JPH1129527A - Side-chain type radically polymerizable compound and liquid crystal device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound, having sufficient low-voltage driving properties and a high contrast, improved in electrooptical characteristics in a low-temperature region and useful for a liquid crystal device. SOLUTION: This compound is represented by formula I [R1 is CH2 or CH2 CH2 COOCH2 ; R2 and R3 are each an aliphatic group, an aromatic group or a substitution product thereof; R4 and R5 , are each H or CH3 ; X is CH2 , an ether or an ester bond; (n) is 2-4; (p) and (q) are each 0 or 1], e.g. a compound represented by formula II. The compound represented by formula I is obtained by reacting a compound having epoxy group with an epoxy acrylate composed of a carboxylic acid having (meth)acryloyl group, a carboxylic acid or a carboxylic acid chloride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal device having a large area, and more particularly, to blocking, opening, and limiting transmission of light or illumination light.
The screen can be controlled electrically or thermally to block or transmit light, such as a building window or a show window, etc.
Use as a curtain for daylighting control, display characters and figures, and switch the display electrically with high-speed response to display advertising boards, decorative display boards, clocks, display devices at the end of computers, and projection. The present invention relates to a liquid crystal device used as an apparatus.

[0002]

2. Description of the Related Art Japanese Patent Publication No. 58-501631 discloses a liquid crystal device dispersed in a polymer by encapsulating the liquid crystal as a large, inexpensive liquid crystal device that does not require a polarizing plate and an alignment treatment, and has a bright, good contrast. Then, a liquid crystal device using a film formed as a light control layer is disclosed, and JP-A-1-198725 discloses that a three-dimensional network-like transparent polymer material is provided in a continuous layer of a liquid crystal material. There is disclosed a liquid crystal device using a light control layer with an intervening one. Among these, the latter liquid crystal device has attracted attention as a large and inexpensive display material because it exhibits a threshold voltage and can reduce the driving voltage.

However, in the latter liquid crystal device, although the driving voltage is low, the driving voltage range is 10 to 30 V, and an IC driver for driving a general-purpose liquid crystal display device is used. Was extremely difficult.

To solve this problem, Japanese Patent Laid-Open Publication No.
Japanese Patent No. 32761 discloses a three-dimensional network transparent polymer substance represented by the general formula (IV):

[0005]

Embedded image

(Wherein, R ⁶ and R ⁷ each independently represent an aliphatic group, an alicyclic group, an aromatic group, a heterocyclic group or a substituted product thereof, and R ⁸ represents —H or —CH ₃ And X is-
Y represents -O- or -COO-;
Or -N- which may form a ring, wherein n is 2 to
Represents an integer of 4. Liquid crystal devices using a polymer comprising a polymerizable composition containing a side chain polymerizable compound represented by the formula (1) have been proposed.

[0007]

However, the liquid crystal device described in Japanese Patent Application Laid-Open No. Hei 6-32761 can be driven at a low voltage, but it is still insufficient, and the electro-optical characteristics sometimes deteriorate in a low temperature range. There was a problem of doing.

An object of the present invention is to provide a liquid crystal device having a sufficiently low voltage drivability, high contrast, and improved electro-optical characteristics in a low temperature range.

[0009]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made intensive studies on a polymerizable composition used for a light control layer of a liquid crystal device. As a liquid crystal device using a polymer material obtained by polymerizing a radical polymerizable composition containing a side chain type radical polymerizable compound having a specific structure, exhibits low voltage driving, high steepness, high contrast, and The inventors have found that the characteristics change with temperature is small, and have completed the present invention.

That is, the present invention provides (1) a compound represented by the following general formula (I):

[0011]

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(Where R₁Is -CH_Two-Or -CH_TwoCH
_TwoCOOCH_Two-Represents R_TwoAnd R _ThreeAre each independently
Aliphatic group, cycloaliphatic group, aromatic group or a substituted product thereof
And R_FourAnd R_FiveIs -H or -CH_ThreeAnd X
Is -CH_Two-Represents an ether bond or an ester bond.
Y represents an ether bond or an ester bond, and n represents
Represents an integer of 2 to 4, and p and q represent 0 or 1.
You. A) a side-chain type radical polymerizable compound represented by the formula:

(2) General formula (II)

[0014]

Embedded image

(Where R₁Is -CH_Two-Or -CH_TwoCH
_TwoCOOCH_Two-Represents R_TwoAnd R _ThreeAre each independently
Aliphatic group, cycloaliphatic group, aromatic group or a substituted product thereof
And R_FourAnd R_FiveIs -H or -CH_ThreeAnd X
Is -CH_Two-Represents an ether bond or an ester bond.
Y represents an ether bond or an ester bond, and n represents
Represents an integer of 2 to 4. To the general formula (I)
Wherein p = 1 and q = 0 in the side chain type according to the above (1).
Radical polymerizable compound,

(3) General formula (III)

[0017]

Embedded image

(Where R₁Is -CH_Two-Or -CH_TwoCH
_TwoCOOCH_Two-Represents R_TwoAnd R _ThreeAre each independently
Aliphatic group, cycloaliphatic group, aromatic group or a substituted product thereof
And R_FourAnd R_FiveIs -H or -CH_ThreeAnd X
Is -CH_Two-Represents an ether bond or an ester bond.
Y represents an ether bond or an ester bond, and n represents
Represents an integer of 2 to 4. To the general formula (I)
Wherein p = 0 and q = 1 in the side chain type according to the above (1).
Radical polymerizable compound,

(4) The above (1), (2) or (2) which is a reaction product of an epoxy acrylate comprising a compound having an epoxy group, a carboxylic acid having a (meth) acryloyl group, and carboxylic acid or carboxylic acid chloride. 3)
The side chain type radical polymerizable compound described,

(5) The above (1), (2), (3) or (4) wherein R ₂ is a saturated alkyl group having 4 to 20 carbon atoms.
The side chain type radical polymerizable compound described,

(6) A liquid crystal comprising at least one transparent substrate having an electrode layer and a light modulating layer composed of a liquid crystal material (B) and a transparent polymer material supported between these substrates. In the device, a liquid crystal device in which the transparent polymer substance is a polymer substance obtained by polymerizing the side chain type radical polymerizable compound according to any one of the above (1) to (5),

(7) The liquid crystal device according to the above (6), wherein a light modulating layer made of a three-dimensional network transparent polymer is provided in the continuous layer of the liquid crystal material.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds represented by the general formula (I) of the present invention have different production methods depending on the values of p and q, and therefore, the compounds of the general formula (II) representing compounds having different values of p and q
And the method for producing the compound is roughly described below.

(1) In the general formula (I), p = 1 and q
The compound of the general formula (II) wherein = 0 The side-chain type polymerizable compound represented by the general formula (II) is, for example, a compound (a) having a polyvalent epoxy group and an active hydrogen capable of reacting with the epoxy group. It can be easily synthesized by reacting a radical polymerizable compound (b) having the same with a generated hydroxyl group and a compound (c) having a group capable of reacting with the hydroxyl group. Is
It is as follows.

(1-1) When X is an ether bond and Y is an ester bond, polyvalent glycidyl ether compounds such as neopentyl glycodiglycidyl ether, bisphenol A diglycidyl ether and 1,6-hexanediol diglycidyl ether To (a-1), 1.1 equivalents of an acrylic group-containing carboxylic acid (b-1) such as (meth) acrylic acid or acrylic acid dimer is added to 1 equivalent of glycidyl group, and triphenylphosphine, N, N -A radical polymerizable compound having a hydroxyl group is produced by reacting with dimethylbenzylamine or the like as a catalyst at 80 to 120 ° C. In this reaction, if the reaction temperature is 120 ° C. or higher, the acrylic group may be polymerized. Therefore, the reaction is preferably performed at a temperature as low as possible.

Next, a monocarboxylic acid (c-1) such as caprylic acid, capric acid, lauric acid, cyclohexanecarboxylic acid or benzoic acid is added in an amount of 1.2 equivalents to 1 equivalent of the hydroxyl group of the radical polymerizable compound having a hydroxyl group. ) And these acid chlorides (c-2) to produce side chain-type radically polymerizable compounds. When a carboxylic acid (c-1) is used in this reaction, 1.2 equivalents of carboxylic acid and dicyclohexylcarbodiimide are added to 1 equivalent of the hydroxyl group of the radical polymerizable compound having a hydroxyl group, and dimethylaminopyridine is used as a catalyst. ,
By reacting for 24 hours at room temperature under anhydrous toluene,
A side chain type radical polymerizable compound can be produced.
This reaction is known and gives a high yield. References to this reaction include B. Neise
s), "Angewandete Chemie International International" by W. Steglich
Edition in English (Angewandte Che
mie International Edition in English) Volume 17 Number 522
P. (1978), "Tetrahedron Lett." Vol. 30, No. 4985 (1989) by Niwa, Ogawa and Yamada. On the other hand, acid chlorides (c-2)
Is used, 1.1 equivalents of an acid chloride and 1.1 equivalents of triethylamine are added to 1 equivalent of the hydroxyl group of the hydroxyl-containing radically polymerizable compound, and the mixture is refluxed for 4 hours under anhydrous isopropyl ether. A chain-type radically polymerizable compound can be produced.

