Resin composition, resin film, and liquid crystal display element
阅读说明：本技术 树脂组合物、树脂膜以及液晶显示元件 (Resin composition, resin film, and liquid crystal display element ) 是由 保坂和义 片山雅章 铃木加名子 高桥真文 于 2020-03-06 设计创作，主要内容包括：本发明的目的在于提供一种显现良好的光学特性、液晶显示元件的驱动电压变低的液晶显示元件。一种液晶显示元件,其特征在于,所述液晶显示元件是如下透射散射型的液晶显示元件：具有对配置于具备电极的一对基板之间的包含液晶和聚合性化合物的液晶组合物赋予活性能量射线和热中的至少一方来使其固化而成的液晶层,并且,在基板的至少一方具备树脂膜,而且,所述液晶显示元件在未施加电压时成为散射状态,在施加电压时成为透明状态,所述树脂膜是使用包含具有选自下述式[1-1]和式[1-2]中的至少一种结构的聚合物的树脂组合物而得到的。式中的记号的定义如说明书中所述。,-X～(7)-X～(8)[1-2]。(The invention provides a liquid crystal display element exhibiting excellent optical characteristics and having a low driving voltage. A liquid crystal display element characterized in that the liquid crystal display element is transmissive as followsScattering-type liquid crystal display element: the liquid crystal display device comprises a liquid crystal layer obtained by applying at least one of active energy rays and heat to a liquid crystal composition comprising a liquid crystal and a polymerizable compound disposed between a pair of substrates provided with electrodes and curing the composition, wherein at least one of the substrates is provided with a resin film, and the liquid crystal display element is in a scattering state when no voltage is applied and is in a transparent state when a voltage is applied, and the resin film is used by including a material having a structure selected from the following formulas [1-1 ]]And formula [1-2 ]]A resin composition of a polymer having at least one structure of (1). The symbols in the formula are defined as the specification. ，‑X 7 ‑X 8 [1‑2]。)
1. A liquid crystal display element is characterized in that,
the liquid crystal display element is a transmission scattering type liquid crystal display element as follows: the liquid crystal display device includes a liquid crystal layer obtained by applying at least one of active energy rays and heat to a liquid crystal composition containing a liquid crystal and a polymerizable compound disposed between a pair of substrates provided with electrodes and curing the composition, and a resin film provided on at least one of the substrates, wherein the liquid crystal display element is in a scattering state when no voltage is applied and is in a transparent state when a voltage is applied,
the resin film is obtained by using a resin composition containing a polymer having at least one structure selected from the following formulas [1-1 ] and [1-2 ],
formula [1-1 ]]In, X1Represents a group selected from a single bond, - (CH)2)a－、－O－、－CH2O－、－CONH－、－NHCO－、－CON(CH3)－、－N(CH3)CO－At least one of-COO-or-OCO-, the- (CH)2)aIn the formula, a is an integer of 1-15; x2Represents a single bond or- (CH)2)b-, said- (CH)2)bIn the formula, b is an integer of 1-15; x3Represents a group selected from a single bond, - (CH)2)c－、－O－、－CH2At least one of O-, -COO-or-OCO-, and the- (CH)2)cIn the formula, c is an integer of 1 to 15; x4Represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms, wherein any hydrogen atom in the cyclic group is optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms or a fluorine atom; x5Represents a cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, wherein any hydrogen atom on the cyclic group is optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom; xn represents an integer of 0 to 4; x6Represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluoroalkoxy group having 1 to 18 carbon atoms,
-X7-X8 [1-2]
formula [1-2 ]]In, X7Represents a single bond, -O-, -CH2O－、－CONH－、－NHCO－、－CON(CH3)－、－N(CH3) CO-, -COO-or-OCO-, X8Represents an alkyl group having 8 to 22 carbon atoms or a fluoroalkyl group having 6 to 18 carbon atoms.
2. The liquid crystal display element according to claim 1,
the polymer further has at least one structure selected from the following formulas [ 2-a ] to [ 2-i ],
wherein, YARepresents a hydrogen atom or a benzene ring.
3. The liquid crystal display element according to claim 1 or 2,
the resin composition further comprises: a polymer having at least one structure selected from the following formulae [ 2-a ] to [ 2-i ],
wherein, YARepresents a hydrogen atom or a benzene ring.
4. The liquid crystal display element according to any one of claims 1 to 3,
the polymer is at least one selected from the group consisting of acrylic polymers, methacrylic polymers, novolac resins, polyhydroxystyrene, polyimide precursors, polyimide, polyamide, polyester, cellulose, and polysiloxane.
5. The liquid crystal display element according to claim 4,
the polymer is a polyimide precursor obtained by a reaction of a diamine component and a tetracarboxylic acid component, or a polyimide obtained by imidizing the polyimide precursor.
6. The liquid crystal display element according to claim 5,
the diamine component comprises: a diamine having at least one structure selected from the group consisting of the formulas [1-1 ] and [1-2 ].
7. The liquid crystal display element according to claim 6,
the diamine having at least one structure selected from the group consisting of the formula [1-1 ] and the formula [1-2 ] is the following formula [1a ],
in the formula [1a ], X represents the formula [1-1 ] or the formula [1-2 ], and Xm represents an integer of 1-4.
8. The liquid crystal display element according to any one of claims 5 to 7,
the diamine component contains a diamine having a structure represented by the following formula [2],
formula [2]]In, Y1Represents a single bond, -O-, -NH-, -N (CH)3)－、－CH2O－、－CONH－、－NHCO－、－CON(CH3)－、－N(CH3) CO-, -COO-or-OCO-; y is2An alkylene group having 1 to 18 carbon atoms or an organic group having 6 to 24 carbon atoms and having a cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, wherein any hydrogen atom in the cyclic group is optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms or a fluorine atom; y is3Represents a single bond, -O-, -NH-, -N (CH)3)－、－CH2O－、－CONH－、－NHCO－、－CON(CH3)－、－N(CH3) At least one of CO-, -COO-and-OCO-; y is4Represents a group selected from the formula [ 2-a]-formula [ 2-i]At least one structure of (a); yn represents an integer of 1 to 4.
9. The liquid crystal display element according to claim 8,
the diamine having the structure of the formula [2] is represented by the following formula [2a ],
in the formula [2a ], Y represents the structure of the formula [2], and Ym represents an integer of 1 to 4.
10. The liquid crystal display element according to any one of claims 5 to 9,
the tetracarboxylic acid component comprises a tetracarboxylic dianhydride represented by the following formula [3],
in the formula [3], Z represents any of the following formulas [3a ] to [3l ],
wherein Z isA～ZDRespectively represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, ZEAnd ZFEach represents a hydrogen atom or a methyl group.
11. The liquid crystal display element according to claim 4,
the polymer comprises: a polysiloxane obtained by polycondensing an alkoxysilane of the formula [ A1] or a polysiloxane obtained by polycondensing an alkoxysilane of the formula [ A1] with an alkoxysilane of the formula [ A2] and/or the formula [ A3],
(A1)mSi(A2)n(OA3)p [A1]
formula [ A1]In (A)1Represents said formula [1-1]Or formula [1-2]，A2Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, A3Represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, and p represents0 to 3, wherein m + n + p is 4,
(B1)mSi(B2)n(OB3)p [A2]
formula [ A2]In (B)1Represents an organic group having 2 to 12 carbon atoms selected from at least one of a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacryloyl group, an acryloyl group, a ureido group and a cinnamoyl group, B2Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, B3Represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, p represents an integer of 0 to 3, wherein m + n + p is 4,
(D1)nSi(OD2)4-n [A3]
formula [ A3]In (D)1Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, D2Represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3.
12. The liquid crystal display element according to any one of claims 1 to 11,
the liquid crystal composition comprises a compound of the following formula [5a ],
formula [5a ]]In, S1Represents the following formula [5-a]-formula [5-j]Any of (1); s2Represents a single bond, -O-, -NH-, -N (CH)3)-、-CH2O-、-CONH-、-NHCO-、-CON(CH3)-、-N(CH3) CO-, -COO-or-OCO-; s3Represents a single bond or- (CH)2)a-, said- (CH)2)aIn the formula, a is an integer of 1-15; s4Represents a single bond, -O-, -OCH2-, -COO-or-OCO-; s5Represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a steroid skeleton and 17 to 51 carbon atoms, any hydrogen atom on the cyclic group being optionally substituted by 1 to up to one carbon atom3 alkyl, alkoxy having 1 to 3 carbon atoms, fluoroalkyl having 1 to 3 carbon atoms, fluoroalkoxy having 1 to 3 carbon atoms, or fluorine atom; s6Represents a single bond, -O-, -CH2－、－OCH2－、－CH2O-, -COO-or-OCO-; s7Represents a cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, wherein any hydrogen atom on the cyclic group is optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom; s8Represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluoroalkoxy group having 1 to 18 carbon atoms; sm represents an integer of 0 to 4,
wherein S isARepresents a hydrogen atom or a benzene ring.
13. The liquid crystal display element according to claim 12,
the compound of the formula [5a ] is any of the following formulae [5 a-1 ] to [5 a-11 ],
wherein S isaEach represents-O-or-COO-, SbEach represents an alkyl group having 1 to 12 carbon atoms, p1 represents an integer of 1 to 10, p2 represents an integer of 1 or 2,
wherein S iscEach represents a single bond, -COO-or-OCO-, SdEach represents an alkyl group or an alkoxy group having 1 to 12 carbon atoms, each p3 represents an integer of 1 to 10, each p4 represents an integer of 1 or 2,
wherein S iseEach represents-O-or-COO-, SfEach represents a divalent organic group having a steroid skeleton and 17 to 51 carbon atoms, SgEach represents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 18 carbon atoms, and each p5 represents an integer of 1 to 10.
14. The liquid crystal display element according to any one of claims 1 to 13,
the resin composition further comprises: a crosslinkable compound having at least one member selected from the group consisting of an epoxy group, an isocyanate group, an oxetanyl group, a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group.
15. The liquid crystal display element according to any one of claims 1 to 14,
the substrate of the liquid crystal display element is a glass substrate or a plastic substrate.
16. A resin film which is a resin film for a liquid crystal display element described in any one of claims 1 to 15, the resin film being formed from a resin composition containing a polymer having at least one structure selected from the group consisting of the formula [1-1 ] and the formula [1-2 ].
17. A resin composition for forming the resin film of claim 16, comprising a polymer having at least one structure selected from the group consisting of the formula [1-1 ] and the formula [1-2 ].
Technical Field
The present invention relates to a transmission/scattering type liquid crystal display element which is brought into a scattering state when no voltage is applied and into a transmissive state when a voltage is applied.
Background
As a liquid crystal display element, a TN (twisted nematic) mode is put into practical use. In this mode, a polarizing plate is used to switch light by utilizing the optical rotation characteristics of liquid crystal. When the polarizing plate is used, the light use efficiency is lowered.
As a liquid crystal display element not using 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. Generally, a device using a polymer Dispersed Liquid crystal (also referred to as pdlc (polymer Dispersed Liquid crystal)) or a polymer Network Liquid crystal (also referred to as pnlc (polymer Network Liquid crystal)) is known.
