KR102558626B1 - Resin composition, resin film and liquid crystal display element - Google Patents

Abstract

단, 상기 식 중, X^a 는 수소 원자 또는 벤젠 고리를 나타낸다.A resin composition for forming a novel resin film in a liquid crystal display element capable of improving the adhesion between a liquid crystal layer and an electrode and suppressing peeling of the element, generation of air bubbles and deterioration of optical properties even in harsh environments exposed to high temperature, high humidity or light irradiation for a long time.
In a liquid crystal display device having a liquid crystal layer cured by irradiating ultraviolet rays with respect to a liquid crystal composition containing a liquid crystal and a polymerizable compound disposed between a pair of substrates having electrodes, a resin composition for forming a resin film formed on a substrate having the electrodes to prevent contact between the electrodes and the liquid crystal layer,
The resin composition characterized by containing the polymer which has at least 1 sort(s) of structure chosen from the group which the said resin composition consists of the following formula [1-a] - formula [1-i].

However, in the formula, X ^a represents a hydrogen atom or a benzene ring.

Description

Resin composition, resin film and liquid crystal display element

The present invention relates to a resin composition for forming a resin film preferably used in a transmission/scattering type liquid crystal display element that enters a transmission state when a voltage is applied.

As a liquid crystal display element, TN (Twisted Nematic) mode is put into practical use. In this mode, it is necessary to use a polarizing plate in order to perform light switching by utilizing the polarization characteristics of liquid crystals. However, when a polarizing plate is used, light utilization efficiency is lowered.

As a liquid crystal display element that does not use a polarizing plate, there is an element that switches between a transmissive state (also referred to as a transparent state) and a scattering state of liquid crystal. Specifically, it is known that a polymer dispersed liquid crystal (PDLC) or a polymer network liquid crystal (PNLC) is used.

In these liquid crystal display devices, a liquid crystal composition containing a polymerizable compound polymerized by ultraviolet rays is placed between a pair of substrates provided with electrodes, and the liquid crystal composition is cured by irradiation with ultraviolet rays to form a composite of a liquid crystal and a cured product of the polymerizable compound (eg, polymer network). And, in this liquid crystal display element, the scattering state and transmission state of the liquid crystal are controlled by application of a voltage.

In a liquid crystal display element using PDLC or PNLC, since the liquid crystal faces in a random direction when no voltage is applied, it becomes cloudy (scattered) state, and when voltage is applied, the liquid crystal is aligned in the direction of the electric field, and transmits light to become a transmission state (also referred to as a normal element). In this case, since the liquid crystal when no voltage is applied is random, there is no need for a liquid crystal alignment film or alignment treatment for orienting the liquid crystal in one direction. Therefore, in this liquid crystal display element, the electrode and the liquid crystal layer (the composite of the cured product of the liquid crystal and the polymerizable compound) are in direct contact (see Patent Documents 1 and 2).

Japanese Patent Publication No. 3552328 Japanese Patent Publication No. 4630954

The polymerizable compound in the liquid crystal composition has a role of forming a polymer network to obtain desired optical properties and a role of enhancing adhesion between the liquid crystal layer and the electrode. However, since inorganic electrodes such as ITO (Indium Tin Oxide) are used in the above-mentioned normal-type elements, compatibility with organic polymeric compounds, ie, adhesion tends to be low. If the adhesion is low, long-term use, particularly harsh environments such as high temperature, high humidity, or environments exposed to light irradiation, cause peeling of the element, generation of bubbles, and further deterioration of the optical properties in the scattering state and the transparent state. It becomes easy to cause.

In addition, in the normal type element or the like, since the electrode and the liquid crystal layer are in direct contact, when an ITO-PET (polyethylene terephthalate) film or the like is used for the substrate, there is a possibility that a short circuit (short circuit) may occur when a voltage is applied due to slight lifting or defect of the ITO electrode, which tends to occur when the ITO electrode is produced by sputtering. Therefore, a resin film for suppressing this is required.

An object of the present invention is to provide a novel resin composition for forming a resin film that can be used in a liquid crystal display element capable of improving the adhesion between a liquid crystal layer and an electrode and suppressing peeling of the element, generation of bubbles, and deterioration of optical properties even in a harsh environment exposed to high temperature, high humidity or light irradiation for a long time.

As a result of intensive research to achieve the above object, the present inventors have completed the present invention.

That is, the present invention is a liquid crystal display device having a liquid crystal layer cured by irradiating ultraviolet rays to a liquid crystal composition containing a liquid crystal and a polymerizable compound disposed between a pair of substrates provided with electrodes, as a resin composition for forming a resin film formed on a substrate provided with electrodes,

The resin composition characterized by containing the polymer which has at least 1 sort(s) of structure chosen from the group which the said resin composition consists of the following formula [1-a] - formula [1-i].

[Formula 1]

However, in the formula, X ^a represents a hydrogen atom or a benzene ring.

According to the liquid crystal display element having a resin film formed of the resin composition of the present invention on a substrate provided with electrodes, the adhesion between the liquid crystal layer and the electrode is improved, and even in a harsh environment exposed to high temperature, high humidity or light irradiation for a long time, peeling of the element, generation of bubbles, and deterioration of optical properties can be suppressed. Therefore, the liquid crystal display element according to the present invention, particularly the normal element, can be used in a wide range of devices, such as a liquid crystal display for display purposes, a light control window and an optical shutter element that control light blocking and transmission.

<liquid crystal composition>

The liquid crystal composition in the present invention has a liquid crystal and a polymerizable compound.

As the liquid crystal in the liquid crystal composition, a nematic liquid crystal, a smectic liquid crystal or a cholesteric liquid crystal can be used. Among them, those having positive dielectric anisotropy are preferred. Further, from the viewpoint of low-voltage driving and scattering characteristics, it is preferable that the dielectric constant anisotropy is large and the refractive index anisotropy is large. In addition, two or more types of liquid crystals may be mixed and used for the liquid crystal according to the respective physical property values of the phase transition temperature, dielectric constant anisotropy, and refractive index anisotropy.

In order to drive a liquid crystal display element as an active element such as a TFT (Thin Film Transistor), it is required that the liquid crystal has a high electrical resistance and a high voltage holding ratio (also referred to as VHR). Therefore, it is preferable to use a fluorine-type or chlorine-type liquid crystal which has high electrical resistance and does not lower VHR by active energy rays such as ultraviolet rays for the liquid crystal.

In addition, the liquid crystal display element can also be made into a guest host type element by dissolving a dichroic dye in the liquid crystal composition. In this case, an element that is absorbed (scattered) when no voltage is applied and becomes transparent when a voltage is applied is obtained. Moreover, in this liquid crystal display element, the direction of the liquid crystal director (direction of orientation) changes 90 degrees depending on whether voltage is applied or not. Therefore, this liquid crystal display element can obtain a higher contrast than a conventional guest host type element that switches between random orientation and vertical orientation by utilizing the difference in light absorption characteristics of dichroic dyes. In addition, in a guest host type element in which a dichroic dye is dissolved, when the liquid crystal is oriented in the horizontal direction, it becomes colored and becomes opaque only in a scattering state. Therefore, as a voltage is applied, it is also possible to obtain an element that switches from a colored opaque state to a colored transparent state and a colorless transparent state when no voltage is applied.

The polymerizable compound in the liquid crystal composition undergoes a polymerization reaction to form a curable resin by irradiation with ultraviolet rays during production of the liquid crystal display device. Therefore, a polymer obtained by polymerizing a polymerizable compound in advance may be introduced into the liquid crystal composition. However, even when it is made of a polymer, it is necessary to have a site that undergoes a polymerization reaction by irradiation with ultraviolet rays. As the polymerizable compound, it is preferable to use a liquid crystal composition containing a polymerizable compound from the viewpoint of handling of the liquid crystal composition, that is, suppression of increase in viscosity of the liquid crystal composition and solubility in the liquid crystal.

The polymerizable compound is not particularly limited as long as it is dissolved in the liquid crystal, but when the polymerizable compound is dissolved in the liquid crystal, a temperature at which part or all of the liquid crystal composition exhibits a liquid crystal phase must be present. Even when a part of the liquid crystal composition exhibits a liquid crystal phase, the liquid crystal display element should be visually confirmed, and substantially constant transparency and scattering characteristics should just be obtained throughout the element.