(1-2) When X is an ester bond and Y is an ester bond: Diglycidyl ester of long-chain dibasic acid (trade name: IPS-
22G, manufactured by Okamura Oil Co., Ltd.), a polyvalent glycidyl ester compound (a-2) such as diglycidyl dimer acid ester and diglycidyl sebacate ester, and an acrylic group-containing carboxylic acid such as (meth) acrylic acid and acrylic acid dimer. 1.1 equivalents of b-1) are added to 1 equivalent of glycidyl group, and the reaction is carried out at 80 to 120 ° C. using triphenylphosphine, N, N-dimethylbenzylamine or the like as a catalyst to form a hydroxyl group. To produce a radically polymerizable compound. Next, the radical polymerizable compound having a hydroxyl group is converted to a carboxylic acid (c-1) in the same manner as in the above (1-1).
And a carboxylic acid chloride (c-2) to produce a side chain type radically polymerizable compound.

(1-3) When X is an ether bond and Y is an ether bond In the same manner as in the above (1-1), the polyvalent glycidyl ether compound (a-1) is added with (meth) acrylic acid and acrylic Acrylic group-containing carboxylic acid (b-1) such as an acid dimer is added in an amount of 1.1 equivalent to 1 equivalent of glycidyl group, and triphenylphosphine, N, N-dimethylbenzylamine or the like is used as a catalyst at 80 to 120 ° C. By reacting under the conditions, a radical polymerizable compound having a hydroxyl group is produced.

Next, 1.5 equivalents of an alkyl chloride (c) such as dodecyl chloride, lauryl chloride, octyl chloride or the like is added to 1 equivalent of the hydroxyl group of the radical polymerizable compound having a hydroxyl group.
-3) and adding the same amount of sodium hydroxide as the hydroxyl group of the hydroxyl group-containing radically polymerizable compound, and reacting with tetra-n-butylammonium bromide as a catalyst for 4 hours while maintaining at 60 ° C. in an oil bath under anhydrous toluene. Thus, a side chain type radical polymerizable compound can be produced.

(1-4) When X is —CH ₂ — and Y is an ester bond In the above (1-1), instead of the polyvalent glycidyl ether compound (a-1), 1,2,3 A side chain type radical polymerizable compound is produced in the same manner as in the above (1-1) except that an epoxy compound (a-3) such as 1,4-diepoxybutane or 1,2,7,8-diepoxyoctane is used. can do.

(1-5) When X is —CH ₂ — and Y is an ether bond In the above (1-3), instead of the polyvalent glycidyl ether compound (a-1), 1,2,3 A side-chain type radical polymerizable compound is produced in the same manner as in the above (1-3) except that an epoxy compound (a-3) such as 1,4-diepoxybutane, 1,2,7,8-diepoxyoctane is used. can do.

(2) In the general formula (I), p = 0 and q
= 1 The compound of the general formula (III) wherein the side chain type radically polymerizable compound represented by the general formula (III) has a compound (a ') having a monoepoxy group and an active hydrogen capable of reacting with the epoxy group. The compound can be easily produced by reacting a radical polymerizable compound (b) with a compound (c ') having two or more groups capable of reacting with a hydroxyl group formed in a molecule, and further reacting the resulting hydroxyl group. It is possible, but specifically, as follows.

(2-1) When X is an ester bond and Y is an ether bond: Monoglycidyl ether compounds such as butyl glycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether and phenyl glycidyl ether (a-
To 4), 1.1 equivalents of an acrylic group-containing carboxylic acid (b-1) such as (meth) acrylic acid or acrylic acid dimer is added to 1 equivalent of glycidyl group, and triphenylphosphine, N, N-dimethyl is added. The reaction is carried out at 80 to 120 ° C. using benzylamine or the like as a catalyst to produce a radical polymerizable compound having a hydroxyl group.

Next, a polyvalent carboxylic acid (c-4) such as sebacic acid, adipic acid, terephthalic acid or dimer acid is used in an amount of 1.2 equivalents to 1 equivalent of the hydroxyl group of the radical polymerizable compound having a hydroxyl group. By reacting the acid chloride (c-5) of formula (I), a side-chain type radically polymerizable compound can be produced. When a carboxylic acid is used, 1.2 equivalents of a carboxylic acid and 1 equivalent of dicyclohexylcarbodiimide are added to 1 equivalent of a hydroxyl group to a radical polymerizable compound having a hydroxyl group, and the mixture is reacted for one day at room temperature under anhydrous toluene with dimethylaminopyridine as a catalyst. Let it. This reaction is known and high yields are obtained. In addition, when an acid chloride is used, 1.1 equivalents of an acid chloride and 1.1 equivalents of triethylamine are added to 1 equivalent of a hydroxyl group to a radical polymerizable compound having a hydroxyl group, and the mixture is added under anhydrous isopropyl ether for 4 hours. By refluxing, a side chain type radically polymerizable compound can be produced.

(2-2) When X is an ester bond and Y is an ester bond: Monoglycidyl ester compounds (a-5) such as glycidyl laurate, glycidyl cyclohexanecarboxylate, glycidyl myristate, etc.
Acrylic group-containing carboxylic acid (b-1) such as (meth) acrylic acid or acrylic acid dimer is added in an amount of 1.1 equivalent per 1 equivalent of glycidyl group, and triphenylphosphine is added.
Using N, N-dimethylbenzylamine or the like as a catalyst, 80
The reaction is carried out at a temperature of up to 120 ° C. to produce a radical polymerizable compound having a hydroxyl group.

Next, the radical polymerizable compound having a hydroxyl group was converted into a carboxylic acid (c-
By reacting with 4) or carboxylic acid chloride (c-5), a side chain type radical polymerizable compound can be produced.

(2-3) When X is an ether bond and Y is an ether bond In the same manner as in the above (2-1), the monoglycidyl ether compound (a-4) is added to (meth) acrylic acid, acrylic An acrylic group-containing carboxylic acid (b-1) such as an acid dimer;
1.1 equivalents are added to 1 equivalent of the glycidyl group, and the reaction is carried out at 80 to 120 ° C using triphenylphosphine, N, N-dimethylbenzylamine or the like as a catalyst to produce a radical polymerizable compound having a hydroxyl group. Reaction temperature is 1
If the temperature is higher than 20 ° C., the acrylic group may be polymerized. Therefore, this reaction is preferably performed at a temperature as low as possible.

Next, 1.5 equivalents of a chlorinated compound (c-6) such as 1,4-dichlorobutane and 1,6-dichlorohexane and 1 equivalent of the hydroxyl group of the radical polymerizable compound having a hydroxyl group are used. Sodium hydroxide in an amount equivalent to the hydroxyl group of the radical polymerizable compound having
By reacting with -butylammonium bromide as a catalyst in an oil bath under anhydrous toluene at 60 ° C. for 4 hours, a side chain type radical polymerizable compound can be produced.

(2-4) X is an ester group and Y is -CH
_In the case of _{2- In the} above (2-1), instead of the monoglycidyl ether compound (a-4), 1,2-epoxyhexane,
Except for using an epoxy compound (a-6) such as 1,2-epoxydecane, a long-chain alkyl group epoxy compound (trade name: AOEX24, AOEX68, manufactured by Daicel Chemical Industries, Ltd.), in the same manner as in the above (2-1), A side chain type radical polymerizable compound can be produced.

(2-5) X is an ester group and Y is -CH
_In the case of _{2- In the} above (2-3), instead of the monoglycidyl ether compound (a-4), 1,2-epoxyhexane,
Except for using an epoxy compound (a-6) such as 1,2-epoxydecane, a long-chain alkyl group epoxy compound (trade name: AOEX24, AOEX68, manufactured by Daicel Chemical Industries, Ltd.), the same as (2-3) above. A side chain type radical polymerizable compound can be produced.

The compound (a) having a polyepoxy group used in the above reaction can be prepared by reacting (methyl) epichlorohydrin with a polyhydric alcohol and a polyhydric phenol, or besides the above. It can be produced by oxidizing a compound having a saturated group with hydrogen peroxide, peracetic acid, metachloroperbenzoic acid or the like. More specifically, an epibis-type epoxy resin synthesized from (methyl) epichlorohydrin and bisphenol A, bisphenol F and its ethylene oxide and propylene oxide modified products; phenol,
Reaction products of biphenol and the like with (methyl) epichlorohydrin; aromatic (methyl) glycidyl ester compounds of terephthalic acid, isophthalic acid and pyromellitic acid; Also, glycols such as (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, (poly) tetramethylene glycol, neopentyl glycol, trimethylolpropane, trimethylolethane, glycerin, diglycerin, erythritol, Aliphatic polyhydric alcohols such as pentaerythritol, sorbitol, 1,4-butanediol, 1,6-hexanediol, and (methyl)
Glycidyl ether compounds which are reaction products with epichlorohydrin; adipic acid, sebacic acid, maleic acid,
Aliphatic (methyl) glycidyl ester compounds of polycarboxylic acids such as itaconic acid and long-chain dibasic acid; 1,2,7,
8-diepoxyoctane, 3,9 divinyl spiro (m
-Dioxane) diepoxide and the like.