In these liquid crystal display devices, a liquid crystal composition containing a polymerizable compound that is polymerized by ultraviolet light is disposed between a pair of substrates having electrodes, and the liquid crystal composition is cured by irradiation of ultraviolet light to form a composite of the liquid crystal and a cured product (for example, a polymer network) of the polymerizable compound. In addition, the scattering state and the transmission state of the liquid crystal are controlled by applying a voltage to the liquid crystal display element.
A liquid crystal display element using PDLC or PNLC is a liquid crystal display element (also referred to as a normal mode element) in which liquid crystal is in a white turbid (scattering) state because liquid crystal is oriented in a random direction when no voltage is applied, and is in a transmissive state when liquid crystal is aligned in an electric field direction when a voltage is applied. In this case, since the liquid crystal is random when no voltage is applied, a liquid crystal alignment film or an alignment treatment for aligning the liquid crystal in one direction is not necessary. Therefore, in this liquid crystal display device, the electrode and the liquid crystal layer (the composite of the liquid crystal and the cured product of the polymerizable compound) are directly connected (see patent documents 1 and 2).
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 3552328
Patent document 2: japanese patent No. 4630954
Disclosure of Invention
Problems to be solved by the invention
The polymerizable compound in the liquid crystal composition has an action of forming a polymer network to obtain desired optical characteristics and an action of improving adhesion between the liquid crystal layer and the electrode. However, in order to achieve these effects, a tight polymer network needs to be formed, and thus driving of liquid crystal molecules with respect to an applied voltage is hindered. Therefore, the driving voltage of the liquid crystal display device is higher than that of a TN mode liquid crystal display device or the like.
From the above viewpoint, an object of the present invention is to provide a liquid crystal display element exhibiting excellent optical characteristics and having a low driving voltage.
Means for solving the problems
The present inventors have conducted intensive studies to achieve the above object, and as a result, have completed the present invention having the following gist.
That is, the liquid crystal display device is a transmission/scattering type liquid crystal display device as follows: the liquid crystal display device includes a liquid crystal layer obtained by applying at least one of active energy rays and heat to a liquid crystal composition containing a liquid crystal and a polymerizable compound, which is disposed between a pair of substrates provided with electrodes, and curing the liquid crystal composition, and further includes a resin film provided on at least one of the substrates, wherein the liquid crystal display element is in a scattering state when no voltage is applied, and is in a transparent state when a voltage is applied, and the resin film is obtained by using a resin composition containing a polymer having at least one structure (also referred to as a specific structure (1)) selected from the following formulas [1-1 ] and [1-2 ].
X1Represents a single bond, - (CH)2)a- (a is an integer of 1 to 15), -O-, -CH2O－、－CONH－、－NHCO－、－CON(CH3)－、－N(CH3) CO-, -COO-or-OCO-. X2Represents a single bond or- (CH)2)b- (b is an integer of 1 to 15). X3Represents a single bond, - (CH)2)c- (c is an integer of 1 to 15), -O-, -CH2O-, -COO-or-OCO-. X4Represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms, wherein any hydrogen atom in the cyclic group is optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms or a fluorine atom. X5Represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, any hydrogen atom on the cyclic group is optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms orFluorine atom substitution. Xn represents an integer of 0 to 4. X6Represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluoroalkoxy group having 1 to 18 carbon atoms.
-X7-X8 [1-2]
X7Represents a single bond, -O-, -CH2O－、－CONH－、－NHCO－、－CON(CH3)－、－N(CH3) CO-, -COO-or-OCO-. X8Represents an alkyl group having 8 to 22 carbon atoms or a fluoroalkyl group having 6 to 18 carbon atoms.
Effects of the invention
According to the present invention, a liquid crystal display element having excellent optical characteristics and a low driving voltage of the liquid crystal display element can be obtained.
The mechanism for obtaining a liquid crystal display element having the above-described excellent characteristics by the present invention is not necessarily clear, but is estimated as follows.
The specific structure (1) has a long-chain alkyl group having a benzene ring, a cyclohexane ring, or the like. It is therefore assumed that: the resin film obtained from the resin composition containing the specific structure (1) can promote the driving of liquid crystal with the application of voltage, and reduce the driving voltage of the liquid crystal display element.
Further, since the structure of the formula [1-1 ] is rigid, the above-described effects can be obtained even with a small amount of use. Therefore, the hydrophobic structure on the resin film can be reduced, so that the adhesion between the liquid crystal layer and the resin film in the liquid crystal display device can be improved, and the reliability of the liquid crystal display device can be improved.
Then, a liquid crystal display element using a resin composition containing a polymer having the specific structure (1) becomes a liquid crystal display element having the above-described characteristics. Therefore, the liquid crystal display element of the present invention can be used for a liquid crystal display for display purposes, a light control window for controlling the cut-off and transmission of light, an optical shutter (optical shutter) element, and the like.
Detailed Description
< specific Structure (1) >
The specific structure (1) is a structure of the formula [1-1 ] or the formula [1-2 ].
Formula [1-1 ]]In, X1～X6And Xn are as defined above, wherein the following structures are preferred, respectively.
X is derived from the availability of raw materials and the ease of synthesis1Preferably a single bond, - (CH)2)a- (a is an integer of 1 to 15), -O-, -CH2O-or-COO-. More preferably a single bond, - (CH)2)a- (a is an integer of 1 to 10), -O-, -CH2O-or-COO-.
X2Preferably a single bond or- (CH)2)b- (b is an integer of 1 to 10).
From the viewpoint of ease of synthesis, X3Preferably a single bond, - (CH)2)a- (a is an integer of 1 to 15), -O-, -CH2O-or-COO-. More preferably a single bond, - (CH)2)a- (a is an integer of 1 to 10), -O-, -CH2O-or-COO-.
From the viewpoint of ease of synthesis, X4Preferably a benzene ring, a cyclohexane ring or an organic group having a steroid skeleton and having 17 to 51 carbon atoms.
X5Preferably a benzene ring or a cyclohexane ring.
X6Preferably an alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluoroalkoxy group having 1 to 10 carbon atoms. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Particularly preferably an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.
In view of availability of raw materials and ease of synthesis, Xn is preferably 0 to 3. More preferably 0 to 2.
X1～X6Preferable combinations of Xn and Xn include the same combinations as (2-1) to (2-629) described in tables 6 to 47 on pages 13 to 34 of International publication WO2011/132751 (published 2011.10.27). In tables of International publication, X in the present invention1～X6Represented by Y1-Y6, Xn is n, Y1-Y6 can be read as X1～X6N can be interpreted as Xn. In addition, (2-605) to (2-629) described in each table of the international publication, the organic group having 17 to 51 carbon atoms of the steroid skeleton in the present invention is represented by an organic group having 12 to 25 carbon atoms of the steroid skeleton, but the organic group having 12 to 25 carbon atoms of the steroid skeleton can be interpreted as an organic group having 17 to 51 carbon atoms of the steroid skeleton.
Among them, preferred is a combination of (2-25) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-268) to (2-315), (2-364) to (2-387), (2-436) to (2-483), or (2-603) to (2-615). Particularly preferred are (2-49) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-603) to (2-606), (2-607) to (2-609), (2-611), (2-612), and (2-624).
Formula [1-2 ]]In, X7And X8As defined above, among them, the following structures are preferred, respectively.
X7Preferably a single bond, -O-, -CH2O－、－CONH－、－CON(CH3) -or-COO-. More preferably a single bond, -O-, -CONH-or-COO-.
X8The alkyl group preferably has 8 to 18 carbon atoms.
As described above, the specific structure (1) in the present invention is preferably a structure represented by the formula [1-1 ] in terms of more efficiently reducing the driving voltage of the liquid crystal display element.
The specific structure (1) is preferably contained in a form of a repeating unit constituting the polymer. The polymer preferably contains 0.1 to 60 mol% of the repeating unit having the specific structure (1) based on the whole repeating units constituting the polymer, and more preferably contains 1 to 30 mol% of the repeating unit having the specific structure (1).
< specific Structure (2) >)
The polymer in the present invention preferably further has at least one structure (also referred to as specific structure (2)) selected from the following formulae [ 2-a ] to [ 2-i ].
YARepresents a hydrogen atom or a benzene ring.
Among them, the formulae [ 2-a ] to [ 2-f ] are preferable. More preferably, the formula is [ 2-a ] to [ 2-e ]. In particular, the formula [ 2-a ], the formula [ 2-b ], the formula [ 2-d ] or the formula [ 2-e ] is preferable in view of adhesion between the liquid crystal layer and the resin film.
In addition, the resin composition in the present invention preferably further contains a polymer having the specific structure (2).
It is considered that by using the specific structure (2), in the step of irradiating with ultraviolet rays and heating in the production of a liquid crystal display element, the photoreaction with the reactive group of the polymerizable compound in the liquid crystal composition proceeds, and the adhesion between the liquid crystal layer and the resin film becomes strong.
< Polymer >
The polymer is not particularly limited, but is preferably at least one polymer selected from the group consisting of an acrylic polymer, a methacrylic polymer, a Novolac resin (Novolac resin), polyhydroxystyrene, a polyimide precursor, polyimide, polyamide, polyester, cellulose, and polysiloxane. More preferably a polyimide precursor, polyimide or polysiloxane.
When a polyimide precursor or a polyimide (also collectively referred to as a polyimide-based polymer) is used as the polymer, a polyimide precursor or a polyimide obtained by reacting a diamine component with a tetracarboxylic acid component is preferable.
The polyimide precursor has a structure represented by the following formula [ A ].
R1Represents a tetravalent organic group. R2Represents a divalent organic group. A. the1And A2Each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. A. the3And A4Respectively representA hydrogen atom, an alkyl group having 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 examples of the tetracarboxylic acid component include a tetracarboxylic acid compound, a tetracarboxylic acid dianhydride, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or a tetracarboxylic acid dialkyl ester dihalide compound.
For the reason that a polyimide-based polymer can be obtained relatively easily by using a tetracarboxylic dianhydride represented by the following formula [ B ] and a diamine represented by the following formula [ C ] as raw materials, a polyamic acid having a structural formula of a repeating unit represented by the following formula [ D ] or a polyimide obtained by imidizing the polyamic acid is preferable.
R1And R2And formula [ A]R as defined1And R2The same is true.
R1And R2And formula [ A]R as defined1And R2The same is true.
Further, the compound represented by the formula [ D ] can be synthesized by a general synthesis method]Into the polymer of the formula [ A ]]A in (A)1And A2An alkyl group having 1 to 8 carbon atoms and the formula [ A]A in (A)3And A4An alkyl group or acetyl group having 1 to 5 carbon atoms.
As a method for introducing the specific structure (1) into the polyimide-based polymer, it is preferable to use a diamine having the specific structure (1) as a part of the raw material. Among them, a diamine having at least one structure selected from the formulas [1-1 ] and [1-2 ] (also referred to as a specific diamine (1)) is preferably used.
