TW202003814A - Phase-shifting modulation element and antenna - Google Patents

Abstract

A phase-shifting modulation element in which a liquid crystal layer is used in a variable permittivity member, wherein the phase-shifting modulation element has a liquid crystal layer containing a liquid crystal compound having an isothiocyanate group, and an alignment control layer disposed so as to be in contact with the liquid crystal layer, the alignment control layer having a specific functional group represented by the following formula (N-1) or (N-2). [Chemical formula 1] In the formula, *1 is a bond connecting to a carbon atom, an oxygen atom, or a hydrogen atom, and at least two of the *1 connects to a carbon atom or a nitrogen atom. *2 and *3 are bonds connecting to a carbon atom, an oxygen atom, or a hydrogen atom, and at least one of the *2 and *3 connects to a carbon atom or a nitrogen atom. However, *1 and *2 do not connect to a carbonyl group.

Description

Phase shift modulation element and antenna

The present invention relates to a phase shift modulation element used in a scanning antenna and the like, and particularly to a phase shift modulation element using a liquid crystal compound having an isothiocyanate group in a dielectric constant variable member.

With the expansion of the use of communications technology using geostationary satellites, attention is being paid to devices that can arbitrarily control the amplitude or phase of so-called microwave or millimeter wave high-frequency signals by external stimulation.

In the past, satellite communications have mainly been used in combination with parabolic antennas fixed with stationary satellites. In this case, in the case of a mobile trusted satellite communication side, a drive system for tracking satellites is necessary, and there is a disadvantage that the device is large-scale and expensive. In addition, although a phase array antenna is known which makes it possible to electronically scan radio waves by combining a plurality of element antennas and a phase shifter, the conventional phase array antenna is expensive and becomes an obstacle to the popularization of consumer products.

In response to this, there has been proposed a technique for controlling the resonance frequency or phase of an element antenna and using an antenna with a variable dielectric constant member. As the aforementioned variable dielectric constant member, it is proposed to use a liquid crystal (Patent Document 1 to Patent Document) 4). In this antenna, an element that controls the resonance frequency or phase (hereinafter also referred to as a phase-shift modulation element) already has a structure in which the liquid crystal layer is held by two substrates, and the alignment state of the liquid crystal molecules is changed by the application of voltage , Thereby changing the dielectric constant of the liquid crystal layer.

In the antenna for transmitting and receiving high-frequency signals called microwaves or millimeter waves, the liquid crystal mounted on the phase-shift modulation element described above needs to have a large dielectric anisotropy for the electromagnetic waves in the high-frequency band. It is seen that a special liquid crystal different from the user of the liquid crystal display element is used (Patent Document 5 and Patent Document 6). Among them, a liquid crystal compound having an isothiocyanate group at the terminal is promising as a liquid crystal material used for the antenna as described above.

However, in general, it is known that a liquid crystal system having a large dielectric anisotropy has a poor retention rate of applied voltage and deteriorates durability. For example, there is a proposal for a liquid crystal compound having an isothiocyanate group at the end. The reaction between the isothiocyanate group and a carboxyl group causes a decrease in antenna characteristics, and a polymer without a carboxyl group is used in a liquid crystal alignment film, etc. (Patent Document 7, Patent Document 8). [Prior Technical Literature] [Patent Literature]

[Patent Literature 1] Japanese Special Publication No. 2009-538565 [Patent Document 2] Japanese Special Publication No. 2014-531843 [Patent Document 3] Japanese Special Publication No. 2017-506467 [Patent Document 4] International Publication No. 2017/061526 [Patent Document 5] Japanese Patent Laid-Open No. 2005-120208 [Patent Document 6] Japanese Patent Laid-Open No. 2016-37607 [Patent Document 7] International Publication No. 2018/016398 [Patent Literature 8] International Publication No. 2018/021093

[Problem to be solved by invention]

The purpose of the present invention is to use the liquid crystal layer in the phase shift modulation element of the dielectric constant variable member to improve the reliability of the element. [Means to solve the problem]

The inventors of the present invention have repeated the results of diligent research to solve the above-mentioned problems, and finally completed the present invention.

The gist of the present invention is as described in the following <1>. <1> A phase shift modulation element that uses a liquid crystal layer as a dielectric constant variable member, and is characterized by having a liquid crystal layer containing a liquid crystal compound having an isothiocyanate group, and the foregoing The alignment control layer arranged in contact with the liquid crystal layer has the specific functional group represented by the following formula (N-1) or (N-2).

In the formula, *1 is a bonding part connected to a carbon atom, an oxygen atom, and a hydrogen atom, and at least two of *1 are connected to a carbon atom and a nitrogen atom. *2 and *3 are bonding parts connected to carbon atoms, oxygen atoms and hydrogen atoms, and at least one of *2 and *3 is connected to carbon atoms and nitrogen atoms. However, *1, *2 are not connected to the carbonyl group. [Effect of the invention]

According to the present invention, the reliability of an antenna element using liquid crystal in a dielectric constant variable member can be improved.

The phase shift modulation device of the present invention is as described above, and it is an element that uses a liquid crystal layer as a dielectric constant variable member to become a liquid crystal compound having an isothiocyanate group contained in the liquid crystal layer, and also for the liquid crystal The alignment control layer has a specific functional group.

Here, the so-called "phase-shift modulation element" means an element such as an array antenna used to control the resonance frequency or phase of the element antenna. In addition, the term "a liquid crystal layer is used in a phase shift modulation element of a dielectric constant variable member" means a change in the dielectric constant of the liquid crystal layer accompanying the change in the alignment of liquid crystal molecules in the phase shift modulation element.