The polymerizable compound may be any compound that is polymerized by ultraviolet rays, and at that time, polymerization may proceed in any reaction format to form a curable resin. Radical polymerization, cationic polymerization, anionic polymerization, or polyaddition reaction is mentioned as a specific reaction format.

Especially, as for the reaction form of a polymeric compound, radical polymerization is preferable from the point of the optical characteristic of a liquid crystal display element. In that case, as a polymeric compound, the following radical type polymerizable compound or its oligomer can be used. Moreover, as mentioned above, the polymer which polymerized these polymeric compounds can also be used.

As for the specific example of a radical type polymeric compound or its oligomer, the radical type polymeric compound described in 69 pages - 71 pages of International Publication No. 2015/146987 is mentioned.

The use ratio of the radical polymerizable compound or oligomer thereof is preferably 70 to 150 parts by mass with respect to 100 parts by mass of the liquid crystal in the liquid crystal composition from the viewpoint of adhesion between the liquid crystal layer and the electrode of the liquid crystal display element. More preferably, it is 80-110 mass parts. Moreover, according to each characteristic, you may mix and use two or more types of radical type polymeric compounds.

In order to promote the formation of the curable resin, it is preferable to introduce a radical initiator (also referred to as a polymerization initiator) that generates radicals by ultraviolet rays for the purpose of accelerating radical polymerization of polymerizable compounds in the liquid crystal composition.

Specifically, the radical initiator described in page 71 - page 72 of International Publication No. 2015/146987 is mentioned.

The use ratio of the radical initiator is preferably from 0.01 to 10 parts by mass with respect to 100 parts by mass of the liquid crystal in the liquid crystal composition from the viewpoint of adhesion between the liquid crystal layer of the liquid crystal display element and the electrode. More preferably, it is 0.05-5 mass parts. Moreover, a radical initiator can also be used in mixture of 2 or more types according to each characteristic.

<Resin composition>

A resin film is obtained from the resin composition containing the polymer (henceforth a specific polymer) which has the specific structure of said formula [1-a] - formula [1-i].

As for the said specific structure, the point of photoreaction with the polymeric compound in a liquid crystal composition to formula [1-a] - formula [1-f] are preferable. Especially, formula [1-a] - formula [1-e] are preferable, More preferably, they are formula [1-a], formula [1-b], formula [1-d], or formula [1-e] from the adhesiveness of a liquid crystal layer and an electrode.

As the specific polymer having a specific structure, at least one polymer selected from the group consisting of acrylic polymers, methacrylic polymers, novolak resins, polyhydroxystyrenes, polyimide precursors, polyimides, polyamides, polyesters, celluloses, and polysiloxanes is preferable. More preferably, it is a polyimide precursor, polyimide, or polysiloxane.

When using a polyimide precursor or polyimide (it is also collectively called a polyimide type polymer) for a specific polymer, they are preferably a polyimide precursor or polyimide obtained by making a diamine component and a tetracarboxylic acid component react.

A polyimide precursor has a structure of following formula [A].

[Formula 2]

However, R ¹ represents a tetravalent organic group. R ² represents a divalent organic group. A ¹ and A ² each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. A ³ and A ⁴ each represent a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, or an acetyl group. n represents a positive integer.

The diamine component is a diamine having two primary or secondary amino groups in the molecule, and the tetracarboxylic acid component includes a tetracarboxylic acid compound, tetracarboxylic dianhydride, tetracarboxylic acid dihalide compound, tetracarboxylic acid dialkyl ester compound or tetracarboxylic acid dialkyl ester dihalide compound.

The polyimide polymer is obtained relatively easily by using tetracarboxylic dianhydride of the following formula [B] and diamine of the following formula [C] as raw materials, so that a polyamic acid having a structural formula of a repeating unit of the following formula [D] or a polyimide obtained by imidizing the polyamic acid is preferable.

[Formula 3]

However, R ¹ and R ² are the same as those defined in Formula [A].

[Formula 4]

However, R ¹ and R ² are the same as those defined in Formula [A].

In addition, by a conventional synthesis method, the C1-C8 alkyl groups of ^A1 and ^A2 in Formula [A], and the C1-C5 alkyl groups or acetyl groups of ^A3 and ^A4 in Formula [A] can also be introduced into the polymer of formula [D] obtained above.

As a method for introducing a specific structure into a polyimide polymer, it is preferable to use diamine having a specific structure for a part of the diamine component as a raw material. In particular, a diamine having a structure of the following formula [1] (also referred to as specific diamine) is preferable.

[Formula 5]

However, X ¹ represents a single bond, -O-, -NH-, -N(CH ₃ )-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- or -OCO-. Especially, a single bond, -O-, -CH ₂ O-, -CONH-, -COO- or -OCO- is preferable. More preferably, it is a single bond, -O-, -CH ₂ O-, or -COO- from the viewpoint of availability of raw materials and ease of synthesis.

X ² represents a single bond, an alkylene group of 1 to 18 carbon atoms, or an organic group of 6 to 24 carbon atoms having a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group of 1 to 3 carbon atoms, an alkoxyl group of 1 to 3 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, or a carbon atom. It may be substituted by the fluorine-containing alkoxyl group of -3 or a fluorine atom. Especially, a single bond, a C1-C12 alkylene group, a benzene ring, or a cyclohexane ring is preferable. More preferably, it is a single bond or an alkylene group of 1 to 12 carbon atoms in terms of adhesion between the liquid crystal layer and the electrode.

X ³ represents a single bond, -O-, -NH-, -N(CH ₃ )-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- or -OCO-. Especially, a single bond, -O-, -COO-, or -OCO- is preferable. More preferably, it is a single bond or -OCO-.

X ⁴ represents a structure selected from the group consisting of the above formula [1-a] to formula [1-i], and formula [1-a] to formula [1-f] are preferable. Especially, formula [1-a] - formula [1-e] are preferable. More preferably, it is formula [1-a], formula [1-b], formula [1-d], or formula [1-e] with respect to the adhesiveness of a liquid crystal layer and an electrode.

m represents the integer of 1-4. Especially, 1 or 2 is preferable.

It is preferable to use the diamine of following formula [1a] for specific diamine.

[Formula 6]

However, X represents the said formula [1] in formula [1a]. Moreover, in Formula [1], the details of X ¹ , X ² , X ³ , X ⁴ , and m and their preferred combinations are as described in Formula [1] above. n represents the integer of 1-4. Especially, 1 is preferable.

As more specific specific diamine, following formula [1a-1] - formula [1a-12] are mentioned, It is preferable to use these.

[Formula 7]

However, n1 represents the integer of 2-12.

[Formula 8]

However, n2 represents the integer of 0-12. n3 represents the integer of 2-12.

Especially, formula [1a-1], formula [1a-2], formula [1a-5] - formula [1a-7], formula [1a-11], or formula [1a-12] is preferable. More preferably, it is a formula [1a-5] - a formula [1a-7], a formula [1a-11], or a formula [1a-12].

10-70 mol% is preferable with respect to the whole diamine component, and, as for the usage ratio of a specific diamine, 20-60 mol% is more preferable with respect to the optical characteristic of a liquid crystal display element, and the adhesive point of a liquid crystal layer and an electrode. Two or more types can be used for specific diamine according to each characteristic.

As a diamine component for producing a polyimide polymer, in addition to specific diamine, it is preferable to also use diamine (also referred to as second diamine) of the following formula [2a].

[Formula 9]

However, Y represents a structure selected from the group consisting of the following formula [2-a] to formula [2-d]. m represents an integer of 1 to 4, and 1 is preferable.

[Formula 10]

However, a represents an integer of 0 to 4, and is preferably 0 or 1 from the viewpoint of availability of raw materials or ease of synthesis. b represents an integer of 0 to 4, and is preferably 0 or 1 from the viewpoint of availability of raw materials or ease of synthesis. Y ^a and Y ^b each represent a hydrocarbon group having 1 to 12 carbon atoms. Y ^c represents an alkyl group having 1 to 5 carbon atoms.