The compound (c) having a group capable of reacting with a hydroxyl group used in the above reaction includes halides, carboxylic acids, carboxylic acid chlorides and the like.
Specific compounds include formic acid, acetic acid, butyric acid, caprylic acid, caproic acid, lauric acid, stearic acid, cyclohexanecarboxylic acid, myristyl acid, isostearic acid,
Palmitic acid, 2-ethylhexanoic acid, 2-decyldodecanoic acid, 2-dodecyltetradecanoic acid, 3-pentyloctanoic acid, 3-heptyldecanoic acid, 3-nonyldodecanoic acid, benzoic acid, p-toluic acid, α-phenylbutyric acid, etc. And halides such as acid chlorides thereof, myristyl chloride, lauryl chloride, and stearyl chloride.

The compound (a ') having a monoepoxy group used in the above reaction includes, for example, (methyl) glycidyl ester of an aliphatic carboxylic acid such as caprylic acid, myristyl acid, lauric acid, stearyl acid and isostearyl acid. A (methyl) glycidyl ester of an aromatic carboxylic acid such as benzoic acid; butyl (methyl) cricidyl ether, cetyl (methyl) glycidyl ether, stearyl (methyl) glycidyl ether, morpholino (methyl) glycidyl ether, 2-ethylhexyl (methyl) ) Glucidyl ethers such as glycidyl ether and phenyl (methyl) glycidyl ether; "AOEX24" and "AOEX6" which are epoxy compounds having long-chain alkyl groups
8 "(manufactured by Daicel Chemical Industries, Ltd.).

Examples of the compound (c ') having two or more groups capable of reacting with a hydroxyl group used in the above reaction include adipic acid, sebacic acid, terephthalic acid, and the like.
Examples thereof include pyromellitic acid, maleic acid, long-chain dibasic acid, dimer acid, and acid chlorides thereof.

The side chain type radically polymerizable compound of the present invention comprises
It can be synthesized by the above method, but more preferably from the viewpoint of optical characteristics such as low driving voltage and high scattering property, the side chain R
₂ and more preferably (meth) acrylic ester monomers bifunctional which is a linear and branched alkyl groups having 4-20 carbon atoms.

The liquid crystal device of the present invention has a light control layer made of a transparent polymer material and a liquid crystal material. The light modulating layer of the liquid crystal device may be one in which the transparent polymer material is dispersed in the liquid crystal material in the form of particles or fibers, or the liquid crystal material is dispersed in the form of droplets in the transparent polymer material. However, it is preferable that a transparent polymer substance having a three-dimensional network structure is formed in a continuous layer of a liquid crystal material. Liquid crystal devices having these types of dimming layers can be separately formed depending on the types and ratios of the liquid crystal and the radical polymerizable composition (A) to be used as the dimming layer forming material, the polymerization conditions, and the like.

The liquid crystal device of the present invention comprises, for example, a radically polymerizable composition (A) containing the side chain type radically polymerizable compound of the present invention between two transparent substrates having at least one electrode layer. And a light modulating layer forming material containing the liquid crystal material (B), and then irradiating the light modulating layer forming material with heat or active energy rays to polymerize the radical polymerizable composition (A), It can be manufactured by forming a light control layer composed of (B) and a transparent polymer substance.

The transparent polymer material is not limited to a rigid one, but may be one having flexibility, flexibility and elasticity as long as it can meet the purpose.

The transparent polymer material formed by polymerizing the radically polymerizable composition (A) is sufficient only with the side chain type radically polymerizable compound of the present invention, but for the purpose of obtaining a lower driving voltage. And other radically polymerizable compounds. As such radical polymerizable compounds,
For example, ethyl (meth) acrylate, butyl (meth)
Acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, Methyl carbitol (meth) acrylate, ethyl carbitol (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth)
Acrylate, 2-hydroxyethyl (meth) acrylate, phenoxy (meth) acrylate, methoxydipropylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, dimethylamino (meth) acrylate, morpholinoethyl (meth) acrylate, triethylene Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, epichlorohydrin-modified 1,6-hexanediol di (meth) acrylate, dicyclopentenyl di (meth) acrylate , Bisphenol A di (meth) acrylate, epichlorohydrin-modified bisphenol A di (meth) acrylate, bisphenol A di (meth) acrylate, propylene oxa Modified bisphenol A di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 3,3-dimethylolpentane di (meth) acrylate, 3,3 -Dimethylol heptane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth)
Acrylic ester monomers such as acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and N, N-dimethylacrylamide; And acrylamide compounds such as N-dimethylaminopropylacrylamide.

The liquid crystal material (B) may be a single liquid crystal compound or a mixture containing two or more liquid crystal compounds or a substance other than the liquid crystal compound. What is recognized may be any, and among them, those having a positive dielectric anisotropy are preferable. The liquid crystal used is preferably a nematic liquid crystal, a smectic liquid crystal, or a cholesteric liquid crystal, and particularly preferably a nematic liquid crystal. In order to improve the performance, a cholesteric liquid crystal, a chiral nematic liquid crystal, a chiral smectic liquid crystal, a chiral compound, or the like may be appropriately contained.

The liquid crystal material (B) is a compounded composition composed of the compounds shown below. The properties of the liquid crystal material, that is, the phase transition temperature, melting point, viscosity, birefringence of isotropic liquid and liquid crystal It can be appropriately selected and blended for the purpose of considering the ratio, the dielectric anisotropy (Δε), or adjusting the solubility with the polymerizable composition or the like.

As the liquid crystal material (B), benzoic acid ester type, cyclohexanecarboxylic acid ester type, biphenyl type, terphenyl type, phenylcyclohexanoic acid type,
Various liquid crystal compounds such as biphenylcyclohexanoic acid, pyrimidine, dioxane, cyclohexanecyclohexane ester, tolan, alkenyl, and fluoro compounds are used.

As such a liquid crystal compound, for example,
4-substituted benzoic acid 4'-substituted phenyl ester, 4-substituted cyclohexanecarboxylic acid 4'-substituted phenyl ester, 4-substituted cyclohexanecarboxylic acid 4'-substituted biphenyl ester, 4- (4-substituted cyclohexanecarbonyloxy) benzoic acid 4'-substituted phenyl esters, 4
-(4-substituted cyclohexyl) benzoic acid 4'-substituted phenyl ester, 4- (4-substituted cyclohexyl) benzoic acid 4'-substituted cyclohexyl ester, 4-substituted 4 "-
Substituted terphenyl, 4-substituted biphenyl 4′-substituted cyclohexane, 2- (4-substituted phenyl) -5-substituted pyrimidine and the like can be mentioned.

The content of the liquid crystal material (B) in the light control layer is 5
The range is preferably from 0 to 99% by weight, particularly preferably from 60 to 90% by weight.

Examples of the means for polymerizing the radically polymerizable composition (A) include active energy rays such as heat and ultraviolet rays. In the case of thermal polymerization, a thermal polymerization initiator (C1) is required as the polymerization initiator (C), and the thermal polymerization initiator (C1)
For example, benzoyl peroxide, 2,4
-Dichlorobenzoyl peroxide, 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4'-di (tert-butylperoxy) valerate, dicumylper Peroxides such as oxide; azo compounds such as 7-azobisisobutylnitrile; and tetramethylthiuram disulfide.

Further, it is preferable to carry out the polymerization using an active energy ray because the production process is easy. When ultraviolet rays are used as the active energy rays, it is usually necessary to add a photopolymerization initiator (C2) as the polymerization initiator (C) to the radically polymerizable composition (A). The photopolymerization initiator (C2) can be roughly classified into two types: an intramolecular bond cleavage type and an intramolecular hydrogen abstraction type. As an example of the former,
Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1- (4-isopropylphenyl) -2-
Hydroxy-2-methylpropan-1-one, 4- (2
-Hydroxyethoxy) phenyl- (2-hydroxy-
2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-
Acetophenones such as thiomethylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoin such as benzoin, benzoin isopropyl ether and benzoin isobutyl ether; Acylphosphine oxides such as 4,6-trimethylbenzoyldiphenylphosphine oxide; benzyl and methylphenylglyoxyester; On the other hand, examples of the latter include benzophenone, methyl o-benzoylbenzoate,
4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylated benzophenone, 3,3 ', 4,4'-tetra (t-
Butylperoxycarbonyl) benzophenone, 3,
Benzophenones such as 3'-dimethyl-4-methoxybenzophenone;2-isopropylthioxanthone;
Thioxanthones such as 4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone; aminobenzophenones such as Michler's ketone and 4,4'-diethylaminobenzophenone; 10-
Butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone and the like.

