TW201702289A - Polyimide precursor, and liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element having precursor - Google Patents

Abstract

The present invention provides a polyimide precursor in which the quantity of radicals generated is relatively large. Through this polyimide precursor, reaction of a polymerizable compound is accelerated, the pretilt angle in liquid crystals is efficiently set to the desired value, and a liquid crystal display element having enhanced response speed is provided. The present invention provides a polyimide precursor which uses a first photoradical generating diamine, the polyimide precursor being characterized in that the quantity of radicals generated during photoirradiation under the same conditions is greater than in a second polyimide precursor formed under the same conditions as the polyimide precursor except that the first photoradical generating diamine is replaced therein with a second photoradical generating diamine represented by formula (1).

Description

Polyimine precursor, liquid crystal alignment agent having the precursor, liquid crystal alignment film, and liquid crystal display element

The present invention relates to a polyimine precursor having a relatively large amount of radical generation, such as a vertical alignment type liquid crystal display element produced by irradiating ultraviolet rays to a liquid crystal molecule, and having the polyimine precursor. A liquid crystal alignment agent, a liquid crystal alignment film formed of the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.

In a liquid crystal display device in which a liquid crystal molecule which is vertically aligned with respect to a substrate is responsive to an electric field (also referred to as a vertical alignment (VA) method), the manufacturing process includes applying a voltage to the liquid crystal molecules. The step of irradiating ultraviolet rays.

In the liquid crystal display device of the vertical alignment type, it is known that a photopolymerizable compound is added to the liquid crystal composition in advance, and a vertical alignment film such as a polyimide film is used, and a voltage is applied to the liquid crystal cell. A technique for accelerating the response speed of a liquid crystal (PSA (Polymer Sustained Alignment) type element, for example, refer to Patent Document 1 and Non-Patent Document 1).

In the PSA mode element, it is generally known that the tilt direction of the liquid crystal molecules responsive to the electric field can be controlled by a protrusion provided on the substrate or a slit provided on the display electrode, but by liquid crystal When a photopolymerizable compound is added to the composition and a voltage is applied to the liquid crystal cell, ultraviolet rays are irradiated, and a polymer structure in which an oblique direction of the liquid crystal molecules is stored can be formed on the liquid crystal alignment film, compared to the protrusion or the narrow The method of sewing to control the tilt direction of the liquid crystal molecules, the response speed of the liquid crystal display element becomes faster.

On the other hand, in the liquid crystal display device of the PSA type, there is a problem that the solubility of the polymerizable compound added to the liquid crystal is low, and the amount of addition increases at a low temperature, but the addition of the polymerizable compound is reduced. A good alignment state cannot be obtained. In addition, the unreacted polymerizable compound remaining in the liquid crystal may cause impurities (contamination) in the liquid crystal and cause a problem that the reliability of the liquid crystal display element is lowered. Further, in the UV irradiation treatment required in the PSA method, if the amount of irradiation is large, the components in the liquid crystal are decomposed, resulting in a decrease in reliability.

Further, it has been reported that by adding a photopolymerizable compound to a liquid crystal alignment film instead of being added to a liquid crystal composition, the response speed of the liquid crystal display element is increased (SC-PVA type liquid crystal display, for example, refer to the non-patent literature) 2).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2003-307720

[Non-patent literature]

[Non-Patent Document 1] K. Hanaoka, SID 04 DIGEST, P.1200-1202

[Non-Patent Document 2] K.H Y.-J.Lee, SID 09 DIGEST, P.666-668

In recent years, as the quality of liquid crystal display elements has improved, it has been expected that the response speed to liquid crystals to which voltage is applied becomes faster. Therefore, the polymerizable compound is required to efficiently react with long-wavelength ultraviolet rays (which are not accompanied by decomposition of components in the liquid crystal), and exhibits an alignment fixing ability. Further, it is necessary to leave no unreacted polymerizable compound after ultraviolet irradiation, and it does not adversely affect the reliability of the liquid crystal display element.

An object of the present invention is to provide a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element which can improve the response speed of a liquid crystal display element, and which are not accompanied by the above-mentioned problems of the prior art, and are used in liquid crystal and/or It is obtained by the step of reacting a polymerizable compound in the liquid crystal alignment film.

More specifically, the object of the present invention is to provide a polyimide precursor having a relatively large amount of radical generation, and to promote a reaction of a polymerizable compound with the polyimide precursor, so that the pretilt angle in the liquid crystal is efficiently obtained as a desired value. To increase the response speed of the liquid crystal display element.

As a result of the intensive review, the present inventors have found that a polymer having a liquid crystal alignment agent is introduced into a specific structure in which a radical is generated by ultraviolet irradiation and a radical is generated in a relatively large amount, and the polyimide precursor is introduced into the polyimine precursor. Further, by using a liquid crystal alignment agent having the polyimide precursor, the reactivity of the polymerizable compound in the liquid crystal display element obtained by the step of reacting the polymerizable compound in the liquid crystal and/or the liquid crystal alignment film is improved. The above problems can be achieved and the invention detailed below will be completed.

<1> A polyimine precursor using a diamine for generating a first photo radical, wherein the characteristic phase is replaced by the second light represented by the formula (1) in addition to the first photoradical generating diamine In addition to the diamine used for radical generation, the second polyimine imine precursor formed under the same conditions as the polyimine precursor has a large amount of radical generation upon light irradiation under the same conditions.

<2> In the above <1>, the light wavelength at the time of light irradiation is preferably from 300 nm to 400 nm.

<3> In the above <1> or <2>, in the 100% by mole of the total diamine constituting the polyimide precursor, the first photoactive radical-generating diamine is preferably 0.1 to 100 mol%.

<4> In the above <1> to <3>, the first photoradical generating diamine has the formula (A) (wherein, Ar is an aromatic hydrocarbon group which may have a substituent, and R ¹⁰¹ is a divalent organic group) , R ¹⁰² ~ R ¹⁰⁴ are each independent, indicating a monovalent organic group)

The structure is suitable.

<5> In the above <4>, -R ¹⁰¹ - is -T ₁ -ST ₂ - (wherein T ₁ and T ₂ are each independently, and are a single bond, -O-, -COO-, -OCO-, - NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-, S is a single bond, or a non- a alkyl group having 1 to 20 carbon atoms which is substituted or substituted by a fluorine atom (-CH ₂ - or -CF ₂ - in the alkyl group is -CH=CH-, or a group which can be selected by the lower group G ( However, the groups selected by the group G are not adjacent to each other (group G: -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, divalent carbon ring or divalent Heterocycle)))

Expressed as appropriate.

<6> In the above <4> or <5>, any one of R ¹⁰² to R ¹⁰⁴ is -OR ¹¹¹ (R ¹¹¹ is a straight chain having 1 to 20 carbon atoms which are unsubstituted or substituted by a fluorine atom or a branched or cyclic alkyl group (-CH ₂ - or -CF ₂ - in the alkyl group is -CH=CH-, or a group selectable by the lower group G (however, the group selected by the group G is mutually Substituted) (group G: -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, divalent carbocyclic or divalent heterocyclic ring), the other two Independently, it is a linear or branched or cyclic alkyl group having 1 to 20 carbon atoms, -OR ¹¹² (R ¹¹² is a linear or branched chain having 1 to 20 carbon atoms which are unsubstituted or substituted by a fluorine atom. Or a cyclic alkyl group, a group having a substituent of 6 to 20 carbon atoms in the group selected from the group consisting of a group, a benzyl group, or a phenethyl group (the other two are the aforementioned alkyl groups or When -OR ¹¹² , it is preferable to bond each other to form a ring).

<7> In any of the above <4> to <6>, Ar is preferably a phenyl group.

<8> In any one of the above <1> to <7>, the diamine for generating the first photoradical is preferably represented by the following formula (2) (wherein, Ar and R ¹⁰¹ to R ¹⁰⁴ are the same as defined above) .

<9> In any one of the above <1> to <8>, the first photoradical generating diamine is preferably represented by the following formula (3).

<10> In any one of the above <1> to <9>, the polyimine precursor preferably has a side chain which vertically aligns the liquid crystal.

<11> In any one of the above <1> to <10>, the polyimine precursor is preferably a side chain having a photoreactive group in the structure.

<12> A polyimine obtained by subjecting the polyimine precursor of any of <1> to <11> to ruthenium iodide.

<13> A liquid crystal alignment agent comprising the polyimine precursor of any one of <1> to <11> and/or the polyimine of the above <12>.

<14> In the above <13>, it is preferable to use a polymerizable compound in a liquid crystal and/or a liquid crystal alignment film, and a liquid crystal display element obtained by reacting the polymerizable compound by irradiating ultraviolet rays while applying a voltage.

<15> A liquid crystal alignment film formed by the liquid crystal alignment agent of the above <13> or <14>.

<16> A liquid crystal display element comprising the liquid crystal alignment film of the above <15>.

<17> has the following formula (A): wherein Ar is an aromatic hydrocarbon group which may have a substituent, R ¹⁰¹ is a divalent organic group, and R ¹⁰² to R ¹⁰⁴ are each independently and represent a monovalent organic group.

The diamine of the structure shown.

<18> In the above <17>, -R ¹⁰¹ - is -T ₁ -ST ₂ - (wherein T ₁ and T ₂ are each independently, and are a single bond, -O-, -COO-, -OCO-, - NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-, S is a single bond, or a non- a alkyl group having 1 to 20 carbon atoms which is substituted or substituted by a fluorine atom (-CH ₂ - or -CF ₂ - in the alkyl group is -CH=CH-, or a group which can be selected by the lower group G ( However, the groups selected by the group G are not adjacent to each other (group G: -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, divalent carbon ring or divalent Heterocycle)))

The indicator is appropriate.

<19> In the above <17> or <18>, any one of R ¹⁰² to R ¹⁰⁴ is -OR ¹¹¹ (R ¹¹¹ is a straight chain having 1 to 20 carbon atoms which are unsubstituted or substituted by a fluorine atom or a branched or cyclic alkyl group (-CH ₂ - or -CF ₂ - in the alkyl group is -CH=CH-, or a group selectable by the lower group G (however, the group selected by the group G is mutually Substituted) (group G: -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, divalent carbocyclic or divalent heterocyclic ring), the other two Independently, it is a linear or branched or cyclic alkyl group having 1 to 20 carbon atoms, -OR ¹¹² (R ¹¹² is a linear or branched chain having 1 to 20 carbon atoms which are unsubstituted or substituted by a fluorine atom. Or a cyclic alkyl group, a group having a substituent of 6 to 20 carbon atoms in the group selected from the group consisting of a group, a benzyl group, or a phenethyl group (the other two are the aforementioned alkyl groups or When -OR ¹¹² , it is preferable to bond each other to form a ring).

<20> The diamine of any of <17> to <19> is preferably represented by the following formula (2) (Ar and R ¹⁰¹ to R ¹⁰⁴ have the same definitions as defined above).

<21> The diamine of any of <17> to <20> is represented by the following formula (4) (R ¹⁰³ and R ¹⁰⁴ and R ¹¹¹ have the same meanings as defined above, and X ¹⁰¹ is a single bond or CO). should.

<22> The diamine of any of <17> to <21> is preferably selected from the group consisting of the following formulas (3) to (3)-12.

<23> In the formula (2), wherein Ar is an aromatic hydrocarbon group which may have a substituent, R ¹⁰¹ is a divalent organic group, and R ¹⁰² to R ¹⁰⁴ are each independently and represent a monovalent organic group.

The diamine represented.

<24> A diamine represented by the following formula (3).

<25> A diamine selected from the group consisting of the following formulas (3) to (3)-12.

<26> A polyimide intermediate of a diamine of any of <17> to <25> above.

<27> In the above <26>, in the 100% by mole of the total diamine constituting the polyimide precursor, the diamine of any of the above <17> to <25> is preferably 0.1 to 100 mol%.

<28> In the above-mentioned <26> or <27> polyimine precursor, It is preferable to have a side chain for vertically aligning the liquid crystal.

