄ，２Ｈ）、２．０６－２．００（ｍ，２Ｈ）、１．７４－１．５１（ｍ、１６Ｈ）、１．１９－１．０２（ｍ，８Ｈ）０．８８（ｔ，６Ｈ）． [Example 5]
(Synthesis of 2,4-diethyl-2,4-dicyclohexylcyclobutanediamine carbonate (Compound No. 2-2-1-27))

30 g (97.9 mmol) of the compound (1-2-1-14) obtained in Example 4 was dissolved in 200 mL of tetrahydrofuran (THF), a bubbler was introduced, carbon dioxide was blown thereinto, and the obtained solid was separated by filtration. . After that, the solid was washed with ethyl acetate and diethyl ether and dried under reduced pressure. 27) (36.1 g: 116.3 mmol) was obtained.
¹ H-NMR (CDCl ₃ ) δ: 2.65 (d, 2H), 2.06-2.00 (m, 2H), 1.74-1.51 (m, 16H), 1.19-1 .02 (m, 8H) 0.88 (t, 6H).

[Example 6]
(Synthesis of polyamic acid)
In a 200 ml four-necked flask, 2.70 g (compound No. 2-1-1-1) synthesized in exactly the same manner as in Example 1 was placed and dissolved in NMP (27 mL). Pyromellitic dianhydride (PMDA) (0.80 g) and cyclobutanetetracarboxylic dianhydride (MMDA) (0.72 g) were added to the solution and stirred for 12 hours. By diluting the resulting solution with a mixed solvent of NMP (18 mL) and BC (5 mL), a transparent liquid having a polyamic acid concentration of 6% by weight was obtained. The viscosity of this solution at 25° C. was 15 mPa·s, and the weight average molecular weight of the polymer contained in this solution was 32,000. This solution is called varnish B.

[Example 7]
(Synthesis of polyimide)
Acetic anhydride (3.76 g) and pyridine (2.91 g) were added to the varnish B obtained in Example 6, and the mixture was heated under reflux at 100° C. for 3 hours. After cooling, the reaction mixture was poured into methanol to reprecipitate the polymer and filtered to obtain a crude product. This crude product was boiled and washed twice with pure water (500 ml) and once with methanol (500 ml) for about 30 minutes each. Then, it was dried under reduced pressure at 120° C. for 8 hours to obtain polyimide (4.1 g). The weight average molecular weight of this polyimide was 40,000.

[Comparative Example 1]
(Synthesis of polyamic acid)
1,4-Phenylenediamine (0.8 g) was placed in a 200 ml four-necked flask and dissolved in NMP (27 mL). Pyromellitic dianhydride (PMDA) (0.80 g) and cyclobutanetetracarboxylic dianhydride (MMDA) (0.72 g) were added to the solution and stirred for 12 hours. By diluting the resulting solution with a mixed solvent of NMP (18 mL) and BC (5 mL), a transparent liquid having a polyamic acid concentration of 6% by weight was obtained. The viscosity of this solution at 25° C. was 15 mPa·s, and the weight average molecular weight of the polymer contained in this solution was 20,000. Let this solution be varnish Y.

Evaluation 1 of [Example 2] and [Comparative Example 1]
(Measurement of transmitted light spectrum of varnish)
The transmitted light spectrum of the polyimide film produced from the varnish A prepared in Example 2 and the varnish Y prepared in Comparative Example 1 was measured by the method described above. The spectrum is shown in FIG. The polyimide film derived from varnish Y of Comparative Example absorbs and does not transmit in the high-energy short wavelength region of 300 nm or less, while the varnish A derived from diamine carbonate of Example 1 does not transmit in the short wavelength region of 300 nm or less. It can be seen that there is no absorption at all, and in addition, it has excellent transmittance in the entire wavelength range.

Evaluation 2 of [Example 2] and [Comparative Example 1]
(Pencil hardness measurement of polyimide film made from varnish)
The pencil hardness of the polyimide film produced from the varnish A prepared in Example 2 and the varnish Y prepared in Comparative Example 1 was measured by the method described above. Table 1 shows the results. It can be seen that the polyimide film produced from varnish A has hardness equivalent to that of varnish Y of Comparative Example 2.

<Table 1>

When the diamine derivative of the present invention having a cyclobutane ring and the diamines containing the diamine salt are used as raw materials for polymers such as polyimides and polyamides, compared with the case of using conventional aromatic diamines, the light of the polymer Transmittance can remain high down to the shorter wavelength region. As a result, molded articles including films using these polymers have high transparency and high physical stability, so high transparency in a wide wavelength range such as flexible displays is required. It is suitable as a substrate material.