The amount of the polymerization initiator (C) to be added is preferably in the range of 0.01 to 10% by weight, particularly preferably in the range of 1 to 5% by weight of the radically polymerizable composition (A). When the radical polymerizable composition (A) is irradiated with ultraviolet rays, the composition is cured only by the addition of the photopolymerization initiator (C2), but in order to further improve the curability, a photosensitizer (D) is used in combination. Is preferred. Examples of the photosensitizer (D) include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid ( Examples thereof include amines such as 2-dimethylamino) ethyl, (n-butoxy) ethyl 4-dimethylaminobenzoate, and 2-ethylhexyl 4-dimethylaminobenzoate. The compounding amount of the photosensitizer (D) is 0.01 to 10% by weight, preferably 0.05 to 5% by weight in the radical polymerizable composition.

Further, the radical polymerizable composition (A) includes:
In addition to the above, antioxidants, ultraviolet absorbers, non-reactive oligomers and inorganic fillers, organic fillers, polymerization inhibitors, defoamers, leveling agents, plasticizers, silane coupling agents, and the like may be added. .

The substrate used in the present invention may be a rigid material, for example, glass or metal, or a flexible material, for example, a plastic film. The two substrates are opposed to each other and are obtained at an appropriate interval. At least one of them must be transparent so that the light control layer sandwiched between the two can be seen from the outside. However, complete transparency is not required. If it acts on light passing from one side of the device to the other,
When this liquid crystal device is used, the two substrates are:
Both have appropriate transparency. An appropriate transparent or opaque electrode may be disposed on the entire or partial surface of the substrate according to the purpose. However, a flexible material such as plastic can be used for the liquid crystal device of the present invention after being fixed to a rigid material such as glass or metal.

A light modulating layer made of a liquid crystal material (B) and a transparent polymer substance is interposed between the two substrates, but between the two substrates, usually, as in a well-known liquid crystal device, It is desirable to interpose a spacer for maintaining the interval.

As the spacer, for example, those for various liquid crystal cells such as plastic beads, silica beads, and alumina can be used.

The thickness of the light control layer of the liquid crystal device of the present invention is:
A range of 5 to 100 microns is preferred, more preferably a range of 6 to 50 microns.

The light modulating layer is preferably formed of a transparent polymer material in a continuous layer of a liquid crystal material to form a three-dimensional network structure in view of low voltage driving property, high speed response and the like. The size of the liquid crystal droplet or the average size of the three-dimensional network structure is preferably in the range of 0.2 to 5 microns, particularly preferably in the range of 0.5 to 3 microns.

The method of forming a continuous layer of a liquid crystal material and a light control layer containing a transparent polymer substance having a uniform three-dimensional network structure on the continuous layer on the substrate includes the following methods. A uniform solution of a light modulating layer forming material comprising a polymerizable composition (A), a liquid crystal material (B) and, if necessary, a polymerization initiator (C) is sandwiched between two substrates having an electrode layer. Is irradiated with an active energy ray or thermally polymerized to form a three-dimensional network-like layer containing a transparent polymer material. (2) Using a coater such as a spin coater, a bar coater, or an applicator, a uniform solution of a light modulating layer forming material may be applied on the electrode layer of one substrate, and then the other substrate may be overlaid. Irradiation with an energy beam or thermal polymerization and curing forms a three-dimensional network-like layer containing a transparent polymer material.

The active energy rays used in the present invention include ionizing radiations such as ultraviolet rays, electron beams, α rays, β rays and γ rays,
Visible light, microwave, high frequency, etc., may be any energy species as long as radical active species can be generated. Examples of those that generate ultraviolet light include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp,
Metal halide lamps, chemical lamps, black light lamps, mercury-xenon lamps, short arc lamps,
These may be selected in consideration of the absorption wavelength of the compound generating the radical active species.

In particular, a photopolymerization method using ultraviolet light is preferable. Irradiation with ultraviolet light while maintaining the isotropic liquid state of the light modulating layer forming material is preferable for forming a uniform light modulating layer.

Further, as the light irradiation method, uniform irradiation with time and in a plane means that radical polymerization composition (A) interposed between the substrates is instantaneously irradiated with strong light to cause polymerization to proceed. This is effective in making the mesh size uniform. That is, by irradiating ultraviolet light in a pulsed manner with appropriate intensity, a transparent polymer substance having a uniform three-dimensional network structure can be formed in the liquid crystal layer,
As a result, the obtained liquid crystal device has a clear threshold voltage and sharpness, and time-division driving is possible.

The liquid crystal device of the present invention has a high ratio of the liquid crystal material in the light control layer. When a continuous layer is formed, the liquid crystal device has a low driving voltage and high transparency when a voltage is applied.

[0069]

The present invention will be described in more detail with reference to the following examples. However, the invention is not limited to the scope of these examples. In the following examples, "%" and "part" represent "% by weight" and "part by weight", respectively, and the symbols, meanings and contents of the evaluation characteristics are shown in Table 1 below.

[0070]

[Table 1]

The illuminance of the ultraviolet light was measured using a Unimeter UIT-with a photo detector “UVD-365PD” manufactured by Ushio Inc.
101 ". First, a synthesis example of the side chain type radical polymerizable compound of the present invention will be described.

Example 1 Epichlorohydrin-modified 1,6-hexanediol epoxy acrylate (trade name of Nippon Kayaku Co., Ltd.) was placed in a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a condenser tube and a thermometer. R-167 ", 21 g of hydroxyl value 268.7 KOH mg / g), 20 mg of p-methoxyphenol, 15.1 g of triethylamine (0.1 g).
15 mol) and 500 ml of tetrahydrofuran, and the mixture was kept at 5 ° C. in a water-ice bath under a nitrogen stream. Next, 16.3 g (0.1 mol) of n-octanoyl chloride was slowly dropped over 1 hour. After dropping, remove the water ice bath,
The mixture was refluxed for 5 hours to complete the reaction. After completion of the reaction, the precipitated hydrochloride was separated by filtration and concentrated. The concentrated solution is toluene 200
After washing with 300 ml of 0.1N hydrochloric acid solution and further with pure water and saturated saline, the organic layer was dried over anhydrous sodium sulfate. The concentrated solution obtained by evaporating the solvent of the organic layer under reduced pressure is purified by silica gel chromatography (using 40 times the amount of silica gel with respect to the concentrated solution),

[0073]

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15 g of a transparent liquid side-chain type radically polymerizable compound (A-1) represented by the following formula was obtained. As the mobile phase, a mixed solution of toluene / ethyl acetate was used.
When the volume fraction of ethyl acetate was 9: 1, the Rf value of the thin plate was 0.4. Further, from the infrared absorption spectrum (IR), it was confirmed that the absorption of the hydroxyl group at 3200 to 3600 cm ^-1 disappeared, and that the esterification was completed.

<Physical properties> ¹ H-nuclear magnetic resonance spectrum (NMR) (solvent deuterated chloroform) δ: 6.43 (2H), 6.12 (2H), 5.84 (2H), 5.24 (2H), 4.33 (2H)
H), 4.25 (2H), 3.58 (4H), 3.46 (4H), 2.32 (4H), 1.63 (4
H), 1.59 (4H), 1.3-1.25 (20H), 0.87 (6H)

¹³ C-NMR (solvent deuterated chloroform) δ: 173.4, 173.1, 165.7, 165.4, 131.3, 131.2, 128.
2, 128.1, 71.63, 70.56, 69.99, 68.95, 63.1, 62.7,
34.3, 31.9, 29.6-29.0, 25.8, 24.9, 22.6, 14.1

Infrared absorption spectrum (IR) (KBr) cm ^-1 : 2925, 2854, 1742, 1643-1620, 1173, 807.5

Elemental analysis: C = 64.22% (65.20%), H =
9.31% (9.26%), theoretical values in parentheses

<Example 2> In Example 1, n-chloride was added.
Lauroyl chloride 2 instead of 16.3 g of octanoyl
Except that 1.8 (0.1 mol) was used, the formula was changed in the same manner as in Example 1.

[0080]

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20 g of a transparent liquid side-chain type radically polymerizable compound (A-2) represented by the following formula was obtained. R of thin plate
The f-value was 0.5. Further, from the infrared absorption spectrum (IR), it was confirmed that the absorption of the hydroxyl group at 3200 to 3600 cm ^-1 disappeared, and that the esterification was completed.