In addition, the "alignment control layer" means a layer that controls the alignment state of liquid crystal when there is no external stimulus to change the alignment of the liquid crystal molecules.

The phase-shift modulation element for controlling the high-frequency signal of so-called microwave or millimeter wave is preferably used for the liquid crystal material having a large anisotropy of the dielectric constant of the liquid crystal layer for high frequencies. In the present invention, as a liquid crystal material having a high dielectric constant anisotropy in a high frequency region, a liquid crystal material containing a liquid crystal compound having an isothiocyanate group (-NCS) is used. Generally speaking, the liquid crystal material is a mixture of a plurality of liquid crystal compounds (liquid crystal molecules), and the liquid crystal material used in the liquid crystal layer of the present invention can be mixed with a plurality of liquid crystal compounds having isothiocyanate groups, and the liquid crystal material None of the contained liquid crystal compounds have isothiocyanate groups.

The isothiocyanate group is contained in the liquid crystal molecule as an atomic group represented by the following chemical formula, for example.

In the above chemical formula, any hydrogen atom in the phenylene group may be replaced by a fluorine atom.

As the liquid crystal compound having the atomic group represented by the above chemical formula, a well-known compound can be used. For example, as a suitable specific example, the compound described in Japanese Patent Laid-Open No. 2016-37607 can be cited.

The control of the dielectric constant of the liquid crystal layer is performed by, for example, applying a voltage to the liquid crystal layer to change the alignment of the liquid crystal molecules. However, in general, since the specific resistance of the liquid crystal material having an isothiocyanate group is low, the retention rate of the applied voltage is low. When the liquid crystal material is deteriorated, the specific resistance is further reduced, and the voltage retention rate is further reduced. When the voltage retention rate is low, it becomes impossible to align liquid crystal molecules in a predetermined direction, thereby degrading the antenna characteristics.

Although the phase shift modulation device of the present invention has an alignment control layer in contact with the above liquid crystal layer, the inventors found that by introducing a specific functional group to this alignment control layer, the liquid crystal having an isothiocyanate group can be improved The voltage retention rate of the material is low.

As one of the causes of deterioration of the liquid crystal material having an isothiocyanate group, a reaction with extremely slight moisture contained in the liquid crystal layer can be cited. Moreover, as shown below, it is speculated that the reaction of the isothiocyanate group with water is promoted by free protons, and in the presence of water and protons, the isothiocyanate group easily changes into an amine group. Furthermore, it is considered that the generated amine group reacts with the isothiocyanate group of other liquid crystal molecules to dimerize the liquid crystal.

In the present invention, it is considered that the presence of a specific functional group in the alignment control layer in contact with the liquid crystal layer reduces the protons associated with the deterioration of the liquid crystal material by the basicity (proton tolerance) of the functional group.

In the present invention, the specific functional group included in the alignment control layer in contact with the liquid crystal layer is a specific functional group represented by the following formula (N-1) or (N-2).

In the formula, *1 is a bonding part connected to a carbon atom, an oxygen atom, and a hydrogen atom, and at least two of *1 are connected to a carbon atom and a nitrogen atom. *2 and *3 are bonding parts connected to carbon atoms, oxygen atoms and hydrogen atoms, and at least one of *2 and *3 is connected to carbon atoms and nitrogen atoms. However, *1, *2 are not connected to the carbonyl group.

In (N-1), when the nitrogen atom is part of the ring structure, it is preferred that the isolated electron pair on the nitrogen atom is not delocalized in the entire ring.

As specific examples of the aforementioned specific functional group, although NR ₁ R ₂ R ₃ may include pyrrolidine, imidazolidine, piperidine, piperazine, quinine, morpholine, imidazole, pyrazole, pyridine, pyrimidine, pyridazine, pyrazine , Azaindazine, triazole, etc., but not limited to these. Here, R ₁ , R ₂ and R ₃ represent a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and at least two of R ₁ to R ₃ represent an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group .

The aliphatic hydrocarbon group in R ₁ to R ₃ may be in a linear or branched form. The aliphatic hydrocarbon group and the alicyclic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. In addition, the position of the unsaturated bond of an unsaturated hydrocarbon group may be either within the molecular chain or at the end of the molecular chain, and may have any position. Here, in this specification, the "alicyclic hydrocarbon group" is a concept for removing an aliphatic hydrocarbon group that does not have a cyclic structure. In addition, in this specification, the so-called "alicyclic hydrocarbon group" and "aromatic hydrocarbon group" are not only a group composed of a ring structure, but also include the concept that the ring structure further replaces the group of the aliphatic hydrocarbon group. The structure may contain at least an alicyclic hydrocarbon or an aromatic hydrocarbon.

In the present invention, the material constituting the alignment control layer in contact with the liquid crystal layer is not particularly limited, and examples thereof include polyamic acid, polyimide, polyamic acid ester, polysiloxane, polyester, and polyacrylic acid. Amines, polyureas, cellulose derivatives, polyacetals, polystyrene derivatives, poly(styrene-phenylmaleimide) derivatives, poly(meth)acrylates, azobenzene derivatives, etc. The polymer as the main skeleton.

Hereinafter, an orientation control layer having a specific functional group will be described using polyamic acid, polyimide, and polyamic acid ester as examples. 1. Alignment control layer for polymers with specific functional groups in the main chain or side chain Specific examples of the polyamic acid, polyimide, and polyamic acid ester include, for example, structural units represented by the following formula (1-1) or structural units represented by the following formula (1-2) polymer.