<29> In the above <28>, the side chain in which the liquid crystal is vertically aligned is represented by the following formula [II-1] (in the formula [II-1], X ¹ is a single bond, -(CH ₂ ) _a -(a Is an integer from 1 to 15,) -O-, -CH ₂ O-, -COO- or OCO-. X ² is a single bond or (CH ₂ ) _b - (b is an integer from 1 to 15). X ³ is a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or OCO-. X ⁴ is a benzene ring, a cyclohexane ring, and a hetero a divalent cyclic group selected from the ring, and any hydrogen atom of the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a fluorine-containing alkyl group having 1 to 3 carbon atoms. And a fluorine-containing alkoxy group having a carbon number of 1 to 3 or a fluorine atom, and further, X ⁴ may be a divalent organic group selected from an organic group having a carbon number of 17 to 51 having a steroid skeleton. X ⁵ is a benzene ring, a divalent cyclic group selected from a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a carbon number of 1 ~3 is a fluorine-containing alkyl group, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom; n is an integer of 0 to 4. X ⁶ is an alkyl group having 1 to 18 carbon atoms and a carbon number of 1 to 18 a fluorine-containing alkyl group, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms.) and [II-2] (formula [II- In 2], X ⁷ is a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- or OCO - X ⁸ is an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms.

At least one of the selected ones is preferred.

<30> The polyimine precursor of any of <26> to <29> is preferably a side chain having a photoreactive group in the structure.

<31> In the above <30>, the side chain containing a photoreactive group in the structure is represented by the following formula [III] (in the formula [III], R ⁸ is a single bond, -CH ₂ -, -O-, -COO- , -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-.R ⁹ is a single bond, a C 1~20 alkyl group which may be substituted by a fluorine atom, and an alkyl group -CH ₂ - may be optionally substituted by -CF ₂ - or -CH=CH-, any of the following groups When they are not adjacent to each other, they may be substituted by such groups; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring or a heterocyclic ring. R ¹⁰ is as follows a photoreactive group selected from the group consisting of R ¹⁰ -1 to R ¹⁰ -7. or formula (IV) (Y ₁ is -CH ₂ -, -O-, -CONH-, -NHCO-, - COO-, -OCO-, -NH-, or -CO-. Y ₂ is an alkylene group having a carbon number of 1 to 30, a divalent carbon ring or a heterocyclic ring, and an alkyl group, a divalent carbon ring or a heterocyclic ring. One or more hydrogen atoms may be substituted by a fluorine atom or an organic group. When Y _{2 is} not adjacent to each other, -CH ₂ - may be substituted by such groups; -O-, -NHCO-, -CONH-, - COO-, -OCO-, -NH-, -NHCONH-, -CO-. Y ₃ is -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH- , -CO-, or Single bond. Y ₄ is a cinnamyl group. Y ₅ is a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbon ring or a heterocyclic ring, and 1 alkyl group, a divalent carbon ring or a heterocyclic ring. A plurality of hydrogen atoms may be substituted by a fluorine atom or an organic group. When Y _{5 is} not adjacent to each other, -CH ₂ - may be substituted by such groups; -O-, -NHCO-, -CONH-, -COO- , -OCO-, -NH-, -NHCONH-, -CO-. Y ₆ is a photopolymerizable group of an acryl group or a methacryl fluorenyl group.)

The indicator is appropriate.

<31> A polyimine obtained by imidating a polyimine precursor precursor of any of <26> to <30>.

<32> A liquid crystal alignment agent comprising the polyimine precursor of any one of <26> to <31> and/or the polyimine of the above <31>.

<33> In the above <32>, it is preferable to use a polymerizable compound in a liquid crystal and/or a liquid crystal alignment film, and to irradiate ultraviolet rays while applying a voltage to cause a liquid crystal display element obtained by reacting the polymerizable compound.

<34> A liquid crystal alignment film formed by the liquid crystal alignment agent of the above <32> or <33>.

<35> A liquid crystal display element comprising the liquid crystal alignment film of the above <34>.

According to the present invention, a polyimine precursor having a relatively large amount of radical generation can be provided.

Further, according to the present invention, by using a liquid crystal alignment agent having the polyimide precursor and/or a liquid crystal alignment film having the liquid crystal alignment agent, even if the ultraviolet irradiation amount is relatively low, it can be in the liquid crystal. A desired pretilt angle is obtained, and along with this, a vertical alignment type liquid crystal display element having a fast response speed, in particular, a PSA type liquid crystal display element can be provided.

[Best Mode for Carrying Out the Invention]

The present invention provides a polyimine precursor having a relatively large amount of radical generation, a diamine constituting the polyimine, a liquid crystal alignment agent having the polyimide precursor, and a liquid crystal alignment formed by the liquid crystal alignment agent. a film, and the liquid crystal display element. The following is explained in order.

<Polyimide precursors with relatively high amount of free radicals>

The present invention provides a polyimine precursor having a relatively high amount of free radical production.

Specifically, the present invention provides a polyimide intermediate precursor using a diamine for producing a first photoradical.

Polyimine precursor using diamine for the first photo radical generation, The second polyimine precursor formed under the same conditions as the second photo-radical-generating diamine represented by the formula (1) except that the first photo-radical-generating diamine is substituted with the diamine. The amount of free radicals generated by light irradiation under the same conditions is large.

Here, the wavelength of light "when irradiated under the same conditions" is preferably from 300 nm to 400 nm, preferably from 310 to 380 nm, more preferably from 350 to 370 nm.

In the present specification, the term "polyimine precursor" means a reaction in which a diamine component and a tetracarboxylic dianhydride component are reacted.

In addition, in the present specification, "a polyimide precursor using a ~~ diamine" or a "polyimine precursor is formed using a ~~diamine" means a raw material used as a polyimide precursor. ~~Diamine". Here, the "diamine" includes a part or all of the raw materials.

In the present specification, "~~diamine constituting a polyimide precursor" means a polydiimide precursor which is a raw material of a polyimide precursor and uses "~~ diamine". Here, the "diamine" includes a part or all of the raw materials.

The polyimine precursor of the present invention constitutes a polyimine In the 100% by mole of the total diamine of the precursor, the diamine for the first photoradical generation is 0.1 to 100 mol%, preferably 10 to 80 mol%, more preferably 30 to 50 mol%.

The first photoradical generating diamine has the formula (A) (wherein, Ar is an aromatic hydrocarbon group which may have a substituent, R ¹⁰¹ is a divalent organic group, and R ¹⁰² to R ¹⁰⁴ are each independently, and represents a monovalent organic group. base)

The structure is suitable.

-R ¹⁰¹ - is preferably a group represented by -T ₁ -ST ₂ -.

Here, T ₁ and T ₂ are each independently and are a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N (CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-, S is a single bond, or an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom -CH ₂ - or -CF ₂ - is -CH=CH-, or may be substituted by the group selected by the lower group G (however, the groups selected by the group G are not adjacent to each other) (group G: -O- , -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring or a divalent heterocyclic ring)).

Any one of R ¹⁰² to R ¹⁰⁴ is -OR ¹¹¹ (R ¹¹¹ is a linear or branched or cyclic alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom. -CH ₂ - or -CF ₂ - is -CH=CH-, or may be substituted by the group selected by the lower group G (however, the groups selected by the group G are not adjacent to each other) (group G: -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, divalent carbocyclic or divalent heterocyclic ring), the other two are independent, a linear chain of 1 to 20 carbon or a branched or cyclic alkyl group, -OR ¹¹² (R ¹¹² is a linear or branched or cyclic alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, and a carbon which may have a substituent a group represented by a group selected from the group consisting of 6 to 20 aryl groups, a benzyl group, or a phenethyl group (when the other two are the aforementioned alkyl group or -OR ¹¹² , they may bond each other to form a ring) should.

Ar is preferably selected from the group consisting of a phenyl group, a naphthyl group and a phenyl group.

Since Ar bonded to the carbonyl group is related to the absorption wavelength of ultraviolet rays, it is preferable to have a long conjugated structure such as an extended naphthyl group or a stretched phenyl group when the wavelength is long. Ar may have a substituent, and the substituent is preferably an electron-donating organic group such as an alkyl group, a hydroxyl group, an alkoxy group or an amine group.

However, when Ar is an anthranyl group or a phenyl-like structure, the solubility is deteriorated and the ease of synthesis is also high. Therefore, when the wavelength of the ultraviolet light is in the range of 300 nm to 400 nm, preferably 310 to 380 nm, even if it is a phenyl group, sufficient characteristics can be obtained, so that the phenyl group is optimal.

The diamine for generating the first photoradical is preferably represented by the following formula (2) (Ar and R ¹⁰¹ to R ¹⁰⁴ have the same meanings as defined above). Further, although the diaminobenzene may be any one of o-phenylenediamine, m-phenylenediamine, or p-phenylenediamine, m-phenylenediamine is used in view of reactivity with acid dianhydride. Or p-phenylenediamine is preferred.

In particular, the diamine for generating the first photoradical is preferably a diamine represented by the following formula (4) (R ¹⁰³ and R ¹⁰⁴ and R ¹¹¹ have the same meanings as defined above, and X ¹⁰¹ is a single bond or CO).

Specifically, the diamine for generating the first photoradical is, for example, the following formulas (3) to (3)-12, but is not limited thereto. The diamine for the first photo radical generation is preferably a diamine represented by the formula (3).

<Side chain for vertical alignment of liquid crystal>

The polyimine precursor of the present invention is preferably one having a side chain which vertically aligns the liquid crystal.

The side chain in which the liquid crystal is vertically aligned is represented by the following formula [II-1] or formula [II-2].

In the formula [II-1], X ¹ to X ⁶ and n are as defined above. Further, in the formula [II-2], X ⁷ and X ⁸ are as defined above.

Among them, x ^{1 is} preferably a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O from the viewpoint of availability of raw materials or ease of synthesis. - or COO-, further preferably a single bond, -(CH ₂ ) _a - (a is an integer from 1 to 10), -O-, -CH ₂ O- or COO-. Among them, X ^{2 is} preferably a single bond or (CH ₂ ) _b - (b is an integer of 1 to 10). Among them, from the viewpoint of easiness of synthesis, X ^{3 is} preferably a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O- or COO-, Further preferred is a single bond, -(CH ₂ ) _c - (c is an integer of from 1 to 10), -O-, -CH ₂ O- or COO-.

Among them, from the viewpoint of easiness of synthesis, X ^{4 is} preferably a benzene ring, a cyclohexane ring or an organic group having a carbon number of 17 to 51 having a steroid skeleton. Among them, X ^{5 is} preferably a benzene ring or a cyclohexane ring. Among them, n is preferably from 0 to 3, and more preferably from 0 to 2, from the viewpoint of availability of raw materials or ease of synthesis.

Among them, X ^{6 is} preferably an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms. Further, it is preferably an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Particularly preferred are alkyl groups having 1 to 9 carbon atoms or alkoxy groups having 1 to 9 carbon atoms.

A preferred combination of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and n in the formula [II-1] can be exemplified by the international publication WO2011/132751 (2011.10.27 publication). (2-1) to (2-629) described in Tables 6 to 47 on pages ～34 are the same combinations. In the tables of the International Publications, X ¹ to X ⁶ in the present invention are represented by Y1 to Y6, but Y1 to Y6 are interpreted as X ¹ to X ⁶ .

Further, (2-605) to (2-629) described in the respective tables of the international publications, the organic group having a carbon number of 17 to 51 having a steroid skeleton in the present invention has a carbon number of 12 having a steroid skeleton. The organic group of ~25 is represented, but an organic group having a carbon number of 12 to 25 having a steroid skeleton is interpreted as an organic group having a carbon number of 17 to 51 having a steroid skeleton. Among them, it is preferably (2-25)~(2-96), (2-145)~(2-168), (2-217)~(2-240), (2-268)~(2 -315), a combination of (2-364)~(2-387), (2-436)~(2-483) or (2-603)~(2-615). The most preferable combinations are (2-49)~(2-96), (2-145)~(2-168), (2-217)~(2-240), (2-603)~(2- 606), (2-607)~(2-609), (2-611), (2-612) or (2-624).

In the formula [II-2], wherein X ^{7 is} preferably a single bond, -O-, -CH ₂ O-, -CONH-, -CON(CH ₃ )- or COO-, more preferably a single bond, - O-, -CONH- or COO-. In X ⁸ , an alkyl group having 8 to 18 carbon atoms is preferred.

The side chain to which the liquid crystal is vertically aligned is preferably a structure represented by the formula [II-1] from the viewpoint of high liquid crystal alignment and stability.

Further, a polyimide precursor having a side chain in which the liquid crystal is vertically aligned, The ability to vertically align the liquid crystal differs depending on the structure of the side chain in which the liquid crystal is vertically aligned. Generally, when the amount of the side chain in which the liquid crystal is vertically aligned is large, the ability to vertically align the liquid crystal is improved, and the ability to decrease is small. Further, the annular structure tends to have a higher ability to vertically align the liquid crystal than those having no annular structure.