Specific examples of the second diamine include the following.

For example, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, in addition to the following formula [2 a-1] and diamines of [2a-2].

[Formula 11]

Among them, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, and diamine of formula [2a-1] or formula [2a-2] are preferable. More preferably, it is 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 3,5-diaminobenzoic acid, or the diamine of formula [2a-1] from the viewpoint of the solubility of the polyimide polymer in a solvent or the optical properties in a liquid crystal display device.

As a diamine component for producing a polyimide polymer, diamines other than diamines of formula [1a] and formula [2a] (also referred to as other diamines) can also be used.

Specifically, other diamine compounds described in pages 27 to 30 of International Publication No. WO2015/012368, and diamine compounds of formula [DA1] to formula [DA14] described in pages 30 to 32 of the same publication are exemplified. Moreover, other diamine can be used 1 type or in mixture of 2 or more types according to each characteristic.

As the tetracarboxylic acid component for producing the polyimide polymer, it is preferable to use tetracarboxylic dianhydride of the following formula [3], tetracarboxylic acid derivative thereof, tetracarboxylic acid dihalide compound, tetracarboxylic acid dialkyl ester compound, or tetracarboxylic acid dialkyl ester dihalide compound (all collectively referred to as a specific tetracarboxylic acid component).

[Formula 12]

However, Z represents the structure chosen from the group which consists of following formula [3a] - formula [3l].

[Formula 13]

Z ¹ to Z ⁴ each represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring. Z ⁵ and Z ⁶ each represent a hydrogen atom or a methyl group.

Among them, Z in formula [3] is preferably formula [3a], formula [3c], formula [3d], formula [3e], formula [3f], formula [3g], formula [3k] or formula [3l] from the viewpoint of the ease of synthesis and the ease of polymerization reactivity when producing a polymer. More preferably, they are formula [3a], formula [3e], formula [3f], formula [3g], formula [3k] or formula [3l]. Especially preferably, they are formula [3a], formula [3e], formula [3f], formula [3g], or formula [3l] from the point of the optical characteristic in a liquid crystal display element.

As for the usage ratio of a specific tetracarboxylic acid component, 1 mol% or more is preferable with respect to all the tetracarboxylic acid components. More preferably, it is 5 mol% or more, and particularly preferably 10 mol% or more. Most preferably, it is 10-90 mol% from the point of the optical characteristic of a liquid crystal display element.

Other tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used for the polyimide-based polymer. Examples of other tetracarboxylic acid components include tetracarboxylic acid compounds, tetracarboxylic dianhydrides, dicarboxylic acid dihalide compounds, dicarboxylic acid dialkyl ester compounds, and dialkyl ester dihalide compounds shown below.

Specifically, other tetracarboxylic acid components described in pages 34 to 35 of International Publication No. WO2015/012368 are exemplified.

A specific tetracarboxylic acid component and other tetracarboxylic acid components can be used 1 type or in mixture of 2 or more types according to each characteristic.

A method for synthesizing the polyimide polymer is not particularly limited. It is usually obtained by reacting a diamine component and a tetracarboxylic acid component. Specifically, the method described in 35 pages - 36 pages of International Publication WO2015/012368 is mentioned.

Reaction of a diamine component and a tetracarboxylic acid component is normally performed in the solvent containing a diamine component and a tetracarboxylic acid component. The solvent used in that case is not particularly limited as long as the produced polyimide precursor dissolves therein.

Specifically, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl-imidazolidinone, etc. are mentioned. Moreover, when the solvent solubility of a polyimide precursor is high, the solvent of methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or following formula [D1] - formula [D3] can be used.

[Formula 14]

However, D ¹ and D ² represent an alkyl group having 1 to 3 carbon atoms. D ³ represents an alkyl group having 1 to 4 carbon atoms.

Moreover, these solvents may be used independently or may be used in mixture. Moreover, even if it is a solvent which does not dissolve a polyimide precursor, you may mix with the said solvent and use it within the range in which a polyimide precursor does not precipitate. In addition, since moisture in the organic solvent inhibits the polymerization reaction and causes hydrolysis of the resulting polyimide precursor, it is preferable to use a dehydrated organic solvent.

A polyimide is a polyimide obtained by ring-closing a polyimide precursor, and the ring-closing ratio of the amic acid group in the polyimide (also referred to as the imidation ratio) is not necessarily 100% and can be adjusted depending on the use or purpose. Especially, 30 to 80% is preferable from the point of the solubility to the solvent of a polyimide-type polymer. More preferably, it is 40 to 70%.

The polyimide-based polymer preferably has a weight average molecular weight (Mw) of 5,000 to 1,000,000, more preferably 10,000 to 150,000, as measured by GPC (Gel Permeation Chromatography) method, in view of the strength of the resin film obtained, workability during resin film formation, and coating properties.

When using polysiloxane as a specific polymer in the present invention, polysiloxane obtained by polycondensing an alkoxysilane of the following formula [A1], or polysiloxane obtained by polycondensing an alkoxysilane of the formula [A1] and an alkoxysilane of the following formula [A2] is preferably used.

Alkoxysilane of formula [A1]:

[Formula 15]

A ¹ represents an organic group having 2 to 12 carbon atoms and having at least one structure selected from the group consisting of the formula [1-a] to formula [1-i], and formula [1-a] to formula [1-f] are preferable. Especially, formula [1-a] - formula [1-e] are preferable. More preferably, it is formula [1-a], formula [1-b], formula [1-d], or formula [1-e] with respect to the adhesiveness of a liquid crystal layer and an electrode.

A ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Especially, a hydrogen atom or a C1-C3 alkyl group is preferable.

A ³ represents an alkyl group of 1 to 5 carbon atoms. Especially, from the reactivity of polycondensation, a C1-C3 alkyl group is preferable.

m represents an integer of 1 or 2; Especially, 1 is preferable from the ease of synthesis|combination.

n represents the integer of 0-2.

p represents an integer of 0 to 3; Especially, from the reactivity of polycondensation, the integer of 1-3 is preferable. More preferably, it is 2 or 3.

m + n + p is 4.

Specific examples of the alkoxysilane of the formula [A1] include allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-(triethoxysilyl)propylmethacrylate, 3-(trimethoxysilyl)propylacrylate or 3 - (Trimethoxysilyl) propyl methacrylate is mentioned, and it is preferable to use these.

The alkoxysilane of formula [A1] can mix and use two or more types according to each characteristic.

Alkoxysilane of formula [A2]:

[Formula 16]

B ¹ represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms. Especially, a hydrogen atom or a C1-C3 alkyl group is preferable.

B ² represents an alkyl group of 1 to 5 carbon atoms. Especially, from the reactivity of polycondensation, a C1-C3 alkyl group is preferable.

n represents the integer of 0-3.

Specific examples of the alkoxysilane of the formula [A2] include specific examples of the alkoxysilane of the formula [2c] described in pages 24 to 25 of International Publication WO2015/008846.

Moreover, in formula [A2], tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, or tetrabutoxysilane is mentioned as an alkoxysilane whose n is 0, and it is preferable to use these alkoxysilanes as an alkoxysilane of formula [A2].

The alkoxysilane of formula [A2] can mix and use two or more types according to each characteristic.

It is preferable to use the polysiloxane obtained by polycondensing the polysiloxane type polymer of the alkoxysilane of the formula [A1], or the polysiloxane obtained by polycondensing the alkoxysilane of the formula [A1] and the alkoxysilane of the formula [A2].

Especially, the polysiloxane obtained by polycondensing multiple types of alkoxysilanes is preferable from the viewpoint of the reactivity of polycondensation and the solubility of the polysiloxane-based polymer in a solvent. That is, it is preferable to use polysiloxane obtained by polycondensing two types of alkoxysilanes of formula [A1] and formula [A2]. In that case, as for the usage rate of the alkoxysilane of Formula [A1], 1-70 mol% is preferable among all alkoxysilanes. Especially, 1-50 mol% is preferable, More preferably, it is 1-30 mol%. Moreover, as for the usage rate of the alkoxysilane of Formula [A2], 30-99 mol% is preferable among all the alkoxysilanes. Especially, 50-99 mol% is preferable, More preferably, it is 70-99 mol%.