<Physical Properties> ¹ H-NMR (solvent deuterated chloroform) δ: 6.42 (2H), 6.10 (2H), 5.86 (2H), 5.24 (2H), 4.34 (2H)
H), 4.26 (2H), 3.51 (4H), 3.45 (4H), 2.31 (4H), 1.64 (4
H), 1.60 (4H), 1.3-1.24 (36H), 0.87 (6H)

¹³ C-NMR (solvent deuterated chloroform) δ: 173.6, 173.3, 165.5, 165.3, 131.3, 131.1, 128.
1, 128.1, 70.63, 70.56, 70.05, 68.85, 63.1, 63.1,
34.3, 31.9, 29.6-29.0, 25.8, 24.9, 22.6, 14.6

IR (KBr) cm ^-1 : 2925, 2854, 1742, 1652 to 1620, 1176, 807.9 Elemental analysis: C = 68.01% (68.26%), H = 10.22% (10.
09)

<Example 3> In Example 1, n-chloride was used.
Instead of octanoyl 16.3 g, stearoyl chloride 3
Except that 0.3 (0.1 mol) was used, the formula was changed in the same manner as in Example 1.

[0086]

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22 g of a transparent liquid side-chain type radical polymerizable compound (A-3) represented by the following formula was obtained. R of thin plate
The f-value was 0.5. Further, from the infrared absorption spectrum (IR), it was confirmed that the absorption of the hydroxyl group at 3200 to 3600 cm ^-1 disappeared, and that the esterification was completed.

<Physical Properties> ¹ H-NMR (solvent deuterated chloroform) δ: 6.43 (2H), 6.19 (2H), 5.89 (2H), 5.30 (2H), 4.39 (2H)
H), 4.26 (2H), 3.58 (4H), 3.50 (4H), 2.39 (4H), 1.61 (4
H), 1.61 (4H), 1.45-1.25 (60H), 0.87 (6H)

¹³ C-NMR (solvent deuterated chloroform) δ: 173.9, 173.7, 165.8, 165.6, 131.9, 131.7, 128.
2, 128.1, 78.63, 90.56, 69.99, 68.95, 63.7, 62.7,
34.3, 31.9, 30.6-29.2, 25.8, 24.9, 22.7, 14.6

IR (KBr) cm ^-1 : 2935, 2864, 1747, 1652-1625, 1175, 807.8

Elemental analysis: C = 71.32% (71.54%), H =
10.96% (10.81)

<Example 4> In Example 1, n-chloride was added.
Benzoyl chloride 1 instead of 16.3 g of octanoyl
Except that 0.5 (0.1 mol) was used, in the same manner as in Example 1, a light yellow liquid side-chain type radical polymerizable compound (A
-4) 11 g was obtained. The Rf value of the thin plate is 0.3
Met. Also, from the infrared absorption spectrum (IR), 3
The absorption of the hydroxyl group at 200 to 3600 cm ^-1 has disappeared,
It was confirmed that it was completely esterified.

[0093]

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<Physical Properties> ¹ H-NMR (solvent deuterated chloroform) δ: 8.15 (4H) 7.45 (4H), 7.30 (2H), 6.45 (2H), 6.22 (2H)
H), 5.96 (2H), 5.34 (2H), 4.32 (2H), 4.28 (2H), 3.59 (4
H), 3.50 (4H), 1.63 (4H), 1.28 (4H)

¹³ C-NMR (solvent deuterated chloroform) δ: 168.9, 168.6, 165.9, 165.6, 133.8, 131.5, 131.
3, 130.9, 128.9, 128.2, 128.0, 71.93, 70.66, 70.
0, 68.95, 63.1, 62.7, 29.8, 25.8, 24.9

IR (KBr) cm ^-1 : 2929, 2842, 1742, 1643-1620, 1605, 1589, 11
73, 807.4

Elemental analysis: C = 59.12% (59.82%), H =
6.58% (6.52)

<Example 5> Trimethylolpropane triglycidyl ether (trade name "Epiol TMP-100", manufactured by NOF CORPORATION) was placed in a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube, and a thermometer. 100g (0.33
Mol), 108 g (1.5 mol) of acrylic acid, 150 mg of p-methoxyphenol and 1.31 g of N, N-dimethylbenzylamine as a catalyst were stirred at 80 ° C. Next, the reaction solution was slowly heated to 110 ° C., and stirred for 10 hours while maintaining the same temperature to complete the reaction. The reaction mixture was washed with 300 ml of a 5% sodium hydroxide solution, further washed with pure water and saturated saline, and the organic layer was dried over anhydrous sodium sulfate.
A light brown transparent liquid product having an acid value of 1.5 and a hydroxyl value of 294 was obtained.

Next, the liquid product 2 was placed in a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube and a thermometer.
6.0 g, 20 mg of p-methoxyphenol, 20.0 g (0.20 mol) of triethylamine and 500 ml of tetrahydrofuran were added, and the mixture was kept at 5 ° C. using a water-ice bath under a nitrogen stream. Next, 24.5 g of n-octanoyl chloride
(0.15 mol) was slowly added dropwise over 1 hour. After completion of the dropwise addition, the water-ice bath was removed, and the mixture was refluxed for 5 hours to complete the reaction. After completion of the reaction, the precipitated hydrochloride was separated by filtration and concentrated. The concentrated solution is dissolved in 200 ml of toluene, and 0.1N
After washing with 300 ml of a hydrochloric acid solution and further with pure water and saturated saline, the organic layer was dried over anhydrous sodium sulfate. The solvent of the organic layer was distilled off under reduced pressure, and the concentrated solution was purified by silica gel chromatography (using 40 times the amount of silica gel with respect to the concentrated solution),

[0100]

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33 g of a transparent liquid side-chain type radically polymerizable compound (A-5) represented by the following formula was obtained. R of thin plate
The f-value was 0.4. Further, from the infrared absorption spectrum (IR), it was confirmed that the absorption of the hydroxyl group at 3200 to 3600 cm ^-1 disappeared, and that the esterification was completed.

<Physical Properties> ¹ H-NMR (solvent deuterated chloroform) δ: 6.44 (3H), 6.20 (3H), 5.89 (3H), 5.29 (3H), 4.38 (3H)
H), 4.29 (3H), 3.58 (6H), 3.48 (6H), 2.34 (6H), 1.60 (6
H), 1.35-1.25 (26H), 0.89 (12H)

¹³ C-NMR (solvent deuterated chloroform) δ: 173.6, 173.4, 165.7, 165.4, 131.5, 131.3, 128.
6, 128.4, 71.68, 70.53, 69.99, 68.95, 63.1, 62.7,
41.4, 34.5, 31.4, 29.6-29.0, 25.8, 24.9, 22.8, 1
4.6

IR (KBr) cm ^-1 : 2920, 2852, 1745, 1650 to 1622, 1180, 807.1

Elemental analysis: C = 64.20% (64.30%), H =
9.03% (8.92)

Example 6 In a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a condenser tube and a thermometer, epichlorohydrin-modified 1,6-hexanediol epoxy acrylate (trade name of Nippon Kayaku Co., Ltd.) R-167 ", hydroxyl value 268.7 KOH mg / g) 21 g, p-methoxyphenol 20 mg, cyclohexanecarboxylic acid 12.8
g (0.1 mol), 500 ml of tetrahydrofuran and 4
-6.0 g of dimethylaminopyridine are added as catalyst,
The temperature was kept at 5 ° C. using a water ice bath. Next, a solution of 20.6 g (0.10 mol) of dicyclohexylcarbodiimide in 50 ml of tetrahydrofuran was slowly dropped over 1 hour. After completion of the dropwise addition, the water-ice bath was removed, and the reaction was completed by stirring at room temperature for 24 hours. After completion of the reaction, the precipitated dicyclohexylurea was separated by filtration and concentrated. The concentrated solution is toluene 20
After dissolving in 0 ml and washing with pure water and saturated saline, the organic layer was dried over anhydrous sodium sulfate. The solvent of the organic layer was distilled off under reduced pressure, and the concentrated solution was purified by silica gel chromatography (using 40 times the amount of silica gel with respect to the concentrated solution),

[0107]

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35 g of a transparent liquid side-chain type radically polymerizable compound (A-6) represented by the following formula was obtained. R of thin plate
The f value was 0.3. Further, from the infrared absorption spectrum (IR), it was confirmed that the absorption of the hydroxyl group at 3200 to 3600 cm ^-1 disappeared, and that the esterification was completed.