<Photoreactive side chain>

The polyimine precursor of the present invention may have a photoreactive side chain. The photoreactive side chain has a functional group which is reacted by irradiation with light such as ultraviolet rays (UV) to form a covalent bond (also referred to as a photoreactive group in the present specification). That is, the polyimine precursor of the present invention preferably has a side chain having a photoreactive group in its structure.

The photoreactive side chain can be directly bonded to the main chain of the polymer or bonded through the bonding group. The photoreactive side chain is represented, for example, by the following formula [III].

[Chem. 20] -R ⁸ -R ⁹ -R ¹⁰ [III]

In the formula [III], R ⁸ , R ⁹ and R ¹⁰ are as defined above. Wherein R ^{8 is} preferably a single bond, -O-, -COO-, -NHCO, or -CONH-. R ⁹ can be formed by a usual organic synthesis method, but from the viewpoint of easiness of synthesis, a single bond or an alkylene group having 1 to 12 carbon atoms is preferable.

Further, in place of the divalent carbon ring or hetero ring of any -CH ₂ - in R ⁹ , specifically, the following may be mentioned.

R ¹⁰ is preferably a methacryl oxime group, an acryl group or a vinyl group from the viewpoint of photoreactivity.

The amount of the photoreactive side chain present is preferably within a range in which the reaction speed of the liquid crystal can be accelerated by reacting by ultraviolet irradiation and forming a covalent bond, in order to further accelerate the response speed of the liquid crystal, without causing other characteristics Within the scope of the impact, as much as possible, the better.

<Polyimine precursor forming a liquid crystal alignment agent>

A method of producing a polyimine precursor using a diamine for producing a first photoradical agent and a polyimine which is imidized by the polyimine precursor is not particularly limited. For example, a method of polymerizing a diamine and a tetracarboxylic dianhydride for producing a first photoradical, a method of polymerizing a diamine of a first photoradical generation, and a diamine and a tetracarboxylic dianhydride.

Regarding manufacturing, it has side chains that vertically align the liquid crystals and/or The method of the polyimine precursor of the photoreactive side chain and the polyimine which imidizes the polyimine precursor ruthenium may be exemplified by the same method as described above. In the same manner, the first photoradical generating diamine containing a side chain which vertically aligns the liquid crystal and/or the first photoradical generating diamine and the tetracarboxylic acid containing a photoreactive side chain are similarly used. The method of dianhydride polymerization is preferred.

<Synthesis of a diamine for producing a first photoradical agent>

In the present invention, the diamine for generating a first photoradical can be a dinitrogen or a monoamine having an amine group which is subjected to a protecting step which can be removed by a reduction step, or a synthetic diamine. It is obtained by converting a nitro group into an amine group or deprotecting a protecting group by a usual reduction reaction.

The method for synthesizing the first photo-active radical diamine of the present invention is not particularly limited, and for example, the following formula (5) can be synthesized (in the formula (5), Ar, R ¹⁰¹ to R ^{104 are the} same as in the above formula (A). The dinitro compound represented by the respective definitions, and the method of synthesizing the nitro group to an amine group.

The method for reducing the nitro group is not particularly limited, and for example, by using palladium-carbon, platinum oxide, nickel reef, platinum-carbon, ruthenium-alumina, sulfur A method in which platinum, carbon, reduced iron, ferric chloride, tin, tin chloride, zinc, or the like is used as a catalyst by hydrogen gas, helium, hydrogen chloride, ammonium chloride or the like.

When constructing a site having an unsaturated bond, a reduction method in which an unsaturated bond is not reduced can be used.

When the unsaturated bond is not reduced, the reduction method is not particularly limited, and examples thereof include reduction of iron, tin, tin chloride, poisoned palladium-carbon, poisoned platinum-carbon as a catalyst, and hydrogen gas. , hydrazine, hydrogen chloride, ammonium chloride, etc.

When the structure has a benzyl bond site, a reduction method in which the benzyl group is not cleaved can be used.

When the benzyl group is not cleaved, the reduction method thereof is not particularly limited, and for example, platinum ruthenium, rhodium-alumina, sulphurized platinum carbon, reduced iron, ferric chloride, tin, tin chloride, zinc, or the like is used as a catalyst. A method carried out by hydrogen gas, helium, hydrogen chloride, ammonium chloride or the like.

As the reaction solvent, a solvent which does not affect the reaction can be used. For example, an ester solvent such as ethyl acetate or methyl acetate; an aromatic hydrocarbon solvent such as toluene or xylene; or an aliphatic hydrocarbon solvent such as n-hexane, n-heptane or cyclohexane; - an ether solvent such as dimethoxyethane, tetrahydrofuran or dioxane; an alcohol solvent such as methanol or ethanol; a ketone solvent such as 2-butanone or 4-methyl-2-pentanone; An aprotic polar solvent such as N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethylhydrazine, or the like. These organic solvents may be used singly or in combination of two or more kinds.

The reaction temperature does not decompose or dissolve in the raw materials or products. The boiling point of the agent below the boiling point can be carried out at a temperature at which the reaction proceeds efficiently. Specifically, the temperature is preferably from -78 ° C to the boiling point of the solvent or less, and the temperature of from 0 ° C to the boiling point of the solvent is more preferably from the viewpoint of ease of synthesis.

The method of synthesizing the compound of the formula (5) is not particularly limited. For example, when R ¹⁰² of the formula (5) is OR ¹¹¹ (R ^{111 is} as defined in the above <6>), for example, the following formula (6) is synthesized. (In the formula (6), a dinitro group represented by Ar, R ¹⁰¹ , R ¹⁰³ and R ¹⁰⁴ as defined in the above formula (A)), and a method of introducing a substituent into the OH group.

The method of introducing a substituent into the OH group is not particularly limited, and for example, the following formula (7) (L ¹ in the formula (7) is a halogen, an alkanesulfonyloxy group, or an aromatic hydrocarbonsulfonyloxy group, The method of reacting a halogenated alkane or an alkylsulfonate represented by R ¹¹¹ with the definition of the above <6> under neutral conditions or under alkali conditions.

【化24】 LR ¹¹¹ (7)

Although the reaction solvent and the reaction temperature are as described above, the alcohol solvent and water may be poorly reacted with the raw material.

Examples of the halogenated alkane include methyl iodide, ethyl iodide, n-propane iodide, n-butane iodide, n-octadecane iodide, benzyl iodide, ethyl bromide, 1-bromopropane, and 1- Bromobutane, 1-bromooctadecane, benzyl bromide, ethyl chloride, 1-chloropropane, 1-chlorobutane, 1-chlorooctadecane, benzyl chloride, methyl methanesulfonate, A Ethyl sulfonate, n-propyl methanesulfonate, n-butyl methanesulfonate, n-octadecyl methanesulfonate, benzyl methanesulfonate and the like.

When the compound represented by the formula (5) is represented by the following formula (8), for example, the compound represented by the above formula (6) and the vinyl ether represented by the following formula (9) are not subjected to a catalyst, or Synthesis method of reaction under acid catalyst.

Further, in the formula (8), Ar, R ¹⁰¹ , R ¹⁰³ and R ¹⁰⁴ are each as defined in the above formula (A), and R ²¹¹ is a straight chain having 1 to 18 carbon atoms which are unsubstituted or substituted by a fluorine atom or a branched or cyclic alkyl group (-CH ₂ - or -CF ₂ - in the alkyl group is -CH=CH-, or a group selectable by the lower group G (however, the group selected by the group G is mutually Substituted by (group G: -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, divalent carbocyclic or divalent heterocyclic ring).).

Further, in the formula (9), with the definition of R ²¹¹ in the formula (8) of the R ^211.

Examples of the vinyl ether include ethyl vinyl ether, n-butyl vinyl ether, n-octadecyl vinyl ether, and diethylene glycol monovinyl ether.

The acid catalyst may, for example, be p-toluenesulfonic acid, pyridinium p-toluenesulfonate or methanesulfonic acid.

When the compound represented by the formula (5) is represented by the following formula (10) (in the formula (10), Ar, R ¹⁰¹ , R ¹⁰³ and R ¹⁰⁴ are each as defined in the above formula (A), for example, A method for synthesizing a compound represented by the formula (6) with 3,4-dihydropyran under a catalyst-free or acid catalyst.

When the compound represented by the formula (5) is represented by the following formula (11) (in the formula (11), Ar, R ¹⁰² to R ^{104 are the} same as defined in the above formula (A), and S, T _{2 is the} same as the above <5>. The definition of the description is, for example, a dinitro compound represented by the following formula (12) (wherein L ² is a halogen in the formula (12)) and a formula (13) (in the formula (13), Ar, R ¹⁰² A method in which -R ^{104 is the} same as defined in the above formula (A), and S, T _{2 is the} same as defined in the above <5>, and the reaction is carried out in the presence of a base. Although the reaction solvent and the reaction temperature are as described above, the protic solvent such as an alcohol solvent or water may be used without being reacted with the raw material.

The compound represented by the formula (12) may, for example, be 2,4-dinitrofluorobenzene, 2,4-dinitrochlorobenzene, 2,4-dinitrobromobenzene or 2,4-dinitro group. Iodobenzene, 3,5-dinitrochlorobenzene, 3,5-dinitroiodobenzene, 3,4-dinitrofluorobenzene, 3,4-dinitrochlorobenzene, 2,3-dinitro Chlorobenzene, etc.

The synthesis method of the compound represented by the formula (13) is not particularly limited. For example, when R ^{102 of the} formula (13) is represented by OR ¹¹¹ , for example, the following formula (14) (in the formula (14), Ar, R ¹⁰³ and R ^{104 are the} same as defined in the above formula (A), and S, T ₂ and the primary hydroxyl group of the compound represented by the above <5> are protected by a protecting group, and the remaining tertiary hydroxyl group is substituted. A method of deprotecting a protecting group of a primary hydroxyl group after the base.

The compound represented by the formula (14) may, for example, be 2-hydroxy-1-(4-(hydroxymethyl)phenyl)-2-methyl-1-propanone or 1-hydroxycyclohexyl (4-(2). -hydroxyethyl)phenyl)) ketone, 1-hydroxycyclohexyl (4-hydroxyphenyl) ketone, 2-hydroxy-1-(4-((2-hydroxyethyl)thio)phenyl)-2 -Methyl-1-propanone, 2-hydroxy-1-(4-hydroxyphenyl)-2-methyl-1-propanone, 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl -2-methyl-1-propanone, 1-(3,4-dihydroxyphenyl)-2-hydroxy-2-methyl-1-propanone, 2-hydroxy-1-(4-(2-hydroxyl) Ethyl)phenyl)-2-methyl-1-propanone, 2-hydroxy-1-(4-(3-hydroxypropyl)phenyl)-2-methyl-1-propanone, and the like.

The protecting group is not particularly limited, and examples thereof include tetrahydropyranyl group, benzyl group, p-methoxybenzyl group, methoxymethyl group, trimethylsulfanyl group, t-butyldimethylmethyl group, and B. Sulfhydryl, benzhydryl, trityl and the like.

The method of introducing a primary hydroxyl group of the compound represented by the formula (14) into a tertiary hydroxyl group is not particularly limited. For example, when R ¹⁰² of the formula (5) is OR ¹¹¹ , a compound represented by the formula (6) can be used. The same conditions as in the case of synthesizing the compound represented by the formula (5).

The deprotection method of each protecting group is not particularly limited, and general deprotection reaction conditions can be used.

The compound represented by the formula (5) is represented by the following formula (15) (in the formula (15), Ar, R ¹⁰² to R ^{104 are the} same as defined in the above formula (A), and S, T _{2 are} as described in the above <5>. In the case of the definition, the dinitro compound represented by the following formula (16) (wherein L ^{1 is the} same as defined by L ¹ in the formula (7)) and the formula (13) are used. An alcohol, a method of carrying out a reaction in the presence of a base, or the like. Although the reaction solvent and the reaction temperature are as described above, the protic solvent such as an alcohol solvent or water may be used without being reacted with the raw material.

The compound represented by the formula (16) may, for example, be 3,5-di Nitrobenzyl chloride, methanesulfonic acid (3,5-dinitrobenzyl), 2,4-dinitrobenzyl chloride, methanesulfonic acid (2,4-dinitrobenzyl) and the like.