Here, X ₁ is a tetravalent organic group, and Y ₁ is a divalent organic group. R ₁ is a hydrogen atom or a monovalent organic group. In addition, any one of X ₁ , Y ₁ and R ₁ has the aforementioned specific functional group. Examples of Y _1, to obtain the effect of the present invention in view, although preferably at least one of the foregoing having a specific functional group is preferably, but more preferably having at least one selected from the group consisting of the following formulas (nb1) ~ ( nb44) Specific functional groups in the formed group.

R ^a represents a hydrogen atom, a linear hydrocarbon group having 1 to 12 carbon atoms or a branched hydrocarbon group having 1 to 12 carbon atoms. R ^b and R ^c each independently represent a hydrogen atom or a methyl group. R ^d represents a linear hydrocarbon group having 1 to 12 carbon atoms or a branched hydrocarbon group having 1 to 12 carbon atoms. R _ak represents an alkyl group having 1 to 18 carbon atoms, and R _ar represents an aryl group having 6 to 18 carbon atoms.

Examples of Y ₁ having a specific functional group include those derived from the following formulas (y1) to (y23), 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-di Aminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4 -Diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis(3-aminopropyl)piperazine, 2,4-diamino-6-isopropyl Oxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1, 3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino- 2-vinyl-s-triazine, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8- Diamine-6-phenylmorphine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine .

X ₂ is a single bond, oxygen atom, carbonyl, *-COO-, *-OCO-, -NH-, *-Ar ₁ -O-, *-O-Ar ₁ -, *-COO-Ar ₁ -or * -R ₂ -OCO-(However, Ar ₁ is a divalent group bonded to a phenylene group or a phenylene group, R ₂ is an alkanediyl group having 1 or 2 carbon atoms. "*" indicates a bond with G Location). X ₃ is a single bond or a carbonyl group. G is a group selected from (nb6) to (nb8) and (nb13) to (nb16). When G is (nb6) to (nb7), G is bonded to the X ₃ nitrogen atom. In addition, when G is (nb8), X ₂ represents a single bond, a carbonyl group, *-COO-, *-Ar ₁ -O-, *-COO-Ar ₁ -or *-R ₂ -OCO-.

In the formula, A _{1 is} independently a single bond, a methylene group, a C 2-6 alkylene group, a phenyl group, a naphthyl group, a pyridyl group, a pyrimidinyl group, or a triazine group, each of which has a carbon atom At least one of the hydrogen atoms can be substituted. B _{1 is} independently a single bond, -CO-, -COO- or -CO-NH-. m is an integer from 0 to 3.

X ₄ is methylene, 2,2-propylene, alkylene having 2 to 18 carbon atoms, oxygen atom, ester bond or amide bond, n1 is 0 or 1; R in formula (y4) is 2 In each case, they are independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, X ₅ is a methylene group, 2,2-propylene group, and an alkylene group having 2 to 12 carbon atoms. Group, an aryl group having 6 to 18 carbon atoms, an oxygen atom, an ester bond or an amide bond, and n2 is 0 or 1.

X ₆ is a biphenyl ring or a stilbene ring, Y _{2 is} independently a group selected from a benzene ring, a biphenyl ring, or -phenyl-Z-phenyl-, and Z is -O-, -NH-, -CH _2- , -SO ₂ -, -C(CH ₃ ) ₂ -or -C(CF ₃ ) ₂ -represents a divalent group. A ₂ and B ₂ are a hydrogen atom or a methyl group.

(R ¹ is a hydrogen atom or a methyl group, X ₇ is an oxygen atom, *-OCO-, -C(=O)O-(-(CH ₂ )aOC(=O)-)b-(a is 1-12 Integer, b is an integer from 0 to 5 (but, above, the bonding part with "*" attached to the piperidine ring), methylene or alkylene having 2 to 6 carbon atoms.

Ac ² is (nb35), (nb40) or (nb41).

R ² is a single bond or a divalent organic group. R ³ is a divalent organic group. X ¹ is a group selected from (nb29) to (nb38). The divalent organic group of R ² is selected from the group represented by -CO-, *2-OCO- ("*2" represents a bonding portion bonded to a diaminophenyl group) or the following (r-1) base.

A ₃ is a single bond, -O-, -CO-, *3-OCO- or *3-COO-, A ₄ is a single bond, -CO- or -OCO-*4, R ⁴ is a single bond, alkane The di- or alkane diyl has a divalent group of -O-, -CO-O-, -CO-NH- or -CO- between carbon-carbon bonds. "*3" and "*4" indicate the bonding part. However, "*3" is bound to diaminophenyl. Examples of the divalent organic group of R ⁴ include a divalent hydrocarbon group and a carbon-carbon bond of the hydrocarbon group having -O-, -NH-, -CO-O-, -CO-NH-, -CO-,- Divalent groups and linkages of functional groups such as S-, -SO ₂ -, -Si(CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -O- Hydrocarbon, and -O-, -NH-, -CO-O-, -CO-NH-, -CO-, -S-, -SO ₂ -, -Si(CH ₃ ) ₂ -, -O-Si( CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -O- and other functional groups are divalent groups, at least one hydrogen atom in the hydrocarbon group is replaced by a fluorine atom or a chlorine atom, a bromine atom, an iodine atom Divalent groups such as halogen atoms or hydroxyl groups substituted by others. Examples of the divalent hydrocarbon group include methylene, ethylidene, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, and the like, which have a carbon number of 1 to 10 and are divalent. Hydrocarbyl, etc.