In particular, a diamine of the following formula [1a ] is preferably used.
X represents said formula [1-1]Or formula [1-2]. Further, the formula [1-1]X in (1)1～X6And Xn, and the preferred combinations are as described above for formula [1-1]Said, formula [1-2 ]]X in (1)7And X8In detail, and a preferred combination thereof, the above formula [1-2 ]]The method is as follows.
Xm represents an integer of 1 to 4. Among them, 1 or 2 is preferable.
As formula [1-1]Specific examples of the specific diamine (1) include those described in International patent publication WO2013/125595 (published 2013.8.29) on pages 15 to 19 and [ 2-1 ]]-formula [ 2-6]Is of the formula [ 2-9]-formula [ 2-36]The diamine compound of (1). In the description of International publication WO2013/125595, the formula [ 2-1 ]]-formula [ 2-3]R in (1)2And formula [ 2-4 ]]-formula [ 2-6]R in (1)4Represents an alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluoroalkoxy group having 1 to 18 carbon atoms. Furthermore, the formula [ 2-13]A in (A)4Represents a linear or branched alkyl group having 3 to 18 carbon atoms. In addition thereto, the formula [ 2-4]-formula [ 2-6]R in (1)3represents-O-, -CH2O-, -COO-or-OCO-.
Among them, preferred diamines are those of the formulae [ 2-1 ] to [ 2-6 ], the formulae [ 2-9 ] to [ 2-13 ] or the formulae [ 2-22 ] to [ 2-31 ] described in International publication WO 2013/125595.
From the viewpoint of optical characteristics of the liquid crystal display element, diamines of the following formulae [1 a-32 ] to [1 a-41 ] are more preferable.
R1And R2Each represents an alkyl group having 3 to 12 carbon atoms.
R3And R4Each represents an alkyl group having 3 to 12 carbon atoms, and cis-trans isomerization of a1, 4-cyclohexylidene group into a trans-isomer.
The diamines of the formulae [1 a-35 ] to [1 a-37 ], [1 a-40 ] or [1 a-41 ] are most preferable from the viewpoint of optical characteristics of the liquid crystal display element.
As formula [1-2]Specific examples of the specific diamine (1) include those described in International patent publication WO2013/125595 (published 2013.8.29) on page 23 of [ DA1]]-formula [ DA11]The diamine compound of (1). In the description of International publication WO2013/125595, the formula [ DA1]]-formula [ DA5]A in (A)1Represents an alkyl group having 8 to 22 carbon atoms or a fluoroalkyl group having 6 to 18 carbon atoms.
The ratio of the specific diamine (1) to be used is preferably 0.1 to 60 mol% based on the whole diamine component, from the viewpoint of optical properties of the liquid crystal display device and adhesion between the liquid crystal layer and the resin film. More preferably 1 to 30 mol%. The specific diamine (1) may be used singly or in combination of two or more depending on the characteristics.
As a method for introducing the specific structure (2) into the polyimide-based polymer, it is preferable to use a diamine having the specific structure (2) as a part of the raw material. Particularly, a diamine having a structure represented by the following formula [2] (also referred to as the specific diamine (2)) is preferably used.
Y1Represents a single bond, -O-, -NH-, -N (CH)3)－、－CH2O－、－CONH－、－NHCO－、－CON(CH3)－、－N(CH3) CO-, -COO-or-OCO-. Among them, a single bond, -O-, -CH is preferable2O-, -CONH-, -COO-or-OCO-. From the viewpoint of availability of raw materials and ease of synthesis, a single bond, -O-, -CH is more preferable2O-or-COO-.
Y2Represents a single bond, an alkylene group having 1 to 18 carbon atoms, or an organic group having 6 to 24 carbon atoms and having a cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, wherein any hydrogen atom in the cyclic group is optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms, or a fluorine atom. Among them, a single bond, an alkylene group having 1 to 12 carbon atoms, a benzene ring or a cyclohexane ring is preferable. In terms of adhesion between the liquid crystal layer and the resin film, a single bond or an alkylene group having 1 to 12 carbon atoms is more preferable.
Y3Represents a single bond, -O-, -NH-, -N (CH)3)－、－CH2O－、－CONH－、－NHCO－、－CON(CH3)－、－N(CH3) CO-, -COO-or-OCO-. Among them, a single bond, -O-, -COO-or-OCO-is preferable. More preferably a single bond or-OCO-.
Y4Represents a group selected from the formula [ 2-a]-formula [ 2-i]At least one structure of (1). Among them, the formula [ 2-a ] is preferred]-formula [ 2-f]. More preferably of the formula [ 2-a]-formula [ 2-e]. Particularly preferred is the formula [ 2-a ] in view of adhesion between the liquid crystal layer and the resin film]Is of the formula [ 2-b]Is of the formula [ 2-d]Or formula [ 2-e]。
Yn represents an integer of 1 to 4. Among them, 1 or 2 is preferable.
As the specific diamine (2), a diamine represented by the following formula [2a ] is preferably used.
Y represents the formula [2]]The structure of (1). Further, formula [2]Y in (1)1～Y4And Yn are as defined above for formula [2]The method is as follows.
Ym represents an integer of 1 to 4. Among them, 1 is preferable.
More specific diamines (2) include the following formulas [2 a-1 ] to [2 a-12 ], and the following formulas [2 a-1 ] to [2 a-12 ] are preferably used.
n1 represents an integer of 2 to 12.
n2 represents an integer of 0 to 12. n3 represents an integer of 2 to 12.
Among them, preferred are the formulae [2 a-1 ], [2 a-2 ], [2 a-5 ] to [2 a-7 ], [2 a-11 ] and [2 a-12 ]. More preferably, the compound is represented by any one of the formulae [2 a-5 ] to [2 a-7 ], [2 a-11 ] or [2 a-12 ].
The ratio of the specific diamine (2) to the diamine component as a whole is preferably 5 to 70 mol% in view of the optical properties of the liquid crystal display device and the adhesion between the liquid crystal layer and the resin film. More preferably 10 to 60 mol%. The specific diamine (2) may be used singly or in combination of two or more depending on the characteristics.
As the diamine component used for producing the polyimide-based polymer, diamines (also referred to as other diamines) other than the specific diamine (1) and the specific diamine (2) may be used.
Specifically, there may be mentioned other diamine compounds described on pages 27 to 30 of International patent publication WO2015/012368 (published 2015.1.29) and diamine compounds of the formulae [ DA1] to [ DA14] described on pages 30 to 32 of the publication. The other diamine may be used singly or in combination of two or more depending on the characteristics.
In the present invention, both the specific diamine (1) and the specific diamine (2) are preferably used in view of the optical properties of the liquid crystal display element and the adhesion between the liquid crystal layer and the resin film.
As the tetracarboxylic acid component used for producing the polyimide-based polymer, a tetracarboxylic dianhydride represented by the following formula [3], a tetracarboxylic acid dihalide, a tetracarboxylic acid dialkyl ester or a tetracarboxylic acid dialkyl ester dihalide as a derivative thereof (all of which are also collectively referred to as specific tetracarboxylic acid components.) are preferably used.
Z represents any of the following formulas [3a ] to [31 ].
ZA～ZDRespectively represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring. ZEAnd ZFEach represents a hydrogen atom or a methyl group.
Among them, Z in the formula [3] is preferably represented by the formula [3a ], the formula [3c ], the formula [3d ], the formula [3e ], the formula [3f ], the formula [3g ], the formula [3k ] or the formula [3l ] in view of ease of synthesis and ease of polymerization reactivity in producing a polymer. More preferably formula [3a ], formula [3e ], formula [3f ], formula [3g ], formula [3k ] or formula [3l ]. In particular, from the viewpoint of optical characteristics of the liquid crystal display element, the formula [3a ], the formula [3e ], the formula [3f ], the formula [3g ] or the formula [31] is preferable.
The ratio of the specific tetracarboxylic acid component to be used is preferably 1 mol% or more based on the total tetracarboxylic acid component. More preferably 5 mol% or more, and particularly preferably 10 mol% or more. The amount of the organic compound is most preferably 10 to 90 mol% from the viewpoint of optical characteristics of the liquid crystal display device.
In the polyimide-based polymer, tetracarboxylic acid components other than the specific tetracarboxylic acid component may be used. Examples of the other tetracarboxylic acid component include tetracarboxylic acid compounds, tetracarboxylic dianhydrides, dicarboxylic acid compound dihalides, dicarboxylic acid dialkyl ester compounds, and dialkyl ester dihalide compounds shown below.
Specifically, other tetracarboxylic acid components described in International patent publication WO2015/012368 (published 2015.1.29) on pages 34 to 35 can be mentioned.
The specific tetracarboxylic acid component and the other tetracarboxylic acid component may be used alone or in combination of two or more depending on the characteristics.
The method for synthesizing the polyimide-based polymer is not particularly limited. Usually, the diamine component is reacted with a tetracarboxylic acid component. Specifically, the method described in International patent publication WO2015/012368 (published 2015.1.29) on pages 35 to 36 can be mentioned.
The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in a solvent containing the diamine component and the tetracarboxylic acid component. The solvent used in this case is not particularly limited as long as it dissolves the polyimide precursor formed.
Specific examples thereof include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ -butyrolactone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and 1, 3-dimethyl-2-imidazolidinone. When the polyimide precursor has high solubility in the solvent, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or a solvent represented by the following formulae [ D1] to [ D3] may be used.
D1And D2Represents an alkyl group having 1 to 3 carbon atoms. D3Represents an alkyl group having 1 to 4 carbon atoms.
Further, they may be used alone or in combination. Further, even if the solvent is a solvent which does not dissolve the polyimide precursor, the solvent may be used in a mixture with the polyimide precursor in a range where the polyimide precursor to be produced is not precipitated. Further, since moisture in the organic solvent inhibits the polymerization reaction and causes hydrolysis of the polyimide precursor to be produced, it is preferable to use a dehydrated and dried organic solvent.
In the polymerization reaction of the polyimide precursor, the total mole number of the tetracarboxylic acid component is preferably 0.8 to 1.2, assuming that the total mole number of the diamine component is 1.0. When the total mole number of the tetracarboxylic acid component is less than 1.0, that is, when the total mole number of the tetracarboxylic acid component is less than the mole number of the diamine component, the terminal of the polymer has a structure of an amino group, and when the total mole number of the tetracarboxylic acid component is greater than 1.0, that is, when the total mole number of the tetracarboxylic acid component is greater than the mole number of the diamine component, the terminal of the polymer has a structure of a carboxylic anhydride or a dicarboxylic acid. In the present invention, the total mole number of the tetracarboxylic acid component is preferably more than 1.0, that is, the total mole number of the tetracarboxylic acid component is preferably more than the mole number of the diamine component, from the viewpoint of further improving the effect by the specific compound. Specifically, the total mole number of the tetracarboxylic acid component is preferably 1.05 to 1.20, assuming that the total mole number of the diamine component is 1.0.
