KR102498939B1 - Functional resin composition for biphasic modulation device using liquid crystal - Google Patents

Abstract

According to the present invention, a functional resin composition capable of maintaining a voltage applied during liquid crystal drive with high precision and obtaining a highly durable drive control film, and a planar antenna having a drive control film obtained from the composition are provided. The present invention relates to a functional resin composition for a liquid crystal drive control film of a microwave anomalous modulation element using a liquid crystal, containing at least one polymer selected from polyamic acid derivatives and polyimides as imidates thereof.

Description

Functional resin composition for biphasic modulation device using liquid crystal

The present invention relates to a functional resin composition used in a biphasic modulator using a liquid crystal, a drive control film obtained from the composition, and a biphasic modulation element having the same.

As the use of high frequencies such as mobile phones and radars expands, devices capable of arbitrarily controlling the amplitude and phase of high frequency signals such as microwaves and millimeter waves by external stimuli are attracting attention. Since the permittivity of liquid crystals can be easily controlled by orientation change accompanying voltage application, liquid crystals are promising as materials for high-frequency phasors (Japanese Patent Laid-Open No. 2005-120208 (Patent Document 1)). Particularly, in recent years, a study to use a phased array antenna equipped with a high-frequency phaser using liquid crystal for satellite communication has become active.

For conventional satellite communication, a combination of a geostationary satellite and a fixed parabolic antenna has been mainly used. In this case, when the side receiving the satellite communication is moving, a drive system for tracking the satellite is essential, and there has been a drawback that the device becomes large-scale and expensive.

In contrast, a planar antenna technology capable of obtaining high gain for transmission and reception of a wide range of radio waves without physically moving the antenna by controlling the phase of electromagnetic waves and expressing directivity in all directions has been proposed (Japanese published patent). Publication 2014-531843 (Patent Document 2) and US20150236412A1 (Patent Document 3)). This antenna has a structure in which liquid crystal is sandwiched between two glass substrates, and the direction of radio waves transmitted and received is controlled by driving the liquid crystal.

Japanese Unexamined Patent Publication No. 2005-120208 Japanese Published Patent Publication No. 2014-531843 US Patent Publication No. US20150236412A1

The liquid crystal mounted on the above-mentioned high-frequency phasor needs to have a large dielectric anisotropy with respect to electromagnetic waves in the microwave band in order to control the phase of electromagnetic waves. And, in order to control the driving of such a liquid crystal with high precision, a thin film (hereinafter also referred to as a driving control film) is formed between the glass substrate and the liquid crystal.

In the drive control film, in addition to being able to maintain the voltage applied during driving with high precision, when the high frequency phasor is applied to a planar antenna, it is capable of withstanding continuous driving in harsh external environments such as outdoor use. A high degree of durability is required. However, it is generally known that liquid crystals having a large dielectric anisotropy have poor retention of applied voltage and poor durability.

An object of the present invention is to provide a functional resin composition capable of maintaining a voltage applied during liquid crystal driving with high precision and obtaining a highly durable driving control film, and a high frequency phaser equipped with a driving control film obtained from the composition. will be.

The present inventors have come to complete the present invention as a result of repeating earnest research in order to solve the above problems.

The gist of the present invention is as described in <1> below.

<1> A functional resin composition for use in a liquid crystal drive control film of a microwave abnormal modulation element using a liquid crystal, containing at least one polymer selected from polyamic acid derivatives and polyimides as imidates thereof.

According to the functional resin composition of the present invention, driving of a liquid crystal mounted on a high frequency phaser can be controlled with high precision, and a highly durable driving control film can be obtained.

As described above, the functional resin composition according to the present invention is used for a liquid crystal drive control film of a microwave anomalous modulation element using liquid crystals, and contains at least one polymer selected from polyamic acid derivatives and polyimides as imidates thereof. it will be done

Here, "microwave anomalous modulation element using a liquid crystal" means an element capable of controlling the dielectric constant by an alignment change accompanying the application of a voltage to the liquid crystal, and arbitrarily controlling the amplitude and phase of a high-frequency signal such as a microwave or millimeter wave. .

In addition, the "liquid crystal drive control film" refers to a film having voltage holding characteristics such that driving of a liquid crystal can be controlled with high precision.

According to a preferred embodiment of the present invention, the functional resin composition of the present invention has a voltage retention (initial value) of 90% or more obtained by measuring according to the following voltage retention measurement test, and a voltage retention (value after durability test) of 80 will be more than 1%.

[Measurement test of voltage holding ratio]

A liquid crystal drive control film is formed by spin-coating and firing the functional resin composition of the subject on a glass substrate, and a liquid crystal cell is produced using the liquid crystal drive control film,

A voltage of 5 V is applied to the liquid crystal cell at a temperature of 70 ° C. for 60 μs, and the voltage after 16.67 ms is measured to obtain a voltage retention rate (initial value) of how much the voltage is maintained,

Next, after leaving the liquid crystal cell at a temperature of 100°C for 200 hours, it was returned to room temperature, and a voltage of 5 V was applied for 60 μs to the liquid crystal cell under a temperature of 70°C, similarly to the case of the initial value, and after 16.67 ms The voltage is measured to obtain the voltage holding ratio (value after durability test).

Regarding the measurement test of voltage retention, more specifically, it can be carried out according to the method described in the Example mentioned later.

In addition, the voltage holding ratio can be measured and calculated according to a conventional device/method. As a conventional device, a voltage holding ratio measurement system (VHR-AMP01, manufactured by Toyo Technica Co., Ltd.) is exemplified. In addition, as a conventional method, reference can be made to, for example, "Voltage Holding Characteristics of TFT-LCD I", Preliminary Collection of Lectures at the 14th Liquid Crystal Debate, No.2B110, pp.78-79 (1998) as literature. there is.

Hereinafter, each configuration requirement is described in detail.

<Polymer>

The polymer contained in the functional resin composition of the present invention is at least one selected from polyamic acid derivatives and polyimides which are imidates thereof, and has good voltage retention characteristics such as being able to control driving of liquid crystals with high precision. However, it is not particularly limited as long as it has high durability.

Therefore, as a polymer that can be used in the present invention, for example, a polyamic acid derivative obtained by polymerizing a diamine component and at least one kind of tetracarboxylic acid derivative component selected from tetracarboxylic acid and its derivatives, and this polyamic acid derivative. and polyimides obtained by imidizing a mix acid derivative.

Further, the form of the polymer may be, for example, a form such as a branched polymer such as a dendrimer, a hyperbranched polymer, or a star-like polymer, or a non-covalent polymer such as polycatenan or polyrotaxane. In addition, as a monomer for synthesizing these polymers, when the polymer is a polyamic acid derivative or a polyimide, at least one kind of tetracarboxylic acid component selected from tetracarboxylic acid and its derivatives and a diamine component can be cited. . Of course, the polymer or the monomer for synthesizing these polymers may be one type or may use two or more types together.

In addition, a polyamic acid derivative refers to a polyamic acid and polyamic acid ester.

Among these, at least one polymer selected from a polyamic acid derivative (hereinafter also referred to as a specific polymer) and a polyimide obtained by imidizing this polyamic acid derivative from the viewpoint of practicality as a functional resin composition and mechanical and electrical properties of a coating film desirable.

According to a preferred embodiment of the present invention, the polymer preferably used in the functional resin composition of the present invention has a voltage retention (initial value) of 90% or more obtained by measuring the functional resin composition according to the following voltage retention measurement test , and the voltage holding ratio (value after durability test) is selected so that it becomes 80% or more.

The polymer contained in the functional resin composition of the present invention can be produced according to a conventional method that is usually practiced. For example, a polyamic acid derivative and a polyimide are obtained by carrying out polymerization reaction of at least 1 sort(s) of tetracarboxylic acid derivative component chosen from tetracarboxylic acid and its derivative(s), and a diamine component.

<specific polymer>

The polyamic acid derivative which is a specific polymer contained in the functional resin composition of the present invention can be represented by the following formula (1).

[Formula 1]

In the formula, X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ₁ is a divalent organic group derived from diamine, and R ₁ represents a hydrogen atom or an alkylene having 1 to 5 carbon atoms. . From the viewpoint of the ease of advancing of the imidation reaction during heating, R ₁ is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.