(G₅ 為碳數1～10之伸烷基，R表示氫原子或甲基)。

(G ₅ is an alkylene group having 1 to 10 carbon atoms, and R represents a hydrogen atom or a methyl group).

L ₁ is a divalent chain hydrocarbon group having a carbon number of 1 to 10, such as methylene, ethylidene, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, or the like At least one methylene group of the aforementioned divalent chain hydrocarbon group is represented by -O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS-, or -Si(CH ₃ ) ₂ -(R is a hydrogen atom or a monovalent organic group) substituted group. A ₅ and A ₆ represent a hydrogen atom, a methyl group, and a phenyl group.

(L ₂ and L ₃ are the divalent values of carbon number 1 to 10 for methylene, ethylidene, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, etc. The chain hydrocarbon group or at least one methylene group in the aforementioned divalent chain hydrocarbon group is represented by -O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS-, or -Si (CH ₃ ) _2- (R is a hydrogen atom or a monovalent organic group) substituted group). A ₇ represents a hydrogen atom, a methyl group, and a phenyl group.

X ₈ is a group selected from the following formulas (M1) to (M6).

X ² is (nb13), (nb15) or (nb16). R ⁵ is a single bond, a C1-C6 alkane diyl group or a cyclohexyl group, R ⁶ is a hydrogen atom or a C1-C6 alkyl group, or two R ² are bonded to each other to form two nitrogen Together, atoms and R ¹ form a divalent alicyclic heterocyclic group having 2 to 10 carbon atoms. The two R ⁶ may be the same or different. p is 0 or 1).

Z ¹ and Z ² are independently +-Z-(CH ₂ ) _a- (however, Z is a single bond, +-COO-, +-OCO-, +-CO-, +-O-, +-NRCO- , +-CONR- or +-NR- (here, R is a hydrogen atom or a methyl group), a is an integer of 0 to 3. n is 1 to 2. In the above-mentioned bonding part with "+" and the amine Phenyl bonding.

In the formula, X ₉ is selected from the group consisting of _{-O -, - NQ 1 -,} - CONQ 1 -, -NQ 1 CO -, - CH 2 O- and the group consisting of -OCO- in the at least one kind of divalent Organic group, Q ₁ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X ₁₀ is a single bond or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group and an aromatic hydrocarbon group the at least one divalent organic group, X ₁₁ is a single bond or selected from the group consisting of _{-O -, - NQ 2 -,} - CONQ 2 -, - NQ 2 CO -, - COO -, - OCO- and -O (CH ₂ ) _m- (m is an integer of 1 to 5) at least one kind of divalent organic group in the group, Q ₂ is a hydrogen atom or a C 1-3 alkyl group, X ₁₂ is selected from ( nb31) to (nb38) or (nb41) to (nb42).

A ¹ and A ⁵ are each independently a single bond or an alkylene group having 1 to 5 carbon atoms, A ² and A ⁴ are each independently an alkylene group having 1 to 5 carbon atoms, and A ³ is an alkylene group having 1 to 6 carbon atoms Group or cyclic alkyl group, B ¹ and B ² are independently a single bond, -O-, -NH-, -NMe-, -C(=O)-, -C(=O)O-, -C( =O)NH-, -C(=O)NMe-, -OC(=O)-, -NHC(=O)- or -N(Me)C(=O)-, a is 0 or 1).

R ^a represents a hydrogen atom, a linear hydrocarbon group having 1 to 12 carbon atoms or a branched hydrocarbon group having 1 to 12 carbon atoms. R ^b and R ^c each independently represent a hydrogen atom or a methyl group. R ^d represents a linear hydrocarbon group having 1 to 12 carbon atoms or a branched hydrocarbon group having 1 to 12 carbon atoms.

In the formula, A ₈ represents a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic ring having a divalent carbon number of 1-20, A may have various substituents, and E is a single bond or a saturation of a divalent carbon number of 1-20 Hydrocarbon group, unsaturated hydrocarbon group, aromatic hydrocarbon group or heterocyclic ring, F represents single bond or ether bond (-O-), ester bond (-OCO-, -COO-).

R ₃ is hydrogen, -OH, C 1-6 alkyl or C 1-6 alkoxy; X ² and X ³ are independently C 1-8 alkylene and/or benzene Bivalent organic radical.

X ₁₃ is -NH-. Q is an alkylene group having 1 to 5 carbon atoms. G ₁ is a group selected from (nb6), (nb7) to (nb8), (nb13) to (nb16).

Still, the above Y ₁ can be formed during the process of making the alignment film. For example, the structure (Y ₁ ′) in which the firing step of the alignment film is changed to the above Y _{1 may} be mentioned. As a specific example of such a structure (Y ₁ ′), for example, the following diamine (y-v1) may be mentioned. ~(y-v8).

A ⁶ and A ¹⁰ are independently a single bond or a C 1-5 alkylene group, A ⁷ and A ⁹ are independently a C 1-5 alkylene group, and A ⁸ is a C 1-6 alkylene group Group or cyclic alkyl group, B ³ and B ⁴ are independently a single bond, -O-, -NH-, -NMe-, -C(=O)-, -C(=O)O-, -C( =O)NH-, -C(=O)NMe-, -OC(=O)-, -NHC(=O)- or -N(Me)C(=O)-, a is 0 or 1. D represents a hydrogen atom or a thermally detachable group. When a=0, D represents a thermally detachable group. When a=1, at least one of the two D is a thermally detachable group.

X ₁₄ is methylene, 2,2-propylene, C2-C12 alkylene, C6-C18 aryl, oxygen atom, ester bond or amide bond, n2 is 0 or 1 . D represents a hydrogen atom or a thermally detachable group. When n=0, D represents a thermally detachable group. When n=1, at least one of the two D is a thermally detachable group.