When the compound represented by the formula (5) is represented by the following formula (17) (in the formula (17), Ar, R ¹⁰² to R ¹⁰⁴ , S, and T _{2 are} as defined in the above <5>), for example, (13) the alcohol represented by (18) (L ² in the formula (L ² are as defined in 12), in the formula (18)) represented by the above formula dinitro compound of formula, the reaction is carried out in the presence of a base A method or a method of reacting a dinitro compound represented by the formula (19) with an alcohol represented by the formula (13) in the presence of a dehydrating condensing agent. Although the reaction solvent and the reaction temperature are as described above, the protic solvent such as an alcohol solvent or water may be used without being reacted with the raw material.

The compound represented by the formula (18) may, for example, be a 3,5-dinitrobenzimidyl chloride or the like.

The compound represented by the formula (19) may, for example, be a 3,5-dinitrobenzoin Acid, etc. The dehydrating condensing agent may, for example, be dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, diisopropylcarbodiimide. Imine, 1,1'-carbonyldiimidazole, bis(2-oxo-3-oxazole)phosphinic acid chloride, di-2-pyridyl carbonate, triphenylphosphite, dimethoxy 1,3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate , O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thione-3-benzene And oxazolyl) diphenyl ester of phosphonic acid and the like.

<Polyimine precursor having a side chain which vertically aligns liquid crystals>

A method of introducing a side chain in which a liquid crystal is vertically aligned is introduced into a polyimide precursor, and a diamine having a specific side chain structure is preferably used as a part of the diamine component. In particular, a diamine represented by the following formula [2] (also referred to as a specific side chain type diamine compound) is preferably used.

In the formula [2], X is a structure represented by the above formula [II-1] or formula [II-2], and n is an integer of 1 to 4, particularly preferably 1.

As the specific side chain type diamine, a diamine represented by the following formula [2-1] is preferably used from the viewpoint of obtaining a high and stable liquid crystal vertical alignment property.

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , and n in the above formula [2-1] are the same as those defined in the above formula [II-1], and each of them is preferably also The respective definitions in the above formula [II-1] are the same.

Further, in the formula [2-1], m is an integer of 1 to 4. Preferably, it is an integer of one.

Specific examples of the side chain type diamine are, for example, the structures represented by the following formula [2a-1] to the formula [2a-31].

Further, in the formula, R ¹ is -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or CH ₂ OCO-, and R ² is a linear or branched alkyl group having 1 to 22 carbon atoms. A linear or branched alkoxy group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group or a fluorine-containing alkoxy group having 1 to 22 carbon atoms.

R ³ is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or CH ₂ -, and R ⁴ is a carbon number a linear or branched alkyl group of 1 to 22, a linear or branched alkoxy group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkyl group or a fluorine-containing alkane having 1 to 22 carbon atoms; Oxygen.

R ⁵ is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ -, -O- or NH-, R ⁶ is a fluorine group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a decyl group, an ethyl group, an ethoxy group or a hydroxyl group.

R ⁷ is a linear or branched alkyl group having 3 to 12 carbon atoms, and a cis-trans isomer of 1,4-cyclohexene, each being a trans isomer.

R ⁸ is a linear or branched alkyl group having 3 to 12 carbon atoms, and a cis-trans isomer of 1,4-cyclohexene, each being a trans isomer.

A ₄ is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, A ₃ is 1,4-cyclohexenyl or 1,4-phenylene, and A ₂ is an oxygen atom or COO-* (but, note that the "*" key is bonded to the A ₃ bond), and A ₁ is an oxygen atom or COO-* (however, the "*" bond and the (CH ₂ )a ₂ ) key are noted. Knot). Further, a ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1.

In the above formula [2a-1] to [2a-31], particularly preferred are the formula [2a-1]~form [2a-6], the formula [2a-9]~form [2a-13] or the formula [2a] -22]~[2a-31].

In addition, examples of the diamine having a specific side chain structure represented by the formula [II-2] include diamines represented by the following formulas [2b-1] to [2b-10].

A ¹ is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.

In the above formula [2b-5] to formula [2b-10], A ¹ is represented by -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or NH. -, A ² is a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.

The diamine may be used alone or in combination of two or more kinds in the liquid crystal alignment, the pretilt angle, the voltage holding property, and the charge accumulated in the liquid crystal alignment film.

The diamine having a side chain which vertically aligns the liquid crystal is preferably 5 to 50 mol% of the diamine component used in the synthesis of polyamic acid, and is preferably a diamine component. 10~40% by mole, especially good for 15~30%.

When a diamine having a side chain in which the liquid crystal is vertically aligned is used, it is particularly excellent in terms of an increase in the response speed or an ability to fix the alignment of the liquid crystal.

<Diamine containing photoreactive side chain>

The diamine having a photoreactive side chain, for example, a diamine having a side chain represented by the formula [3], and specifically, for example, the following general formula [3] (R ⁸ , R ⁹ in the formula [3] And R ^{10 is as} defined in the above formula [III]), but is not limited thereto.

The bonding position of the two amine groups (-NH ₂ ) in the formula [3] is not limited. Specifically, the bonding group of the side chain may be a position of 2, 3 on the benzene ring, a position of 2, 4, a position of 2, 5, a position of 2, 6, a position of 3, 4, 3,5 position. Among them, from the viewpoint of the reactivity in synthesizing polyamic acid, it is preferably a position of 2, 4, a position of 2, 5, or a position of 3, 5. Further, when the ease of synthesizing the diamine is further increased, the position of 2, 4 or 3, 5 is more preferable.

Specific examples of the diamine having a photoreactive side chain include the following.

In the formula, X ⁹ and X ¹⁰ are each independently a single bond, a -O-, -COO-, -NHCO-, or -NH- linkage group, and Y is a carbon number 1 to 20 which can be substituted by a fluorine atom. Alkyl.

In addition, the diamine having a photoreactive side chain may, for example, be a diamine having a group which causes a photodimerization reaction represented by the following formula and a group which causes a photopolymerization reaction.

In the above formula, Y ₁ is represented by -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, or -CO-. Y ₂ is an alkylene group having a carbon number of 1 to 30, a divalent carbon ring or a heterocyclic ring, and one or a plurality of hydrogen atoms of the alkyl group, the divalent carbocyclic ring or the hetero ring may be substituted by a fluorine atom or an organic group. When Y _{2 is} not adjacent to each other, -CH ₂ - may be substituted by such groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH -, -CO-. Y ₃ is represented by -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-, or a single bond. Y _{4 is} shown as a cassia base. Y ₅ is a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbon ring or a heterocyclic ring, and one or a plurality of hydrogen atoms of the alkyl group, the divalent carbocyclic ring or the heterocyclic ring may be a fluorine atom or an organic group. Substituted. When Y _{5 is} not adjacent to each other, -CH ₂ - may be substituted by such groups: -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH -, -CO-. Y ₆ is a photopolymerizable group of an acryl group or a methacryl oxime group.

The diamine having a photoreactive side chain can be used as a liquid crystal alignment property, a pretilt angle, a voltage holding property, and an accumulated charge when used as a liquid crystal alignment film, and can be used as a response speed of a liquid crystal in a liquid crystal display element. One type or a mixture of two or more types is used.

Further, the diamine having a photoreactive side chain is preferably 10 to 70 mol% of the diamine component used in the synthesis of polyamic acid. It is preferably 20 to 60 mol%, and particularly preferably 30 to 50 mol%.

<Other diamines>

Further, when a polyimide precursor and/or a polyimide is produced, a diamine other than the above diamine may be used in combination as a diamine component without impairing the effects of the present invention. Specific examples thereof include p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, and m-benzene. Amine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diamine Phenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diamine Biphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'- Dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3 , 3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diamino Biphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenyl Methane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diamino Diphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diamino group Diphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, two Methyl-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4 , 4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine , 2, 3'-two Aminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl ( 3,4'-Diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl) Amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-Diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diamine Naphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2 - bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-double ( 3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl 4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4- Aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy) Benzene, 4,4'-[1,4-phenylene bis (nara )]Diphenylamine, 4,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,4'-[1,4-phenylenebis(methylene)]diphenylamine , 3,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,3'-[1,4-phenylenebis(methylene)]diphenylamine, 3,3 '-[1,3-Exophenylbis(methylene)]diphenylamine, 1,4-phenylene bis[(4-aminophenyl)methanone], 1,4-phenylene bis[ (3-aminophenyl)methanone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl) Methyl ketone], 1,4-phenylene bis(4-aminobenzoate), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene (4-Aminobenzoic acid ester), 1,3-phenylphenylbis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, double (3- Aminophenyl)terephthalate, bis(4-aminophenyl) Phthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N, N'-(1,3-phenylene) bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)terephthalamide, N,N '-Bis(3-Aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl)m-xylyleneamine, N,N'-bis(3-amino group Phenyl)m-xylyleneamine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'- Bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis ( 4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoro Propane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methyl Phenyl)propane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-amine Phenoxy group) propane, 1,4-double (4- Phenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3- Aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis (4) -aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis (3 -aminophenoxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,9-bis(3-aminophenoxy)decane, 1,10-(4 -aminophenoxy)decane, 1,10-(3-aminophenoxy)decane, 1,11-(4-aminophenoxy)undecane, 1,11-(3- An aromatic diamine such as an aminophenoxy)undecane, 1,12-(4-aminophenoxy)dodecane or 1,12-(3-aminophenoxy)dodecane, Bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, etc. Alicyclic diamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7- Diamino heptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12 An aliphatic diamine such as diaminododecane.

The above-mentioned other diamines may be used alone or in combination of two or more kinds depending on the properties of the liquid crystal alignment, the pretilt angle, the voltage retention characteristics, and the charge accumulation.

<tetracarboxylic dianhydride>

The tetracarboxylic dianhydride component which reacts with the above diamine component is not specifically limited. Specific examples thereof include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, and 1,4,5,8-naphthalenetetracarboxylic acid. Acid, 2,3,6,7-nonanetetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3 ',4-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyl Phenyl) hydrazine, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro- 2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyl decane, bis(3,4-dicarboxyphenyl)diphenyl decane, 2 ,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4 , 9,10-decanetetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, oxybisphthalic acid, 1,2,3,4 - cyclobutane tetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-tetramethyl- 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,3-dimethyl-1,2, 3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptane IV Carboxylic acid, 2,3,4,5-tetrahydrofuran tetracarboxylic acid, 3,4-dicarboxy-1-cyclohexyl succinic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy- 1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic acid, bicyclo[4,3,0]decane -2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]decane-2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]nonane-2,4 , 8,10-tetracarboxylic acid, tricyclo[6.3.0.0<2,6>]undecane-3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid 4-(2,5-dioxyloxytetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, bicyclo[2,2,2]oct-7- Alkene-2,3,5,6-tetracarboxylic acid, 5-(2,5-di-oxo-tetrahydrofuranyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo[ 6,2,1,1,0,2,7]dodecane-4,5,9,10-tetracarboxylic acid, 3,5,6-tricarboxynorbornane-2:3,5:6 Carboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and the like. Of course, the tetracarboxylic dianhydride may be used alone or in combination of two or more kinds in the liquid crystal alignment film, the voltage retention property, and the charge accumulation.

<Polymerizable compound>

In the liquid crystal alignment agent of the present invention, a polymerizable compound having a group capable of photopolymerization or photocrosslinking at two or more terminals may be contained as required, and such a polymerizable compound has two or more compounds. The end having a group for photopolymerization or photocrosslinking. Here, the polymerizable compound having a group for photopolymerization means that the compound has a functional group which generates polymerization by irradiation with light. Further, the compound having a group for performing photocrosslinking means that the compound has a polymer which can react with a polymerizable compound by irradiation with light, or can be selected from a polyimine precursor and the polyimine. Polymerization of at least one of polyimine obtained by imidization of a precursor The functional group reacts with and crosslinks with these. Further, a compound having a group for photocrosslinking may be reacted with a compound having a group for photocrosslinking.

By using the liquid crystal alignment agent of the present invention containing the above polymerizable compound in a vertical alignment type liquid crystal display element such as an SC-PVA liquid crystal display or the like, it has a side chain and a photoreaction which vertically aligns the liquid crystal compared to the use of the liquid crystal display element of the SC-PVA type liquid crystal display or the like. In the case of the polymer of the side chain or the polymerizable compound, the response speed can be remarkably improved, and even a small amount of the polymerizable compound can sufficiently increase the response speed.

The group which performs photopolymerization or photocrosslinking is a valence group represented by the following formula (IV), for example.

In the formula, R ¹² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Z ¹ is a divalent aromatic ring or a heterocyclic ring which may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Z ² is a monovalent aromatic ring or a heterocyclic ring which may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.