In the formula, A ₁ and A ₂ each independently represent a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 2 to 5 carbon atoms, or an alkynyl group of 2 to 5 carbon atoms. Among them, A ₁ and A ₂ are preferably a hydrogen atom or a methyl group.

Hereinafter, each component used as the raw material constituting the polymer in the present invention is described in detail.

<<diamine>>

The diamine used for polymerization of the polymer having the structure of the formula (1) is represented by the following formula (2).

[Formula 2]

In the formula (2), A ₁ and A ₂ have the same definitions as A ₁ and A ₂ in the formula (1), including preferred examples.

Moreover, if the structure of _Y1 in Formula (2) is illustrated, it is as follows.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

In formula, n is an integer of 1-6, and m is an integer of 1-12.

[Formula 12]

In the above formula, Boc represents a tert-butoxycarbonyl group.

[Formula 13]

[Formula 14]

Examples of structures capable of exhibiting the effects of the present invention include formulas (Y-7) to (Y-9), (Y-14), and (Y-14) among the exemplary formulas of the structure of Y ₁ described above. 16) ~ Formula (Y-18), Formula (Y-20), Formula (Y-21), Formula (Y-27), Formula (Y-28), Formula (Y-32), Formula (Y-43) ), Formula (Y-56), Formula (Y-62), Formula (Y-63), Formula (Y-67), Formula (Y-68), Formula (Y-72) ~ Formula (Y-75) , formula (Y-149) to formula (Y-153), formula (Y-164) to formula (Y-167), formula (Y-169), formula (Y-174), formula (Y-176), Formula (Y-182) and Formula (Y-185) are mentioned.

Among them, formula (Y-8), formula (Y-16) to formula (Y-18), formula (Y-20), formula (Y-28), formula (Y-63), formula (Y-68 ), Formula (Y-72), Formula (Y-75), Formula (Y-149), Formula (Y-153), Formula (Y-164), Formula (Y-165), Formula (Y-167) , Formula (Y-174) is more preferable.

10 mol% - 100 mol% of all the diamine components are preferable, and, as for the diamine containing the preferable structure illustrated above, 30 mol% - 100 mol% are more preferable.

Moreover, since there exists a possibility of reducing a voltage holding ratio when an aromatic carboxylic acid structure is contained excessively, 50% or less of diamine which has an aromatic carboxylic acid structure is preferable, and 30% or less is more preferable.

<<tetracarboxylic acid derivative component>>

As the tetracarboxylic acid derivative component for preparing the polymer having the structural unit of formula (1) contained in the functional resin composition of the present invention, not only tetracarboxylic dianhydride but also the tetracarboxylic acid derivative A tetracarboxylic acid, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or a tetracarboxylic acid dialkyl ester dihalide compound can also be used.

In the present invention, the above-described "at least one polymer selected from polyamic acid derivatives and polyimides that are imidates thereof" is a tetracarboxylic acid derivative component containing tetracarboxylic dianhydride and a diamine component It is preferably a reactant. More preferably, tetracarboxylic dianhydride or a derivative thereof has an alicyclic structure.

As tetracarboxylic dianhydride or its derivative, it is more preferable to use at least 1 selected from tetracarboxylic dianhydride represented by following formula (3) or its derivative(s).

[Formula 15]

In Formula (3), X ₁ is a tetravalent organic group, and the structure is not particularly limited. X ₁ preferably has an alicyclic structure.

Specific preferable examples of X ₁ include the following formulas (X-1) to (X-25). These are things which have an alicyclic structure in tetracarboxylic dianhydride or its derivative(s) represented by Formula (3), and are aliphatic acid anhydrides. In addition, aliphatic acid dianhydride refers to acid dianhydride in which the carboxylic acid involved in the imidization reaction is an aliphatic carboxylic acid.

[Formula 16]

[In formulas (X-1) to (X-4), R ₃ to R ₂₃ are each independently a hydrogen atom, a halogen atom, an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, and a carbon atom of 2 to 6 carbon atoms. an alkynyl group, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, which may be the same or different. Among them, R ₃ to R ₂₃ are preferably a hydrogen atom, a halogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.]

[Formula 17]

Moreover, as a specific structure of said formula (X-1), the structure represented by the following formula (X1-1) - (X1-6) is mentioned.

[Formula 18]

According to a preferred aspect of the present invention, in formula (3), as X ₁ , formula (X-1) to formula (X-9), formula (X-11), formula (X-12), and formula ( The structure represented by X-21) is mentioned. Specific examples of more preferable X ₁ include the following formulas (X-1) to (X-9) and (X-21).

According to a more preferred aspect of the present invention, from the viewpoint of durability of voltage retention, formula (X1-1), formula (X1-2), formula (X-5), formula (X-7), formula (X-8 ), formula (X-9), formula (X-11), formula (X-12), and formula (X-21) are particularly preferred.

Moreover, as a specific example of the acid anhydride combined with formula (3), following formula (4) is mentioned. Preferred specific examples of X _a include (Xa-1) to (Xa-20). These are things which have an aromatic ring structure in tetracarboxylic dianhydride or its derivative(s) represented by Formula (3), and are aromatic anhydrides.

[Formula 19]

[Formula 20]

In formula, m represents the integer of 1-12.

According to one preferred aspect of the present invention, the tetracarboxylic acid derivative component for producing a polymer having a structural unit of the above formula (1) contained in the functional resin composition of the present invention is tetracarboxylic acid derivative having an alicyclic structure. It is preferable to contain carboxylic dianhydride. As the tetracarboxylic acid derivative component, an aromatic anhydride having an aromatic ring structure can also be used, but even in this case, it is preferable to use in combination with tetracarboxylic dianhydride having an alicyclic structure.

These points are demonstrated by taking tetracarboxylic dianhydride or its derivative(s) represented by said Formula (3) as an example. Here, as the aliphatic acid dianhydride having an alicyclic structure, in tetracarboxylic dianhydride or a derivative thereof represented by the above formula (3), X ₁ is represented by the formulas (X-1) to (X-25) can be heard that Moreover, as an aromatic anhydride which has an aromatic ring structure, in tetracarboxylic dianhydride or its derivative(s) represented by said formula (4), what Xa is formula (Xa-1) - (Xa-20) is mentioned. there is.

According to a preferred aspect of the present invention, in formula (3), X ₁ is selected from formulas (X-1) to (X-25), is used as tetracarboxylic dianhydride or a derivative thereof, and According to this, in formula (4), Xa can be used by further combining those selected from formulas (Xa-1) to (Xa-20).

Tetracarboxylic dianhydride and its derivatives, which are raw materials for the polyamic acid derivative and polyimide described in the present invention, have tetracarboxylic dianhydride represented by the above formula (3) relative to 1 mole of all tetracarboxylic dianhydride and derivatives thereof. It is preferable to contain 10-100 mol% of acid dianhydride and its derivative(s). Since durability of high voltage retention is obtained, 30 mol% - 100 mol% are more preferable, and 50 mol% - 100 mol% are still more preferable.

<Method for producing polyamic acid>

The polyamic acid, which is a polyamic acid derivative used in the present invention, can be synthesized by the method shown below.

Specifically, tetracarboxylic dianhydride and diamine are reacted in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably 1 to 12 hours It can be synthesized by

The organic solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the viewpoint of solubility of monomers and polymers, and one or two of these are preferred. You may mix and use the above. The concentration of the polymer is preferably from 1 to 30% by mass, and more preferably from 5 to 20% by mass, from the viewpoint that precipitation of the polymer does not occur easily and a high molecular weight body is easily obtained.

The polyamic acid obtained in the above manner can precipitate and recover a polymer by injecting the reaction solution into a poor solvent while stirring it well. Moreover, the powder of the polyamic acid refine|purified can be obtained by performing precipitation several times, washing|cleaning with a poor solvent, and drying at normal temperature or heat. Although a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, a butyl cellosolve, acetone, toluene, etc. are mentioned.

<Method for producing polyamic acid ester>

Polyamic acid ester, which is one of the polyamic acid derivatives used in the present invention, can be synthesized by the method of (PAE-1), (PAE-2) or (PAE-3) shown below.