X ₁₅ is a biphenyl ring or a stilbene ring, Y ₃ is a group selected from a benzene ring, a biphenyl ring or -phenyl-Z ³ -phenyl-, Z ³ is -O-, -NH-, -CH _2- , -SO ₂ -, -C(CH ₃ ) ₂ -or -C(CF ₃ ) ₂ -represents a divalent group. D represents a hydrogen atom or a thermally detachable group, and at least one of the two D is a thermally detachable group.

L ⁴ is a bivalent chain hydrocarbon group having a carbon number of 1 to 10, such as methylene, ethylidene, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, or the like At least one methylene group of the aforementioned divalent chain hydrocarbon group is represented by -O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS-, or -Si(CH ₃ ) ₂ -(R is a hydrogen atom or a monovalent organic group) substituted group. D represents a hydrogen atom or a thermally detachable group, and at least one of the two D is a thermally detachable group.

L ⁵ and L ⁶ are divalent chains with 1 to 10 carbon atoms, such as methylene, ethylidene, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, etc. Hydrocarbon group or at least one methylene group in the aforementioned divalent chain hydrocarbon group with -O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS- or -Si( CH ₃ ) _2- (R is a hydrogen atom or a monovalent organic group) substituted group. D represents a thermally detachable radical.

X ₁₆ is -ND-. Q ₁ is an alkylene group having 1 to 5 carbon atoms. G ₃ is a group selected from (nb6), (nb7) to (nb8), (nb13) to (nb16).

In the formula, A ₉ represents a saturated hydrocarbon group, unsaturated hydrocarbon group, aromatic hydrocarbon group or heterocyclic ring having a divalent carbon number of 1-20, A may have various substituents, and E ₁ is a single bond or a saturation of a divalent carbon number of 1-20 Hydrocarbon group, unsaturated hydrocarbon group, aromatic hydrocarbon group or heterocyclic ring, F ₁ represents single bond or ether bond (-O-), ester bond (-OCO-, -COO-), m is 1 or 0, D represents thermal desorption Sex group, * means bonding with other atoms). The substitution position of the amine group in the above formula (y-v7) and the above formula (y-v8) is not particularly limited, but from the viewpoint of ease of synthesis or availability of the reagent, the amide bond is used as a reference In this case, the meta or para position is preferred, and from the viewpoint of liquid crystal alignment, the para position is particularly preferred. Furthermore, even if the aminobenzene does not have an amine group protected by a thermally detachable group, when the amide bond is also used as a reference, the meta or para position is preferred, and from the viewpoint of solubility, it is preferred The position of the meta position is preferably the position of the alignment position from the viewpoint of liquid crystal alignment. In addition, the hydrogen of the aminobenzene that does not have -NH-D may be substituted with a halogen atom such as an organic group or fluorine.

From the viewpoint of solubility, A ₉ in the above formula is preferably a divalent hydrocarbon group, etc. As a preferable example, a linear alkylene group or a cyclic alkylene group, etc. may be mentioned. This hydrocarbon may have an unsaturated bond. In addition, from the viewpoint of liquid crystal alignment and electrical characteristics, a divalent aromatic hydrocarbon group, heterocyclic ring, or the like is preferred. From the viewpoint of liquid crystal alignment, although A ₉ does not have a substituent, it is preferred. From the viewpoint of solubility, a hydrogen atom is preferably substituted with a carboxylic acid group, a fluorine atom, or the like.

Still, the above structures (y-v7) and (y-v8) can obtain a structure containing a specific functional group by the ring-closing reaction shown in the following scheme (i).

G ₅ is an alkylene group having 1 to 10 carbon atoms, and D represents a thermally detachable group.

In the structural unit represented by the aforementioned formula (1-1), the carbonyl group of the amide imine moiety may be condensed with a primary amine to form a nitrogen-containing cyclic group. When a specific example of a cyclic group containing nitrogen is given, a cyclic group containing the aforementioned specific functional group can be cited. As an example, (nb-24) can be formed according to the following flow (ii). n represents 0 or 1.

As a preferable structure of Y ₁ changed to a cyclic group including the above-mentioned specific functional group, the following formulas (y-h1) to (y-h3) may be mentioned.

D represents a thermally detachable radical. D ₁ and D _{2 are} independently an amine group substituted with a hydrogen atom or a thermally detachable group, and at least one of D ₁ and D ₂ is an amine group substituted with a thermally detachable group. R ₄ and R ₅ are each independently a hydrogen atom or a C 1-5 alkyl group.

In this specification, if the thermally detachable group is a functional group in which a hydrogen atom is replaced by heat, the structure is not particularly limited. From the viewpoint of the storage stability of the liquid crystal alignment agent, the protective group D is preferably not removed at room temperature, preferably a protective group that is thermally detached at a temperature of 80°C or higher, and more preferably at a temperature of 100°C or higher. Preferably, it is a protecting group that is detached by heat above 120°C. The temperature for detachment is preferably 250°C or lower, more preferably 230°C or lower. Excessively high detachment temperature is undesirable due to the decomposition of the polymer. From the point of view of the temperature at which it leaves, D is particularly preferably tert-butoxycarbonyl or 9-oxylmethoxycarbonyl.

D ₁ and D _{2 are} preferably a hydrogen atom, -NHBoc or -N(Boc) ₂ , and at least one of D ₁ and D ₂ is -NHBoc or -N(Boc) ₂ . Still, Boc means tert-butoxycarbonyl.