The polyimide is obtained by ring-closing a polyimide precursor. In this polyimide, the ring-closure ratio of the amic acid group (also referred to as imidization ratio) does not necessarily have to be 100%, and can be arbitrarily adjusted depending on the application and purpose. Among them, from the viewpoint of solubility of the polyimide polymer in a solvent, it is preferably 30% to 80%. More preferably 40% to 70%.
The molecular weight of the polyimide polymer is preferably 5000 to 1000000 in terms of Mw (weight average molecular weight) measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the resin film obtained thereby, and workability and coating properties at the time of forming the resin film. More preferably 10000-150000.
When a polysiloxane is used as the polymer, it is preferable to use a polysiloxane obtained by polycondensing an alkoxysilane of the formula [ a1] below or a polysiloxane (also collectively referred to as a polysiloxane polymer) obtained by polycondensing an alkoxysilane of the formula [ a1] below with an alkoxysilane of the formula [ a2] and/or the formula [ A3 ].
An alkoxysilane of the formula [ A1 ]:
(A1)mSi(A2)n(OA3)p [A1]
A1represents the above formula [1-1]Or formula [1-2]. Further, the formula [1-1]X in (1)1～X6And Xn, and the preferred combinations are as described above for formula [1-1]Said, formula [1-2 ]]X in (1)7And X8Details and advantages ofOptionally combined as shown in the above formula [1-2]The method is as follows. Among them, the formula [1-1 ] is preferably used in view of more efficiently reducing the driving voltage of the liquid crystal display element]The structure of (1).
A2Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.
A3Represents an alkyl group having 1 to 5 carbon atoms. Among them, an alkyl group having 1 to 3 carbon atoms is preferable in view of the reactivity of the polycondensation.
m represents an integer of 1 or 2. Among them, 1 is preferable from the viewpoint of ease of synthesis.
n represents an integer of 0 to 2.
p represents an integer of 0 to 3. Among them, 1 to 3 are preferable from the viewpoint of reactivity of polycondensation. More preferably 2 or 3.
m + n + p is 4.
Specific examples of the alkoxysilane of the formula [ A1] include alkoxysilanes of the formulae [2 a-1 ] to [2 a-32 ] described in International patent publication WO2015/008846 (2015.1.22) at pages 17 to 21. Among them, alkoxysilanes of the formulae [2 a-9 ] to [2 a-21 ], [2 a-25 ] to [2 a-28 ] or [2 a-32 ] in the above publication are preferable.
The alkoxysilane of the formula [ A1] may be used singly or in combination of two or more depending on the characteristics.
An alkoxysilane of the formula [ A2 ]:
(B1)mSi(B2)n(OB3)p [A2]
B1the organic group has 2-12 carbon atoms and is selected from at least one of vinyl, epoxy, amino, sulfydryl, isocyanate group, methacryloyl, acryloyl, ureido and cinnamoyl. Among them, from the viewpoint of ease of obtaining, an organic group having an alkenyl group, an epoxy group, an amino group, a methacryloyl group, an acryloyl group, or a ureido group is preferable. More preferably an organic group having a methacryloyl group, an acryloyl group or a ureido group.
B2Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. It is composed ofAmong them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.
B3Represents an alkyl group having 1 to 5 carbon atoms. Among them, an alkyl group having 1 to 3 carbon atoms is preferable in view of the reactivity of the polycondensation.
m represents an integer of 1 or 2. Among them, 1 is preferable from the viewpoint of ease of synthesis.
n represents an integer of 0 to 2.
p represents an integer of 0 to 3. Among them, 1 to 3 are preferable from the viewpoint of reactivity of polycondensation. More preferably 2 or 3.
m + n + p is 4.
Specific examples of the alkoxysilane of the formula [ A2] include alkoxysilanes of the formula [2b ] described in International patent publication WO2015/008846 (2015.1.22) on pages 21 to 24.
Among them, preferred is allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl 3-glycidoxypropyl (dimethoxy) methylsilane, 3-glycidoxypropyl (diethoxy) methylsilane, 3-glycidoxypropyltrimethoxysilane, or 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.
The alkoxysilane of the formula [ A2] may be used singly or in combination of two or more depending on the characteristics.
An alkoxysilane of the formula [ A3 ]:
(D1)nSi(OD2)4-n [A3]
D1represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.
D2Represents an alkyl group having 1 to 5 carbon atoms. Among them, the C1-3 alkane is preferable from the viewpoint of the reactivity of the polycondensationAnd (4) a base.
n represents an integer of 0 to 3.
Specific examples of the alkoxysilane of the formula [ A3] include alkoxysilanes of the formula [2c ] described in International patent publication WO2015/008846 (2015.1.22) at pages 24 to 25.
In the formula [ A3], examples of the alkoxysilane in which n is 0 include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane, and the alkoxysilane in the formula [ A3] is preferably used.
The alkoxysilane of the formula [ A3] may be used singly or in combination of two or more depending on the characteristics.
The polysiloxane polymer is a polysiloxane obtained by polycondensing an alkoxysilane of the formula [ A1], or a polysiloxane obtained by polycondensing an alkoxysilane of the formula [ A1] with an alkoxysilane of the formula [ A2] and/or the formula [ A3 ]. Namely, the polysiloxane polymer is any one of the following polysiloxanes: a polysiloxane obtained by polycondensing only an alkoxysilane of the formula [ A1], a polysiloxane obtained by polycondensing two alkoxysilanes of the formulae [ A1] and [ A2], a polysiloxane obtained by polycondensing two alkoxysilanes of the formulae [ A1] and [ A3], and a polysiloxane obtained by polycondensing three alkoxysilanes of the formulae [ A1], [ A2] and [ A3 ].
Among them, polysiloxanes obtained by polycondensing a plurality of kinds of alkoxysilanes are preferable in view of reactivity in polycondensation and solubility of the polysiloxane polymer in a solvent. That is, any of the following polysiloxanes is preferably used: polysiloxanes obtained by polycondensation of two alkoxysilanes of the formula [ A1] and [ A2], polysiloxanes obtained by polycondensation of two alkoxysilanes of the formula [ A1] and [ A3], and polysiloxanes obtained by polycondensation of three alkoxysilanes of the formula [ A1], the formula [ A2] and the formula [ A3 ].
When a plurality of alkoxysiloxanes are used for producing the polysiloxane polymer, the ratio of the alkoxysilane of the formula [ A1] to be used is preferably 0.1 to 60 mol% based on the total amount of the alkoxysilanes. More preferably 1 to 30 mol%. The ratio of the alkoxysilane of the formula [ A2] is preferably 5 to 70 mol% based on the total amount of the alkoxysilane. More preferably 10 to 60 mol%. The ratio of the alkoxysilane of the formula [ A3] is preferably 1 to 99 mol% based on the total amount of the alkoxysilane. More preferably 1 to 80 mol%.
The method for polycondensing the polysiloxane polymer is not particularly limited. Specifically, the method described in International patent publication WO2015/008846 (published 2015.1.22) on pages 26 to 29 is mentioned.
In the polycondensation reaction for producing the polysiloxane polymer, when a plurality of alkoxysilanes of the formula [ a1], the formula [ a2] or the formula [ A3] are used, the reaction may be carried out using a mixture in which a plurality of alkoxysilanes are mixed in advance, or the reaction may be carried out while sequentially adding a plurality of alkoxysilanes.
In the present invention, the solution of the polysiloxane polymer obtained by the above-mentioned method may be used as it is as a polymer, or the solution of the polysiloxane polymer obtained by the above-mentioned method may be concentrated or diluted with a solvent to be used as a polymer instead of another solvent, if necessary.
The solvent used for dilution (also referred to as an addition solvent) may be a solvent used for the polycondensation reaction or another solvent. The solvent to be added is not particularly limited as long as it uniformly dissolves the polysiloxane polymer, and one or two or more kinds thereof may be arbitrarily selected. Examples of the solvent to be added include, in addition to the solvents used for the polycondensation reaction: ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as methyl acetate, ethyl acetate, and ethyl lactate.
When the polysiloxane polymer and the other polymer are used as the polymer, it is preferable that the alcohol generated in the polycondensation reaction of the polysiloxane polymer is distilled off under normal pressure or reduced pressure before the polysiloxane polymer and the other polymer are mixed.
< resin composition >
The resin composition is a composition containing a polymer having the specific structure (1), preferably a solution for forming a resin film, and is a solution containing a polymer having the specific structure (1) and a solvent. In this case, two or more kinds of the polymers having the specific structure (1) can be used.
The concentration of the polymer having the specific structure (1) in the resin composition is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, and particularly preferably 30 to 100% by mass.
The polymer components contained in the resin composition may all be polymers having the specific structure (1), but in the present invention, as described above, it is preferable to have both the specific structure (1) and the specific structure (2). In this case, one polymer having both the specific structure (1) and the specific structure (2) may be used, or a polymer having the specific structure (1) and a polymer having the specific structure (2) may be used together. When used together, the proportion of the polymer having the specific structure (2) is preferably 10 to 400 parts by mass per 100 parts by mass of the polymer having the specific structure (1). More preferably 50 to 200 parts by mass. The polymer having the specific structure (2) may be used alone or in combination of two or more depending on the characteristics.
Further, the polymer component may be a mixture of a polymer having the specific structure (1) and a polymer other than the polymer having the specific structure (2). In this case, the amount of the polymer having no specific structure is preferably 10 to 200 parts by mass per 100 parts by mass of the total polymers having specific structures. More preferably 10 to 100 parts by mass.
The content of the solvent in the resin composition can be appropriately selected from the viewpoint of the method of applying the resin composition and obtaining a desired film thickness. Among them, the content of the solvent in the resin composition is preferably 50 to 99.9% by mass from the viewpoint of forming a uniform resin film by coating. More preferably 60 to 99% by mass. Particularly preferably 65 to 99 mass%.
The solvent used in the resin composition is not particularly limited as long as it dissolves a polymer having a specific structure. Among them, in the case where the polymer is a polyimide precursor, polyimide, polyamide or polyester, or in the case where the solubility of an acrylic polymer, a methacrylic polymer, a novolac resin, polyhydroxystyrene, cellulose or polysiloxane in a solvent is low, the following solvents (also referred to as solvents a) are preferably used.
For example, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ -butyrolactone, 1, 3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ -butyrolactone is preferably used. Further, they may be used alone or in combination.
When the polymer is an acrylic polymer, a methacrylic polymer, a novolac resin, polyhydroxystyrene, cellulose, or polysiloxane, and further when the polymer is a polyimide precursor, polyimide, polyamide, or polyester, and the solubility of these polymers in a solvent is high, the following solvents (also referred to as solvents B.) can be used.
Specific examples of the solvent B include those described in International patent publication WO2014/171493 (published 2014.10.23) on pages 58 to 60. Among them, 1-hexanol, cyclohexanol, 1, 2-ethylene glycol, 1, 2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, or the above-mentioned formulas [ D1] to [ D3] are preferably used.
In addition, when these solvents B are used, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ -butyrolactone of the solvents a in combination for the purpose of improving the coatability of the resin composition. More preferably gamma-butyrolactone is used in combination.