(PAE-1) Synthesis from polyamic acid

Polyamic acid ester is compoundable by esterifying the polyamic acid obtained from tetracarboxylic dianhydride and diamine.

Specifically, by reacting a polyamic acid and an esterifying agent in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably 1 to 4 hours can be synthesized.

The esterifying agent is preferably one that can be easily removed by purification, and N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamidedineopentylbutylacetal, N,N-dimethylformamidedi-t-butylacetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene , 1-propyl-3-p-tolyltriazene, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, and the like. The addition amount of the esterifying agent is preferably 2 to 6 molar equivalents with respect to 1 mol of the repeating unit of the polyamic acid.

The solvent used for the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the viewpoint of polymer solubility, and these are used singly or as a mixture of two or more. You may use it. The concentration at the time of synthesis is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint that precipitation of the polymer is less likely to occur and a high molecular weight body is easily obtained.

(PAE-2) When synthesized by reaction of tetracarboxylic diester dichloride and diamine

Polyamic acid ester is compoundable from tetracarboxylic acid diester dichloride and diamine.

Specifically, tetracarboxylic acid diester dichloride and diamine are mixed in the presence of a base and an organic solvent at -20°C to 150°C, preferably 0°C to 50°C, for 30 minutes to 24 hours, preferably 1 to 150°C. It can be synthesized by reacting for 4 hours.

Although pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used for the base, pyridine is preferred because the reaction proceeds mildly. The addition amount of the base is an amount that is easy to remove and is preferably 2 to 4 times mole with respect to the tetracarboxylic acid diester dichloride from the viewpoint of obtaining a high molecular weight body.

As for the solvent used for said reaction, N-methyl-2-pyrrolidone or (gamma)-butyrolactone is preferable from the solubility of a monomer and a polymer, and you may use these 1 type or in mixture of 2 or more types. The polymer concentration at the time of synthesis is preferably from 1 to 30% by mass, and more preferably from 5 to 20% by mass, from the viewpoint that precipitation of the polymer does not occur easily and a high molecular weight body is easily obtained. In addition, in order to prevent hydrolysis of tetracarboxylic acid diester dichloride, it is preferable that the solvent used for the synthesis of polyamic acid ester is dehydrated as much as possible, and it is preferable to prevent mixing of outside air in a nitrogen atmosphere.

(PAE-3) Synthesis of polyamic acid ester from tetracarboxylic acid diester and diamine

Polyamic acid ester is compoundable by polycondensation of tetracarboxylic-acid diester and diamine.

Specifically, tetracarboxylic diester and diamine are mixed in the presence of a condensing agent, a base, and an organic solvent at 0°C to 150°C, preferably 0°C to 100°C, for 30 minutes to 24 hours, preferably 3 It can be synthesized by reacting for about 15 hours.

The condensing agent includes triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N,N'-carbonyldiimidazole, dimethoxy-1 ,3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, O-(benzotriazole- 1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphite, (2,3-dihydro-2-thioxo-3-benzooxazolyl)phosphonic acid diphenyl, etc. can be used As for the addition amount of a condensing agent, 2-3 times mole is preferable with respect to the tetracarboxylic diester.

Tertiary amines such as pyridine and triethylamine can be used for the base. The addition amount of the base is a quantity that is easy to remove and is preferably 2 to 4 times mole with respect to the diamine component from the viewpoint of being easy to obtain a high molecular weight body.

In the above reaction, the reaction proceeds efficiently by adding a Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably 0 to 1.0 times mole with respect to the diamine component.

Since high molecular weight polyamic acid ester is obtained among the said 3 synthetic methods of polyamic acid ester, the said (PAE-2) or said (PAE-3) synthetic method is especially preferable.

A polymer can be deposited by inject|pouring into a poor solvent, stirring well the solution of the polyamic acid ester obtained by performing it above. After performing precipitation several times, washing|cleaning with a poor solvent, it is made to dry at normal temperature or heat, and can obtain the powder of the polyamic acid ester refine|purified. Although a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, a butyl cellosolve, acetone, toluene, etc. are mentioned.

<Method for producing polyimide>

The polyimide used for this invention can be manufactured by imidating the said polyamic acid ester or polyamic acid. When manufacturing a polyimide from polyamic acid ester, chemical imidation which adds a basic catalyst to the said polyamic acid ester solution or the polyamic acid ester solution obtained by dissolving polyamic acid ester resin powder in an organic solvent is simple. Chemical imidation is preferable because the imidation reaction proceeds at a relatively low temperature and the molecular weight of the polymer does not decrease easily in the process of imidation.

Chemical imidation can be performed by stirring the polyamic acid ester to be imidated in basic catalyst presence in an organic solvent. As the organic solvent, the solvent used in the polymerization reaction described above can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, triethylamine is preferable because it has sufficient basicity to advance the reaction.

The temperature at the time of imidation is -20°C to 140°C, preferably 0°C to 100°C, and the reaction time can be 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 mole times the amic acid ester group, preferably 2 to 20 mole times. The imidation rate of the resulting polymer can be controlled by adjusting the catalyst amount, temperature, and reaction time. Since the added catalyst and the like remain in the solution after the imidation reaction, it is preferable to collect the obtained imidized polymer by the means described below and redissolve it in an organic solvent to obtain the functional resin composition of the present invention. do.

In the case of producing polyimide from polyamic acid, chemical imidation by adding a catalyst to a solution of the polyamic acid obtained by the reaction of the diamine component and tetracarboxylic dianhydride is simple. Chemical imidation is preferable because the imidation reaction proceeds at a relatively low temperature and the molecular weight of the polymer does not decrease easily in the process of imidation.

Chemical imidation can be performed by stirring the polymer to be imidated in the presence of a basic catalyst and an acid anhydride in an organic solvent. As the organic solvent, the solvent used in the polymerization reaction described above can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has a basicity suitable for advancing the reaction. Moreover, acetic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. are mentioned as an acid anhydride, Since the refinement|purification after completion|finish of reaction becomes easy when acetic anhydride is used especially, it is preferable.

The temperature at the time of imidation is -20°C to 140°C, preferably 0°C to 100°C, and the reaction time can be 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 mole times, preferably 2 to 20 mole times, the amount of the amic acid group, and the amount of the acid anhydride is 1 to 50 mole times, preferably 3 to 30 mole times the amic acid group. The imidation rate of the resulting polymer can be controlled by adjusting the catalyst amount, temperature, and reaction time.

Since the added catalyst and the like remain in the solution after the imidation reaction of the polyamic acid ester or the polyamic acid, the obtained imidized polymer is recovered by the means described below and redissolved in an organic solvent to obtain the solution of the present invention. It is preferable to set it as a functional resin composition.

A polymer can be deposited by inject|pouring into a poor solvent, stirring well the solution of the polyimide obtained by performing it above. After performing precipitation several times, washing|cleaning with a poor solvent, it is made to dry at normal temperature or heat, and can obtain the powder of the polyamic acid ester refine|purified.

Although the said poor solvent is not specifically limited, Methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, etc. are mentioned.

<Functional resin composition>

The functional resin composition according to the present invention has a form of a solution in which a polymer having a specific structure is dissolved in an organic solvent.

The molecular weight of the polyamic acid derivative and polyimide used in the functional resin composition of the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, still more preferably 10,000 to 100,000 in terms of weight average molecular weight. Further, the number average molecular weight is preferably from 1,000 to 250,000, more preferably from 2,500 to 150,000, still more preferably from 5,000 to 50,000.

The concentration of the polymer in the functional resin composition according to the present invention can be appropriately changed according to the setting of the thickness of the coating film to be formed, but it is preferably 1% by weight or more in terms of forming a uniform and defect-free coating film, From the point of storage stability of a solution, it is preferable to set it as 10 weight% or less.

<<Solvent>>

The solvent used for the functional resin composition of the present invention is not particularly limited as long as it is a solvent that dissolves the polymer described in the present invention (also referred to as a good solvent). Below, although the specific example of a good solvent is given, it is not limited to these examples.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylpropanamide or 4-hydroxy-4-methyl-2-pentanone, etc. can be heard Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 1,3-dimethyl-2- Preference is given to using imidazolidinone.