<Physical Properties> ¹ H-NMR (solvent deuterated chloroform) δ: 6.44 (2H), 6.11 (2H), 5.86 (2H), 5.26 (2H), 4.33 (2H)
H), 4.25 (2H), 3.60 (4H), 3.48 (4H), 2.42 (2H), 1.65 (4
H), 1.62 (8H), 1.42-1.35 (12H), 1.31 (4H)

¹³ C-NMR (solvent deuterated chloroform) δ: 173.5, 173.2, 165.9, 165.6, 131.53, 131.3, 12
8.4, 128.3, 71.63, 70.56, 69.99, 68.95, 63.1, 62.
7, 42.4, 34.9, 29.6-29.0, 25.8, 24.9, 22.6

IR (KBr) cm ^-1 : 2930, 2861, 1744, 1652-1622, 1176, 807.5

Elemental analysis: C = 64.42% (64.76%), H =
8.53% (8.41) <Example 7> A dibasic acid epoxy acrylate (trade name “IPS-22G manufactured by Okamura Oil Co., Ltd.) was placed in a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube, and a thermometer.
A ", hydroxyl value 175.2 KOH mg / g) 32 g, p-
30 mg of methoxyphenol, 15.1 of triethylamine
g (0.15 mol) and 500 ml of tetrahydrofuran were added, and the mixture was kept at 5 ° C. using a water-ice bath under a nitrogen stream.
Next, 21.9 g (0.1 mol) of lauroyl chloride was slowly added dropwise over 1 hour. After completion of the dropwise addition, the water-ice bath was removed, and the mixture was refluxed for 5 hours to complete the reaction. After the reaction,
The precipitated hydrochloride was filtered off and concentrated. The concentrate was dissolved in 200 ml of toluene, washed with 300 ml of a 0.1N hydrochloric acid solution, further washed with pure water and a saturated saline solution, and then the organic layer was dried over anhydrous sodium sulfate. The solvent of the organic layer was distilled off under reduced pressure, and the concentrated solution was purified by silica gel chromatography (using 40 times the amount of silica gel with respect to the concentrated solution),

[0113]

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20 g of a transparent liquid side-chain type radical polymerizable compound (A-7) represented by the following formula was obtained. R of thin plate
The f value was 0.6. Further, from the infrared absorption spectrum (IR), it was confirmed that the absorption of the hydroxyl group at 3200 to 3600 cm ^-1 disappeared, and that the esterification was completed.

<Physical Properties> ¹ H-NMR (solvent deuterated chloroform) δ: 6.50 (2H), 6.19 (2H), 5.91 (2H), 5.41 (2H), 4.33 (2H)
H), 4.25 (2H), 4.21 (4H), 2.35 (4H), 2.34 (4H), 1.60 (4
H), 1.59 (4H), 1.57 (2H), 1.4-1.21 (56H), 0.87 (12H)

¹³ C-NMR (solvent deuterated chloroform) δ: 173.4, 173.1, 165.7, 165.4, 162.5, 131.3, 131.
2, 128.2, 128.1, 69.9, 68.5, 63.1, 63.0, 62.7, 34.
3, 33.6, 33.1, 31.9, 29.6-29.0, 25.8, 24.9, 22.
6, 14.8, 14.1

IR (KBr) cm ^-1 : 2926, 2854, 1743, 1649 to 1625, 1172, 807.9

Elemental analysis: C = 70.8.% (70.2%), H = 1
0.54% (10.47)

<Example 8> In Example 7, 21.9 g of lauroyl chloride was replaced by isostearoyl chloride 3
Except that 0.3 (0.1 mol) was used, the same procedure as in Example 7 was carried out to formula

[0120]

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20 g of a light yellow liquid side chain type radically polymerizable compound (A-8) represented by the following formula was obtained. The Rf value of the thin plate was 0.6. Further, from the infrared absorption spectrum (IR), it was confirmed that the absorption of the hydroxyl group at 3200 to 3600 cm ^-1 disappeared, and that the esterification was completed.

<Physical properties> ¹ H-NMR (solvent deuterated chloroform) δ: 6.51 (2H), 6.19 (2H), 5.90 (2H), 5.42 (2H), 4.33 (2H)
H), 4.27 (2H), 4.20 (4H), 2.73 (2H), 2.34 (4H), 1.69 (4
H), 1.59 (4H), 1.57 (2H), 1.55 (4H), 1.35 to 1.21 (36
H), 0.89-0.86 (48H)

¹³ C-NMR (solvent deuterated chloroform) δ: 173.7, 173.5, 165.7, 165.3, 162.5, 131.5, 131.
2, 128.2, 128.1, 69.9, 68.5, 63.1, 63.0, 62.7, 41.
4, 40.5, 34.3, 33.6, 33.0, 31.9, 29.6-29.2, 26.0
~ 24.9, 22.6, 14.8 ~ 14.3

IR (KBr) cm ^-1 : 2925, 2853, 1743, 1651-1626, 1172, 807.5

Elemental analysis: C = 73.1% (73.7%), H = 1
0.15% (10.08)

Example 9 In a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube and a thermometer, a dibasic acid epoxy acrylate (trade name "I" manufactured by Okamura Oil Co., Ltd.) was added.
PS-22GA ", hydroxyl value 175.2 KOHmg / g)
32 g, p-methoxyphenol 30 mg, 4-dimethylaminopyridine 3.1 g, 3-nonyldodecanoic acid
7 g (0.1 mol) and 500 ml of tetrahydrofuran were added, and the mixture was kept at 5 ° C. using a water-ice bath under a nitrogen stream.
Next, 20.6 g of dicyclohexylcarbodiimide
(0.1 mol) in 100 ml of tetrahydrofuran
It was dripped slowly over time. After the addition, the water-ice bath was removed, and the mixture was stirred at room temperature for 24 hours to complete the reaction. After completion of the reaction, the precipitated dicyclohexylurea was separated by filtration and concentrated. The concentrate was dissolved in 200 ml of toluene, washed with pure water and saturated saline, and then the organic layer was dried over anhydrous sodium sulfate. The solvent of the organic layer was distilled off under reduced pressure, and the concentrated solution was purified by silica gel chromatography (using 40 times the amount of silica gel with respect to the concentrated solution),

[0127]

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35 g of a transparent liquid side-chain type radically polymerizable compound (A-9) represented by the following formula was obtained. R of thin plate
The f value was 0.6. Further, from the infrared absorption spectrum (IR), it was confirmed that the absorption of the hydroxyl group at 3200 to 3600 cm ^-1 disappeared, and that the esterification was completed.

<Physical properties> ¹ H-NMR (solvent deuterated chloroform) δ: 6.51 (2H), 6.20 (2H), 5.94 (2H), 5.42 (2H), 4.33 (2
H), 4.26 (2H), 4.22 (4H), 2.35 (4H), 2.34 (4H), 1.81 (2
H), 1.60 (4H), 1.60 (4H), 1.57 (2H), 1.5-1.22 (88H),
0.88 (18H)

¹³ C-NMR (solvent deuterated chloroform) δ: 173.4, 173.1, 165.7, 165.4, 162.5, 131.3, 131.
2, 128.2, 128.1, 69.9, 68.5, 63.1, 63.0, 62.7, 41.
2, 34.3, 33.6, 33.1, 31.9, 29.9-29.0, 25.8-24.
9, 22.6, 14.8, 14.5

IR (KBr) cm ^-1 : 2926, 2856, 1743, 1653 to 1625, 1172, 807.5

Elemental analysis: C = 73.0% (73.46%), H = 1
1.21% (11.11)

Example 10 A four-necked flask equipped with a stirrer, a condenser and a thermometer was charged with 462.5 g (1 mol) of bisphenol full orange glycidyl ether, 180 g (2.5 mol) of acrylic acid, 180 mg of methoxyphenol and 1.61 g of N, N-dimethylbenzylamine as a catalyst were added and stirred at 80 ° C. Next, slowly raise the temperature of the reaction solution to 110 ° C., and while maintaining the same temperature,
The reaction was completed by stirring for 10 hours. Next, the reaction mixture is washed with 300 ml of 5% sodium hydroxide solution,
After washing with pure water and a saturated saline solution and drying the organic layer with anhydrous sodium sulfate, the organic solvent was distilled off to obtain an acid value of 1.
6. A light brown transparent liquid product having a hydroxyl value of 1750 was obtained.

Next, the liquid product 30 was placed in a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube and a thermometer.
g, p-methoxyphenol 10 mg, triethylamine 15.1 g (0.15 mol) and tetrahydrofuran 5
The mixture was kept at 5 ° C. in a water-ice bath under a nitrogen stream. Next, 16.3 g (0.1 mol) of octanoyl chloride was slowly dropped over 1 hour. After completion of the dropwise addition, the water-ice bath was removed, and the mixture was refluxed for 5 hours to complete the reaction. After completion of the reaction, the precipitated hydrochloride was separated by filtration and concentrated. The concentrated solution is dissolved in 200 ml of toluene, and 0.1N hydrochloric acid solution 30
After washing with 0 ml and further with pure water and saturated saline, the organic layer was dried over anhydrous sodium sulfate. The solvent of the organic layer is distilled off under reduced pressure, and the concentrate is subjected to silica gel chromatography (using 40 times the amount of silica gel with respect to the concentrate).
And purified using the formula

[0135]

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19 g of a transparent liquid side-chain type radical polymerizable compound (A-10) represented by the following formula was obtained. The Rf value of the thin plate was 0.3. Further, from the infrared absorption spectrum (IR), it was confirmed that the absorption of the hydroxyl group at 3200 to 3600 cm ^-1 disappeared, and that the esterification was completed.