In the case where a polyimide precursor, a polyimide, a polyamide or a polyester is used as the polymer, it is preferable to use these solvents B in combination with the above-mentioned solvent a in order to improve the coatability and surface smoothness of the resin film when the resin composition is applied. In this case, the solvent B is preferably 1 to 99% by mass of the entire solvent contained in the resin composition. Among them, it is preferably 10 to 99% by mass. More preferably 20 to 95 mass%.
In order to improve 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 oxetanyl group, a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group (also collectively referred to as a specific crosslinkable compound) into the resin composition. In this case, these groups need to have two or more in the compound.
Specific examples of the crosslinkable compound having an epoxy group or an isocyanate group include crosslinkable compounds having an epoxy group or an isocyanate group described on pages 63 to 64 of International publication WO2014/171493 (published 2014.10.23).
Specific examples of the crosslinkable compound having an oxetanyl group include crosslinkable compounds of the formulae [4a ] to [4k ] described in international publication WO2011/132751(2011.10.27 publication) at pages 58 to 59.
Specific examples of the crosslinkable compound having a cyclocarbonate group include crosslinkable compounds of the formulae [ 5-1 ] to [ 5-42 ] described in International patent publication WO2012/014898 (published 2012.2.2) on pages 76 to 82.
Specific examples of the crosslinkable compound having a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group include melamine derivatives and Benzoguanamine derivatives described in international publication No. 2014/171493 (published 2014.10.23) at pages 65 to 66, and crosslinkable compounds of formulae [ 6-1 ] to [ 6-48 ] described in international publication No. WO2011/132751 (published 2011.10.27) at pages 62 to 66.
The amount of the specific crosslinkable compound used in the resin composition is preferably 0.1 to 100 parts by mass per 100 parts by mass of the total polymer components. In order to perform the crosslinking reaction, the amount of the crosslinking agent is more preferably 0.1 to 50 parts by mass. Particularly preferably 1 to 30 parts by mass.
It is preferable to introduce at least one kind of generator (also referred to as a specific generator) selected from a group consisting of a base generator, a photoacid generator, and a photobase generator into the resin composition.
Specific examples of the specific propellant include those described in International patent publication No. 2014/171493 (published 2014.10.23) at pages 54 to 56. Among them, the specific generator is preferably a photo-radical generator in view of adhesion between the liquid crystal layer and the resin film.
In the resin composition, a compound that improves the uniformity of film thickness and surface smoothness of the resin film when the resin composition is applied can be used. Further, a compound or the like which improves the adhesion between the resin film and the substrate may be used.
Examples of the compound for improving the uniformity of the film thickness and the surface smoothness of the resin film include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. Specifically, the surfactant described in international publication WO2014/171493 (publication 2014.10.23) on page 67 can be mentioned. The amount of the polymer is preferably 0.01 to 2 parts by mass per 100 parts by mass of the total polymer components. More preferably 0.01 to 1 part by mass.
Specific examples of the compound for improving the adhesion between the resin film and the substrate include compounds described in international publication WO2014/171493 (published 2014.10.23) on pages 67 to 69. The amount of the polymer is preferably 0.1 to 30 parts by mass per 100 parts by mass of the total polymer components. More preferably 1 to 20 parts by mass.
In addition to the above-mentioned compounds, a dielectric or conductive substance may be added to the resin composition for the purpose of changing electrical characteristics such as dielectric constant and conductivity of the resin film.
< liquid crystal composition >
The liquid crystal composition has a liquid crystal and a polymerizable compound.
The liquid crystal may use nematic liquid crystal, smectic liquid crystal, or cholesteric liquid crystal. Among them, in the liquid crystal display element of the present invention, a liquid crystal having positive dielectric anisotropy is preferably used. In this case, from the viewpoint of low-voltage driving and scattering characteristics, liquid crystals having a large anisotropy of dielectric constant and a large anisotropy of refractive index are preferable. In addition, two or more kinds of liquid crystals may be mixed and used depending on the respective physical property values of the phase transition temperature, the dielectric anisotropy, and the 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 high resistance and high voltage holding ratio (also referred to as VHR). Therefore, among the liquid crystals, fluorine-based and chlorine-based liquid crystals having high resistance and a VHR that is not lowered by active energy rays such as ultraviolet rays are preferable.
Further, the liquid crystal display element may be a Guest Host (Guest Host) type element in which a dichroic dye is dissolved in a liquid crystal composition. In this case, an element which absorbs (scatters) when no voltage is applied and becomes transparent when a voltage is applied was obtained. In this element, the direction of the director (direction of alignment) of the liquid crystal changes by 90 degrees depending on the presence or absence of an applied voltage. Therefore, in this element, a high contrast (contrast) can be obtained by utilizing the difference in light absorption characteristics of the dichroic dye, as compared with a conventional guest-host type element in which switching is performed between random alignment and vertical alignment. In the guest-host type element in which the dichroic dye is dissolved, the liquid crystal is colored when it is aligned in the horizontal direction, and is opaque only in the scattering state. Therefore, an element can be obtained in which the colored opaque state when no voltage is applied is switched to the colored transparent state and the colorless transparent state with the application of a voltage.
The polymerizable compound in the liquid crystal composition is used for forming a polymer network (also referred to as a curable resin) by a polymerization reaction with active energy rays or heat during the production of a liquid crystal display device. The polymerization reaction in the present invention is preferably carried out by irradiation with ultraviolet rays.
The polymerizable compound may be a polymer obtained by polymerizing the polymerizable compound in advance, and the polymer may be introduced into the liquid crystal composition, but from the viewpoint of handling of the liquid crystal composition, that is, suppression of an increase in viscosity of the liquid crystal composition and solubility in a liquid crystal, it is preferable to use a liquid crystal composition containing the polymerizable compound.
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 a part or the whole of the liquid crystal composition exhibits a liquid crystal phase needs to be present. Even when a part of the liquid crystal composition exhibits a liquid crystal phase, the liquid crystal display element can be visually confirmed to have almost the same transparency and scattering property as the whole element.
The polymerizable compound may be any compound that can be polymerized by ultraviolet light or heat, and in this case, the polymerizable compound may be polymerized in any reaction form to form a curable resin. Specific reaction forms include radical polymerization, cationic polymerization, anionic polymerization, and addition polymerization (polyaddition).
Among them, radical polymerization is preferable as a reaction form of the polymerizable compound in view of optical characteristics of the liquid crystal display element. In this case, the following radical type polymerizable compound or oligomer thereof can be used as the polymerizable compound. As described above, a polymer obtained by polymerizing these polymerizable compounds may be used.
Specific examples of the radical polymerizable compound or oligomer thereof include radical polymerizable compounds described on pages 69 to 71 of International patent publication No. 2015/146987 (published 2015.10.1).
The amount of the radical polymerizable compound or oligomer thereof used is preferably 70 to 150 parts by mass based on 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 resin film. More preferably 80 to 110 parts by mass. The radical polymerizable compound may be used alone or in combination of two or more depending on the characteristics.
For the purpose of promoting radical polymerization of the polymerizable compound, it is preferable to introduce a radical initiator (also referred to as a polymerization initiator) that generates radicals by ultraviolet rays into the liquid crystal composition.
Specifically, the radical initiator described on pages 71 to 72 of International patent publication WO2015/146987 (published 2015.10.1) can be mentioned.
The amount of the radical initiator used is preferably 0.01 to 20 parts by mass per 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 resin film. More preferably 0.05 to 10 parts by mass. The radical initiator may be used alone or in combination of two or more depending on the characteristics.
< specific liquid Crystal addition Compound >
In the liquid crystal composition, a compound of the following formula [5a ] (also referred to as a specific liquid crystal additive compound) is preferably introduced.
S1Represents the following formula [5-a]-formula [5-j]Any of the formulae (1). Among them, the formula [5-a ] is preferred]Is of the formula [ 5-b]Is of the formula [ 5-c]Is of the formula [ 5-d]Formula [ 5-e]Or formula [ 5-f]. More preferably [5-a ]]Is of the formula [ 5-b]Is of the formula [ 5-c]Or formula [ 5-e]. Particularly preferred is a compound of the formula [5-a]Or formula [ 5-b]。
SARepresents a hydrogen atom or a benzene ring.
S2Represents a single bond, -O-, -NH-, -N (CH)3)－、－CH2O－、－CONH－、－NHCO－、－CON(CH3)－、－N(CH3) CO-, -COO-or-OCO-. Among them, a single bond, -O-, -CH is preferable2O-, -CONH-, -COO-or-OCO-. More preferably a single bond, -O-, -COO-or-OCO-.
S3Represents a single bond or- (CH)2)a- (a is an integer of 1 to 15). Among them, a single bond or- (CH) is preferable2)a- (a is an integer of 1 to 10). More preferably- (CH)2)a- (a is an integer of 1 to 10).
S4Represents a single bond, -O-, -OCH2-, -COO-or-OCO-. Among them, a single bond, -O-or-COO-is preferable. More preferably-O－。
S5Represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms, wherein any hydrogen atom in the cyclic group is optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms or a fluorine atom. Among them, benzene ring, cyclohexane ring, or a divalent organic group having 17 to 51 carbon atoms and having a steroid skeleton is preferable. More preferably a benzene ring or a divalent organic group having 17 to 51 carbon atoms and having a steroid skeleton.
S6Represents a group selected from a single bond, -O-, -CH2－、－OCH2－、－CH2At least one of O-, -COO-or-OCO-. Among them, a single bond, -O-, -COO-or-OCO-is preferable. More preferably a single bond, -COO-or-OCO-.
S7Represents a cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, and any hydrogen atom on the cyclic group is optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. Among them, preferred is a benzene ring or a cyclohexane ring.
S8Represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluoroalkoxy group having 1 to 18 carbon atoms. Among them, an alkyl group or an alkoxy group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms is preferable. More preferably an alkyl group or alkoxy group having 1 to 12 carbon atoms.
Sm represents an integer of 0 to 4. Among them, 0 to 2 is preferable.
A site having a rigid structure such as a benzene ring or a cyclohexane ring, and the compound having the formula [5a ]]S in (1)1The site where polymerization reaction proceeds by ultraviolet rays or heat is shown. Therefore, when the specific liquid crystal additive compound is contained in the liquid crystal composition, the site of the rigid structure of the specific liquid crystal additive compound can improve the sag of the liquid crystalThe direct alignment property promotes the driving of the liquid crystal with the application of voltage, and reduces the driving voltage of the liquid crystal display element. Further, by the formula [5a ]]S in (1)1The site (b) reacts with the polymerizable compound to keep the polymer network in a tight state.
More specific liquid crystal additive compounds include compounds represented by the following formulae [5 a-1 ] to [5 a-11 ], and they are preferably used.
SaEach represents-O-or-COO-. SbEach represents an alkyl group having 1 to 12 carbon atoms. p1 represents an integer of 1 to 10. p2 represents the integer 1 or 2, respectively.
ScEach represents a single bond, -COO-or-OCO-. SdEach represents an alkyl group or an alkoxy group having 1 to 12 carbon atoms. p3 represents an integer of 1 to 10. p4 represents the integer 1 or 2, respectively.