Moreover, when the solubility to the solvent of the polyamic acid derivative and polyimide described in this invention is high, it is preferable to use the solvent represented by the following formula [D-1] - formula [D-3].

[Formula 21]

(In formula [D-1], D ¹ represents an alkyl group of 1 to 4 carbon atoms, in formula [D-2], D ² represents an alkyl group of 1 to 4 carbon atoms, in formula [D-3], D ³ represents an alkyl group having 1 to 4 carbon atoms).

It is preferable that it is 20-99 mass % of the whole solvent, as for the good solvent in the functional resin composition of this invention, 20-90 mass % is more preferable, and its 30-80 mass % is especially preferable.

The functional resin composition can contain a solvent (also referred to as a poor solvent) that improves the coating properties and surface smoothness of the functional resin composition when the functional resin composition is applied, as long as the effect of the present invention is not impaired. As for these poor solvents, 1-80 mass % of the whole solvent contained in a functional resin composition is preferable. Especially, 10-80 mass % is preferable. More preferably, it is 20-70 mass %.

Below, although the specific example of a poor solvent is given, it is not limited to these examples. For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methyl Cyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl Ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl Acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2-(methoxymethoxy)ethanol, butyl cellosolve, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyl) Siloxy)ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, 1-butoxy-2-propanol, 1-(butoxyethoxy)propanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene Glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, butyl cellosolve acetate, ethylene Glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate diacetone alcohol, propylene glycol diacetate, diisopentyl ether, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol mono Methyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3-E Methylethyl oxypropionate, 3-methoxyethylpropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropylpropionate, 3-methoxybutylpropionate, methyl lactate, ethyl lactate, n-propyl lactate Ester, lactic acid n-butyl ester, lactic acid isoamyl ester, diisobutyl ketone, ethyl carbitol, or the solvent represented by the said formula [D-1] - formula [D-3], etc. are mentioned.

Among them, dipropylene glycol monomethyl ether, diacetone alcohol, diisopentyl ether, propylene glycol diacetate, 1-butoxy-2-propanol, diethylene glycol diethyl ether, butyl cellosolve, butyl cellosolve acetate , diisobutyl ketone, ethyl carbitol or dipropylene glycol dimethyl ether is preferably used.

<<Optional ingredients>>

In the functional resin composition of the present invention, a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a crosslinking compound having at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group It may contain a sexual compound or a crosslinkable compound having a polymerizable unsaturated bond. It is necessary to have two or more of these substituents and polymerizable unsaturated bonds in a crosslinkable compound.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolak epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, and tetraglycidylaminodiphenylene. , tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroaceto Diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis( 2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidylmethaxylenediamine, 2-(4-(2,3-epoxypropoxy)phenyl)-2- (4-(1,1-bis(4-(2,3-epoxypropoxy)phenyl)ethyl)phenyl)propane or 1,3-bis(4-(1-(4-(2,3-epoxypro) Poxy)phenyl)-1-(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol; and the like.

A crosslinkable compound having an oxetane group is a compound having at least two oxetane groups represented by the following formula [4A].

[Formula 22]

Specifically, the crosslinkable compound represented by formula [4a] - formula [4k] published on pages 58-59 of international publication WO2011/132751 (published on October 27, 2011) is mentioned.

The crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5A].

[Formula 23]

Specifically, crosslinkable compounds represented by formula [5-1] to formula [5-42] published on pages 76 to 82 of International Publication No. WO2012/014898 (published on February 2, 2012) are exemplified.

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include amino resins having a hydroxyl group or an alkoxyl group, such as melamine resins, urea resins, and guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, or ethyleneurea-formaldehyde resin. Specifically, a melamine derivative, a benzoguanamine derivative, or a glycoluril in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group or both thereof can be used. This melamine derivative or benzoguanamine derivative can also exist as a dimer or a trimer. It is preferable that these have an average of 3 or more and 6 or less methylol groups or alkoxymethyl groups per triazine ring.

Examples of the above melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 methoxymethyl groups substituted per triazine ring of a commercial product, and 5.8 methoxymethyl groups substituted per triazine ring on average. MW-30 (above, manufactured by Sanwa Chemical Co., Ltd.), methoxymethylated melamine such as Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 236, 238, 212 , methoxymethylated butoxymethylated melamine such as 253 and 254, butoxymethylated melamine such as Cymel 506 and 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, and methoxymethylated such as Cymel 1123. Toxymethylated benzoguanamines, methoxymethylated butoxymethylated benzoguanamines such as Cymel 1123-10, butoxymethylated benzoguanamines such as Cymel 1128, methoxymethylated ethoxymethylated carboxyl groups such as Cymel 1125-80 Benzoguanamine (above, Mitsui Cyanamide Co., Ltd. make) is mentioned. Moreover, as an example of a glycoluril, butoxymethylation glycoluril like Cymel 1170, methylolation glycoluril like Cymel 1172, etc., a methoxymethylolation glycoluril like Powder Link 1174, etc. are mentioned.

Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris(methoxymethyl)benzene, 1,2,4-tris(isopropoxymethyl)benzene, 1 ,4-bis(sec-butoxymethyl)benzene or 2,6-dihydroxymethyl-p-tert-butylphenol.

More specifically, the crosslinkable compound of formula [6-1] - formula [6-48] published on pages 62-66 of international publication WO2011/132751 (published on October 27, 2011) is mentioned. .

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and tri(meth)acrylate. ) A crosslinkable compound having three polymerizable unsaturated groups in the molecule, such as acryloyloxyethoxytrimethylolpropane or glycerin polyglycidyl ether poly(meth)acrylate, furthermore, ethylene glycol di(meth)acrylate, di Ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol Di(meth)acrylate, neopentylglycoldi(meth)acrylate, ethylene oxide bisphenol A type di(meth)acrylate, propylene oxide bisphenol type di(meth)acrylate, 1,6-hexanedioldi(meth) Acrylates, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, A crosslinkable compound having two polymerizable unsaturated groups in the molecule, such as phthalic acid diglycidyl ester di(meth)acrylate or hydroxypivalic acid neopentylglycol di(meth)acrylate; ) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy Cy-2-hydroxypropylphthalate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerin mono(meth)acrylate, 2-(meth)acryloyloxyethyl phosphate or N-methylol ( and crosslinkable compounds having one polymerizable unsaturated group in the molecule, such as meth)acrylamide.

Moreover, the compound represented by following formula [7A] can also be used.

[Formula 24]

(In formula [7A], E ₁ is a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, or a phenanthrene ring. and E ₂ represents a group selected from the following formula [7a] or formula [7b], and n represents an integer of 1 to 4).

[Formula 25]

The above is an example of a crosslinkable compound, and is not limited thereto. In addition, one type of crosslinkable compound used for the functional resin composition of the present invention may be used, or two or more types may be combined.

The content of the crosslinkable compound in the functional resin composition of the present invention is preferably from 0.1 to 150 parts by mass with respect to 100 parts by mass of all polymer components. Among them, 0.1 to 100 parts by mass is preferable with respect to 100 parts by mass of all the polymer components in order to promote the crosslinking reaction and express the target effect. More preferably, it is 1-50 mass parts.

In the functional resin composition of the present invention, a compound that improves the film thickness uniformity and surface smoothness of the drive control film when the functional resin composition is applied can be used as long as the effects of the present invention are not impaired.

Examples of compounds that improve the uniformity of film thickness and surface smoothness of the drive control film include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

More specifically, for example, F Top EF301, EF303, EF352 (above, manufactured by Tochem Products), Megafac F171, F173, R-30 (above, manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (above, manufactured by Dainippon Ink Co., Ltd.) As mentioned above, Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Suplon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, Asahi Glass Co., Ltd. make), etc. are mentioned.

The amount of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of all the polymer components contained in the functional resin composition.

Further, in the functional resin composition of the present invention, as a compound that promotes charge transfer in a drive control film and promotes charge leakage of an element, International Publication WO2011/132751 (published on October 27, 2011) on pages 69 to 73 Nitrogen-containing heterocyclic amine compounds represented by formula [M1] to formula [M156] may be added. This amine compound may be directly added to the functional resin composition, but it is preferably added after preparing a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. This solvent is not particularly limited as long as it dissolves the functional resin composition.