<Physical Properties> ¹ H-NMR (solvent deuterated chloroform) δ: 7.23 (4H), 7.15 (4H), 6.99 (4H), 6.88 (4H), 6.82 (4H)
H), 6.45 (2H), 6.18 (2H), 5.88 (2H), 5.26 (2H), 4.33 (2
H), 4.26 (2H), 4.12 (4H), 2.34 (4H), 1.78 (6H), 1.59 (4
H), 1.25 (16H), 0.87 (6H)

IR (KBr) cm ^-1 : 2925, 2854, 1742, 1643 to 1620, 1605, 1587, 11
73, 807.5 Elemental analysis: C = 69.97% (70.02%), H = 5.82% (5.7
0)

Example 11 142 g (1 mol) of 1,2,7,8-diepoxyoctane and 180 g of acrylic acid were placed in a four-necked flask equipped with a stirrer, a condenser and a thermometer.
(2.5 mol), p-methoxyphenol 180 mg and N, N-dimethylbenzylamine 1.61 g as catalyst
And stirred at 80 ° C. Next, the reaction solution was slowly heated to 110 ° C., and stirred for 10 hours while maintaining the same temperature to complete the reaction. Next, the reaction mixture was washed with 300 ml of a 5% sodium hydroxide solution, further washed with pure water and saturated saline, and the organic layer was dried over anhydrous sodium sulfate. Acid value 0.5, hydroxyl value 3
70 light brown transparent liquid products were obtained.

Next, the liquid product 15 was placed in a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube and a thermometer.
g, p-methoxyphenol 10 mg, triethylamine 15.1 g (0.15 mol) and tetrahydrofuran 5
Then, the mixture was kept at 5 ° C. in a water-ice bath under a nitrogen stream. Next, 21.9 g (0.1 mol) of lauroyl chloride was slowly added dropwise over 1 hour. After completion of the dropwise addition, the water-ice bath was removed, and the mixture was refluxed for 5 hours to complete the reaction. After completion of the reaction, the precipitated hydrochloride was separated by filtration and concentrated. The concentrated solution is dissolved in 200 ml of toluene, and 0.1N hydrochloric acid solution 30
After washing with 0 ml and further with pure water and saturated saline, the organic layer was dried over anhydrous sodium sulfate. The solvent of the organic layer is distilled off under reduced pressure, and the concentrate is subjected to silica gel chromatography (using 40 times the amount of silica gel with respect to the concentrate).
And purified using the formula

[0141]

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15 g of a transparent liquid side-chain type radically polymerizable compound (A-11) represented by the following formula was obtained. The Rf value of the thin plate was 0.4. Further, from the infrared absorption spectrum (IR), it was confirmed that the absorption of the hydroxyl group at 3200 to 3600 cm ^-1 disappeared, and that the esterification was completed.

<Physical Properties> ¹ H-NMR (solvent deuterated chloroform) δ: 6.42 (2H), 6.11 (2H), 5.86 (2H), 5.16 (2H), 4.35 (2
H), 4.27 (2H), 2.34 (4H), 1.72 (4H), 1.59 (4H), 1.32-
1.25 (36H), 0.89 (6H)

¹³ C-NMR (solvent deuterated chloroform) δ: 173.4, 173.1, 165.7, 165.4, 131.3, 131.2, 128.
2, 128.1, 70.56, 68.95, 63.1, 62.7, 34.3, 32.6, 3
1.9, 29.6-29.0, 25.8, 24.9, 22.6, 14.1

IR (KBr) cm ^-1 : 2927, 2858, 1742, 1651 to 1625, 807.5

Elemental analysis: C = 73.2% (73.8%), H = 1
0.89% (10.67)

Example 12 In a four-necked flask equipped with a stirrer, a condenser and a thermometer, 71 g (1 mol) of 1,2,7,8-diepoxyoctane, an acrylic acid dimer (Toa Gosei Co., Ltd.) Product name “M5600”) (2.
5 mol), 180 mg of p-methoxyphenol, and 1.61 g of N, N-dimethylbenzylamine as a catalyst were stirred at 80 ° C. Next, the temperature of the reaction solution was slowly raised to 110 ° C., and the mixture was stirred for 10 hours while maintaining the temperature to complete the reaction. Next, the reaction mixture was washed with 300 ml of a 5% sodium hydroxide solution, further washed with pure water and saturated saline, and the organic layer was dried over anhydrous sodium sulfate. Acid value 1.0, hydroxyl value 250
A light brown transparent liquid product was obtained.

Next, the above liquid product 22. was placed in a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube and a thermometer.
5 g, 10 mg of p-methoxyphenol, 15.1 g (0.15 mol) of triethylamine and 500 ml of tetrahydrofuran were added, and the mixture was kept at 5 ° C. under a nitrogen stream using a water-ice bath. Next, 21.9 g (0.1 mol) of lauroyl chloride was slowly added dropwise over 1 hour. Subsequent operations are
In the same manner as in Example 11, the formula

[0149]

Embedded image

20 g of a transparent liquid side-chain type radically polymerizable compound (A-12) represented by the following formula was obtained. The Rf value of the thin plate was 0.3. Further, from the infrared absorption spectrum (IR), it was confirmed that the absorption of the hydroxyl group at 3200 to 3600 cm ^-1 disappeared, and that the esterification was completed.

<Physical properties> ¹ H-NMR (solvent deuterated chloroform) δ: 6.42 (2H), 6.11 (2H), 5.86 (2H), 5.21 (2H), 4.41 (4
H), 4.37 (2H), 4.29 (2H), 2.46 (4H), 2.34 (4H), 1.72 (4
H), 1.59 (4H), 1.32-1.25 (36H), 0.88 (6H)

¹³ C-NMR (solvent deuterated chloroform) δ: 173.4, 173.1, 165.7, 165.4, 162.0, 131.3, 131.
2, 128.2, 128.1, 70.56, 68.95, 64.2, 63.1, 62.7, 3
5.2, 34.3, 32.6, 31.9, 29.6-29.0, 25.8, 24.9, 22.
6, 14.1

IR (KBr) cm ^-1 : 2927, 2858, 1748, 1651 to 1625, 807.5

Elemental analysis: C = 66.11% (66.52%), H =
9.42% (9.31)

Example 13 A four-necked flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube and a thermometer was charged with β-epichlorohydrin-modified bisphenol A (trade name “Epiclon HM-” of Dainippon Ink and Chemicals, Inc.). 81 ") 18
5 g, 108 g (1.5 mol) of acrylic acid, 150 mg of p-methoxyphenol and 1.31 g of N, N-dimethylbenzylamine as a catalyst were added and stirred at 80 ° C.
Next, the temperature of the reaction solution was slowly raised to 110 ° C., and the mixture was stirred for 10 hours while maintaining the temperature to complete the reaction. next,
The reaction mixture was washed with 300 ml of a 5% sodium hydroxide solution, further washed with pure water and saturated saline, and the organic layer was dried over anhydrous sodium sulfate.
A light brown transparent liquid product having an acid value of 0.7 and a hydroxyl value of 204 was obtained.

Next, the liquid product 2 was placed in a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube, and a thermometer.
7.5 g, 10 mg of p-methoxyphenol, 15.1 g (0.15 mol) of triethylamine and 500 ml of tetrahydrofuran were added, and the mixture was added under a nitrogen stream using a water-ice bath.
C. Next, 10.5 g of benzoyl chloride (0.1
Mol) was slowly added dropwise over 1 hour. Subsequent operations were performed in the same manner as in Example 11,

[0157]

Embedded image

22 g of a light yellow liquid side chain type radical polymerizable compound (A-13) represented by the following formula was obtained. The Rf value of the thin plate was 0.4. Further, from the infrared absorption spectrum (IR), it was confirmed that the absorption of the hydroxyl group at 3200 to 3600 cm ^-1 disappeared, and that the esterification was completed.