SeEach represents-O-or-COO-. SfEach represents a divalent organic group having a steroid skeleton and 17 to 51 carbon atoms. SgEach represents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 18 carbon atoms. p5 represents an integer of 1 to 10.
The ratio of the specific liquid crystal additive compound is preferably 0.1 to 30 parts by mass relative 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 resin film. More preferably 0.5 to 20 parts by mass. Particularly preferably 1 to 10 parts by mass. The specific liquid crystal additive compound may be used singly or in combination of two or more kinds depending on the respective characteristics.
Examples of the method for producing the liquid crystal composition include: a method of mixing a liquid crystal, a polymerizable compound, and a specific liquid crystal additive compound together; a method of mixing a mixed polymerizable compound and a specific liquid crystal additive compound in advance, and then mixing the resultant with a liquid crystal.
Among them, in the present invention, a method of mixing a compound having a mixed polymerizability and a specific liquid crystal additive compound in advance and then mixing the resultant with a liquid crystal is preferable.
In the case of preparing the liquid crystal composition as described above, heating may be performed depending on the solubility of the polymerizable compound and the specific liquid crystal additive compound. The temperature at this time is preferably less than 100 ℃.
< method for manufacturing 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 a plastic substrate such as an acrylic substrate, a polycarbonate substrate, or a PET (polyethylene terephthalate) substrate may be used in addition to the glass substrate, and further, a film thereof may be used. In particular, when used for a light control window or the like, a plastic substrate or film is preferable. In addition, from the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode, an IZO (Indium Zinc Oxide) electrode, an IGZO (Indium Gallium Zinc Oxide) electrode, an organic conductive film, and the like are formed for driving liquid crystal. In the case of a reflective liquid crystal display element, a silicon wafer, a metal such as aluminum, or a substrate on which a dielectric multilayer film is formed can be used as long as the substrate is a single-sided substrate.
The liquid crystal display element has a resin film obtained from a resin composition containing a polymer having a specific structure (1) on at least one substrate. It is particularly preferable that a resin film is present on both substrates.
The method of applying the resin composition is not particularly limited, and there are industrial methods such as screen printing, gravure printing, flexographic printing, inkjet method, dipping method, roll coating method, slit coating method, spin coating method, and spray coating method, and it can be appropriately selected depending on the kind of substrate and the film thickness of the resin film to be targeted.
After coating the resin composition on a substrate, the resin film can be produced by evaporating the solvent at 30 to 300 ℃, preferably 30 to 250 ℃ depending on the kind of the substrate and the solvent used in the resin composition by a heating means such as a hot plate, a thermal cycle oven, or an IR (infrared) oven. In particular, when a plastic substrate is used as the substrate, the treatment is preferably performed at a temperature of 30 to 150 ℃.
The thickness of the resin film after firing is preferably 5 to 500nm, because it is disadvantageous in terms of power consumption of the liquid crystal display element if it is too thick, and because it is likely to lower the reliability of the element if it is too thin. More preferably 10 to 300 nm. Particularly preferably 10 to 250 nm.
The liquid crystal composition used in the liquid crystal display element is the liquid crystal composition described above, and a spacer (spacer) for controlling an electrode gap (also referred to as a gap) of the liquid crystal display element may be introduced thereto.
The method of injecting the liquid crystal composition is not particularly limited, and examples thereof include the following methods. That is, when a glass substrate is used as the substrate, a pair of substrates on which a resin film is formed is prepared, a sealant is applied by removing a part of the four sides of one substrate, and then the other substrate is bonded so that the surface of the resin film is inside, thereby producing an empty cell. Then, a method of injecting the liquid crystal composition under reduced pressure from a place where the sealant is not applied to obtain a liquid crystal composition injection unit is exemplified. When a plastic substrate or film is used as the substrate, the following methods can be mentioned: a method of preparing a pair of substrates on which resin films are formed, dropping a liquid crystal composition by an ODF (One Drop Filling) method, an ink jet method, or the like on One side of the substrates, and then bonding the other One side of the substrates to obtain a liquid crystal composition injection unit.
The gap of the liquid crystal display element can be controlled by the spacer or the like. The method includes, as described above: a method of introducing a spacer of a target size into a liquid crystal composition, a method of using a substrate having a column spacer (column spacer) of a target size, and the like. In the case where a plastic or film substrate is used as the substrate and the substrates are laminated (laminated), 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. Particularly preferably 2 to 30 μm. If the gap is too small, the contrast of the liquid crystal display element decreases, and if the gap is too large, the driving voltage of the element increases.
The liquid crystal display element is obtained by curing a liquid crystal composition in a state where a part or the whole of the liquid crystal composition exhibits liquid crystallinity to form a liquid crystal layer. The liquid crystal composition is cured by irradiating the liquid crystal composition injection unit with ultraviolet rays and heating the liquid crystal composition injection unit. In the present invention, as described above, irradiation with ultraviolet rays is preferable.
Examples of the light source of the ultraviolet irradiation device used for the irradiation of ultraviolet rays include a metal halide lamp and a high-pressure mercury lamp. The wavelength of the ultraviolet ray is preferably 250 to 400 nm. Among them, the preferable range is 310 to 370 nm. Further, the ultraviolet ray may be irradiated and then heat treatment may be performed. The temperature at this time is preferably 40 to 120 ℃. More preferably 40 to 80 ℃.
Examples of the apparatus used for heating include a heating unit used after the resin composition is applied to a substrate. The temperature at this time can be appropriately selected depending on the temperature at which the reaction of the polymerizable compound proceeds and the type of the substrate. Specifically, it is preferably 80 to 200 ℃.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
The abbreviations used hereinafter are as follows.
Compounds used for polyimide-based polymer "
< specific diamine (1) >)
< specific diamine (2) >)
< other diamines >
< specific tetracarboxylic acid component >
Compounds used in polysiloxane polymers "
E2: octadecyltriethoxysilane.
E3: 3-methacryloxypropyltrimethoxysilane.
E4: 3-ureidopropyltriethoxysilane.
E5: tetraethoxysilane.
"crosslinkable compound"
Solvent "
NMP: n-methyl-2-pyrrolidone.
gamma-BL: gamma-butyrolactone.
BCS: ethylene glycol monobutyl ether.
PB: propylene glycol monobutyl ether.
PGME: propylene glycol monomethyl ether.
And (3) ECS: ethylene glycol monoethyl ether.
EC: diethylene glycol monoethyl ether.
Compounds for use in liquid crystal compositions "
< specific liquid Crystal addition Compound >
< polymerizable Compound >
R1: IBXA (manufactured by Osaka organic chemical industries, Ltd.).
R2: 2-hydroxyethyl methacrylate (manufactured by Tokyo chemical industry Co., Ltd.).
R3: KAYARADFM-400 (manufactured by Nippon chemical Co., Ltd.).
R4: EBECRYL 230 (manufactured by Daicel Allnex).
R5: KARENZ MT PE1 (product of SHOWA AND ELECTRICITY CO., LTD.).
< photo radical initiator >
P1: IRGACURE 184 (manufactured by BASF corporation).
< liquid Crystal >
L1: MLC-3018 (Merck).
"molecular weight measurement of polyimide-based Polymer"
The measurement was carried out in the following manner using a Gel Permeation Chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko K.K.) and a column (KD-803, KD-805) (manufactured by Shodex K.K.).
Temperature of the column: at 50 ℃.
Eluent: n, N-dimethylformamide (as additive, lithium bromide monohydrate (LiBr. H)2O) 30mmol/L (liter), phosphoric acid/anhydrous crystals (O-phosphoric acid) 30mmol/L, Tetrahydrofuran (THF) 10 ml/L).
Flow rate: 1.0 ml/min.
Calibration curve preparation standard sample: TSK-standard polyethylene oxides (molecular weight; about 900000, 150000, 100000 and 30000, manufactured by Tosoh corporation) and polyethylene glycols (molecular weight; about 12000, 4000 and 1000, manufactured by Polymer Laboratory corporation).
"measurement of imidization ratio of polyimide-based Polymer"
To an NMR (nuclear magnetic resonance) sample Tube (NMR Sampling Tube Standard,(manufactured by Softysciences corporation)) was added 20mg of the polyimide powder, and deuterated dimethyl sulfoxide (DMSO-d 6, 0.05 mass% TMS (tetramethylsilane) mixture) (0.53ml) was added thereto, followed by ultrasonic wave application to completely dissolve the polyimide powder. The proton NMR of the solution at 500MHz was measured by an NMR spectrometer (JNW-ECA 500) (manufactured by electronic DATUM, Japan). The imidization ratio was determined by the following method: the proton derived from a structure which did not change before and after imidization was determined as a reference proton, and the peak integral value of this proton and the peak integral value of a proton derived from an amic acid-derived NH group appearing in the vicinity of 9.5ppm to 10.0ppm were used to obtain the following formula.
Imidization ratio (%) - (1-. alpha.x/y). times.100
(x is the peak integral value of the NH group-derived NH group of amic acid, y is the peak integral value of the standard proton, and α is the number ratio of the standard proton to one NH group proton of amic acid in the case of polyamic acid (imidization ratio of 0%))
Synthesis of polyimide-based Polymer "
< Synthesis example 1 >
D2(1.36g, 5.44mmol), A1(1.05g, 2.76mmol) and C1(1.19g, 11.0mmol) were mixed with NMP (10.4g) and reacted at 80 ℃ for 4 hours, then D1(1.60g, 8.16mmol) and NMP (5.21g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution (1) having a resin solid concentration of 25 mass%. The polyamic acid had a number average molecular weight (also referred to as Mn.) of 21500 and a weight average molecular weight (also referred to as Mw.) of 64700.
< Synthesis example 2 >
D2(2.21g, 8.83mmol), A1(1.71g, 4.49mmol), B1(2.96g, 11.2mmol) and C1(0.73g, 6.75mmol) were mixed with NMP (20.4g) and reacted at 80 ℃ for 4 hours, and then D1(2.60g, 13.3mmol) and NMP (10.2g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution (2) having a resin solid concentration of 25 mass%. The polyamic acid had Mn of 20500 and Mw of 61000.
< Synthesis example 3 >
To a polyamic acid solution (2) (20.0g) obtained by the method of Synthesis example 2, NMP was added and the solution was diluted to 6 mass%, and then acetic anhydride (1.65g) and pyridine (1.00g) were added as imidization catalysts to conduct a reaction at 60 ℃ for 3 hours. The reaction solution was poured into methanol (450ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ℃ to obtain polyimide powder (3). The polyimide had an imidization ratio of 55%, Mn of 18300 and Mw of 48300.
< Synthesis example 4 >
D4(0.74g, 3.73mmol), A2(0.75g, 1.90mmol), B1(1.50g, 5.68mmol) and C1(0.21g, 1.94mmol) were mixed with γ -BL (8.60g) and reacted at 60 ℃ for 4 hours, and then D1(1.10g, 5.61mmol) and γ -BL (4.30g) were added and reacted at 40 ℃ for 8 hours to obtain a polyamic acid solution (4) having a resin solid content of 25 mass%. The polyamic acid had Mn of 15900 and Mw of 47600.