In addition, in the functional resin composition of the present invention, in addition to the poor solvent, the crosslinkable compound, the compound that improves the uniformity of the film thickness and the surface smoothness of the resin film or the drive control film, as long as the effect of the present invention is not impaired, A polymer other than the polymer described in the present invention, a silane coupling agent for the purpose of improving the adhesion between the driving control film and the substrate, and an imidation accelerator for the purpose of efficiently advancing the imidation by heating of the polyamic acid derivative during firing of the coating film etc. may be added.

<Drive control film and abnormal modulation element>

The driving control film according to the present invention can be obtained by applying the functional resin composition according to the present invention to a substrate, drying, and firing.

When the drive control film is used for a phase modulating element of a scanning type planar antenna, it is preferable that the substrate used has a small dielectric loss with respect to microwaves.

Specifically, a glass substrate or a plastic substrate can be used. The electrode formed on the substrate functions as a wall of the waveguide when the electrode substrate of the liquid crystal phase modulator serves as a waveguide, for example. Therefore, the electrode needs to suppress transmission of microwaves, and is composed of a relatively thick metal layer. As such a metal layer, a Cu layer, an Al layer, etc. are mentioned. When reducing the 10 GHz microwave to 1/150, the thickness of the Cu layer is set to 3.3 μm or more, and the thickness of the Al layer is set to 4.0 μm or more. Although there is no particular restriction on the upper limit of the thickness of the metal layer constituting the electrode, considering the formation of an alignment film, the thinner the better, and the use of the Cu layer as the metal layer has the advantage that it can be made thinner than the Al layer have On the other hand, when the waveguide of the scan type planar antenna is composed of air and glass, the glass is preferably thin from the viewpoint of reducing the waveguide loss. 400 μm or less is preferable, and 300 μm or less is more preferable.

A scanning type planar antenna having a liquid crystal phase modulator changes the phase of microwaves radiated from each electrode by changing the capacitance of the liquid crystal. Therefore, as the liquid crystal to be used, those having a high anisotropy of dielectric constant with respect to microwaves are preferred, and those having a small dielectric loss tangent with respect to microwaves are preferred.

The method of applying the functional resin composition is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing or inkjet method are common. Other coating methods include a dip method, a slit coater method, a spinner method, or a spray method, and these may be used depending on the purpose.

After the functional resin composition is applied on the substrate, the solvent is evaporated by a heating means such as a hot plate, heat circulation type oven or IR (infrared ray) type oven to form a driving control film. For the drying and baking steps after applying the functional resin composition of the present invention, any temperature and time can be selected. Usually, in order to fully remove the contained solvent, the conditions of baking at 50-120 degreeC for 1 to 10 minutes, and then baking at 150-300 degreeC for 5-120 minutes are mentioned. The thickness of the drive control film after firing is preferably 5 to 300 nm, and more preferably 10 to 200 nm, because too thin a reliability of the biphasic modulation element may decrease.

The functional resin composition of the present invention can be used as a driving control film after coating and firing on a substrate, followed by alignment treatment such as rubbing treatment or photo-alignment treatment.

As an example of a method for manufacturing a liquid crystal cell, a liquid crystal drive element having a passive matrix structure will be described as an example. Further, it may be an active matrix structure biphasic modulation element in which a switching element such as a TFT (Thin Film Transistor) is formed in each pixel portion.

Specifically, a transparent glass substrate is prepared, and a common electrode is formed on one substrate and a segment electrode is formed on the other substrate. These electrodes can be, for example, ITO electrodes, and are patterned so that a desired liquid crystal drive can be performed.

Next, a drive control film is formed on each substrate, and one substrate is superimposed on the other substrate so that the drive control film surfaces face each other, and the periphery is bonded with a sealant. In order to control the gap between the substrates, the sealant is usually mixed with a spacer, and it is preferable to spread the spacer for controlling the gap between the substrates also in the in-plane portion where the sealant is not formed. An opening portion capable of being filled with liquid crystal from the outside is formed in a part of the sealant. Next, the liquid crystal material is injected into the space surrounded by the two substrates and the sealant through an opening formed in the sealant, and then the opening is sealed with an adhesive. For injection, a vacuum injection method may be used, or a method using capillarity in the air may be used. As the liquid crystal material, either a positive liquid crystal material or a negative liquid crystal material may be used.

As described above, by using the functional resin composition of the present invention, a drive control film with high durability can be obtained.

Therefore, according to another aspect of the present invention, a driving control film obtained from the functional resin composition of the present invention is provided.

Further, according to another aspect of the present invention, an anomalous modulation element including a driving control film, preferably a microwave anomalous modulation element, is provided.

In addition, here, "anomalous modulation element" means an element capable of arbitrarily controlling the amplitude and phase of a frequency signal by an external stimulus. In addition, "microwave anomalous modulation element" means an anomalous modulation element corresponding to a high frequency, such as a microwave, among others.

Example

Although the present invention will be specifically described below with reference to examples, it goes without saying that the present invention is limited to these examples and should not be construed.

The abbreviation used in the Example is as follows.

(tetracarboxylic acid derivative)

[Formula 26]

(diamine and condensing agent)

[Formula 27]

(organic solvent)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

[Measurement of polymer molecular weight]

The molecular weight of the polymer in the Synthesis Example was measured as follows using a normal temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd. and a column (KD-803, KD-805) manufactured by Shodex.

Column temperature: 50 ℃

Eluent: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr H2O) is 30 mmol/L, phosphoric acid/anhydrous crystal (o-phosphoric acid) is 30 mmol/L, tetrahydrofuran ( THF) is 10 ml / ℓ)

Flow rate: 1.0 ml/min

Standard samples for calibration curve preparation: TSK standard polyethylene oxide (molecular weights: about 9000,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weights: about 12,000, 4,000, 1,000) manufactured by Polymer Laboratory.

[Polymer viscosity measurement]

In Examples and Comparative Examples, the viscosity of the polyamic acid or polyamic acid ester solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample amount of 1.1 ml and a cone rotor TE-1 (1 ° 34 ' , R24), measured at a temperature of 25°C.

<Example 1>

2.10 g (1.40 mmol) of diamine (Z-1) was taken in a 100 ml four-necked flask equipped with a stirrer, 28.1 g of N-methyl-2-pyrrolidone was added, and it was stirred and dissolved while blowing nitrogen. . While stirring this solution, 2.69 g (1.37 mmol) of tetracarboxylic dianhydride (T-1) was added, 7.03 g of N-methyl-2-pyrrolidone was added, and under a nitrogen atmosphere, 23 It stirred at °C for 15 hours to obtain a polyamic acid solution. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 104 mPa*s.

15.0 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer, 16.5 g of N-methyl-2-pyrrolidone and 13.5 g of butyl cellosolve were added, and stirred with a magnetic stirrer for 2 hours to obtain a polyamic acid solution. A mix acid solution was obtained.

<Example 2>

4.09 g (3.00 mmol) of diamine (Z-12) was taken in a 100 ml four-necked flask equipped with a stirrer, 31.2 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred and dissolved while blowing nitrogen. While stirring this solution, 5.77 g (2.94 mmol) of tetracarboxylic dianhydride (T-1) was added, 7.79 g of N-methyl-2-pyrrolidone was further added, and under a nitrogen atmosphere, 23 It stirred at °C for 15 hours to obtain a polyamic acid solution. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 653 mPa*s.

15.0 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer, 37.5 g of N-methyl-2-pyrrolidone and 22.5 g of butyl cellosolve were added, and stirred with a magnetic stirrer for 2 hours to obtain polyamic acid. A mix acid solution was obtained.

<Example 3>

4.13 g (2.75 mmol) of diamine (Z-1) and 5.45 g (2.75 mmol) of diamine (Z-2) were placed in a 200 ml four-necked flask containing a stirrer, and N-methyl-2-pyrrolidone was added. 64.2 g was added and dissolved by stirring while blowing nitrogen. While stirring this solution, 10.46 g (5.34 mmol) of tetracarboxylic dianhydride (T-1) was added, 16.0 g of N-methyl-2-pyrrolidone was added, and under nitrogen atmosphere, 23 It stirred at °C for 15 hours to obtain a polyamic acid solution. The viscosity at the temperature of 25 degreeC of this polyamic-acid solution was 799 mPa*s.