Specific examples of the polymerizable compound include a compound having a group for photopolymerization at each of two terminals represented by the following formula (V); and having the light of "having light" represented by the following formula (VI); a compound at the end of the polymerization group and "the end having a photocrosslinking group"; Alternatively, a compound having a photocrosslinking group at each of the two terminals represented by the following formula (VII).

Yet, by the following formula (V) ~ (VII) in, R ^12, Z Z ² system ^12, Z ^1, and the same as in the formula (IV) R Z ¹ and ^2, Q ¹ is a divalent organic group. Q ^{1 is} preferably a ring having a stretching phenyl group (-C ₆ H ₄ -), a stretching biphenyl group (-C ₆ H ₄ -C ₆ H ₄ -), a cyclohexyl group (-C ₆ H ₁₀ -), or the like. structure. This is because the interaction with the liquid crystal is easily increased.

Specific examples of the polymerizable compound represented by the formula (V) include a polymerizable compound represented by the following formula (R-1). In the following formula (R-1), V and W are each a single bond or -R ¹ O-, and R ¹ is a linear or branched alkyl group having 1 to 10 carbon atoms, preferably -R ¹ O-, R ¹ is a linear or branched alkyl group having 2 to 6 carbon atoms. However, V and W may be the same or different, and when they are the same, the synthesis is easy.

Further, as a group which undergoes photopolymerization or photocrosslinking, a polymerizable compound having an acrylate group or a methacrylate group, even if it does not have an α-methylene-γ-butyrolactone group, The acrylate group or the methacrylate group is a polymerizable compound having a structure in which a phenyl group is bonded to the phenyl group via an interval of an alkyl group or the like, and has an α-methylene-γ-butyl group at both ends. The polymerizable compound of the ester group is the same, and the response speed can be particularly greatly improved. In addition, as long as it is a polymerizable compound having a structure in which an acrylate group or a methacrylate group is bonded to a phenyl group via a spacer such as an alkyl group, the heat stability is improved and the resistance is sufficiently resistant. It is subjected to a high temperature, for example, a firing temperature of 200 ° C or higher.

The method for producing the above polymerizable compound is not particularly limited, and for example, it can be produced by the following synthesis examples. For example, the polymerizable compound represented by the above formula (R-1) can be represented by the following reaction formula by Taragar et al. in P. Talaga, M. Schaeffer, C. Benezra and JLStampf, Synthesis, 530. (1990) A method proposed by synthesizing 2-(bromomethyl)propenoic acid with aldehyde or ketone using SnCl ₂ to synthesize. Further, Amberlyst 15 is a strongly acidic ion exchange resin manufactured by Rohm and Haas.

Further, in the following formula, R' is a monovalent organic group.

Further, 2-(bromomethyl)acrylic acid can be represented by the following reaction formula by Rama Lang et al. in K. Ramarajan, K. Kamalingam, DJO'Donnell and KDBerlin, Organic Synthesis, vol. 61, 56- 59 (1983) proposed method to synthesize.

Specific examples of the synthesis include a polymerizable compound represented by the above formula (R-1) wherein V is -R ¹ O- and W is -OR ² - and R ¹ and R ^{2 are the} same. The two methods shown in the reaction formula are described.

Furthermore, if the synthesis of different R ¹ and R ² in the above formula (R-1) represented by the polymerizable compound, for example may be the method as represented by the following reaction formula.

In the above formula (R-1), when a polymerizable compound in which V and W are a single bond is synthesized, for example, a method represented by the following reaction formula can be mentioned.

<Synthesis of polyaminic acid>

When polylysine is obtained by a reaction of a diamine component and a tetracarboxylic dianhydride, a well-known synthetic method can be used. In general, there is a method of reacting a diamine component with a tetracarboxylic dianhydride component in an organic solvent. The reaction between the diamine component and the tetracarboxylic dianhydride component is advantageous because it is relatively easy to carry out in an organic solvent and does not produce by-products.

The organic solvent used for the above reaction is not particularly limited as long as it is soluble in the produced polylysine. Furthermore, even if the polylysine does not dissolve in the organic solvent, the formed polylysine does not precipitate. It can also be mixed into the above solvent for use. Further, the water in the organic solvent is a factor which hinders the polymerization reaction and further causes hydrolysis of the produced polylysine, and the organic solvent is preferably used for dehydrating and drying the organic solvent.

The organic solvent used in the above reaction may, for example, be N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide or N-methyl. Formamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy -N,N-dimethylpropionamide, N-methylcaprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butane Ester, isopropanol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, Methyl 赛路苏, Ethyl sulcata, Methyl sulphate acetate, Butyl succinate acetate, Ethyl sulphate acetate, Butyl carbitol, Ethyl carbitol , ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, Propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl Ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3- Methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diiso Butyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethyl acetate , propyl carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxy Methyl propionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid Propyl ester, butyl 3-methoxypropionate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, and the like. These organic solvents may be used singly or in combination.

A method of reacting a diamine component and a tetracarboxylic dianhydride component in an organic solvent may, for example, be any one of the following methods: stirring a solution in which a diamine component is dispersed or dissolved in an organic solvent, and further dicarboxylic acid The anhydride component is directly added, or the tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent and then added; instead, the tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent. A method of adding a diamine component; a method of mutually adding a tetracarboxylic dianhydride component and a diamine component, and the like. Further, when the diamine component or the tetracarboxylic dianhydride component is formed of a plurality of compounds, the reaction may be carried out in a state of being mixed in advance, or the reaction may be carried out in an individual order, or the low molecular weight body after the individual reaction may be subjected to a reaction. A high molecular weight body is formed after the mixing reaction.

The temperature at which the diamine component and the tetracarboxylic dianhydride component are reacted is, for example, -20 ° C to 150 ° C, preferably -5 ° C to 100 ° C. Further, in the reaction system, for example, the total concentration of the diamine component and the tetracarboxylic dianhydride component is preferably from 1 to 50% by mass, and more preferably from 5 to 30. the amount%.

In the above polymerization reaction, the ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component can be selected in accordance with the molecular weight of the desired polyamic acid. In the same manner as the general polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the produced poly-proline, and 0.8 to 1.2 if it shows a preferred range.

The method for synthesizing the poly-proline used in the present invention is not limited to the above-described method, and is the same as the general method for synthesizing poly-proline, even if a tetracarboxylic or tetracarboxylic acid having a corresponding configuration is used. A tetracarboxylic acid derivative such as a halide is substituted for the above tetracarboxylic dianhydride and reacted by a known method to obtain a corresponding polyamine.

As a method of imidating the above polyphosphonium amide to form a polyimine, a solution in which a solution of polylysine is directly heated and imidized, and a solution in a solution of polyglycine is added The catalyst of the medium is imidized. Further, the imidization ratio of polydecylamine to polyimine is not necessarily 100%.

The temperature at which the polyaminic acid is thermally imidized in the solution is 100 ° C to 400 ° C, preferably 120 ° C to 250 ° C, and the water edge formed by the imidization reaction is removed to the reaction system. It is better to do it outside.

The catalyst of ruthenium phthalate can be imidized by adding a basic catalyst and an acid anhydride to the solution of polyamic acid, and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. Implementation. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group; the amount of the anhydride is 1 to 50 moles of the amidate group, preferably 3 to 30 moles. Alkaline touch The medium may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine, and among them, pyridine is preferred because it has moderate alkalinity when the reaction proceeds. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic dianhydride. Among them, when acetic anhydride is used, purification after completion of the reaction becomes easy, and it is preferable. The rate of ruthenium imidization caused by the imidization of the catalyst can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

Further, the polyglycolate can be produced by reacting a tetracarboxylic acid diester dichloride with a diamine which is the same diamine as the above polylysine; Alternatively, the tetracarboxylic acid diester and the diamine (which are synthesized as the same diamine as the above polyglycolic acid) are reacted in the presence of a suitable condensing agent or a base. Further, the polyamic acid is synthesized in advance by the above method, and the carboxylic acid in the valeric acid is esterified by a polymer reaction. Specifically, for example, the tetracarboxylic acid diester dichloride and the diamine may be subjected to 30 minutes in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C. The reaction of 24 hours, preferably 1 hour to 4 hours, allows the synthesis of polyphthalate. Then, the polyglycolate is heated at a high temperature to promote dealcoholization to cause ring closure, and polyimine can also be obtained.

When the polyimine precursor such as polyglycolic acid or polyglycolate or polyimine which is produced is recovered from the reaction solution, the reaction solution may be placed in a weak solvent to precipitate. Examples of the weak solvent for precipitation include methanol, acetone, hexane, butyl sirolimus, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. After the polymer which has been precipitated is added to a weak solvent and recovered by filtration, it can be dried under normal pressure or reduced pressure at normal temperature or under heating. Also, redissolving the recovered polymer In the organic solvent, the operation of reprecipitation recovery is repeated 2 to 10 times to reduce impurities in the polymer. In the case of using a weak solvent of three or more kinds selected from the group consisting of alcohols, ketones, hydrocarbons, and the like, it is preferred to further improve the purification efficiency.

<Liquid alignment agent>

The liquid crystal alignment agent of the present invention contains the above polyimine precursor, but the content of the polyimide precursor is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and particularly preferably 3 to 10% by mass. %. In addition, when a polymerizable compound having a group which undergoes photopolymerization or photocrosslinking at each of two or more terminals is contained, the content thereof is preferably from 1 to 50 parts by mass, more preferably from 5 to 100 parts by mass of the polymer. 30 parts by mass.

Further, in the liquid crystal alignment agent of the present invention, other polymers may be contained in addition to the above polyimide precursor. In this case, the content of such other polymer in the entire polymer component is preferably from 0.5 to 80% by mass, and more preferably from 20 to 50% by mass.

The molecular weight of the polymer of the liquid crystal alignment agent is determined by GPC (Gel Permeation Chromatography) method when the strength of the liquid crystal alignment film obtained by coating the liquid crystal alignment agent and the workability at the time of coating film formation and the uniformity of the coating film are considered. The weight average molecular weight is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

The solvent to be contained in the liquid crystal alignment agent is not particularly limited as long as it is a polyimide polyimide precursor and a polymerizable group having a photopolymerization or photocrosslinking at each of two or more terminals contained as required. Chemical The component contained in the compound or the like may be dissolved or dispersed. For example, an organic solvent exemplified in the synthesis of polylysine as described above can be mentioned. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy- N,N-dimethylpropionamide is preferred from the viewpoint of solubility. Of course, it is also possible to use a mixture of two or more kinds.

In addition, it is preferable to use a solvent which improves the uniformity or smoothness of the coating film, and it is preferable to mix it in the solvent with high solubility of the liquid crystal alignment agent containing component. As such a solvent, for example, isopropyl alcohol, methoxymethylpentanol, methyl stilbene, ethyl stilbene, butyl 赛路苏, methyl sarbuta acetate, butyl Kesailusu acetate, ethyl sarbuta acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, Ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl Ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl Ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl 3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl Acetate, butyrate Acid ester, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate , ethyl lactate, acetic acid Ester, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate , 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, 1-methyl Oxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diethyl Acid ester, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol Methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, 2-ethyl-1-hexanol, and the like. These solvents may also be mixed in a plurality of types. When such a solvent is used, it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the total amount of the solvent contained in the liquid crystal alignment agent.

The liquid crystal alignment agent may contain components other than the above. In this case, a compound which improves film thickness uniformity or surface smoothness when a liquid crystal alignment agent is applied, a compound which improves adhesion of a liquid crystal alignment film and a substrate, and the like are mentioned.

Examples of the compound which improves the uniformity of the film thickness or the surface smoothness include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant. More specifically, for example, EFTop EF301, EF303, EF352 (manufactured by TOHKEM PRODUCTS), Megafac F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), Florad FC430, FC431 (manufactured by Sumitomo 3M), AashiGuard AG710 , Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). When using these surfactants, the ratio of use The total amount of the polymer contained in the liquid crystal alignment agent is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the total amount of the polymer contained in the liquid crystal alignment agent.

Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include a functional decane-containing compound or an epoxy group-containing compound. For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-urea Propyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethoxy decane, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxydecyl-1,4,7- Triazanonane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazaindolyl acetate, 9- Triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxy Baseline, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethylene)-3-aminopropyl Trimethoxydecane, N-bis(oxyethylene)-3-amino Propyltriethoxydecane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl- 2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylene Amine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenyl Methane, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxydecane, 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, and the like.

Further, in order to further improve the film strength of the liquid crystal alignment film, 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane or tetrakis(methoxymethyl)bisphenol may be added. Phenolic compound. When the compound is used, the total amount of the polymer contained in the liquid crystal alignment agent is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass.