A method of polycondensing the polysiloxane-based polymer is not particularly limited. Specifically, the method described in the 26th page - 29th page of International Publication WO2015/008846 is mentioned.

In the polycondensation reaction for producing a polysiloxane-based polymer, when using a plurality of alkoxysilanes of the formula [A1] and formula [A2], the reaction may be carried out using a mixture in which a plurality of alkoxysilanes are mixed in advance, or a plurality of alkoxysilanes may be reacted while being added sequentially.

In the present invention, the solution of the polysiloxane-based polymer obtained by the above method may be used as a specific polymer as it is, or, if necessary, the solution of the polysiloxane-based polymer obtained by the above method may be concentrated, diluted by adding a solvent, or substituted with another solvent and used as a specific polymer.

The solvent used for dilution (also referred to as an additive solvent) may be a solvent used for polycondensation reaction or other solvents. This addition solvent is not particularly limited as long as the polysiloxane-based polymer is uniformly dissolved, and one type or two or more types can be arbitrarily selected. Examples of such additive solvents include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester solvents such as methyl acetate, ethyl acetate, and ethyl lactate, in addition to the solvent used for the polycondensation reaction.

In the case of using a polysiloxane-based polymer and other polymers for a specific polymer, alcohol generated during the polycondensation reaction of the polysiloxane-based polymer is preferably distilled off under normal pressure or reduced pressure before mixing the other polymer with the polysiloxane-based polymer.

A resin composition is a solution for forming a resin film, and is a solution containing a specific polymer and a solvent. In that case, a specific polymer can use two or more types.

As for the polymer component in a resin composition, all may be a specific polymer, and polymers other than that may be mixed. In that case, content of a polymer other than that is 0.5-15 mass parts with respect to 100 mass parts of specific polymers, Preferably it is 1-10 mass parts. As polymers other than that, the said polymer which does not have a specific structure is mentioned.

The content of the solvent in the resin composition can be appropriately selected from the viewpoint of the coating method of the resin composition and obtaining the target film thickness. Especially, as for content of the solvent in a resin composition, 50-99.9 mass % is preferable from a viewpoint of forming a uniform resin film by application|coating. Especially, 60-99 mass % is preferable, and it is 65-99 mass % especially preferably.

The solvent used for the resin composition is not particularly limited as long as it is a solvent that dissolves a specific polymer. Among them, when the specific polymer is a polyimide precursor, polyimide, polyamide or polyester, or when the solubility of an acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, cellulose or polysiloxane in a solvent is low, it is preferable to use a solvent (also referred to as solvent A type) as shown below.

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, 4-hydroxy-4-methyl-2-pentanone and the like. Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone. Moreover, these may be used individually or may be used in mixture.

When the specific polymer is an acrylic polymer, methacrylic polymer, novolak resin, polyhydroxystyrene, cellulose or polysiloxane, and furthermore, the specific polymer is a polyimide precursor, polyimide, polyamide or polyester, and these specific polymers have high solubility in the solvent, solvents as shown below (also referred to as solvent B) can be used.

Specific examples of solvent B include solvent B described in pages 58 to 60 of International Publication No. WO2014/171493. Among them, it is preferable to use 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, or a solvent of the above formulas [D1] to [D3].

In addition, when these solvents B are used, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone of the solvent A is preferably used in combination for the purpose of improving the coating properties of the resin composition. More preferably, γ-butyrolactone is used in combination.

Since these type B solvents can improve the coating properties and surface smoothness of the resin film when the resin composition is applied, when a polyimide precursor, polyimide, polyamide or polyester is used for a specific polymer, it is preferable to use in combination with the type A solvent. In that case, as for solvent B, 1-99 mass % of the whole solvent contained in a resin composition is preferable. Especially, 10-99 mass % is preferable. More preferably, it is 20-95 mass %.

In the resin composition, in order to increase the film strength of the resin film, it is preferable to introduce a compound having at least one selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group (referred to collectively as a specific crosslinkable compound). In that case, it is necessary to have two or more of these groups in the compound.

Specific examples of the crosslinkable compound having an epoxy group or isocyanate group include a crosslinkable compound having an epoxy group or isocyanate group described on pages 63 to 64 of International Publication WO2014/171493.

As for the specific example of the crosslinkable compound which has an oxetane group, the crosslinkable compound of formula [4a] - formula [4k] published on page 58 - page 59 of international publication WO2011/132751 is mentioned.

As for the specific example of the crosslinkable compound which has a cyclocarbonate group, the crosslinkable compound of formula [5-1] - formula [5-42] published on page 76 - page 82 of international publication WO2012/014898 is mentioned.

Specific examples of the crosslinkable compound having a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group include the melamine derivative or benzoguanamine derivative described on pages 65 to 66 of International Publication No. 2014/171493, and the formula [6-1] to page 66 of WO2011/132751, which is published cross-linkable compounds of

The content of the specific crosslinkable compound in the resin composition is preferably from 0.1 to 100 parts by mass, more preferably from 0.1 to 50 parts by mass, and most preferably from 1 to 30 parts by mass, based on 100 parts by mass of all polymer components.

It is preferable to introduce into the resin composition at least one type of generator (also referred to as a specific generator) selected from the group consisting of photoradical generators, photoacid generators and photobase generators.

Specific examples of the specific generator include the specific generator described on pages 54 to 56 of International Publication No. 2014/171493. Especially, it is preferable to use an optical radical generating agent for a specific generating agent from the point of adhesiveness of the liquid crystal layer of a liquid crystal display element and an electrode.

For the resin composition, a compound that improves the film thickness uniformity and surface smoothness of the resin film when the resin composition is applied can be used. In addition, a compound or the like that improves the adhesion between the resin film and the substrate may be used.

As a compound which improves the uniformity of the film thickness and surface smoothness of a resin film, a fluorochemical surfactant, a silicone type surfactant, or a nonionic surfactant etc. are mentioned. Specifically, the surfactant described on page 67 of International Publication No. WO2014/171493 is mentioned. Moreover, the use ratio is preferably from 0.01 to 2 parts by mass, more preferably from 0.01 to 1 part by mass, based on 100 parts by mass of all the polymer components contained in the resin composition.

As a specific example of the compound which improves the adhesiveness of a resin film and a board|substrate, the compound described in the 67th page - 69th page of International Publication WO2014/171493 is mentioned. Moreover, the use ratio is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass, based on 100 parts by mass of all the polymer components contained in the resin composition.

In addition to compounds other than those described above, a dielectric or conductive material for the purpose of changing electrical properties such as permittivity and conductivity of the resin film may be added to the resin composition.

<Method for manufacturing resin film and liquid crystal display element>

The substrate used for the liquid crystal display element is not particularly limited as long as it is a substrate having high transparency, and plastic substrates such as acrylic substrates, polycarbonate substrates, PET substrates, and further films thereof can be used in addition to glass substrates. In particular, when used for a light control window or the like, a plastic substrate or film is preferable. Further, from the viewpoint of process simplification, it is preferable to use a substrate on which an ITO electrode for driving a liquid crystal, an indium zinc oxide (IZO) electrode, an indium gallium zinc oxide (IGZO) electrode, an organic conductive film, or the like is formed. Further, in the case of a reflection type liquid crystal display element, a substrate formed with a metal such as a silicon wafer or aluminum or a dielectric multilayer film can be used as long as it is only a substrate on one side.

A liquid crystal display element has a resin film obtained from the resin composition containing a specific polymer on at least one side of the board|substrate provided with an electrode. In particular, it is preferable that there are resin films on both substrates. The method of applying the resin composition is not particularly limited, but industrially, there are screen printing, offset printing, flexographic printing, inkjet method, dip method, roll coater method, slit coater method, spinner method, spray method, etc., and can be appropriately selected according to the type of substrate or the film thickness of the intended resin film.

After the resin composition is applied on the substrate, the solvent is evaporated by a heating means such as a hot plate, a heat circulation oven, an IR (infrared ray) oven, or the like at a temperature of 30 to 300° C., preferably 30 to 250° C., depending on the type of substrate or the solvent used in the resin composition, to form a resin film. In particular, when a plastic substrate is used for the substrate, it is preferable to process at a temperature of 30 to 150°C.