As Y ₁ which does not have a specific functional group, a well-known structure can be suitably used.

Examples of X ₁ having a specific functional group include a tetravalent organic group derived from a tetracarboxylic dianhydride represented by the following formulas (nt-1) to (nt-8), but it is not limited thereto. .

The tetravalent organic group of X ₁ may be a tetravalent organic group that does not have a specific functional group. Examples of such a structure include the following structures.

In the formula, *1 is a bonding portion bonded to one acid anhydride group, and *2 is a bonding portion bonded to another acid anhydride group.

In formula (x-1), R ⁷ to R ¹⁰ represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom, or a benzene ring, and each may be the same or different. As a preferable specific example of (x-1), a structure of the following formula (x1-1) or (x1-2) may be mentioned.

In the formula, *1 is a bonding portion bonded to one acid anhydride group, and *2 is a bonding portion bonded to another acid anhydride group.

In formula (x-7), R ¹¹ and R ¹² represent a hydrogen atom or a methyl group, and each may be the same or different.

In the above formula (1-2), as R ₁ having a specific functional group, for example, a structure in which the OH group is removed from the structure represented by the following formula can be cited, but it is not limited to these.

The monovalent organic group of R ₁ may be a monovalent group that does not have a specific functional group. Examples of such a structure include a hydrogen atom and an alkyl group having 1 to 5 carbon atoms.

2. Alignment control layer used for polymer to add compound with specific functional group The compound having a specific functional group is not particularly limited as long as it has the specific functional group. As preferred specific functional groups, in addition to the aforementioned formulas, functional groups of the following formulas may be mentioned.

As the compound having a specific functional group, an epoxy compound containing the following formula, the above specific functional group, or a compound having a specific functional group and an unsaturated bond, etc. may be mentioned, but it is not limited thereto.

Examples of the epoxy compound having the above-mentioned specific functional group include nitrogen containing aromatic monoamines such as N,N-diglycidyl aniline and N,N-diglycidyl toluidine (Toluidine) as a core. Atomic epoxy compounds; epoxy compounds using alicyclic monoamines such as N,N-diglycidylcyclohexylamine, N,N-diglycidylmethylcyclohexylamine as the parent core; and N, N,N',N'-tetraglycidyl-p-phenylenediamine, N,N,N',N'-tetraglycidyl-m-phenylenediamine, N,N,N', N'-tetraglycidyl-o-phenylenediamine, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N',N '-Tetraglycidyl-3,4'-diaminodiphenylmethane, N,N,N',N'-Tetraglycidyl-3,3'-diaminodiphenylmethane, N, N,N',N'-tetraglycidyl-4,4'-diaminodiphenyl sulfide, N,N,N',N'-tetraglycidyl-1,5-diaminonaphthalene , N,N,N',N'-tetraglycidyl-2,7-diamino stilbene, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenyl Ether, N,N,N',N'-tetraglycidyl-2,2-bis[4-(4-aminophenoxy)phenyl]propane, N,N,N',N'- Tetraglycidyl-9,9-bis(4-aminophenyl) stilbene, N,N,N',N'-tetraglycidyl-2,2-bis[4-(4-aminophenoxy Yl)phenyl]hexafluoropropane, N,N,N',N'-tetraglycidyl-2,2-bis(4-aminophenyl)hexafluoropropane, N,N,N',N' -Tetraglycidyl-4,4'-(p-phenylene diisopropylidene) bisaniline, N,N,N',N'-tetraglycidyl-4,4'-(m-extruded (Phenyldiisopropylidene) bisaniline, N,N,N',N'-tetraglycidyl-1,4-bis(4-aminophenoxy)benzene, N,N,N',N Epoxy compounds with aromatic diamines such as'-tetraglycidyl-4,4'-bis(4-aminophenoxy)biphenyl as the core; N,N,N',N'-tetra Glycidyl-m-xylylenediamine, N,N,N',N'-tetraglycidyl-p-xylylenediamine, 1,3-bis(N,N'-diglycidylamino) (Methyl) cyclohexane, 1,4-bis(N,N'-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-1,4- Cyclohexanediamine, N,N,N',N'-tetraglycidyl-1,3-cyclohexanediamine, N,N,N',N'-tetraglycidyl-4,4' -Epoxy compounds such as alicyclic diamines such as methylene bis(cyclohexylamine) as the core; N,N,N',N'-tetraglycidyl-diaminoethane, N,N ,N',N'-tetraglycidyl-diaminopropane, N,N,N' ,N'-tetraglycidyl-diaminobutane, N,N,N',N'-tetraglycidyl-diaminopentane, N,N,N',N'-tetraglycidyl -Diaminohexane, N,N,N',N'-tetraglycidyl-diaminoheptane, N,N,N',N'-tetraglycidyl-diaminooctane, etc. An epoxy compound having aliphatic diamine as a core, compounds represented by the following formulas (ep-1) to (ep-10), and the like.

Among these, epoxy compounds using an aromatic monoamine as a core, epoxy compounds using an aromatic diamine as a core, and epoxy compounds using an alicyclic diamine as a core are particularly preferred. N,N-diglycidyl aniline, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane and 1,3-bis(N,N'-di Glycidylaminomethyl) cyclohexane.

As the compound having a specific functional group and an unsaturated bond, for example, compounds represented by the following formulas (dw-1) to (dw-4) may be mentioned, but it is not limited thereto.

Still, a compound having a specific functional group can change the firing step used in the alignment film to a compound of a specific functional group. When listing specific examples, a hydrogen atom on a nitrogen atom included in the specific functional group may be replaced by a thermally detachable group Basis. Specific examples of the compound include, for example, compounds represented by the following formulas (C-d1) to (C-d4), but they are not limited thereto.