15.0 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer, 37.5 g of N-methyl-2-pyrrolidone and 22.5 g of butyl cellosolve were added, and stirred with a magnetic stirrer for 2 hours to obtain polyamic acid. A mix acid solution was obtained.

<Example 4>

8.26 g (5.50 mmol) of diamine (Z-1) was taken in a 200 ml four-necked flask equipped with a stirrer, 113.2 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred and dissolved while blowing nitrogen. While stirring this solution, 5.39 g (2.75 mmol) of tetracarboxylic dianhydride (T-1) was added, 28.3 g of N-methyl-2-pyrrolidone was added, and under nitrogen atmosphere, 23 It was stirred at °C for 2 hours. Then, 5.64g (2.59 mmol) of tetracarboxylic dianhydride (T-2) was added, and it stirred by nitrogen atmosphere at 23 degreeC for 15 hours, and obtained the polyamic-acid solution. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 143 mPa*s.

15.0 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer, 16.5 g of N-methyl-2-pyrrolidone and 13.5 g of butyl cellosolve were added, and stirred with a magnetic stirrer for 2 hours to obtain a polyamic acid solution. A mix acid solution was obtained.

<Example 5>

8.26 g (5.50 mmol) of diamine (Z-1) was taken in a 200 ml four-necked flask equipped with a stirrer, 111.8 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred and dissolved while blowing nitrogen. While stirring this solution, 7.55 g (3.85 mmol) of tetracarboxylic dianhydride (T-1) was added, 27.9 g of N-methyl-2-pyrrolidone was further added, and under a nitrogen atmosphere, 23 It was stirred at °C for 2 hours. Then, 3.24g (1.49 mmol) of tetracarboxylic dianhydride (T-2) was added, and it stirred by nitrogen atmosphere at 23 degreeC for 15 hours, and obtained the polyamic-acid solution. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 168 mPa*s.

15.0 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer, 16.5 g of N-methyl-2-pyrrolidone and 13.5 g of butyl cellosolve were added, and stirred with a magnetic stirrer for 2 hours to obtain a polyamic acid solution. A mix acid solution was obtained.

<Example 6>

3.15 g (1.30 mmol) of diamine (Z-3) was taken in a 100 ml four-necked flask equipped with a stirrer, 25.8 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred and dissolved while blowing nitrogen. While stirring this solution, 2.54 g (1.29 mmol) of tetracarboxylic dianhydride (T-1) was added, 6.44 g of N-methyl-2-pyrrolidone was added, and under nitrogen atmosphere, 23 It stirred at °C for 15 hours to obtain a polyamic acid solution. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 78 mPa*s.

15.0 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer, 24.4 g of N-methyl-2-pyrrolidone and 16.9 g of butyl cellosolve were added, and stirred with a magnetic stirrer for 2 hours to obtain a polyamic acid solution. A mix acid solution was obtained.

<Example 7>

6.52 g (3.29 mmol) of diamine (Z-2) and 3.42 g (1.41 mmol) of diamine (Z-3) were placed in a 200 ml four-necked flask containing a stirrer, and N-methyl-2-pyrrolidone was added. 69.3 g was added and dissolved by stirring while blowing nitrogen. While stirring this solution, 11.70 g (4.68 mmol) of tetracarboxylic dianhydride (T-3) was added, 17.31 g of N-methyl-2-pyrrolidone was added, and 60 °C was added under a nitrogen atmosphere. It stirred at °C for 4 hours to obtain a polyamic acid solution. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 383 mPa*s.

15.0 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer, 37.5 g of N-methyl-2-pyrrolidone and 22.5 g of butyl cellosolve were added, and stirred with a magnetic stirrer for 2 hours to obtain polyamic acid. A mix acid solution was obtained.

<Example 8>

3.89 g (1.96 mmol) of diamine (Z-2) and 3.33 g (0.84 mmol) of diamine (Z-9) were placed in a 200 ml four-necked flask containing a stirrer, and N-methyl-2-pyrrolidone was added. 88.2 g was added and dissolved by stirring while passing nitrogen. While stirring this solution, 6.15 g (2.74 mmol) of tetracarboxylic dianhydride (T-4) was added, 9.80 g of N-methyl-2-pyrrolidone was added, and under a nitrogen atmosphere, 23 It stirred at °C for 15 hours to obtain a polyamic acid solution. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 319 mPa*s.

15.0 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer, 16.5 g of N-methyl-2-pyrrolidone and 13.5 g of butyl cellosolve were added, and stirred with a magnetic stirrer for 2 hours to obtain a polyamic acid solution. A mix acid solution was obtained.

<Example 9>

3.26 g (3.01 mmol) of diamine (Z-5) and 7.18 g (1.29 mmol) of diamine (Z-4) were placed in a 200 ml four-neck flask containing a stirrer, and N-methyl-2-pyrrolidone was added. 63.3 g was added and dissolved by stirring while passing nitrogen. While stirring this solution, 5.38 g (2.15 mmol) of tetracarboxylic dianhydride (T-3) is added, 15.82 g of N-methyl-2-pyrrolidone is added, and the temperature is 60 °C under a nitrogen atmosphere. It was stirred at °C for 4 hours. Then, 3.96g (2.02 mmol) of tetracarboxylic dianhydride (T-1) was added, and it stirred by nitrogen atmosphere at 23 degreeC for 15 hours, and obtained the polyamic-acid solution. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 1003 mPa*s.

15.0 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer, 37.5 g of N-methyl-2-pyrrolidone and 22.5 g of butyl cellosolve were added, and stirred with a magnetic stirrer for 2 hours to obtain polyamic acid. A mix acid solution was obtained.

<Example 10>

0.76 g (0.70 mmol) of diamine (Z-5) and 0.78 g (0.30 mmol) of diamine (Z-10) were placed in a 100 ml four-necked flask containing a stirrer, and N-methyl-2-pyrrolidone was added. 11.9 g was added and dissolved by stirring while blowing nitrogen. While stirring this solution, 1.25 g (0.50 mmol) of tetracarboxylic dianhydride (T-3) is added, 2.97 g of N-methyl-2-pyrrolidone is added, and the temperature is 60 °C under a nitrogen atmosphere. It was stirred at °C for 4 hours. Then, 0.92g (0.47 mmol) of tetracarboxylic dianhydride (T-1) was added, and it stirred by nitrogen atmosphere at 23 degreeC for 15 hours, and obtained the polyamic-acid solution. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 316 mPa*s.

15.0 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer, 37.5 g of N-methyl-2-pyrrolidone and 22.5 g of butyl cellosolve were added, and stirred with a magnetic stirrer for 2 hours to obtain polyamic acid. A mix acid solution was obtained.

<Example 11>

3.78 g (3.50 mmol) of diamine (Z-5) and 2.99 g (1.50 mmol) of diamine (Z-11) were placed in a 200 ml four-necked flask containing a stirrer, and N-methyl-2-pyrrolidone was added. 103.5 g was added and dissolved by stirring while passing nitrogen. While stirring this solution, 6.26 g (2.50 mmol) of tetracarboxylic dianhydride (T-3) is added, 25.9 g of N-methyl-2-pyrrolidone is added, and the temperature is 60 °C under a nitrogen atmosphere. It was stirred at °C for 4 hours. Then, 4.61g (2.35 mmol) of tetracarboxylic dianhydride (T-1) was added, and it stirred by nitrogen atmosphere at 23 degreeC for 15 hours, and obtained the polyamic-acid solution. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 184 mPa*s.

15.0 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer, 37.5 g of N-methyl-2-pyrrolidone and 22.5 g of butyl cellosolve were added, and stirred with a magnetic stirrer for 2 hours to obtain polyamic acid. A mix acid solution was obtained.