Further, in addition to the above, the liquid crystal alignment agent may be added with a dielectric for the purpose of changing electrical characteristics such as dielectric constant or conductivity of the liquid crystal alignment film, insofar as the effects of the present invention are not impaired. Conductive material.

The liquid crystal alignment agent is applied onto a substrate and fired to form a liquid crystal alignment film that vertically aligns the liquid crystal. By using the liquid crystal alignment agent of the present invention, the response speed of the liquid crystal display element using the obtained liquid crystal alignment film can be made fast. Further, the liquid crystal alignment agent of the present invention may contain a "polymerizable compound having a photopolymerization or photocrosslinking group at two or more ends", which is not contained in the liquid crystal alignment agent, or The liquid crystal alignment agent is also contained in the liquid crystal, that is, in the so-called PSA mode, the photoreaction can be highly sensitive, and even a small amount of ultraviolet rays can be applied to the tilt angle.

For example, the liquid crystal alignment agent of the present invention may be applied to a substrate, and then dried as necessary, and the cured film obtained by firing may be used as a liquid crystal alignment film as it is. Also, the cured film can be rubbed It is rubbed, or irradiated with a polarized light, light of a specific wavelength, or the like, or treated with an ion beam or the like to be used as an alignment film for PSA, and UV is applied while a voltage is applied to the liquid crystal display element after liquid crystal filling. It is suitable for use as an alignment film for PSA.

In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and for example, a glass plate, a polycarbonate, a poly(meth)acrylate, a polyether oxime, a polyarylate, or a poly Urethane, polyfluorene, polyether, polyether ketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triacetyl cellulose, diethyl hydrazine A plastic substrate such as cellulose or cellulose acetate butyrate. Further, it is preferable to use a substrate on which an ITO electrode or the like for driving a liquid crystal is formed, in terms of simplification of the process. Further, in the case of a reflective liquid crystal display device, an opaque material such as a germanium wafer may be used as the substrate on one side, and a material such as aluminum or the like may be used as the electrode.

The coating method of the liquid crystal alignment agent is not particularly limited, and examples thereof include a printing method such as screen printing, lithography, and flexographic printing, an inkjet method, a spray method, a roll coating method, or a dipping, a roll coater, and the like. A slit coater, a spin coater, or the like. In terms of productivity, industrial transfer printing is widely used, and the present invention is also suitable for use.

The coating film formed by coating the liquid crystal alignment agent by the above method can be used as a cured film after firing. The drying step after the liquid crystal alignment agent is applied onto the substrate is not necessarily required, but it is preferably carried out when the time from the application to the time of baking is not uniform for each substrate, or when it is not directly fired after coating. Drying step. This drying can remove the solvent so as not to be transported by the substrate or the like. The shape of the coating film may be deformed, and the drying means is not particularly limited. For example, it is dried on a hot plate at a temperature of 40 ° C to 150 ° C, preferably 60 ° C to 100 ° C for 0.5 to 30 minutes, preferably 1 to 5 minutes.

The baking temperature of the coating film formed by applying the liquid crystal alignment agent is not limited, and is, for example, 100 to 350 ° C, preferably 120 to 300 ° C, and more preferably 150 ° C to 250 ° C. The firing time is 5 to 240 minutes, preferably 10 to 90 minutes, and more preferably 20 to 90 minutes. The heating can be carried out by a generally known method such as a hot plate, a hot air circulating furnace, an infrared furnace or the like.

Further, the thickness of the liquid crystal alignment film obtained after the firing is not particularly limited, but is preferably 5 to 300 nm, and more preferably 10 to 100 nm.

<Liquid crystal display element>

In the liquid crystal display device of the present invention, after the liquid crystal alignment film is formed on the substrate by the above method, a liquid crystal cell can be produced by a known method. Specific examples of the liquid crystal display device include a liquid crystal display device having a vertical alignment type of a liquid crystal cell, the liquid crystal cell having two substrates disposed in a facing manner, a liquid crystal layer disposed between the substrates, and a setting The liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention between the substrate and the liquid crystal layer. Specifically, it is a liquid crystal display element having a vertical alignment type of a liquid crystal cell, which is formed by applying a liquid crystal alignment agent of the present invention onto two substrates and firing the liquid crystal alignment film to form a liquid crystal alignment film. a two-piece substrate in which the film is disposed in a paired manner, a liquid crystal layer composed of a liquid crystal is sandwiched between the two substrates, and a liquid crystal is provided even if it is in contact with the liquid crystal alignment film. The layer is produced by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer.

By using a liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention, a liquid is applied to the liquid crystal alignment film and the liquid crystal layer while irradiating ultraviolet rays to polymerize the polymerizable compound, and the side of the photoreactive property of the polymer is obtained. The chain or the side chain of the photoreactive property of the polymer reacts with the polymerizable compound, and the alignment of the liquid crystal can be more efficiently immobilized, and the liquid crystal display element is remarkably excellent in response speed.

The substrate to be used for the liquid crystal display device of the present invention is not particularly limited as long as it has high transparency, and is usually a substrate on which a transparent electrode for driving a liquid crystal is formed. Specific examples are the same as those described in the above liquid crystal alignment film. Although a substrate having a conventional electrode pattern or a protrusion pattern can be used, in the liquid crystal display device of the present invention, since the liquid crystal alignment agent of the present invention is used, a line of, for example, 1 to 10 μm is formed on the single-sided substrate. / slit electrode pattern, and can also operate on the opposite substrate without forming a slit pattern or a protrusion pattern, and the liquid crystal display element thus constructed can simplify the manufacturing process. Get high penetration.

Further, in a high-performance element such as a TFT type element, an element such as a transistor formed between an electrode for driving a liquid crystal and a substrate can be used.

In the case of a transmissive liquid crystal display device, a substrate as described above is generally used. However, in a reflective liquid crystal display device, an opaque substrate such as a germanium wafer can be used as long as it is a single substrate. At this time, formed on the base The electrodes on the board can also be made of materials that reflect light such as aluminum.

The liquid crystal material constituting the liquid crystal layer in the liquid crystal display device of the present invention is not particularly limited, and can be used in a liquid crystal material used in a conventional vertical alignment method, for example, a negative type such as MLC-6608 or MLC-6609 manufactured by Merck. liquid crystal. Further, in the PSA mode, for example, a liquid crystal containing a polymerizable compound as represented by the following formula can be used.

In the present invention, a known method is employed in the method of holding the liquid crystal layer between the two substrates. For example, a substrate on which a liquid crystal alignment film is formed is prepared, a spacer such as beads is scattered on a liquid crystal alignment film of one substrate, and a surface on the side on which the liquid crystal alignment film is formed is placed inside to fit another The substrate is then subjected to a method of injecting a liquid crystal under reduced pressure to seal it. In addition, one of the liquid crystal alignment films is formed, and the liquid crystal is deposited on the liquid crystal alignment film of one substrate, and then the liquid crystal is dropped, and then the surface on the side on which the liquid crystal alignment film is formed is placed inside to bond the other substrate. A liquid crystal cell can also be produced by a method of sealing. The thickness of the above interval is preferably from 1 to 30 μm, and more preferably from 2 to 10 μm.

The step of producing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, for example, applying a voltage between electrodes provided on the substrate to apply electricity to the liquid crystal alignment film and the liquid crystal layer Field, and a method of irradiating ultraviolet rays while maintaining the electric field. Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The amount of ultraviolet rays to be irradiated is, for example, 1 to 60 J, preferably 40 J or less, and the less the amount of ultraviolet irradiation, the decrease in reliability due to breakage of members constituting the liquid crystal display element can be suppressed, and the ultraviolet irradiation time can be reduced by reducing the ultraviolet irradiation time. It is better to improve manufacturing efficiency.

As described above, when a voltage is applied to the liquid crystal alignment film and the liquid crystal layer, ultraviolet rays are irradiated, and the polymerizable compound reacts to form a polymer, whereby the polymer can memorize the direction in which the liquid crystal molecules are tilted, and the pretilt angle of the obtained liquid crystal display element can be obtained. Become the desired value and the response speed will be faster. Further, when ultraviolet rays are applied while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, a polyimide intermediate having a side chain which is vertically aligned with the liquid crystal and a photoreactive side chain, and the polyimide precursor are used. The photoreactive side chains of the at least one polymer selected from the polyimide obtained by imidization, or the photoreactive side chain of the polymer, react with the polymerizable compound. Thus, the response speed of the resulting liquid crystal display element can be made faster.

The pretilt angle of the liquid crystal display element differs depending on the liquid crystal alignment film to be used, that is, the liquid crystal alignment agent to be used, the polyimide precursor to be used, and the first photoradical generating diamine to be used. As described above, by using the polyimine precursor of the present invention, in particular, a polyimine precursor having a relatively large amount of radical generation, the amount of radical generated during UV irradiation is increased. Further, when the amount of radical generation is increased, the reaction of the polymerizable compound is promoted. Therefore, the pretilt angle of the liquid crystal display element obtained with a small amount of irradiation at the same wavelength can be a desired value, and the response speed can be increased.

In general, the pretilt angle of the liquid crystal display element tends to be more than 90° when the liquid crystal display element is formed.

[Examples]

The invention will be more specifically illustrated by the following examples, but the invention is not limited to the examples.

Further, the abbreviations, structures, and methods for measuring the respective properties of the following compounds are as follows.

(solvent)

DMF: N, N-dimethylformamide

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

(diamine)

DA-A: 1-(4-(2-(2,4-Diaminophenoxy)ethoxy)phenyl)-2-methoxy-2-methylpropan-1-one

DA-1:1-(4-(2-(2,4-Diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylpropan-1-one

DA-2: 4-(4-(4-heptylcyclohexyl)phenoxy)benzene-1,3-diamine

3AMPDA: 3,5-diamino-N-(pyridin-3-ylmethyl)benzamide

(acid dianhydride)

BODA: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

(additive)

3AMP: 3-pyridylmethylamine

[ ¹ H NMR]

Device: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (made by Varian) 400 MHz

Solvent: heavy chloroform (CDCl ₃ ), or deuterated dimethyl hydrazine (DMSO-d ₆ )

Reference material: tetramethyl decane (TMS)

Cumulative number: 8, or 32.

[ ¹³ C{ ¹ H}NMR]

Device: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (made by Varian) 100 MHz

Solvent: heavy chloroform (CDCl ₃ ), or deuterated dimethyl hydrazine (DMSO-d ₆ )

Reference material: tetramethyl decane (TMS)

Cumulative number: 256.

[molecular weight]

The molecular weight of the polyimine precursor and the ruthenium iodide polymer is measured by a GPC (normal temperature colloidal osmosis chromatography) apparatus, and the number average molecular weight is calculated as a polyethylene glycol or polyethylene oxide equivalent value (hereinafter also Mn.) and weight average molecular weight (hereinafter also referred to as Mw.).

GPC device: Senshu Scientific Co., Ltd. Normal temperature colloidal osmosis chromatography (GPC) device (SSC-7200)

Pipe column: made by Shodex company (inline of KD803, KD805)

Column temperature: 50 ° C

Dissolution: N,N-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr.H ₂ O) is 30 mmol/L, phosphoric acid. Anhydrous crystal (o-phosphoric acid) is 30 mmol/L, tetrahydrofuran (THF) ) is 10ml/L)

Flow rate: 1.0 ml/min.

Standard sample for calibration line preparation: TSK standard polyethylene oxide manufactured by Tosoh Corporation (weight average molecular weight (Mw) about 900,000, 150,000, 100,000, 30,000), and, Polymer Laboratories Polyethylene glycol (peak peak molecular weight (Mp) of about 12,000, 4,000, 1,000) manufactured by Ltd. Measurements In order to avoid peak overlap, two samples of a mixture of four types of 900,000, 100,000, 12,000, and 1,000, and two samples of three types of 150,000, 30,000, and 4,000 were separately measured.

[Determination of sulfhydrylation rate]

The oxime imidization ratio of the polyimine in the synthesis example was measured as follows. 20 mg of polyimine powder was placed in an NMR sample tube (NMR standard sampling tube, 5 (manufactured by Kusano Scientific)), adding dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS (tetramethyl decane) mixture) (1.0 ml), and applying ultrasonic waves to completely dissolve. This solution was measured for proton NMR at 500 MHz by an NMR measuring machine (JNW-ECA500) (manufactured by JEOL Ltd.). The rate of ruthenium iodization, using protons from a structure that has no change before and after imidization as a reference proton, using the peak cumulative value of the proton and the proton peak accumulation from the NH group of proline in the vicinity of 9.5 ppm to 10.0 ppm The value is obtained by the following formula.