When the thickness of the resin film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and when the thickness is too thin, the reliability of the element may decrease. Therefore, it is preferably 5 to 500 nm. More preferably, it is 10-300 nm, Especially preferably, it is 10-250 nm.

The liquid crystal composition used for the liquid crystal display element is the above liquid crystal composition, and a spacer for controlling an electrode gap (also referred to as a gap) of the liquid crystal display element may be introduced into the liquid crystal composition.

The method for injecting the liquid crystal composition into the liquid crystal cell is not particularly limited, and examples thereof include the following method. That is, when a glass substrate is used as a substrate, a pair of substrates on which a resin film is formed is prepared, four substrates on one side are coated with a sealant except for a part, and then the surface of the resin film is turned inside, and the substrate on the other side is bonded to produce an empty cell. Then, a method of obtaining a liquid crystal composition injection cell by injecting the liquid crystal composition under reduced pressure from a place where no sealant is applied is exemplified. In the case of using a plastic substrate or film as the substrate, a pair of substrates on which a resin film is formed is prepared, a liquid crystal composition is dropped onto one substrate by a one drop filling (ODF) method or an inkjet method, and then the other substrate is bonded to obtain a liquid crystal composition injection cell. In the liquid crystal display element of the present invention, since the adhesion between the liquid crystal layer and the electrode is high, it is not necessary to apply the sealant to the four sides of the substrate.

The gap of the liquid crystal display element can be controlled with the above spacer or the like. The method includes, as described above, a method of introducing a spacer of a target size into the liquid crystal composition, a method of using a substrate having a column spacer of a target size, and the like. In addition, when a plastic or film substrate is used for the substrate and the bonding of the substrate is performed by lamination, the gap can be controlled without introducing a spacer.

The size of the gap of the liquid crystal display element is preferably 1 to 100 μm, more preferably 1 to 50 μm. Especially preferably, it is 2-30 micrometers. When the gap is too small, the contrast of the liquid crystal display element is lowered, and when the gap is too large, the drive voltage of the element is high.

A liquid crystal display element is obtained by hardening a liquid crystal composition and forming a liquid crystal layer in a state in which part or all of the liquid crystal composition exhibits liquid crystallinity. Curing of this liquid crystal composition is performed by irradiating ultraviolet rays to the cell into which the said liquid crystal composition was injected. As a light source of an ultraviolet irradiation device, a metal halide lamp or a high-pressure mercury lamp is mentioned, for example. 250-400 nm is preferable and, as for the wavelength of an ultraviolet-ray, 310-370 nm is more preferable. Moreover, you may heat-process after irradiating an ultraviolet-ray. As temperature at that time, 40-120 degreeC is preferable, More preferably, it is 40-80 degreeC.

Example

Although the present invention will be described in more detail below with reference to examples, it is not limited thereto. Abbreviations used below are as follows.

<liquid crystal>

L1: MLC-2003 (manufactured by Merck)

<polymerizable compound>

[Formula 17]

R3: Blemmer TA-604AU (manufactured by Nichiyu Co., Ltd.)

<Optical Radical Initiator>

[Formula 18]

<specific diamine>

[Formula 19]

<Second diamine>

[Formula 20]

<Other diamines>

[Formula 21]

<Specific tetracarboxylic acid component>

[Formula 22]

<Monomer for producing polysiloxane-based polymer>

E1: 3-methacryloxypropyltrimethoxysilane

E2: tetraethoxysilane

<Specific Crosslinkable Compound>

[Formula 23]

＜Specific accelerators＞

[Formula 24]

<Solvent>

NMP: N-methyl-2-pyrrolidone, γ-BL: γ-butyrolactone

BCS: ethylene glycol monobutyl ether

PB: propylene glycol monobutyl ether

PGME: Propylene glycol monomethyl ether

ECS: Ethylene glycol monoethyl ether

EC: Diethylene glycol monoethyl ether

"Measurement of Molecular Weight of Polyimide Polymers"

It was measured as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko) and columns (KD-803, KD-805) (manufactured by Shodex).

Column temperature: 50 ℃

Eluent: N,N'-dimethylformamide (As an additive, lithium bromide-hydrate (LiBr H ₂ O) is 30 mmol/L (liter), 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 weight; about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; about 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratory).

"Measurement of imidation rate of polyimide polymer"

20 mg of polyimide powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Scientific Co., Ltd.)), deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixture) (0.53 ml) was added, and ultrasonic waves were applied to completely dissolve. A 500 MHz proton NMR was measured for this solution with an NMR measuring device (JNW-ECA500) (manufactured by JEOL Datum Co., Ltd.). The imidation rate was determined by determining a proton derived from a structure that does not change before and after imidization as a reference proton, and using the peak integrated value of this proton and the proton peak integrated value derived from the NH group of amic acid appearing around 9.5 ppm to 10.0 ppm, it was obtained by the following formula.

Imidization rate (%) = (1 - α x / y) × 100

(x is the peak integration value of protons derived from the NH group of amic acid, y is the peak integration value of standard protons, and α is the ratio of the number of standard protons to one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%))

"Synthesis of Polyimide Polymers"

<Synthesis Example 1>

D2 (3.06 g, 12.2 mmol), A1 (4.10 g, 15.5 mmol) and C1 (1.68 g, 15.5 mmol) were mixed in NMP (33.2 g) and reacted at 80°C for 4 hours, then D1 (3.60 g, 18.4 mmol) and NMP (16.6 g) were added, It was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (1) whose resin solid content concentration is 20 mass % was obtained. The number average molecular weight (also referred to as Mn) of this polyamic acid was 18,500, and the weight average molecular weight (also referred to as Mw) was 66,500.

<Synthesis Example 2>

After adding NMP to the polyamic acid solution (1) (30.0 g) obtained by the method of Synthesis Example 1 and diluting to 6% by mass, acetic anhydride (3.60 g) and pyridine (2.30 g) were added as an imidation catalyst, and the mixture was reacted at 60°C for 1.5 hours. This reaction solution was poured into methanol (450 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (2). The imidation ratio of this polyimide was 51%, Mn was 16,100, and Mw was 43,500.

<Synthesis Example 3>

D4 (1.01 g, 5.10 mmol) and A1 (3.41 g, 12.9 mmol) were mixed in γ-BL (15.8 g), reacted at 60°C for 6 hours, then D1 (1.50 g, 7.65 mmol) and γ-BL (7.90 g) were added, reacted at 40°C for 8 hours, and the resin solid content A polyamic acid solution (3) having a concentration of 20% by mass was obtained. Mn of this polyamic acid was 10,500 and Mw was 34,700.

<Synthesis Example 4>

D4 (2.36 g, 11.9 mmol), A1 (2.28 g, 8.61 mmol), A2 (0.70 g, 3.44 mmol) and B1 (0.79 g, 5.17 mmol) were mixed in γ-BL (19.0 g), reacted at 60 ° C. for 6 hours, and D1 (1.00 g, 5.1 0 mmol) and γ-BL (9.50 g) were added, and it was made to react at 40 degreeC for 8 hours, and the polyamic acid solution (4) whose resin solid content concentration is 20 mass % was obtained. Mn of this polyamic acid was 12,500 and Mw was 37,700.

<Synthesis Example 5>

D2 (1.70 g, 6.80 mmol), A2 (2.80 g, 13.8 mmol), and B1 (0.52 g, 3.44 mmol) were mixed in γ-BL (18.7 g), reacted at 60°C for 6 hours, and then D1 (2.00 g, 10.2 mmol) and γ-BL (9.37 g) was added, and it was made to react at 40 degreeC for 8 hours, and the polyamic acid solution (5) whose resin solid content concentration is 20 mass % was obtained. Mn of this polyamic acid was 10,900 and Mw was 35,100.