(D表示熱脫離性基)。

(D represents a thermally detachable group).

It is clear from the above that the case where the material constituting the alignment control layer is polyamic acid, polyimide, or polyamic acid ester has been described as an example, but even when other polymers are used as the material of the alignment control layer It can also be easily done by referring to the well-known technology of each polymer.

<The state of the phase shift modulation element> The phase shift modulation device of the present invention can have a form in which the liquid crystal layer is sandwiched between two substrates. At this time, the alignment control layer is provided on the surface of at least one of the two substrates in contact with the liquid crystal layer.

The material of the substrate is not particularly limited. For example, a glass substrate or a plastic substrate can be used. In this case, when a substrate formed of an electrode, a TFT element, or the like that applies a voltage to the liquid crystal layer to change the alignment state is used, it is preferable from the viewpoint of simplification of the manufacturing process. In addition, a diaphragm electrode, a groove electrode, a waveguide, etc. that constitute an antenna element can be provided on this substrate.

As described above, the phase shift modulation device of the present invention can employ various well-known technologies regarding the configuration and arrangement of the liquid crystal layer and the alignment control layer. For reference, the disclosures of the aforementioned Patent Documents 1 to 4 are all incorporated in this specification. [Example]

Although the following examples are given to explain the present invention in more detail, they are not limited to these. In addition, the evaluation device and the reagent used in the following examples are shown below along with abbreviations. [Evaluation machine] ･Viscometer: E-type viscometer TVE-22H, cone-shaped rotor TE-1 (1°34’, R24) ･Voltage retention rate (VHR): Liquid crystal property evaluation system made by Toyo Technica 6254 [Reagent] (Solvent) ･NMP: N-methyl-2-pyrrolidone ･BCS: butyl cellosolve (monomer) ･DA-1: Compound represented by the following formula (DA-1) ･DA-2: Compound represented by the following formula (DA-2) ･DA-3: Compound represented by the following formula (DA-3) ･DA-4: Compound represented by the following formula (DA-4) ･DA-5: Compound represented by the following formula (DA-5) ･DA-6: Compound represented by the following formula (DA-6) ･DA-7: Compound represented by the following formula (DA-7) ･DA-8: Compound represented by the following formula (DA-8) ･DA-9: Compound represented by the following formula (DA-9) ･DA-10: Compound represented by the following formula (DA-10) ･CA-1: Compound represented by the following formula (CA-1) ･CA-2: Compound represented by the following formula (CA-2) ･CA-3: Compound represented by the following formula (CA-3)

(additive) ･AD-1: Compound represented by the following formula (AD-1) ･AD-2: Compound represented by the following formula (AD-2)

<Preparation of polymer and liquid crystal alignment agent> [Synthesis Example 1] In a 100 mL four-necked flask with a stirring device and a nitrogen introduction tube, measure 1.50 g (1.0 mmol) of DA-1 and 5.57 g (1.0 mmol) of DA-2, add 64.0 g of NMP, and stir while transferring nitrogen Let it dissolve. While stirring this diamine solution under water cooling, 3.84 g (2.0 mmol) of CA-1 was added, 16.0 g of NMP was added, and the mixture was stirred at room temperature for 3 hours under a nitrogen atmosphere to obtain a solution of polyamic acid (PAA- 1). Weigh 1.1mL of this solution of polyamic acid and use a viscometer to measure the viscosity at 25°C. The viscosity is 169 mPa･s.

[Synthesis Examples 2-7] Except that the diamine component, the tetracarboxylic acid component, and the solvent shown in Table 1 were used, the polyamic acid solutions (PAA-2) to (PAA-7) were obtained in the same manner as in Synthesis Example 1. The viscosity of the obtained polyamic acid solution was carried out in the same manner as in Synthesis Example 1, and the viscosity was measured.

[Examples 1 to 5] and [Comparative Examples 1 to 2] Separately divide the polyamic acid solutions (PAA-1) to (PAA-7) obtained in Synthesis Examples 1 to 7 into the amounts shown in Table 2, add NMP and BCS, and stir at room temperature for 2 hours using a magnetic stirrer To obtain the liquid crystal alignment agents of Examples 1 to 5 and Comparative Examples 1 to 2.

[Synthesis Example 8] In a 100 mL four-necked flask with a stirring device and a nitrogen introduction tube, measure 0.7 g (0.3 mmol) of DA-6 and 2.92 g (2.7 mmol) of DA-8, add 59.8 g of NMP, and stir while transferring nitrogen Let it dissolve. While stirring this diamine solution under water cooling, 6.56 g (2.9 mmol) of CA-2 was added, and 14.9 g of NMP was added. After stirring at room temperature for 30 minutes under a nitrogen atmosphere, it was further stirred at 40° C. for 9 hours to obtain Polyamide solution (PAA-8). When the viscosity was measured in the same manner as in Synthesis Example 1, the viscosity was 504 mPa･s.

[Synthesis Example 9] In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, measure 0.76 g (0.5 mmol) of DA-9 and 3.99 g (2.0 mmol) of DA-10, add 68.0 g of NMP, and stir while transferring nitrogen Let it dissolve. While stirring this diamine solution under water cooling, 6.84g (2.3mmol) of CA-3 was added, 17.0g of NMP was added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then stirred at 70°C for 15 hours to obtain Polyamide acid solution (PAA-9). When the viscosity was measured by the same method as in Synthesis Example 1, the viscosity was 382 mPa･s.