<Example 12>

4.51 g (3.00 mmol) of diamine (Z-1), 2.38 g (1.20 mmol) of diamine (Z-2), and 10.02 g ( 1.80 mmol) was taken, 135.5 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred and dissolved while blowing nitrogen. While stirring this solution, 7.51 g (3.00 mmol) of tetracarboxylic dianhydride (T-3) is added, 33.9 g of N-methyl-2-pyrrolidone is added, and the temperature is 60 °C under a nitrogen atmosphere. It was stirred at °C for 4 hours. Then, 5.81g (2.96 mmol) of tetracarboxylic dianhydride (T-1) was added, and it stirred by nitrogen atmosphere at 23 degreeC for 15 hours, and obtained the polyamic-acid solution. The viscosity at the temperature of 25 degreeC of this polyamic-acid solution was 444 mPa*s.

70g of polyamic acid solutions were taken, 91.5g of NMP was added, and it stirred for 30 minutes. 10.62 g of acetic anhydride and 4.94 g of pyridine were added to the obtained polyamic acid solution, and it heated at 80 degreeC for 4 hours, and chemical imidation was performed. The obtained reaction liquid was introduced into 531 ml of methanol while stirring, and the deposited precipitate was collected by filtration and subsequently washed with 531 ml of methanol 3 times. Polyimide resin powder was obtained by drying the obtained resin powder at 60 degreeC for 12 hours. The imidation rate of this polyimide resin powder was 51%.

2.00 g of this polyimide resin powder was fractionated into a 100 ml Erlenmeyer flask with a stirrer bar, 33.0 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred under a nitrogen atmosphere at 50°C for 15 hours. After that, 15.0 g of butyl cellosolve was added, and the mixture was stirred with a magnetic stirrer for 2 hours to obtain a polyimide solution.

<Example 13>

3.76 g (2.50 mmol) of diamine (Z-1), 1.98 g (1.00 mmol) of diamine (Z-2), and 5.95 g ( 1.50 mmol) was taken, 102.2 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred and dissolved while blowing nitrogen. While stirring this solution, 6.26 g (2.50 mmol) of tetracarboxylic dianhydride (T-3) is added, 25.6 g of N-methyl-2-pyrrolidone is added, and the temperature is 60 °C under a nitrogen atmosphere. It was stirred at °C for 4 hours. Then, 4.61g (2.35 mmol) of tetracarboxylic dianhydride (T-1) was added, and it stirred by nitrogen atmosphere at 23 degreeC for 15 hours, and obtained the polyamic-acid solution. The viscosity in the temperature of 25 degreeC of this polyamic acid solution was 480 mPa*s.

70g of polyamic acid solutions were taken, 91.5g of NMP was added, and it stirred for 30 minutes. 11.73 g of acetic anhydride and 5.46 g of pyridine were added to the obtained polyamic acid solution, and it heated at 80 degreeC for 4 hours, and chemical imidation was performed. The obtained reaction liquid was injected into 536 ml of methanol while stirring, and the deposited precipitate was collected by filtration and subsequently washed with 536 ml of methanol 3 times. Polyimide resin powder was obtained by drying the obtained resin powder at 60 degreeC for 12 hours. The imidation ratio of this polyimide resin powder was 52%.

2.00 g of this polyimide resin powder was fractionated into a 100 ml Erlenmeyer flask with a stirrer bar, 33.0 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred under a nitrogen atmosphere at 50°C for 15 hours. After that, 15.0 g of butyl cellosolve was added, and the mixture was stirred with a magnetic stirrer for 2 hours to obtain a polyimide solution.

<Example 14>

11.97 g (4.90 mmol) of diamine (Z-6) and 11.69 g (2.10 mmol) of diamine (Z-4) were placed in a 200 ml four-necked flask containing a stirrer, and N-methyl-2-pyrrolidone was added. 118.2 g was added and dissolved by stirring while passing nitrogen. While stirring this solution, 9.01 g (4.55 mmol) of tetracarboxylic dianhydride (T-5) is added, 29.5 g of N-methyl-2-pyrrolidone is added, and 50 g is added under a nitrogen atmosphere. It was stirred at °C for 1 hour. Then, 4.26g (2.17 mmol) of tetracarboxylic dianhydride (T-1) was added, and it stirred by nitrogen atmosphere at 23 degreeC for 15 hours, and obtained the polyamic-acid solution. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 1210 mPa*s.

70g of polyamic acid solutions were taken, 105.0g of NMP was added, and it stirred for 30 minutes. To the obtained polyamic acid solution, 13.55 g of acetic anhydride and 3.15 g of pyridine were added, and the mixture was heated at 40°C for 3 hours to perform chemical imidation. The obtained reaction liquid was injected into 575 ml of methanol while stirring, and the deposited precipitate was collected by filtration and subsequently washed with 575 ml of methanol 3 times. Polyimide resin powder was obtained by drying the obtained resin powder at 60 degreeC for 12 hours. The imidation rate of this polyimide resin powder was 65%.

2.00 g of this polyimide resin powder was fractionated into a 100 ml Erlenmeyer flask with a stirrer bar, 33.0 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred under a nitrogen atmosphere at 50°C for 15 hours. After that, 15.0 g of butyl cellosolve was added, and the mixture was stirred with a magnetic stirrer for 2 hours to obtain a polyimide solution.

<Example 15>

4.22 g (1.62 mmol) of a tetracarboxylic acid derivative (T-8) was taken in a 200 ml four-necked flask equipped with a stirrer, and 76.4 g of N-methyl-2-pyrrolidone was added and stirred to dissolve. Then, 3.61 g (3.57 mmol) of triethylamine and 3.91 g (1.70 mmol) of diamine (Z-7) were added and stirred to dissolve.

Stirring this solution, 13.69 g (3.57 mmol) of DBOP was added, 10.49 g of N-methyl-2-pyrrolidone was added, and it stirred in nitrogen atmosphere at 23 degreeC for 15 hours, and polyamic acid ester solution got The viscosity in the temperature of 25 degreeC of this polyamic acid ester solution was 50.5 mPa*s.

The precipitate obtained by throwing in this polyamic acid ester solution into 674 g of methanol was separated by filtration. After washing this precipitate with methanol, it was made to dry under reduced pressure at the temperature of 100 degreeC, and the powder of polyamic acid ester was obtained.

2.00 g of this polyamic acid ester powder was fractionated into a 100 ml Erlenmeyer flask containing a stirrer, 33.0 g of N-methyl-2-pyrrolidone and 15.0 g of butyl cellosolve were added, and the mixture was stirred with a magnetic stirrer for 2 hours. A polyamic acid ester solution was obtained.

<Example 16>

4.09 g (3.00 mmol) of diamine (Z-12) was taken in a 100 ml four-necked flask equipped with a stirrer, 31.2 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred and dissolved while blowing nitrogen. While stirring this solution, 5.77 g (2.94 mmol) of tetracarboxylic dianhydride (T-1) was added, 7.79 g of N-methyl-2-pyrrolidone was further added, and under a nitrogen atmosphere, 23 It stirred at °C for 15 hours to obtain a polyamic acid solution. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 653 mPa*s.

25g of polyamic acid solutions were taken, 51.9g of NMP was added, and it stirred for 30 minutes. 4.66 g of acetic anhydride and 2.41 g of pyridine were added to the obtained polyamic acid solution, and it heated at 40 degreeC for 3 hours, and chemical imidation was performed. The obtained reaction liquid was injected into 294 ml of methanol while stirring, and the deposited precipitate was collected by filtration and subsequently washed with 168 ml of methanol 3 times. Polyimide resin powder was obtained by drying the obtained resin powder at 60 degreeC for 12 hours. The imidation rate of this polyimide resin powder was 49%.

1.00 g of this polyimide resin powder was fractionated into a 100 ml Erlenmeyer flask with a stirrer, 15.0 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred under a nitrogen atmosphere at 50°C for 15 hours. After that, 4.00 g of butyl cellosolve was added, and the mixture was stirred with a magnetic stirrer for 2 hours to obtain a polyimide solution.

<Example 17>

10 g of the polyamic acid solution obtained in Example 1 was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer, 10 g of the polyamic acid solution obtained in Example 2 was added thereto, and stirred for 2 hours using a magnetic stirrer, , to obtain a polyamic acid solution.

<Example 18>

10 g of the polyamic acid solution obtained in Example 1 was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer, 10 g of the polyamic acid solution obtained in Example 5 was added thereto, and stirred for 2 hours using a magnetic stirrer. , to obtain a polyamic acid solution.