< Synthesis example 5 >
D4(1.18g, 5.96mmol), A2(0.51g, 1.29mmol) and B1(1.94g, 7.34mmol) were mixed with γ -BL (8.25g) and reacted at 60 ℃ for 4 hours, then D1(0.50g, 2.55mmol) and γ -BL (4.13g) were added and reacted at 40 ℃ for 8 hours to obtain a polyamic acid solution (5) having a resin solid content concentration of 25 mass%. The polyamic acid had Mn of 13300 and Mw of 44200.
< Synthesis example 6 >
D4(0.74g, 3.73mmol), A3(0.54g, 1.25mmol), B1(1.66g, 6.28mmol) and C1(0.54g, 4.99mmol) were mixed with NMP (10.4g) and reacted at 80 ℃ for 4 hours, and then D1(1.70g, 8.67mmol) and NMP (5.18g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution (6) having a resin solid concentration of 25 mass%. The polyamic acid had Mn of 22300 and Mw of 68500.
< Synthesis example 7 >
D3(2.00g, 8.92mmol), A2(0.71g, 1.80mmol) and B2(1.47g, 7.23mmol) were mixed with γ -BL (12.6g) and reacted at 40 ℃ for 12 hours to obtain a polyamic acid solution (7) having a resin solid concentration of 25 mass%. The polyamic acid had Mn of 14900 and Mw of 41900.
< Synthesis example 8 >
D3(2.50g, 11.2mmol), A4(0.28g, 0.57mmol), B1(1.79g, 6.77mmol) and C1(0.43g, 3.98mmol) were mixed with NMP (15.0g) and reacted at 40 ℃ for 12 hours to obtain a polyamic acid solution (8) having a resin solid concentration of 25 mass%. The polyamic acid had Mn 16100 and Mw 45200.
< synthetic example 9 >
D2(1.11g, 4.44mmol), A5(0.84g, 2.23mmol), B1(1.48g, 5.60mmol) and C1(0.36g, 3.33mmol) were mixed with NMP (10.2g) and reacted at 80 ℃ for 4 hours, then D1(1.30g, 6.63mmol) and NMP (5.10g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution (9) having a resin solid concentration of 25 mass%. The polyamic acid had Mn of 19900 and Mw of 60500.
< synthetic example 10 >
D2(1.53g, 6.11mmol) and C1(1.68g, 15.5mmol) were mixed in NMP (10.0g) and reacted at 80 ℃ for 4 hours, then D1(1.80g, 9.18mmol) and NMP (5.01g) were added and reacted at 40 ℃ for 6 hours to obtain a polyamic acid solution (10) having a resin solid content of 25 mass%. The polyamic acid had Mn of 28200 and Mw of 73900.
< Synthesis example 11 >
D4(1.08g, 5.45mmol) and C1(1.49g, 13.8mmol) were mixed with γ -BL (8.34g) and reacted at 60 ℃ for 4 hours, and then D1(1.60g, 8.16mmol) and γ -BL (4.17g) were added and reacted at 40 ℃ for 8 hours to obtain a polyamic acid solution (11) having a resin solid content concentration of 25 mass%. The polyamic acid had Mn of 20900 and Mw of 58400.
The polyimide-based polymers obtained in the synthesis examples are shown in table 1.
[ Table 1]
*1: a polyamic acid.
Synthesis of polysiloxane Polymer "
< Synthesis example 12 >
In a 200ml four-necked reaction flask equipped with a thermometer and a reflux tube, ECS (28.3g), E1(4.10g), E3(7.45g) and E5(32.5g) were mixed to prepare a solution of an alkoxysilane monomer. To this solution was added dropwise a solution prepared by mixing ECS (14.2g), water (10.8g) and oxalic acid (0.70g) as a catalyst in advance at 25 ℃ for 30 minutes, and further stirred at 25 ℃ for 30 minutes. Then, after heating and refluxing for 30 minutes using an oil bath, a mixed solution of a methanol solution (1.20g) having an E4 content of 92 mass% and ECS (0.90g) prepared in advance was added. After further refluxing for 30 minutes, cooling was carried out to obtain SiO2Polysiloxane solution (1) having a concentration of 12% by mass as converted.
< synthetic example 13 >
In a 200ml four-necked reaction flask equipped with a thermometer and a reflux tube, EC (29.2g), E1(4.10g) and E5(38.8g) were mixed to prepare a solution of an alkoxysilane monomer. To this solution was added dropwise a solution prepared by mixing EC (14.6g), water (10.8g), and oxalic acid (0.50g) as a catalyst in advance at 25 ℃ for 30 minutes, and further stirred at 25 ℃ for 30 minutes. Then, after heating and refluxing for 30 minutes using an oil bath, a mixed solution of a methanol solution (1.20g) having an E4 content of 92 mass% and EC (0.90g) prepared in advance was added. After further refluxing for 30 minutes, cooling was carried out to obtain SiO2A polysiloxane solution (2) having a concentration of 12% by mass as converted.
< Synthesis example 14 >
In a 200ml four-necked reaction flask equipped with a thermometer and a reflux tube, ECS (28.3g), E2(4.07g), E3(7.45g) and E5(32.5g) were mixed to prepare a solution of an alkoxysilane monomer. To this solution was added dropwise a solution prepared by mixing ECS (14.2g), water (10.8g) and oxalic acid (0.70g) as a catalyst in advance at 25 ℃ for 30 minutes, and further stirred at 25 ℃ for 30 minutes. Then, heating was performed using an oil bathAnd refluxed for 30 minutes, and then a mixed solution of a methanol solution (1.20g) having a content of E4 of 92 mass% and ECS (0.90g) prepared in advance was added. After further refluxing for 30 minutes, cooling was carried out to obtain SiO2A polysiloxane solution (3) having a concentration of 12% by mass as converted.
The polysiloxane polymers obtained in the synthesis examples are shown in table 2.
[ Table 2]
Production of resin composition "
< example 1 >
To the polyamic acid solution (1) (10.0g) obtained by the method of synthesis example 1, NMP (16.0g) and BCS (15.7g) were added, and stirred at 25 ℃ for 6 hours to obtain a resin composition (1). The resin composition was a homogeneous solution without any abnormality such as turbidity and precipitation.
< example 2 >
To polyamic acid solution (2) (10.0g) obtained by the method of Synthesis example 2, NMP (16.0g) and BCS (15.7g) were added, and the mixture was stirred at 25 ℃ for 6 hours to obtain resin composition (2). The resin composition was a homogeneous solution without any abnormality such as turbidity and precipitation.
< example 3 >
To the polyimide powder (3) (2.50g) obtained in synthesis example 3 was added NMP (27.4g), and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NMP. Then, BCS (7.83g) and PB (3.92g) were added thereto, and the mixture was stirred at 25 ℃ for 6 hours to obtain a resin composition (3). The resin composition was a homogeneous solution without any abnormality such as turbidity and precipitation.
< example 4 >
To the polyimide powder (3) (2.50g) obtained in synthesis example 3 was added NMP (27.4g), and the mixture was stirred at 70 ℃ for 24 hours to dissolve the NMP. Then, K1(0.13g), BCS (7.83g) and PB (3.92g) were added thereto, and the mixture was stirred at 25 ℃ for 6 hours to obtain a resin composition (4). The resin composition was a homogeneous solution without any abnormality such as turbidity and precipitation.
< example 5 >
To the polyimide powder (3) (2.50g) obtained by the method of synthesis example 3 was added γ -BL (5.88g), and the mixture was stirred at 60 ℃ for 24 hours to dissolve the same. Then, PGME (33.3g) was added thereto, and the mixture was stirred at 25 ℃ for 6 hours to obtain a resin composition (5). The resin composition was a homogeneous solution without any abnormality such as turbidity and precipitation.
< example 6 >
To the polyamic acid solution (4) (10.0g) obtained by the method of Synthesis example 4 was added γ -BL (0.33g), and the mixture was stirred at 25 ℃ for 4 hours. Then, PGME (31.3g) was added thereto, and the mixture was stirred at 25 ℃ for 6 hours to obtain a resin composition (6). The resin composition was a homogeneous solution without any abnormality such as turbidity and precipitation.
< example 7 >
To the polyamic acid solution (4) (10.0g) obtained by the method of Synthesis example 4 was added γ -BL (0.33g), and the mixture was stirred at 25 ℃ for 4 hours. Then, K2(0.18g) and PGME (31.3g) were added thereto, and the mixture was stirred at 25 ℃ for 6 hours to obtain a resin composition (7). The resin composition was a homogeneous solution without any abnormality such as turbidity and precipitation.
< example 8 >
To the polyamic acid solution (5) (10.0g) obtained by the method of Synthesis example 5 was added γ -BL (0.33g), and the mixture was stirred at 25 ℃ for 4 hours. Then, K2(0.13g) and PGME (31.3g) were added thereto, and the mixture was stirred at 25 ℃ for 6 hours to obtain a resin composition (8). The resin composition was a homogeneous solution without any abnormality such as turbidity and precipitation.
< example 9 >
To polyamic acid solution (6) (10.0g) obtained by the method of Synthesis example 6, K1(0.08g), NMP (19.9g), and PB (11.8g) were added, and the mixture was stirred at 25 ℃ for 6 hours to obtain resin composition (9). The resin composition was a homogeneous solution without any abnormality such as turbidity and precipitation.
< example 10 >
To the polyamic acid solution (7) (10.0g) obtained by the method of Synthesis example 7 was added γ -BL (0.33g), and the mixture was stirred at 25 ℃ for 4 hours. Then, K2(0.08g) and PGME (31.3g) were added thereto, and the mixture was stirred at 25 ℃ for 6 hours to obtain a resin composition (10). The resin composition was a homogeneous solution without any abnormality such as turbidity and precipitation.
< example 11 >
To the polyamic acid solution (8) (10.0g) obtained by the method of Synthesis example 8 were added NMP (16.0g), BCS (7.83g), and PB (7.83g), and the mixture was stirred at 25 ℃ for 6 hours to obtain a resin composition (11). The resin composition was a homogeneous solution without any abnormality such as turbidity and precipitation.
< example 12 >
To the polyamic acid solution (9) (10.0g) obtained by the method of Synthesis example 9 were added NMP (16.0g) and BCS (15.7g), and the mixture was stirred at 25 ℃ for 6 hours to obtain a resin composition (12). The resin composition was a homogeneous solution without any abnormality such as turbidity and precipitation.
< example 13 >
To the polysiloxane solution (1) (20.0g) obtained by the synthesis method of synthesis example 12, ECS (12.5g) and BCS (7.52g) were added, and stirred at 25 ℃ for 6 hours to obtain a resin composition (13). It was confirmed that the resin composition was a uniform solution without any abnormality such as turbidity and precipitation.
< example 14 >
To the polysiloxane solution (2) (20.0g) obtained by the synthesis method of synthesis example 13, EC (8.72g) and BCS (11.3g) were added, and stirred at 25 ℃ for 6 hours to obtain a resin composition (14). It was confirmed that the resin composition was a uniform solution without any abnormality such as turbidity and precipitation.