<Synthesis Example 6>

D2 (1.62 g, 6.46 mmol), A3 (2.32 g, 6.54 mmol), B1 (1.00 g, 6.54 mmol) and C1 (0.35 g, 3.27 mmol) were mixed in γ-BL (19.2 g), reacted at 60 ° C. for 6 hours, and D1 (1.90 g, 9.6 9 mmol) and γ-BL (9.58 g) were added, and it was made to react at 40 degreeC for 8 hours, and the polyamic acid solution (6) whose resin solid content concentration is 20 mass % was obtained. Mn of this polyamic acid was 13,200 and Mw was 45,100.

<Synthesis Example 7>

D3 (3.80 g, 17.0 mmol), A1 (2.72 g, 10.3 mmol), A2 (0.70 g, 3.44 mmol), and C1 (0.37 g, 3.43 mmol) were mixed in NMP (30.4 g), reacted at 40°C for 12 hours, and a polyamic acid having a resin solid content concentration of 20% by mass. A solution (7) was obtained. Mn of this polyamic acid was 15,800 and Mw was 52,500.

<Synthesis Example 8>

After adding NMP to the polyamic acid solution (7) (30.0 g) obtained by the method of Synthesis Example 7 and diluting to 6% by mass, acetic anhydride (3.60 g) and pyridine (2.35 g) were added as imidation catalysts, and the mixture was reacted at 60°C for 2 hours. This reaction solution was poured into methanol (450 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (8). The imidation ratio of this polyimide was 48%, Mn was 14,600, and Mw was 40,900.

<Synthesis Example 9>

D2 (2.13 g, 8.50 mmol) and C1 (2.33 g, 21.5 mmol) were mixed in NMP (18.5 g) and reacted at 80°C for 4 hours. A 0% by mass polyamic acid solution (9) was obtained. The Mn of this polyamic acid was 22,800 and the Mw was 70,200.

<Synthesis Example 10>

D4 (1.35 g, 6.80 mmol), B1 (1.31 g, 8.61 mmol) and C1 (0.93 g, 8.61 mmol) were mixed in γ-BL (14.9 g) and reacted at 60°C for 6 hours, then D1 (2.00 g, 10.2 mmol) and γ-BL (7.45 g) was added, and it was made to react at 40 degreeC for 8 hours, and the polyamic acid solution (10) whose resin solid content concentration is 20 mass % was obtained. Mn of this polyamic acid was 14,800 and Mw was 43,200.

Table 1 shows raw material components and imidation ratios of the polyimide-based polymers obtained in Synthesis Examples 1 to 10. In Table 1, *1 represents polyamic acid.

"Synthesis of polysiloxane polymers"

<Synthesis Example 11>

In a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube, EC (29.0 g), E1 (8.80 g) and E2 (36.2 g) were mixed to prepare an alkoxysilane monomer solution. To this solution, a previously prepared solution by mixing EC (14.5 g), water (11.0 g), and oxalic acid (0.50 g) as a catalyst was added dropwise at 25°C over 30 minutes, and further stirred at 25°C for 30 minutes. Then, after heating using an oil bath and making it reflux for 30 minutes, it stood to cool and obtained the polysiloxane solution (1) whose _SiO2 conversion density|concentration is 12 mass %.

<Synthesis Example 12>

In a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube, ECS (29.0 g), E1 (11.5 g) and E2 (33.5 g) were mixed to prepare an alkoxysilane monomer solution. To this solution, a solution previously prepared by mixing ECS (14.0 g), water (11.0 g), and oxalic acid (0.50 g) as a catalyst was added dropwise at 25°C over 30 minutes, and further stirred at 25°C for 30 minutes. Then, after heating using an oil bath and making it reflux for 30 minutes, it stood to cool and obtained the polysiloxane solution (2) whose _SiO2 conversion density|concentration is 12 mass %.

Each component of the polysiloxane-type polymer obtained in the said synthesis example 11, 12 is shown in Table 2.

"Manufacture of resin composition"

In Examples 1 to 14 and Comparative Examples 1 and 2 to be described below, production examples of resin compositions are described. These resin compositions are used also for manufacture of a liquid crystal display element and its evaluation. The aspect of these resin compositions is shown in Table 3 - Table 5.

"Manufacture of Liquid Crystal Composition"

<Manufacture of liquid crystal composition (1)>

L1 (12.0g), R1 (2.00g), R2 (2.40g), R3 (3.00g) and P1 (0.60g) were mixed, and it stirred at 25 degreeC for 6 hours, and obtained the liquid crystal composition (1).

"Manufacture of liquid crystal display elements (glass substrate)"

The resin composition obtained by the methods of Examples and Comparative Examples described below was filtered under pressure with a membrane filter having a pore diameter of 1 μm. The obtained solution was spin-coated on the ITO surface of a 100 × 100 mm ITO electrode-formed glass substrate (length: 100 mm, width: 100 mm, thickness: 0.7 mm) washed with pure water and IPA (isopropyl alcohol), and heat treatment was performed on a hot plate at 100 ° C. for 5 minutes and at 210 ° C. for 30 minutes in a heat circulation type clean oven to obtain a film thickness An ITO substrate on which a 100 nm resin film was formed was obtained. Two obtained ITO substrates with resin films were prepared, and a spacer having a particle size of 10 µm was applied to the resin film surface of one of the substrates. Thereafter, the liquid crystal composition (1) was dropped on the resin film surface of the substrate coated with the spacer by ODF (One Drop Filling) method, and then bonded so that the resin film interface of the other substrate faced each other to obtain a liquid crystal display device before treatment. In Comparative Example 3, a spacer having a particle diameter of 10 μm was applied to the ITO surface of the ITO substrate without preparing a resin film, and a liquid crystal composition was added dropwise and bonded in the same manner as above, to prepare a liquid crystal display element before treatment.

The liquid crystal display element before this process was irradiated with ultraviolet rays for 40 seconds of irradiation time by cutting a wavelength of 350 nm or less using a metal halide lamp having an illuminance of 20 mW/cm 2 . At that time, the temperature in the irradiation device when irradiating the liquid crystal cell with ultraviolet rays was controlled to 25°C. In this way, a liquid crystal display element (glass substrate) was obtained.

"Manufacture of liquid crystal display elements (plastic substrate)"

The resin composition obtained by the methods of Examples and Comparative Examples described below was filtered under pressure with a membrane filter having a pore diameter of 1 µm. The obtained solution was applied with a bar coater on the ITO surface of a PET (polyethylene terephthalate) substrate (length: 150 mm, width: 150 mm, thickness: 0.2 mm) on which a 150 × 150 mm ITO electrode was formed washed with pure water, and heat treatment was performed at 120 ° C. for 2 minutes in a heat circulation type clean oven to obtain an ITO substrate with a resin film having a film thickness of 100 nm. got it Two obtained ITO substrates with resin films were prepared, and a spacer having a particle size of 10 µm was applied to the resin film surface of one of the substrates. Thereafter, the liquid crystal composition (1) was dropped by the ODF method on the resin film surface of the substrate coated with the spacer, and then bonded so that the resin film interfaces of the other substrate faced each other to obtain a liquid crystal display element before treatment. In Comparative Example 4, without preparing a resin film, a spacer having a particle size of 10 μm was applied to the ITO surface of the ITO substrate, and a liquid crystal composition was added dropwise and bonded in the same manner as above to prepare a liquid crystal display element before treatment.

The liquid crystal display element before this process was irradiated with ultraviolet rays by the method similar to the said "manufacture of liquid crystal display element (glass substrate)", and the liquid crystal display element (plastic substrate) was obtained.

"Evaluation of optical characteristics (scattering characteristics and transparency)"

Evaluation of the scattering characteristics when no voltage was applied visually observed the liquid crystal display elements (glass substrate and plastic substrate) in a state where no voltage was applied. Specifically, those in which the liquid crystal display element was clouded, that is, those in which scattering characteristics were obtained were considered excellent in this evaluation (good marks in the table).

Moreover, as a stability test in a high-temperature, high-humidity environment of a liquid crystal display element, observation after storage in a constant temperature and humidity chamber with a temperature of 80 degreeC and a humidity of 90%RH for 24 hours was also implemented. Specifically, the cloudiness state (scattering state) of the liquid crystal display element and the presence or absence of exfoliation or air bubbles in the element were confirmed, and the cloudiness state was obtained, and no exfoliation or air bubbles were generated. At that time, in Examples 3 to 7, observation after storage in a constant temperature and humidity chamber with a temperature of 80°C and a humidity of 90% RH for 72 hours was also performed as an intensive test in addition to the above standard test. The evaluation method is the same as above.