<Example 19>

10 g of the polyamic acid solution obtained in Example 4 was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer, 10 g of the polyamic acid solution obtained in Example 5 was added thereto, and stirred for 2 hours using a magnetic stirrer. , to obtain a polyamic acid solution.

<Reference Example 1>

4.21 g (2.80 mmol) of diamine (Z-1) was taken in a 200 ml four-necked flask equipped with a stirrer, 59.1 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred and dissolved while blowing nitrogen. While stirring this solution, 5.86 g (2.69 mmol) of tetracarboxylic dianhydride (T-2) was added, 14.8 g of N-methyl-2-pyrrolidone was added, and under nitrogen atmosphere, 23 It stirred at °C for 15 hours to obtain a polyamic acid solution. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 126 mPa*s.

15.0 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer, 16.5 g of N-methyl-2-pyrrolidone and 13.5 g of butyl cellosolve were added, and stirred with a magnetic stirrer for 2 hours to obtain a polyamic acid solution. A mix acid solution was obtained.

<Reference Example 2>

4.21 g (2.80 mmol) of diamine (Z-1) was taken in a 200 ml four-necked flask equipped with a stirrer, 71.1 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred and dissolved while blowing nitrogen. While stirring this solution, 7.91 g (2.69 mmol) of tetracarboxylic dianhydride (T-6) was added, 17.8 g of N-methyl-2-pyrrolidone was added, and under a nitrogen atmosphere, 23 It stirred at °C for 15 hours to obtain a polyamic acid solution. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 121 mPa*s.

15.0 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer, 16.5 g of N-methyl-2-pyrrolidone and 13.5 g of butyl cellosolve were added, and stirred with a magnetic stirrer for 2 hours to obtain a polyamic acid solution. A mix acid solution was obtained.

<Reference Example 3>

6.46 g (4.30 mmol) of diamine (Z-1) was taken in a 200 ml four-neck flask equipped with a stirrer, 54.0 g of N-methyl-2-pyrrolidone was added, and the mixture was stirred and dissolved while blowing nitrogen. While stirring this solution, 5.16 g (1.72 mmol) of tetracarboxylic dianhydride (T-7) was added, 13.50 g of N-methyl-2-pyrrolidone was added, and 60 g was added under a nitrogen atmosphere. It was stirred at °C for 4 hours. Then, 5.25g (2.41 mmol) of tetracarboxylic dianhydride (T-2) was added, and it stirred by nitrogen atmosphere at 23 degreeC for 15 hours, and obtained the polyamic-acid solution. The viscosity at the temperature of 25 degreeC of this polyamic-acid solution was 854 mPa*s.

15.0 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer, 37.5 g of N-methyl-2-pyrrolidone and 22.5 g of butyl cellosolve were added, and stirred with a magnetic stirrer for 2 hours to obtain polyamic acid. A mix acid solution was obtained.

<Reference Example 4>

3.23 g (2.15 mmol) of diamine (Z-1) and 3.27 g (2.15 mmol) of diamine (Z-8) were placed in a 200 ml four-necked flask containing a stirrer, and N-methyl-2-pyrrolidone was added. 49.6 g was added and dissolved by stirring while blowing nitrogen. While stirring this solution, 9.00 g (4.13 mmol) of tetracarboxylic dianhydride (T-2) was added, 12.4 g of N-methyl-2-pyrrolidone was added, and under nitrogen atmosphere, 23 It stirred at °C for 15 hours to obtain a polyamic acid solution. The viscosity at the temperature of 25 degreeC of this polyamic-acid solution was 799 mPa*s.

15.0 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer, 37.5 g of N-methyl-2-pyrrolidone and 22.5 g of butyl cellosolve were added, and stirred with a magnetic stirrer for 2 hours to obtain polyamic acid. A mix acid solution was obtained.

[Production of liquid crystal cell]

The functional resin composition obtained in Example 1 was spin-coated on the ITO surface of a glass substrate on which a transparent electrode made of an ITO film was formed, dried on a hot plate at 70 ° C. for 120 seconds, and then fired in an IR oven at 230 ° C. for 30 minutes. This was carried out to form a driving control film having a film thickness of 100 nm.

Two substrates were prepared, and a bead spacer of 4 μm was spread on the drive control film of one substrate, and then a sealant (XN-1500T manufactured by Kyoritz Chemical Co., Ltd.) was applied. Next, the other substrate was bonded with the driving control film surfaces facing each other, and then the sealing compound was thermally cured at 120°C for 90 minutes to produce an empty cell. A positive liquid crystal (MLC-2293, manufactured by Merck & Co., Ltd.) was injected into this empty cell by a reduced pressure injection method to prepare a liquid crystal cell.

In the same way, liquid crystal cells were produced also for the functional resin compositions obtained in Examples 2 to 16 and Reference Examples 1 to 4.

[Measurement of Voltage Retention Rate]

A voltage of 5 V was applied to the liquid crystal cell obtained above for 60 μs under a temperature of 70° C., the voltage after 16.67 ms was measured, and how much voltage was maintained was calculated as voltage retention (initial value).

Then, the liquid crystal cell was left to stand under the temperature of 100 degreeC for 200 hours, and it returned to room temperature after that. A voltage of 5 V was applied to the liquid crystal cell for 60 μs under a temperature of 70° C., the voltage after 16.67 ms was measured, and how much voltage was maintained was calculated as voltage retention (after durability test).

The results were as shown in Table 1.

Claims (9)

A functional resin composition for a liquid crystal drive control film of a microwave anomalous modulation element using a liquid crystal, containing at least one polymer selected from polyamic acid derivatives and polyimides that are imides thereof,
The functional resin composition in which the said polymer is a polymer which has a structural unit of following formula (1).

(Wherein, X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative and represents a structure selected from the following formulas (X-1) to (X-8) and (X-21), and Y ₁ is diamine derived divalent organic group, R ₁ represents a hydrogen atom or an alkylene having 1 to 5 carbon atoms A ₁ and A ₂ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms and 2 carbon atoms represents an alkenyl group of to 5, or an alkynyl group of 2 to 5 carbon atoms.)

[In Formulas (X-1) to (X-4), R ₃ to R ₂₃ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a carbon atom having 2 to 6 carbon atoms. an alkynyl group of , a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group]. According to claim 1,
The functional resin composition in which X ₁ represents a structure selected from formulas (X-1) to (X-8). According to claim 1,
The functional resin composition in which the structural unit of the said formula (1) is 50 mol% - 100 mol% in a polymer. According to claim 1,
Y ₁ has a structure selected from the following formula, a functional resin composition.

(In (Y-149) and (Y-154) to (Y-157), n is an integer of 1 to 6. In (Y-167) and (Y-171), Boc is a tert-part Represents a oxycarbonyl group.) According to claim 4,
Wherein Y ₁ is, (Y-8), (Y-16) to (Y-18), (Y-20), (Y-28), (Y-63), (Y-68), (Y- 72), (Y-75), (Y-149), (Y-153), (Y-164) to (Y-165) or (Y-167), a functional resin composition. According to claim 4,
The functional resin composition in which the structural unit represented by formula (I) having Y ₁ is 30 mol% to 100 mol% in the polymer. According to claim 1,
With respect to the resin composition, the voltage retention (initial value) obtained by measuring according to the following voltage retention measurement test is 90% or more, and the voltage retention (value after durability test) is 80% or more. Functional resin composition.
[Measurement test of voltage holding ratio]
A liquid crystal drive control film is formed by spin-coating and firing the functional resin composition of the subject on a glass substrate, and a liquid crystal cell is produced using the liquid crystal drive control film,
A voltage of 5 V is applied to the liquid crystal cell at a temperature of 70 ° C. for 60 μs, and the voltage after 16.67 ms is measured to obtain a voltage retention rate (initial value) of how much the voltage is maintained,
Next, after leaving the liquid crystal cell at a temperature of 95°C for 200 hours, the temperature was returned to room temperature, and a voltage of 5 V was applied for 60 μs to the liquid crystal cell at a temperature of 70°C as in the case of the initial value, and after 16.67 ms The voltage is measured to obtain the voltage holding ratio (value after durability test). A driving control film obtained from the functional resin composition according to any one of claims 1 to 7. A microwave anomalous modulation element comprising the driving control film according to claim 8.