[Example 6] to [Example 8] By adding the polyamic acid solutions (PAA-8) and (PAA-9) obtained in Synthesis Example 8 and Synthesis Example 9 to the compositions shown in Table 4, respectively, the solvent and additives were added while stirring, and The mixture was stirred at room temperature for 2 hours and prepared in the same manner as in Example 6.

In addition, in Table 4, ※1, ※2 represents the content (addition) amount (parts by mass) relative to 100 parts by mass of the entire polymer, and ※3 represents the amount of solvent used relative to 100 parts by mass of the liquid crystal alignment agent (Parts by mass).

[Production of liquid crystal lattice] The liquid crystal alignment agent obtained in Example 1 was spin-coated on the ITO surface of a glass substrate with a transparent electrode composed of an ITO film, dried with a hot plate at 70°C for 120 seconds, and then subjected to an IR oven at 230°C for 30 minutes After firing, a liquid crystal alignment film with a thickness of 100 nm is formed. Prepare the above two substrates on the liquid crystal alignment film surface with a roller diameter of 120 mm, a roller rotation speed of 1000 rpm, a stage moving speed of 50 mm/sec, and a friction cloth extrusion pressure of 0.3 mm. Pure water was irradiated with ultrasound for 1 minute and dried at 80°C for 10 minutes. Two substrates as described above were prepared, and a 6 μm bead spacer was spread on the drive control film of one substrate, and a sealant (XN-1500T manufactured by Kyotsu Chemical Co., Ltd.) was applied to the remaining liquid crystal injection port. Next, another substrate was combined in such a way that the rubbing directions became antiparallel, and after the liquid crystal alignment film surfaces faced each other, the sealant was thermally hardened at 120° C. for 90 minutes to produce an empty lattice. After the empty crystal lattice injects the liquid crystal containing thioisocyanate group at room temperature in vacuum, the injection port is sealed as an anti-parallel alignment liquid crystal lattice. Then, the liquid crystal lattice was heated at 120° C. for 30 minutes, and left to stand overnight for use in evaluation. The liquid crystal lattice was produced similarly about Examples 2-5 and Comparative Examples 1-2.

[Measurement of voltage retention] To the liquid crystal lattice obtained above, a voltage of 1 V was applied for 60 μs at a temperature of 60° C. The voltage after 16.67 ms was measured, and how long the voltage could be maintained was calculated as the voltage retention rate (initial value).

Next, the liquid crystal lattice was left at a temperature of 100°C for 144 hours, and then returned to room temperature. The liquid crystal lattice was applied with a voltage of 1 V for 60 μs at a temperature of 60° C. The voltage after 16.67 ms was measured, and how long the voltage could be maintained was calculated as the voltage retention rate (after the durability test).

Still, as the proton-accepting effect of the liquid crystal alignment agent, the voltage retention rate after the durability test is evaluated to be "◎" if it is 85% or more, and if it is within 80 to 85%, it is evaluated as "○", which is as low as 80% The following cases are evaluated as "×".

For the liquid crystal elements using the liquid crystal alignment agents of Examples 1 to 8 and Comparative Examples 1 to 2, the results of evaluation of the voltage retention rate (initial value) and the voltage retention rate after the durability test are shown in the table. 5. In addition, *1 and *2 in Table 5 show the content (parts) (parts by mass) relative to 100 parts by mass of the entire polymer.

From the comparison between Examples 1 to 5 and Comparative Examples 1 to 2, it is believed that the liquid crystal alignment agent contains a monomer with a basic (proton-acceptable) functional group, or the structure changes to a basic functional group after firing. The use of the body has the function of proton tolerance by the liquid crystal alignment film, thereby reducing protons associated with the deterioration of the liquid crystal material. In addition, from the comparison between Examples 6 to 8 and Comparative Examples 1 to 2, it is believed that the liquid crystal alignment film improves the function of proton tolerance by the additive included in the liquid crystal alignment agent including an alkaline (proton-tolerant) functional group, Reduce protons associated with the deterioration of liquid crystal materials. In addition, this system can obtain the same effect even when the polymer is mixed. [Industry availability]

According to the embodiment of the present invention, for example, a scanning antenna used for satellite communication or satellite transmission equipped with a mobile body (ship, aircraft, car, etc.) and a manufacturing method thereof.

Claims (3)

A phase shift modulation element, which is a phase shift modulation element using a liquid crystal layer in a dielectric constant variable member, characterized in that it has a liquid crystal layer containing a liquid crystal compound having an isothiocyanate group, and is in contact with the aforementioned liquid crystal layer An alignment control layer disposed, the alignment control layer having a specific functional group represented by the following formula (N-1) or (N-2),

(In the formula, *1 is a bonding part connected to a carbon atom, an oxygen atom, and a hydrogen atom, at least two of *1 are connected to a carbon atom, a nitrogen atom; *2, *3 are connected to a carbon atom, an oxygen atom, At the bonding part where the hydrogen atom is connected, at least one of *2 and *3 is connected to the carbon atom and the nitrogen atom; however, *1 and *2 are not connected to the carbonyl group). The phase shift modulation element according to claim 1, wherein the specific functional group is NR ₁ R ₂ R ₃ (R ₁ , R ₂ , R ₃ represent a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, R At least 2 of ₁ to R ₃ represent an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group), pyrrolidine, imidazolidine, piperidine, piperazine, quinine, morpholine, imidazole, pyrazole, pyridine, pyrimidine, Pyridazine, pyrazine, azaindazine, triazole structure. An antenna having the phase shift modulation element as described in claim 1.