In addition, as a stability test of the liquid crystal display element against light irradiation, observation after irradiation with 5 J/cm 2 ultraviolet rays in terms of 365 nm was also conducted using a desktop type UV curing device (HCT3B28HEX-1) (manufactured by Senlight Co.). Specifically, the cloudiness state (scattering state) of the liquid crystal display element and the presence or absence of exfoliation or air bubbles in the element were confirmed, and the cloudiness state was obtained, and no exfoliation or air bubbles were generated.

Transparency evaluation at the time of voltage application measured the transmittance|permeability when 45 V was applied by alternating-current drive to the liquid crystal display element (glass substrate and plastic substrate) in voltage application state. Specifically, UV-3600 (manufactured by Shimadzu Corporation) was used for the measuring device, and the measurement was performed under conditions of a temperature of 25°C and a scan wavelength of 300 to 800 nm. At that time, in the case of a liquid crystal display element (glass substrate), a glass substrate with an ITO electrode was used as a reference (reference example), and in the case of a liquid crystal display element (plastic substrate), a PET substrate with an ITO electrode was used. Evaluation was made based on the transmittance|permeability of the wavelength of 550 nm, and the transparency was so excellent that the transmittance|permeability was high.

Moreover, as a stability test in a high-temperature, high-humidity environment of a liquid crystal display element, the measurement after storing for 24 hours in a constant temperature and humidity chamber with a temperature of 80 degreeC and a humidity of 90%RH was also performed. Specifically, it was presupposed that this evaluation was so excellent that the decrease ratio of the transmittance after storage in a constant temperature and humidity chamber was low with respect to the transmittance|permeability (initial value) immediately after liquid crystal display element manufacture. At that time, in Examples 3 to 7, in addition to the above standard test, measurement after storage in a constant temperature and humidity chamber with a temperature of 80°C and a humidity of 90% RH for 72 hours was also performed as an intensive test. The evaluation method is the same as above.

In addition, as a stability test for light irradiation of the liquid crystal display element, a tabletop UV curing device (HCT3B28HEX-1) (manufactured by Senlight) was used, and the transmittance after irradiation with 5 J/cm 2 ultraviolet rays in terms of 365 nm was also measured. Specifically, with respect to the transmittance (initial value) immediately after liquid crystal display element production, it was presupposed that this evaluation was so excellent that the decrease ratio of the transmittance|permeability after ultraviolet irradiation was low.

Tables 6-8 show the evaluation results of scattering characteristics and transmittance (%) immediately after liquid crystal display element production (initial stage), after storage in a constant temperature and humidity chamber (constant temperature and humidity), and after ultraviolet irradiation (ultraviolet rays).

"Evaluation of adhesion between liquid crystal layer and resin film (resin film and electrode)"

The liquid crystal display element (glass substrate and plastic substrate) was stored in a constant temperature and humidity chamber at a temperature of 80 ° C. and a humidity of 90% RH for 24 hours, and peeling of the liquid crystal display element and the presence or absence of air bubbles were confirmed (as a stability test of the liquid crystal display element in a high-temperature, high-humidity environment). Specifically, this evaluation was judged to be excellent in that the separation of the element (a state in which the liquid crystal layer and the resin film, or the resin film and the electrode are separated) did not occur and that bubbles were not generated in the element (good mark in the table). At that time, in Examples 3 to 7, in addition to the above standard test, confirmation after storage in a constant temperature and humidity chamber at a temperature of 80 ° C. and a humidity of 90% RH for 72 hours was also performed as an intensive test. In addition, the evaluation method is the same as the above.

In addition, the liquid crystal display element was checked using a tabletop UV curing device (HCT3B28HEX-1) (manufactured by Senlight Co.) and irradiated with 5 J/cm 2 ultraviolet rays in terms of 365 nm (as a stability test for the liquid crystal display element against light irradiation). Specifically, the fact that the element did not peel off and the element did not generate air bubbles was evaluated as excellent (good marks in the table).

Tables 9 to 11 show the results of adhesion between the liquid crystal layer and the resin film (resin film and electrode) after storage in a constant temperature and humidity chamber (constant temperature and humidity) and after ultraviolet irradiation (ultraviolet rays).

"Manufacture of resin composition"

<Example 1>

NMP (12.1 g) was added to the polyamic acid solution (1) (5.40 g) obtained by the method of synthesis example 1, and it stirred at 25 degreeC for 1 hour. Then, BCS (10.4g) and PB (2.98g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the resin composition (1).

<Example 2>

NMP (15.8g) was added to polyimide powder (2) (1.20g) obtained by the method of synthesis example 2, and it stirred and dissolved at 70 degreeC for 24 hours. Then, BCS (4.32g) and PB (8.64g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the resin composition (2).

<Example 3>

γ-BL (0.15 g) and PGME (22.9 g) were added to the polyamic acid solution (3) (3.00 g) obtained by the method of Synthesis Example 3, and the mixture was stirred at 25°C for 6 hours to obtain a resin composition (3).

<Example 4>

γ-BL (0.15 g), PGME (22.9 g) and K2 (0.042 g) were added to the polyamic acid solution (3) (3.00 g) obtained by the method of Synthesis Example 3, and stirred at 25 ° C. for 6 hours to obtain a resin composition (4).

<Example 5>

γ-BL (0.15 g), PGME (22.9 g), K2 (0.042 g) and N1 (0.018 g) were added to the polyamic acid solution (3) (3.00 g) obtained by the method of Synthesis Example 3, and stirred at 25 ° C. for 6 hours to obtain a resin composition (5).

<Example 6>

γ-BL (2.70 g), PB (2.55 g) and PGME (17.8 g) were added to the polyamic acid solution (4) (3.00 g) obtained by the method of Synthesis Example 4, and stirred at 25 ° C. for 6 hours to obtain a resin composition (6).

<Example 7>

γ-BL (2.70 g), PB (2.55 g), PGME (17.8 g) and K1 (0.060 g) were added to the polyamic acid solution (4) (3.00 g) obtained by the method of Synthesis Example 4, and stirred at 25 ° C. for 6 hours to obtain a resin composition (7).

<Example 8>

γ-BL (3.97 g), PGME (19.1 g) and K1 (0.018 g) were added to the polyamic acid solution (5) (3.00 g) obtained by the method of Synthesis Example 5, and stirred at 25°C for 6 hours to obtain a resin composition (8).

<Example 9>

γ-BL (0.15 g) and PGME (22.9 g) were added to the polyamic acid solution (6) (3.00 g) obtained by the method of Synthesis Example 6, and the mixture was stirred at 25°C for 6 hours to obtain a resin composition (9).

<Example 10>

γ-BL (0.15 g), PGME (22.9 g), K2 (0.060 g) and N1 (0.030 g) were added to the polyamic acid solution (6) (3.00 g) obtained by the method of Synthesis Example 6, and stirred at 25 ° C. for 6 hours to obtain a resin composition (10).

<Example 11>

NMP (13.6 g) was added to the polyamic acid solution (7) (5.40 g) obtained by the method of Synthesis Example 7, and the mixture was stirred at 25°C for 1 hour. Then, PB (11.9g) and K2 (0.054g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the resin composition (11).

<Example 12>

NMP (15.8g) was added to the polyimide powder (8) (1.20g) obtained by the method of synthesis example 8, and it stirred and dissolved at 70 degreeC for 24 hours. Then, BCS (2.88g), PB (10.1g), K2 (0.084g) and N1 (0.036g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the resin composition (12).

<Example 13>

EC (3.93 g) and PB (12.7 g) were added to the polysiloxane solution (1) (10.0 g) obtained by the method of Synthesis Example 11, and the mixture was stirred at 25°C for 6 hours to obtain a resin composition (13).

<Example 14>

ECS (4.78 g), PGME (25.2 g) and N1 (0.036 g) were added to the polysiloxane solution (2) (10.0 g) obtained by the method of Synthesis Example 12, and stirred at 25°C for 6 hours to obtain a resin composition (14).