醯 imidization rate (%) = (1-α.x/y) × 100

In the above formula, x is the proton peak cumulative value derived from the NH group of valine acid, y is the peak cumulative value of the reference proton, and α is the relative one when the polyproline (the imidization ratio is 0%). The ratio of the number of reference protons of one of the NH protons of the amine acid.

[Synthesis of diamine compounds] (Comparative Synthesis Example 1: Synthesis of Aromatic Diamine Compound (DA-1))

Synthesis of Step1:1-(4-(2,4-Dinitrophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylacetone

In a 2L four-necked flask equipped with a stirrer and a nitrogen introduction tube, 100.0 g of 2,4-dinitrofluorobenzene ([Mw: 186.10 g/mol], 0.538 mol), 2-hydroxy-4'-(2- Hydroxyethoxy)-2-methylpropiophenone 120.6 g ([Mw: 224.25 g/mol], 0.538 mol), triethylamine 81.7 g ([Mw: 101.19 g/mol], 0.807 mol), THF 1000 g , reflux for 24 hours. After completion of the reaction, the mixture was concentrated with a rotary evaporating concentrator, and ethyl acetate was added thereto, and washed with pure water and physiological saline several times, and then dried over anhydrous magnesium sulfate.

Anhydrous magnesium sulfate was removed by filtration, and concentrated by a rotary evaporation concentrator, and then recrystallized from ethyl acetate and n-hexane to obtain a pale-white solid, 157.0 g ([Mw: 390.34 g/mol], 0.402 mol, yield: 75%). Nuclear magnetic resonance spectrum confirmed that hydrogen atoms in the molecule ⁽¹ H-NMR spectrum). The measured data is as follows.

¹ H NMR (400 MHz, CDCl ₃ ) δ: 8.75 (Ar: 1H), 8.48 to 8.45 (Ar: 1H), 8.09 to 8.05 (Ar: 2H), 7.34 to 7.31 (Ar: 1H) 7.00 to 6.96 (Ar: 2H), 4.65~4.63 (-CH2-:2H), 4.52~ 4.49 (-CH2-:2H), 4.16 (-OH:1H), 1.66~1.60 (-CH3×2, 6H) Total: 18H.

Synthesis of 1-(4-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylacetone (DA-1)

In a 1 L four-necked flask, 100.0 g ([Mw: 390.34 g/mol], 0.256 mol) of the dinitrobenzene derivative obtained in Step 1, and platinum carbon doped with iron (3 wt% manufactured by Evonic Co., Ltd.) were weighed 10.0. g, 500 ml of THF was added, and degassing under reduced pressure and hydrogen substitution were carried out, and the reaction was carried out at room temperature for 24 hours.

After the completion of the reaction, the platinum carbon was removed by a membrane filter made of PTFE, and the filtrate was removed by a rotary evaporator to precipitate a solid. The obtained solid was washed with isopropyl alcohol and dried under reduced pressure to give 72.7 g ([Mw: 330.38 g/mol], 0.220 mol yield: 86%) of the pale pink solid of the objective compound. ^{The 1} H-NMR spectrum measurement data is as follows.

¹ H NMR (400 MHz, CDCl ₃ ) δ: 8.09 to 8.05 (Ar: 2H), 7.01 to 6.97 (Ar: 2H), 6.70 to 6.68 (Ar: 1H), 6.12 (Ar: 1H), 4.36 to 4.33 (- CH2-: 2H), 4.29~4.27 (-OH&-CH2-:3H), 3.7 (-NH2:2H), 3.39 (-NH2:2H), 1.64~1.63 (-CH3×2:6H) Total: 22H.

<Synthesis Example 1>

Aromatic diamine compound (DA-A): 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-methoxy-2-methylpropane Synthesis of 1-ketone

Synthesis of aromatic diamine compounds using the 5-step route shown below (DA-A). Further, the aromatic diamine compound (DA-A) is the above specific diamine compound.

Step 1: 2-hydroxy-2-methyl-1-(4-(2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy)phenyl)propan-1-one Synthesis of (DA-A-1)

IRGACURE 2959 (2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one, 50.0 g, 223 mmol) was dissolved in THF (200 g), and p-toluene was added. The sulfonic acid monohydrate (0.424 g, 2.23 mmol) was added dropwise to 3,4-dihydro-2H-pyran (23.4 g, 279 mmol) over 10 minutes and allowed to react at room temperature for 3 hours. Thereafter, the filtrate was filtered to concentrate the filtrate to obtain 2-hydroxy-2-methyl-1-(4-(2-tetrahydro-2H-pyran-2-yl)oxy)ethoxylate. Crude product of phenyl)propan-1-one (green liquid, 73.7 g).

¹ H NMR (DMSO-d ₆ ): δ 8.22 (d, J = 9.0 Hz, 2H, C ₆ H ₄ ), 7.02 (d, J = 9.0 Hz, 2H, C ₆ H ₄ ), 5.68 (s, 1H) , OH), 4.66 (t, J = 3.6 Hz, 1H, CH), 4.22 (t, J = 4.8 Hz, 2H, CH ₂ ), 4.07-3.92 (m, 1H, CH ₂ ), 3.81-3.70 (m , 2H, CH ₂ ), 3.47-3.42 (m, 1H, CH ₂ ), 1.77-1.41 (m, 6H, CH ₂ ), 1.40 (s, 6H, C(CH ₃ ) ₂ ). ¹³ C{ ¹ H } NMR (DMSO-d ₆ ): δ 202.4, 162.3, 162.1, 132.9, 127.9, 114.2, 98.5, 93.9, 93.6, 77.1, 70.2, 67.8, 65.5, 63.1, 62.0, 61.7, 59.9, 30.7, 30.6, 28.6, 25.6, 25.4, 20.8, 19.5 (each s).

Step 2: 2-methoxy-2-methyl-1-(4-(2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy)phenyl)propane-1 Synthesis of ketone (DA-A-2)

Sodium hydride (57.1 wt% purity, 15.0 g, 357 mmol) was suspended in THF (448 g), cooled to 3 ° C, and the crude product of DA-A-1 (73.3 g) was dissolved in THF (138 g) in 3 °C, it takes 15 minutes to drip. Thereafter, the mixture was stirred for 30 minutes, and methyl iodide (41.0 g, 357 mmol) was added dropwise over 5 minutes, and stirred at room temperature for 22 hours. Then, water (660 g) and toluene (586 g) were added to the mixture at room temperature, and the aqueous layer was discarded. The organic layer was washed twice with water (650 g), and then the organic layer was concentrated to give 2- Crude product of methoxy-2-methyl-1-(4-(2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy)phenyl)propan-1-one ( Brown liquid, 80.1 g).

¹ H NMR (DMSO-d ₆ ): δ 8.19 (d, J = 8.8 Hz, 2H, C ₆ H ₄ ), 7.06 (d, J = 8.8 Hz, 2H, C ₆ H ₄ ), 4.66 (s, 1H) , CH), 4.24-4.22 (m, 2H, CH 2), 3.97-3.92 (m, 1H, CH), 3.80-3.72 (m, 2H, CH 2), 3.47-3.43 (m, 1H, CH), 3.08 (s, 3H, CH ₃ ), 1.71-1.60 (m, 2H, CH ₂ ), 1.53-1.46 (m, 4H, (CH ₂ ) ₂ ), 1.41 (s, 6H, C(CH ₃ ) ₂ ) ¹³ C{ ¹ H} NMR (DMSO-d ₆ ): δ 201.35, 162.6, 132.2, 127.5, 114.6, 98.5, 83.1, 67.9, 65.5, 61.7, 52.2, 30.6, 24.5, 24.9, 19.4 (each s).

Step 3: Synthesis of 1-(4-(2-hydroxyethoxy)phenyl)-2-methoxy-2-methylpropan-1-one (DA-A-3)

The p-toluenesulfonic acid monohydrate (0.469 g, 2.46 mmol) was dissolved in a mixed solvent of methanol (397 g) and THF (80 g), and the crude product of DA-A-2 was added at room temperature for 3 minutes. (79.4 g) A solution in THF (79 g). Thereafter, the mixture was stirred for 2 hours, and the reaction mixture was concentrated to confirm that the material remained 20%. Then, THF (350g) and water were added to the residue. (290 g), and p-toluenesulfonic acid monohydrate (2.53 g, 13.3 mmol) were stirred at room temperature for 14 hours. Thereafter, toluene (350 g) was added, and after stirring, the aqueous layer was discarded, and the organic layer was washed twice with water (340 g), and the organic layer was concentrated to give 1-(4-(2-hydroxyethoxy)benzene. Crude product of 2-methyl-2-methylpropan-1-one (brown liquid, 50.5 g).

¹ H NMR (DMSO-d ₆ ): δ 8.20 (d, J = 9.0 Hz, 2H, C ₆ H ₄ ), 7.05 (d, J = 9.0 Hz, 2H, C ₆ H ₄ ), 4.96 (t, J = 5.4 Hz, 1H, OH), 4.10 (t, J = 4.8 Hz, 2H, CH ₂ ), 3.97-3.92 (dt, J = 5.4, 4.8 Hz, 2H, CH ₂ ), 3.09 (s, 3H, CH) ₃ ), 1.42 (s, 6H, C(CH ₃ ) ₂ ). ¹³ C{ ¹ H} NMR (DMSO-d ₆ ): δ 200.3, 162.8, 132.2, 127.4, 114.6, 83.1, 70.2, 59.8, 52.2, 24.9 (each s).

Step 4: 1-(4-(2-(2,4-Dinitrophenoxy)ethoxy)phenyl)-2-methoxy-2-methylpropan-1-one (DA- Synthesis of A-4)

The crude product of DA-A-3 (45.7 g) was dissolved in DMF (79.9 g), 1-fluoro-2,4-dinitrobenzene (35.7 g, 192 mmol), and triethylamine (29.1 g) , 288 mmol), stirred at room temperature for 24 hours. Thereafter, toluene (274 g) and water (274 g) were added and stirred, and the aqueous layer was discarded, and the organic layer was washed twice with water (274 g) to concentrate the organic layer. Next, the residue was purified by cerium oxide colloidal chromatography (solvent: toluene/ethyl acetate = 3/1 (v/v), Rf = 0.3) to concentrate the solvent. Then, 2-propanol (193 g) was added to the residue, and the mixture was stirred and filtered at room temperature, and the filtrate was again added to 2-propanol (400 g), stirred at 60 ° C, filtered, and the filtrate was dried to give 1-( 4-(2-(2,4-dinitrophenoxy)ethoxy)phenyl)-2-methoxy-2-methylpropan-1-one (light brown solid, 29.2 g, yield 30% (4 steps)).

¹ H NMR (DMSO-d ₆ ): δ 8.73 (d, J = 2.8 Hz, 1H, C ₆ H ₃ ), 8.50 (dd, J = 9.2, 2.8 Hz, 1H, C ₆ H ₃ ), 8.16 (d) , J = 8.8 Hz, 2H, C ₆ H ₄ ), 7.65 (d, J = 9.2 Hz, 1H, C ₆ H ₃ ), 7.37 (d, J = 8.8 Hz, 2H, C ₆ H ₄ ), 4.71 4.69 (m, 2H, CH ₂ ), 4.45-4.43 (m, 2H, CH ₂ ), 3.04 (s, 3H, CH ₃ ), 1.37 (s, 6H, C(CH ₃ ) ₂ ). ¹³ C{ ¹ _{H} NMR (DMSO-d 6} ): δ 201.4,162.2,156.0,140.3,139.2,132.2,129.7,127.8,121.6,116.4,114.7,83.1,69.6,66.5,52.2,24.8 (each s).