Since the diamines of the present invention can be produced by a short synthetic route at low cost, it is possible to provide a highly functional molded article at a lower cost. In addition, the compound of the present invention can also be used as a raw material for polymer materials having bonding modes other than polyimide.

Claims (15)

A diamine derivative represented by formula (1).

In formula (1),
A ¹ , A ² , A ³ , and A ⁴ are independently hydrogen, cycloalkyl having 3 to 10 carbon atoms, cycloalkenyl having 3 to 10 carbon atoms, phenyl, naphthyl, fluorenyl, or pyridyl, and at least one hydrogen of the ring may be replaced by halogen, alkyl of 1 to 12 carbon atoms, or alkyl of 1 to 12 carbon atoms in which at least one hydrogen is replaced by halogen;
Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently a single bond, alkylene having 1 to 20 carbon atoms, alkenediyl having 2 to 20 carbon atoms, or alkynediyl having 2 to 20 carbon atoms, and these groups at least one hydrogen of may be replaced with a halogen;
-Z ¹ -A ¹ and -Z ² -A ² , or -Z ³ -A ³ and -Z ⁴ -A ⁴ may combine with each other to form a ring structure;
When A ¹ , A ² , A ³ and A ⁴ are simultaneously hydrogen, at least one of Z ¹ , Z ² , Z ³ and Z ⁴ is not a single bond or methylene. 2. The diamine derivative according to claim 1, wherein Z ¹ , Z ² , Z ³ and Z ⁴ in formula (1) are each independently a single bond or an alkylene having 1 to 20 carbon atoms. In formula (1), A ¹ , A ² , A ³ , and A ⁴ are independently hydrogen, cycloalkyl having 3 to 10 carbon atoms, cycloalkenyl having 3 to 10 carbon atoms, phenyl, or fluorenyl; The diamine derivative according to claim 1. 2. The diamine derivative according to claim 1, wherein ^Z1 , ^Z2 , ^Z3 , and ^Z4 in formula (1) are independently a single bond, methylene, or ethylene. In formula (1), A ¹ , A ² , A ³ , and A ⁴ are independently cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, dicyclo[2.2.2]octyl, or phenyl The diamine derivative according to claim 1, wherein A salt formed from a diamine derivative represented by formula (1) and an acid,
The acid is at least one salt selected from carbonic acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, methanesulfonic acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, acetic acid, and propionic acid.

In formula (1),
A ¹ , A ² , A ³ , and A ⁴ are independently hydrogen, cycloalkyl having 3 to 10 carbon atoms, cycloalkenyl having 3 to 10 carbon atoms, phenyl, naphthyl, fluorenyl, or pyridyl, and at least one hydrogen of the ring may be replaced by halogen, alkyl of 1 to 12 carbon atoms, or alkyl of 1 to 12 carbon atoms in which at least one hydrogen is replaced by halogen;
Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently a single bond, alkylene having 1 to 20 carbon atoms, alkenediyl having 2 to 20 carbon atoms, or alkynediyl having 2 to 20 carbon atoms, and these groups at least one hydrogen of may be replaced with a halogen;
-Z ¹ -A ¹ and -Z ² -A ² , or -Z ³ -A ³ and -Z ⁴ -A ⁴ may combine with each other to form a ring structure. In formula (1), Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a single bond or an alkylene having 1 to 20 carbon atoms;
7. The salt of Claim 6, wherein the acid is carbonic acid. In formula (1), A ¹ , A ² , A ³ and A ⁴ are independently hydrogen, cycloalkyl having 3 to 10 carbon atoms, cycloalkenyl having 3 to 10 carbon atoms, phenyl, or fluorenyl;
7. The salt of Claim 6, wherein the acid is carbonic acid. in formula (1), Z ¹ , Z ² , Z ³ , and Z ⁴ are independently a single bond, methylene, or ethylene;
7. The salt of Claim 6, wherein the acid is carbonic acid. In formula (1), A ¹ , A ² , A ³ , and A ⁴ are independently hydrogen, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, dicyclo[2.2.2]octyl, or is phenyl;
7. The salt of Claim 6, wherein the acid is carbonic acid. In formula (1), Z ¹ , Z ² , Z ³ and Z ⁴ are methylene and A ¹ , A ² , A ³ and A ⁴ are hydrogen;
7. The salt of Claim 6, wherein the acid is carbonic acid. A polymer obtained by using the diamine derivative according to any one of claims 1 to 5 or the salt according to any one of claims 6 to 11. 13. The polymer of Claim 12, wherein the polymer is a polyamic acid, polyimide, polyamide, polyamideimide, polyurethane, or epoxy resin. A varnish containing the polymer of claim 13 . A molded article produced using the varnish according to claim 14 .

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