<Comparative Example 1>

NMP (12.1 g) was added to the polyamic acid solution (9) (5.40 g) obtained by the method of Synthesis Example 9, and the mixture was stirred at 25°C for 1 hour. Then, BCS (10.4 g) and PB (2.98 g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the resin composition (15).

<Comparative Example 2>

γ-BL (0.15 g) and PGME (22.9 g) were added to the polyamic acid solution (10) (3.00 g) obtained by the method of Synthesis Example 10, and the mixture was stirred at 25°C for 6 hours to obtain a resin composition (16).

The characteristics of the resin compositions (1) to (16) obtained in Examples 1 to 14 and Comparative Examples 1 and 2 are shown in Tables 3 to 5. Further, in all of these resin compositions (1) to (16), abnormalities such as turbidity and precipitation were not observed, and they were uniform solutions.

In Tables 3 to 5, the numerical values in parentheses for the specific crosslinkable compound and specific generator added to each resin composition indicate the content with respect to 100 parts by mass of the specific polymer, respectively.

<Examples 1 to 14 and Comparative Examples 1 to 4>

As shown in Tables 6 to 11 below, any one of the resin compositions (1) to (16) obtained above and the liquid crystal composition (1) were used to evaluate optical properties (scattering properties and transparency), and to evaluate the adhesion between the liquid crystal layer and the resin film (resin film and electrode). In that case, as mentioned above, in Comparative Examples 3 and 4, the liquid crystal display element was manufactured and each evaluation was performed, without manufacturing a resin film.

Further, in Examples 1, 2, 11, 12 and Comparative Examples 1 and 3, a liquid crystal display element was manufactured with a glass substrate and each evaluation was performed, while Examples 3 to 10, 13 and 14 and Comparative Examples 2 and 4 produced a liquid crystal display element with a plastic substrate and each evaluation was performed. The results of these evaluations were put together in Tables 6 to 11 and shown.

In Examples 3 to 7, in the evaluation of the optical properties (scattering characteristics and transparency) and the evaluation of the adhesion between the liquid crystal layer and the resin film (the resin film and the electrode), evaluation was performed as an emphasis test when stored for 72 hours in a constant temperature and humidity chamber at a temperature of 80 ° C. and a humidity of 90% RH (other conditions are the same as the above conditions).

*1: A small amount of air bubbles were observed in the element.

*2: Air bubbles were seen in the element (more than *1).

*3: Many air bubbles were seen in the element (more than *2).

As can be seen from the above, the liquid crystal display elements of Examples have better optical characteristics than those of Comparative Examples, that is, good liquid crystal display elements after storage in a constant temperature and humidity chamber and transparency after ultraviolet irradiation. Furthermore, it became a liquid crystal display element with high adhesion between the liquid crystal layer and the resin film (resin film and electrode), and even after these were exposed to harsh environments, peeling or air bubbles were not observed in the liquid crystal display element. In particular, even if a plastic substrate was used for the substrate of the liquid crystal display element, these characteristics were good. Specifically, in the comparison under the same conditions, it is a comparison between Example 1 and Comparative Examples 1 and 3, and a comparison between Example 3 and Comparative Examples 2 and 4.

In addition, when a specific crosslinkable compound was introduced into the resin composition, even after storage in a constant temperature and humidity chamber for a long time, particularly in the stress test, there were few bubbles generated in the liquid crystal display element and high transparency was obtained. Specifically, in the comparison under the same conditions, it is a comparison between Example 3 and Example 4 and a comparison between Example 6 and Example 7.

In addition, when a specific generator was introduced into the resin composition, bubbles were not generated in the liquid crystal display element even in the above-mentioned highlighting test, and transparency was high. Specifically, in the comparison under the same conditions, it is a comparison between Example 4 and Example 5.

The liquid crystal display element of the present invention can be suitably used for a normal type element that enters a scattering state when no voltage is applied and becomes a transparent state when voltage is applied. These elements can be used for a liquid crystal display for display purposes, a light control window or an optical shutter element for controlling blocking and transmission of light, and a plastic substrate can be used for the substrate of the element.

In addition, all the content of the JP Patent application 2017-145481, the claim, and the abstract for which it applied on July 27, 2017 is referred here, and it takes in as an indication of the specification of this invention.

Claims (17)

In a liquid crystal display device having a liquid crystal layer cured by irradiating ultraviolet rays to a liquid crystal composition containing a liquid crystal and a polymerizable compound disposed between a pair of substrates provided with electrodes, a resin composition for forming a resin film formed on a substrate provided with electrodes,
The resin composition contains a polymer having at least one structure selected from the group consisting of the following formula [1-a] to formula [1-i],
The resin composition contains a compound represented by the following formula K2,
A resin composition characterized in that it is used for a transmission-scattering type liquid crystal display device that enters a transmission state when a voltage is applied.

However, X ^a represents a hydrogen atom or a benzene ring.
According to claim 1,
The resin composition contains at least one selected from the group consisting of acrylic polymers, methacrylic polymers, novolac resins, polyhydroxystyrenes, polyimide precursors, polyimides, polyamides, polyesters, celluloses and polysiloxanes. According to claim 2,
The resin composition is a polyimide precursor obtained by using a diamine having at least one structure selected from the group consisting of the formula [1-a] to formula [1-i], and a polyimide. A resin composition containing at least one selected from the group consisting of. According to claim 3,
The resin composition in which the said diamine is a diamine which has a structure of following formula [1].

However, X ¹ represents a single bond, -O-, -NH-, -N(CH ₃ )-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- or -OCO-. X ² represents a single bond, an alkylene group of 1 to 18 carbon atoms, or an organic group of 6 to 24 carbon atoms having a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group of 1 to 3 carbon atoms, an alkoxyl group of 1 to 3 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, or a carbon atom. It may be substituted by the fluorine-containing alkoxyl group of -3 or a fluorine atom. X ³ represents a single bond, -O-, -NH-, -N(CH ₃ )-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- or -OCO-. X ⁴ represents a structure selected from the group consisting of the formula [1-a] to formula [1-i]. m represents the integer of 1-4. According to claim 4,
A resin composition wherein the diamine is a diamine of the following formula [1a].

However, X represents the structure of said formula [1]. n represents the integer of 1-4. According to claim 3,
The resin composition containing at least 1 sort(s) chosen from the group which the said resin composition consists of a polyimide precursor and polyimide obtained using the tetracarboxylic-acid component of following formula [3].

However, Z represents the structure chosen from the group which consists of following formula [3a] - formula [3l].

(Z ¹ to Z ⁴ each represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring. Z ⁵ and Z ⁶ each represent a hydrogen atom or a methyl group.) According to claim 1,
The resin composition containing a polysiloxane obtained by polycondensing an alkoxysilane of the following formula [A1], or a polysiloxane obtained by polycondensing an alkoxysilane of the following formula [A1] and an alkoxysilane of the following formula [A2].

However, A ^<1> represents the C2-C12 organic group which has at least 1 sort(s) of structure selected from the group which consists of said formula [1-a] - formula [1-i]. A ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A ³ represents an alkyl group of 1 to 5 carbon atoms. m represents an integer of 1 or 2; n represents the integer of 0-2. p represents an integer of 0 to 3; However, m + n + p is 4.

However, B ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. B ² represents an alkyl group of 1 to 5 carbon atoms. n represents the integer of 0-3. delete delete delete delete According to claim 1,
The resin composition contains at least one selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, and solvents represented by the following formulas [D1] to [D3].

However, D ¹ and D ² represent an alkyl group having 1 to 3 carbon atoms. D ³ represents an alkyl group having 1 to 4 carbon atoms. According to claim 1,
The resin composition containing at least 1 sort(s) chosen from the group which the said resin composition consists of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and (gamma)-butyrolactone. A resin film obtained using the resin composition according to any one of claims 1 to 7, 12 and 13. A liquid crystal display element in which the resin film according to claim 14 is formed on a substrate provided with an electrode. According to claim 15,
A liquid crystal display element in which the substrate provided with the electrode is a plastic substrate. delete