Step 5: 1-(4-(2-(2,4-dinitrophenoxy)ethoxy)phenyl)-2-methoxy-2-methylpropan-1-one (DA- Synthesis of A)

DA-A-4 (10.0 g, 24.7 mmol) was dissolved in THF, and 1% of platinum-carbon (0.2% Fe-doped, aqueous 59.5 wt%, 0.62 g) was added, and the mixture was stirred at a hydrogen pressure of 0.2 to 0.5 MPa. After 3 hours, the reaction was confirmed by HPLC, the catalyst was filtered, and the filtrate was concentrated. Then, toluene (30 g) was added, and the mixture was stirred at 65 ° C for 30 minutes, and then cooled to 0 ° C. The precipitated solid was filtered and dried to give 1 -(4-(2-(2,4-Diaminophenoxy)ethoxy)phenyl)-2-methoxy-2-methylpropan-1-one (purple solid, 7.23 g, Rate 85%)

¹ H NMR (DMSO-d ₆ ): δ 8.20 (d, J = 9.2 Hz, 2H, C ₆ H ₄ ), 7.08 (d, J = 9.2 Hz, 2H, C ₆ H ₄ ), 6.57 (d, J = 8.4 Hz, 1H, C ₆ H ₃ ), 5.96 (d, J = 2.4 Hz, 1H, C ₆ H ₃ ), 5.77 (dd, J = 9.2, 2.8 Hz, 1H, C ₆ H ₃ ), 4.48 (s, 2H, NH ₂ ), 4.42 (s, 2H, NH ₂ ), 4.34 - 4.32 (m, 2H, CH ₂ ), 4.12-4.10 (m, 2H, CH ₂ ), 3.08 (s, 3H, CH ₃ ), 1.41 (s, 6H, C(CH ₃ ) ₂ ). ¹³ C{ ¹ H} NMR (DMSO-d ₆ ): δ 201.4, 162.6, 144.2, 139.6, 137.4, 132.3, 127.6, 116.3, 114.7, 102.7, 101.8, 83.1, 68.9, 67.4, 52.2, 24.9 (each s).

(Examples 1 and 2) <Synthesis of liquid crystal alignment agent>

BODA (10.01g, 40.0mmol), 3AMPDA (4.85g, 20.0mmol), DA-A (13.78g, 40.0mmol), DA-2 (15.22g, 40.0mmol) were dissolved in NMP (166.2g), After reacting at 60 ° C for 5 hours, CBDA (11.57 g, 59.0 mmol) and NMP (55.4 g) were added, and the reaction was carried out at 40 ° C for 10 hours to obtain a polyaminic acid solution.

After the NMP was diluted to 6.5% by mass in the polyamic acid solution (250 g), anhydrous acetic acid (45.9 g) and pyridine (14.2 g) as a ruthenium amide catalyst were added, and the reaction was carried out at 70 ° C for 3 hours. The reaction solution was poured into methanol (3300 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A). The polyimine had a ruthenium iodide ratio of 72%, a number average molecular weight of 14,000, and a weight average molecular weight of 38,000.

NMP (44.0 g) was added to the obtained polyimine powder (A) (6.0 g), and the mixture was stirred at 70 ° C for 20 hours to be dissolved. To the solution, 6.0 g of 3AMP (1 mass% NMP solution), NMP (4.0 g), and BCS (40.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment agent (A1).

<Production of liquid crystal cell>

Using the liquid crystal alignment agent (A1) obtained in Example 1, a liquid crystal cell was produced by the procedure shown below.

The liquid crystal alignment agent (A1) obtained in Example 1 was patterned with an ITO electrode having a pixel size of 100 μm × 300 μm and having a wire/pitch of 5 μm each. The ITO surface of the ITO electrode substrate was spin-coated, dried on a hot plate at 80 ° C for 90 seconds, and then fired in a hot air circulating oven at 200 ° C for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.

Further, the liquid crystal alignment agent (A1) was spin-coated on the ITO surface on which the electrode pattern was not formed, dried on a hot plate at 80 ° C for 90 seconds, and then fired in a hot air circulating oven at 200 ° C for 30 minutes to form. A liquid crystal alignment film having a film thickness of 100 nm.

On the two substrates, a 4 μm bead spacer was spread on the liquid crystal alignment film of one of the substrates, and then a sealant (solvent type thermosetting epoxy resin) was printed thereon. Next, the surface of the other substrate on which the liquid crystal alignment film side is formed is inside, and after bonding to the previous substrate, the sealant is cured to form an empty cell. In the empty cell, liquid crystal MLC-3023 (trade name, manufactured by Merck & Co., Ltd.) containing a polymerizable compound for PSA was injected by a reduced pressure injection method to prepare a liquid crystal cell.

<Measurement of pretilt angle> <<UV irradiation: 6J/cm ² or 10J/cm ² >>

The liquid crystal cell was irradiated with UV 6 J/cm ² or 10 J/cm ² passing through a 365 nm band pass filter from the outside of the liquid crystal cell in a state where a DC voltage of 15 V was applied to the obtained liquid crystal cell. Further, the illuminance of UV was measured using UV-MO3A manufactured by ORC Corporation. After that, in order to deactivate the unreacted polymerizable compound remaining in the liquid crystal cell, the UV-FL irradiation apparatus manufactured by Toshiba Lighting Co., Ltd. was used for 30 minutes without applying a voltage (UV lamp: FLR40SUV32/A). -1).

Thereafter, the pretilt angle of the pixel portion was measured for the unit cell after UV irradiation. Further, the pretilt angle was measured using an LCD analyzer LCA-LUV42A manufactured by Meiryo Technica. The results are shown in Table 1.

<Measurement of response speed>

First, in a measuring apparatus comprising a group of polarizing plates and a light amount detector in a state of backlight and cross nicol, the obtained liquid crystal cell is disposed between a group of polarizing plates. At this time, the pattern of the wire/spaced ITO electrode was set to be 45° to the crossed Nicole. Further, a rectangular wave having a voltage of ±7 V and a frequency of 1 kHz is applied to the liquid crystal cell described above, and the change in brightness observed by the light amount detector until saturation is present on the oscilloscope, and the luminance when the voltage is not applied is 0. %, applying a voltage of ±7V, so that the value of the saturation brightness is 100%, and the time required for the brightness to change from 10% to 90% is the response speed.

(Comparative Examples 1 and 2) <Synthesis of Control Liquid Crystal Alignment Agent>

In the same manner as in Example 1, except that DA-1 (13. Specifically, a control liquid crystal alignment agent (B1) was synthesized as follows.

That is, BODA (10.01g, 40.0mmol), 3AMPDA (4.85g, 20.0mmol), DA-1 (13.22g, 40.0mmol), DA-2 (15.22g, 40.0mmol) are dissolved in NMP (164.6g), 5 hours reaction at 60 ° C Thereafter, CBDA (11.57 g, 59.0 mmol) and NMP (54.9 g) were added, and the mixture was reacted at 40 ° C for 10 hours to obtain a polyaminic acid solution.

After the NMP was diluted to 6.5% by mass in the polyamic acid solution (250 g), anhydrous acetic acid (46.4 g) and pyridine (14.4 g) as a ruthenium amide catalyst were added, and the reaction was carried out at 70 ° C for 3 hours. The reaction solution was poured into methanol (3300 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (B). The polyimine had a ruthenium iodide ratio of 73%, a number average molecular weight of 23,000, and a weight average molecular weight of 64,000.

NMP (44.0 g) was added to the obtained polyimine powder (B) (6.0 g), and the mixture was stirred at 70 ° C for 20 hours to be dissolved. To the solution, 6.0 g of 3AMP (1 mass% NMP solution), NMP (4.0 g), and BCS (40.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment agent (B1).

<Preparation of Control Liquid Crystal Cell, Measurement of Pretilt Angle, and Measurement of Response Speed>

A control liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal alignment agent (B1) was used instead of the "liquid crystal alignment agent (A1)" in Example 1.

Further, the obtained control liquid crystal cell was subjected to the same operation as in the example, and the pretilt angle and the response speed were measured. The results are shown in Table 1.

The following items are known from Table 1.

That is, Comparative Control Examples 1 and 2 (control liquid crystal alignment agent (B1) obtained using control diamine (DA-1)) were compared with Examples 1 and 2 (made) In the liquid crystal cell of the liquid crystal alignment agent (A1) obtained by using the aromatic diamine compound (DA-A), the liquid crystal cells of Examples 1 and 2 were irradiated with light of the same irradiation amount, and the pretilt angle was shifted by 90°.

Further, it is understood that the liquid crystal cells of Examples 1 and 2 have a desired pretilt angle and a desired response speed at a low UV irradiation amount as compared with the liquid crystal cells of Comparative Examples 1 and 2. The aromatic diamine compound (DA-A) used in the liquid crystal cell of Examples 1 and 2 had more radical generation during UV irradiation than the diamine (DA-1) used in the control liquid crystal cell.

Since the liquid crystal cells of Examples 1 and 2 are smaller than the control liquid crystal cells of Comparative Examples 1 and 2, the amount of UV irradiation at the same wavelength is small, so that the damage of the liquid crystal can be reduced by shortening the UV irradiation time, and the liquid crystal can be reduced. The cost of production.

Claims (18)

A polyimine precursor which uses a polyimine precursor of a diamine for producing a first photoradical, which is characterized by being substituted with a diamine for the first photoradical generation ( 1) a second polyimine imine precursor formed under the same conditions as the polyimine precursor other than the diamine for generating a second photoradical represented by the above, and free radical generation upon light irradiation under the same conditions More quantity, The polyimine precursor according to claim 1, wherein the light wavelength at the time of the light irradiation is 300 nm to 400 nm. The polyamidiamine precursor according to claim 1 or 2, wherein the first divalent amine generating diamine is 0.1 to 100 mol% of the total diamine 100 mol% of the polyimine precursor. ear%. The polyimine precursor according to any one of claims 1 to 3, wherein the first photoradical generating diamine has the formula (A) (wherein Ar is an optionally substituted aromatic hydrocarbon group) , R ¹⁰¹ is a divalent organic group, and R ¹⁰² to R ¹⁰⁴ are each independently, and represents a structure of a monovalent organic group) The polyimine precursor according to claim 4, wherein the -R ¹⁰¹ - is -T ₁ -ST ₂ - (wherein T ₁ and T ₂ are each independently a single bond, -O-, - COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO- , S is a single bond, or an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom (-CH ₂ - or -CF ₂ - in the alkyl group is -CH=CH-, or may be The groups selected by the lower group G (but the groups selected by the group G are not adjacent to each other) are substituted (groups G: -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH- , a divalent carbocyclic ring or a divalent heterocyclic ring))). The polyimine precursor according to claim 4 or 5, wherein any one of R ¹⁰² to R ¹⁰⁴ is -OR ¹¹¹ (R ^{111 is} unsubstituted or substituted by a fluorine atom: 1 to 20) a straight or branched chain or a cyclic alkyl group (-CH ₂ - or -CF ₂ - in the alkyl group is -CH=CH-, or a group selectable by the lower group G (however, the group G Substituted groups are not adjacent to each other) (group G: -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, divalent carbocyclic or divalent heterocyclic ring) The other two are independent, and are a linear or branched or cyclic alkyl group having a carbon number of 1 to 20, -OR ¹¹² (R ¹¹² is a straight or unsubstituted or substituted by a fluorine atom and has a carbon number of 1 to 20 a group represented by a group selected from the group consisting of a chain or a branched chain or a cyclic alkyl group, a group having 6 to 20 carbon atoms which may have a substituent, a benzyl group or a phenethyl group (the other two are When the aforementioned alkyl group or -OR ¹¹² is bonded to each other to form a ring). The polyimine precursor according to any one of claims 4 to 6, wherein the Ar is a phenylene group. The polyimine precursor according to any one of claims 1 to 7, wherein the first photo-radical-generating diamine is represented by the following formula (2): wherein Ar and R ¹⁰¹ to R ^{104 are} as described above. The same definition), The polyimine precursor described in any one of the above-mentioned items 1 to 8, wherein the first photo-radical-generating diamine is represented by the following formula (3). The polyimine precursor described in any one of claims 1 to 9, which further has a side chain which vertically aligns the liquid crystal. The polyimine precursor described in any one of claims 1 to 10, further comprising a side chain having a photoreactive group in the structure. A polyimine which is obtained by imidating a polybendimimine precursor described in any one of claims 1 to 11. A liquid crystal alignment agent comprising the polyimine precursor described in any one of claims 1 to 11 and/or the polyamidene described in claim 12. The liquid crystal alignment agent according to claim 13, which is a liquid crystal display element obtained by reacting the polymerizable compound with a polymerizable compound in a liquid crystal and/or a liquid crystal alignment film by irradiating ultraviolet rays while applying a voltage. Manufacturing. A liquid crystal alignment film comprising the liquid crystal alignment agent of claim 13 or 14 formed. A liquid crystal display device comprising the liquid crystal alignment film of claim 15. A diamine characterized by the following formula (2) (wherein, Ar is an aromatic hydrocarbon group which may have a substituent, R ¹⁰¹ is a divalent organic group, and R ¹⁰² to R ¹⁰⁴ are each independently represent a monovalent organic group) Said that A diamine characterized by the following formula (3),