< example 15 >
To the polysiloxane solution (3) (20.0g) obtained by the synthesis method of synthesis example 14, ECS (12.5g) and BCS (7.52g) were added, and stirred at 25 ℃ for 6 hours to obtain a resin composition (15). It was confirmed that the resin composition was a uniform solution without any abnormality such as turbidity and precipitation.
< comparative example 1 >
To the polyamic acid solution (10) (10.0g) obtained by the method of Synthesis example 10, NMP (16.0g) and BCS (15.7g) were added, and the mixture was stirred at 25 ℃ for 6 hours to obtain a resin composition (16). The resin composition was a homogeneous solution without any abnormality such as turbidity and precipitation.
< comparative example 2 >
To polyamic acid solution (11) (10.0g) obtained by the method of Synthesis example 11 were added γ -BL (0.33g) and PGME (31.3g), and the mixture was stirred at 25 ℃ for 6 hours to obtain resin composition (17). The resin composition was a homogeneous solution without any abnormality such as turbidity and precipitation.
The resin compositions obtained in examples and comparative examples are shown in tables 3 to 5.
[ Table 3]
Examples
Resin composition
Polymer and method of making same
Crosslinkable compound 2
1
(1)
Polyamic acid solution (1)
-
2
(2)
Polyamic acid solution (2)
-
3
(3)
Polyimide powder (3)
-
4
(4)
Polyimide powder (3)
K1(5)
5
(5)
Polyimide powder (3)
-
6
(6)
Polyamic acid solution (4)
-
7
(7)
Polyamic acid solution (4)
K2(7)
8
(8)
Polyamic acid solution (5)
K2(5)
9
(9)
Polyamic acid solution (6)
K1(3)
10
(10)
Polyamic acid solution (7)
K2(3)
[ Table 4]
Examples
Resin composition
Polymer and method of making same
Crosslinkable compound 2
11
(11)
Polyamic acid solution (8)
-
12
(12)
Polyamic acid solution (9)
-
13
(13)
Polysiloxane solution (1)
-
14
(14)
Polysiloxane solution (2)
-
15
(15)
Polysiloxane solution (3)
-
[ Table 5]
Comparative example
Resin composition
Polymer and method of making same
Crosslinkable compound 2
1
(16)
Polyamic acid solution (10)
-
2
(17)
Polyamic acid solution (11)
-
*2: the numerical value in parentheses indicates the introduced amount (part by mass) of the crosslinkable compound with respect to 100 parts by mass of the polymer.
Preparation of liquid Crystal composition "
< preparation of liquid Crystal composition (A) >
R1(1.20g), R2(0.30g), R3(1.20g), R4(0.90g) and R5(0.30g) were mixed and stirred at 60 ℃ for 2 hours to prepare a polymerizable compound solution. Then, the prepared polymerizable compound solution, L1(6.00g), and P1(0.10g) were mixed and stirred at 25 ℃ for 6 hours to obtain a liquid crystal composition (A).
< preparation of liquid Crystal composition (B) >
R1(1.20g), R2(0.30g), R3(1.20g), R4(0.90g) and R5(0.30g) were mixed and stirred at 60 ℃ for 2 hours to prepare a polymerizable compound solution. On the other hand, S1(0.20g) and L1(5.80g) were mixed and stirred at 25 ℃ for 2 hours to prepare a liquid crystal containing a specific liquid crystal additive compound. Then, the prepared solution of the polymerizable compound, liquid crystal containing the specific liquid crystal additive compound, and P1(0.10g) were mixed and stirred at 25 ℃ for 6 hours to obtain a liquid crystal composition (B).
< preparation of liquid Crystal composition (C) >
R1(1.20g), R2(0.30g), R3(1.20g), R4(0.90g) and R5(0.30g) were mixed and stirred at 60 ℃ for 2 hours to prepare a polymerizable compound solution. On the other hand, S2(0.40g) and L1(5.60g) were mixed and stirred at 25 ℃ for 2 hours to prepare a liquid crystal containing a specific liquid crystal additive compound. Then, the prepared solution of the polymerizable compound, liquid crystal containing the specific liquid crystal additive compound, and P1(0.10g) were mixed and stirred at 25 ℃ for 6 hours to obtain a liquid crystal composition (C).
Production of liquid crystal display element (glass substrate) "
The resin compositions obtained by the methods of the examples and comparative examples were subjected to pressure filtration using a Membrane filter (Membrane filter) having a pore diameter of 1 μm. The obtained solution was spin-coated on an ITO surface of a 100X 100mm ITO electrode-equipped glass substrate (length: 100mm, width: 100mm, thickness: 0.7mm) cleaned with pure water and IPA (isopropyl alcohol), and subjected to a heat treatment at 100 ℃ for 5 minutes on a hot plate and a heat treatment at 210 ℃ for 30 minutes in a thermal cycle type cleaning oven, to obtain an ITO substrate with a resin film having a film thickness of 100 nm. Two sheets of the ITO substrate with the resin film were prepared, and a spacer of 20 μm was applied to the resin film surface of one of the substrates. Then, the liquid crystal compositions (a) to (C) were dropped on the resin film surface of the substrate coated with the spacer by an odf (one Drop filling) method, and then bonded so that the resin film surface of the other substrate was opposed to each other, to obtain a liquid crystal display element before treatment.
The liquid crystal display element before the treatment was irradiated with 20mW/cm of illumination2The metal halide lamp (4) is irradiated with ultraviolet light for 60 seconds, with the wavelength of 350nm or less being cut off. Thus, a liquid crystal display element (glass substrate) was obtained.
Production of liquid crystal display element (plastic substrate) "
The resin compositions obtained by the methods of the examples and comparative examples were subjected to pressure filtration using a membrane filter having a pore size of 1 μm. The obtained solution was applied to an ITO surface of a 150X 150mm PET substrate (length: 150mm, width: 150mm, thickness: 0.1mm) with an ITO electrode, which was cleaned with pure water, by a bar coater, and subjected to a heat treatment at 120 ℃ for 2 minutes in a heat cycle type oven, to obtain an ITO substrate with a resin film having a film thickness of 100 nm. Two sheets of the ITO substrate with the resin film were prepared, and a spacer of 20 μm was applied to the resin film surface of one of the substrates. Then, the liquid crystal compositions (a) to (C) were dropped on the resin film surface of the substrate coated with the spacer by an odf (one Drop filling) method, and then bonded so that the resin film surface of the other substrate was opposed to each other, to obtain a liquid crystal display element before treatment. When the liquid crystal composition was dropped and bonded by the ODF method, a glass substrate was used as a support substrate for the PET substrate with ITO electrodes. Then, before the ultraviolet rays are irradiated, the support substrate is detached.
The liquid crystal display element before this treatment was irradiated with ultraviolet rays in the same manner as in the above-described "production of a liquid crystal display element (glass substrate)", to obtain a liquid crystal display element (plastic substrate).
Evaluation of optical characteristics (scattering characteristics and transparency) "
The evaluation was carried out by measuring Haze (Haze) of a liquid crystal display element (glass substrate and plastic substrate) in a state of no voltage application (0V) and in a state of voltage application (AC drive: 10V to 60V). In this case, Haze was measured by a Haze meter (HZ-V3, manufactured by SUGA tester) in accordance with JIS K7136. In this evaluation, the higher the Haze in the non-voltage applied state, the more excellent the scattering properties, and the lower the Haze in the voltage applied state, the more excellent the transparency.
In addition, as a stability test in a high-temperature and high-humidity environment of the liquid crystal display element, a measurement was also performed after storing the liquid crystal display element in a constant-temperature and constant-humidity cell at a temperature of 80 ℃ and a humidity of 90% RH for 24 hours. Specifically, it is assumed that: the smaller the change in Haze after storage in the constant temperature and humidity chamber relative to the initial Haze, the more excellent the evaluation.
Further, as a test of stability of the liquid crystal display element against light irradiation, irradiation was performed by using a desktop UV curing apparatus (HCT3B28 HEX-1) (manufactured by SENLIGHT corporation) so as to be 5J/cm in terms of 365nm2Ultraviolet light (c) was observed. Specifically, it is assumed that: the evaluation was more excellent as the change in Haze after ultraviolet irradiation was smaller than that of the initial Haze.
The results of Haze measurements after initial storage in a constant temperature and humidity chamber (constant temperature and humidity) and after ultraviolet irradiation (ultraviolet rays) are summarized in tables 6 to 8.
< example 16 to example 31, comparative example 3 and comparative example 4 >
By using any of the resin compositions (1) to (17) obtained by the methods of the examples and comparative examples and the liquid crystal compositions (a) to (C), the production of a liquid crystal display element and the evaluation of optical characteristics (scattering characteristics and transparency) were performed by the methods. In this case, the production and each evaluation of the liquid crystal display elements were performed using glass substrates in examples 16 to 19, 25, 27, 28, 30 and 3, and plastic substrates were used in examples 20 to 24, 26, 29, 31 and 4.
[ Table 6]
[ Table 7]
[ Table 8]
As described above, the liquid crystal display element of the example using the resin composition containing the polymer having the specific structure (1) has a lower Haze in a voltage applied state than the comparative example not using the resin composition, and the Haze becomes lower at a lower voltage. That is, in the examples, good optical characteristics (transparency) were exhibited, and the driving voltage of the liquid crystal display element was low. Specifically, the results are a comparison between example 16 and comparative example 3 and a comparison between example 21 and comparative example 4.
In addition, when the specific diamine (2) having the specific structure (2) is used in the polymer, the change in Haze after storage in a constant temperature and humidity chamber and after ultraviolet irradiation is small. Specifically, the comparison under the same conditions is a comparison of example 16 with example 17.
Further, when a specific crosslinkable compound is introduced into the resin composition, the Haze of the resin composition after storage in a constant temperature and humidity chamber and after ultraviolet irradiation is less likely to change. Specifically, the comparison under the same conditions is a comparison of example 18 with example 19 and a comparison of example 21 with example 22.
In addition, when a liquid crystal composition containing a specific liquid crystal additive compound is used, Haze in a voltage applied state becomes lower and a driving voltage becomes lower than that in a case where the liquid crystal composition is not used. Specifically, the comparison under the same conditions is a comparison of example 22 and example 23.
Industrial applicability
By using a resin composition containing a polymer having a specific structure, a liquid crystal display element having excellent optical characteristics and a low driving voltage of the liquid crystal display element can be obtained.
The liquid crystal display element of the present invention can be preferably used for a conventional element which is in a scattering state when no voltage is applied and is in a transparent state when a voltage is applied. The element can be used for a liquid crystal display for display purposes, a light control window for controlling light blocking and transmission, a light shutter element, and the like, and a plastic substrate can be used as a substrate of the conventional element.
The entire contents of the specification, claims and abstract of japanese patent application No. 2019-042708, which was filed on 8/3/2019, are incorporated herein by reference as disclosure of the specification of the present invention.
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