<Physical Properties> ¹ H-NMR (solvent deuterated chloroform) δ: 8.51 (4H), 7.43 (4H), 7.30 (2H), 7.23 (4H), 6.88 (4
H), 6.82 (4H), 6.45 (2H), 6.19 (2H), 5.88 (2H), 4.33 (2
H), 4.28 (2H), 4.12 (4H), 1.78 (6H), 1.24 (2H), 0.87 (6
H)

IR (KBr) cm ^-1 : 2925, 2854, 1742, 1643-1620, 1606, 1587, 11
80, 808.0

Elemental analysis: C = 71.21% (71.12%), H =
5.70% (5.77)

Example 14 In a four-necked flask equipped with a stirrer, a condenser and a thermometer, 182 g of epichlorohydrin-modified hydrogenated bisphenol A (trade name "Likaresin HBE-100" manufactured by Nippon Rika Co., Ltd.) and acrylic Acid 108
g (1.5 mol), 150 mg of p-methoxyphenol and 1.31 N, N-dimethylbenzylamine as catalyst.
g and stirred at 80 ° C. Next, the reaction solution was heated to 110 ° C.
Then, the mixture was stirred for 10 hours while maintaining the same temperature to complete the reaction. Next, the reaction mixture was washed with 300 ml of a 5% sodium hydroxide solution, further washed with pure water and saturated saline, and the organic layer was dried over anhydrous sodium sulfate. Acid value 1.0, hydroxyl value 2
40 light brown transparent liquid products were obtained.

Next, the liquid product 2 was placed in a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube, and a thermometer.
3.0 g, lauryl chloride 20.4 g (0.1 mol), tetra-n-butylammonium bromide 0.3 g as a catalyst, and toluene 300 ml were charged and stirred at room temperature. Next, 4.0 g (0.1 mol) of sodium hydroxide was added,
The reaction was completed by stirring at 60 ° C. for 24 hours. After the completion of the reaction, the reaction mixture was washed with pure water and saturated saline, and the organic layer was dried over anhydrous sodium sulfate. The solvent of the organic layer was distilled off under reduced pressure, and the concentrate was purified by silica gel chromatography (using a 40-fold amount of silica gel with respect to the concentrate) to obtain a compound of the formula

[0164]

Embedded image

24 g of a transparent liquid side-chain type radical polymerizable compound (A-14) represented by the following formula was obtained. The Rf value of the thin plate was 0.6. Further, from the infrared absorption spectrum (IR), it was confirmed that the absorption of the hydroxyl group at 3200 to 3600 cm ^-1 had disappeared, and that it was completely etherified.

<Physical properties> ¹ H-NMR (solvent deuterated chloroform) δ: 6.44 (2H), 6.14 (2H), 5.86 (2H), 5.24 (2H), 4.33 (2H)
H), 4.25 (2H), 3.64 (4H), 3.60 (2H), 3.58 (4H), 1.63 (4
H), 1.59 (8H), 1.53 (2H), 1.35-1.22 (44H), 0.89 (12H)

¹³ C-NMR (solvent deuterated chloroform) δ: 165.8, 165.4, 131.3, 131.2, 128.2, 128.1, 78.
2, 71.63, 70.56, 69.99, 68.2, 63.1, 62.7, 34.1, 3
1.9, 29.6-29.0, 25.8, 24.9, 22.6, 14.1, 14.0

IR (KBr) cm ^-1 : 2927, 2856, 1744, 1643-1620, 1175, 807.7

Elemental analysis: C = 73.22% (73.57%), H =
11.13% (11.05)

Example 15 142 g (1 mol) of 1,2,7,8-diepoxyoctane and 180 g of acrylic acid were placed in a four-necked flask equipped with a stirrer, a condenser and a thermometer.
(2.5 mol), p-methoxyphenol 180 mg and N, N-dimethylbenzylamine 1.61 g as catalyst
And stirred at 80 ° C. Next, the temperature of the reaction solution was slowly raised to 110 ° C., and the mixture was stirred for 10 hours while maintaining the temperature to complete the reaction. Next, the reaction mixture was washed with 300 ml of a 5% sodium hydroxide solution, further washed with pure water and saturated saline, and the organic layer was dried over anhydrous sodium sulfate. Acid value 0.5, hydroxyl value 37
A light brown transparent liquid product of 0 was obtained.

Next, the liquid product 1 was placed in a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube, and a thermometer.
5.0 g, 20.4 g (0.1 mol) of lauryl chloride, 0.3 g of tetra-n-butylammonium bromide as a catalyst and 300 ml of toluene were charged and stirred at room temperature. Next, 4.0 g (0.1 mol) of sodium hydroxide was added, and the mixture was stirred at 60 ° C. for 24 hours to complete the reaction. After the completion of the reaction, the reaction mixture was washed with pure water and saturated saline, and the organic layer was dried over anhydrous sodium sulfate. The solvent of the organic layer was distilled off under reduced pressure, and the concentrate was purified by silica gel chromatography (using a 40-fold amount of silica gel with respect to the concentrate) to obtain a compound of the formula

[0172]

Embedded image

Thus, 10 g of a transparent liquid side-chain type radical polymerizable compound (A-15) represented by the following formula was obtained. The Rf value of the thin plate was 0.5. Further, from the infrared absorption spectrum (IR), it was confirmed that the absorption of the hydroxyl group at 3200 to 3600 cm ^-1 had disappeared, and that it was completely etherified.

<Physical Properties> ¹ H-NMR (solvent deuterated chloroform) δ: 6.42 (2H), 6.12 (2H), 5.86 (2H), 4.35 (2H), 4.27 (2H)
H), 3.62 (2H), 3.43 (4H), 1.60 (4H), 1.55 (4H), 1.34-
1.25 (40H), 0.87 (6H)

¹³ C-NMR (solvent deuterated chloroform) δ: 165.6, 165.4, 131.2, 131.0, 128.2, 128.1, 70.5
6, 70.40, 70.38, 68.95, 63.1, 62.7, 34.3, 32.6, 3
2.2, 31.9, 29.6-29.0, 25.8, 24.9, 22.6, 14.1

IR (KBr) cm ^-1 : 2927, 2858, 1742, 1651 to 1625, 1176, 807.5

Elemental analysis: C = 75.35% (75.41%), H =
7.80% (7.85)

Example 16 A four-necked flask equipped with a stirrer, a condenser and a thermometer was charged with 257 g (1.0 mol) of glycidyl laurate and 108 g of acrylic acid.
(1.5 mol), 150 mg of p-methoxyphenol and 1.31 g of N, N-dimethylbenzylamine as a catalyst
And stirred at 80 ° C. Next, the temperature of the reaction solution was slowly raised to 110 ° C., and the mixture was stirred for 10 hours while maintaining the temperature to complete the reaction. Next, the organic layer was washed with 300 ml of a 5% sodium hydroxide solution, further washed with pure water and a saturated saline solution, and the organic layer was dried over anhydrous sodium sulfate. 8 was obtained.

Next, the liquid product 3 was placed in a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube and a thermometer.
3.0 g, p-methoxyphenol 20 mg, 4-dimethylaminopyridine 3.1 g, sebacic acid 10.1 g
(0.05 mol) and 500 ml of tetrahydrofuran were added, and the mixture was kept at 5 ° C. using a water-ice bath under a nitrogen stream. Next, 20.6 g of dicyclohexylcarbodiimide (0.
(1 mol) in 100 ml of tetrahydrofuran was slowly added dropwise over 1 hour. After dropping, remove the water ice bath,
The reaction was completed by stirring at room temperature for 24 hours. After completion of the reaction, the precipitated dicyclohexylurea was separated by filtration and concentrated. The concentrate was dissolved in 200 ml of toluene, washed with pure water and saturated saline, and then the organic layer was dried over anhydrous sodium sulfate. The solvent of the organic layer was distilled off under reduced pressure, and the concentrated solution was purified by silica gel chromatography (using 40 times the amount of silica gel with respect to the concentrated solution),

[0180]

Embedded image

28 g of a transparent liquid side-chain type radically polymerizable compound (A-16) represented by the following formula was obtained. The Rf value of the thin plate was 0.4. Further, from the infrared absorption spectrum (IR), it was confirmed that the absorption of the hydroxyl group at 3200 to 3600 cm ^-1 disappeared, and that the esterification was completed.

<Physical properties> ¹ H-NMR (solvent deuterated chloroform) δ: 6.43 (2H), 6.12 (2H), 5.86 (2H), 5.11 (2H), 4.33 (2H)
H), 4.25 (2H), 4.22 (4H), 2.36 (4H), 2.32 (4H), 1.59 (8
H), 1.34-1.25 (38H), 0.85 (6H)

¹³ C-NMR (solvent deuterated chloroform) δ: 173.4, 173.1, 171.5, 165.7, 165.4, 131.3, 131.
2, 128.2, 128.1, 70.56, 69.99, 68.95, 63.1, 62.7,
62.3, 35.4, 34.3, 31.9, 29.6-29.0, 25.8, 24.9, 2
2.6, 14.1

IR (KBr) cm ^-1 : 2925, 2854, 174-1732, 1651-1624, 807.5

Elemental analysis: C = 65.22% (65.13%), H =
9.98% (10.07)

Example 17 A long-chain alkyl group-containing monoepoxide (trade name “AOEX2” manufactured by Daicel Chemical Co., Ltd.) was placed in a four-necked flask equipped with a stirrer, a condenser, and a thermometer.
4 ") 196 g (1.0 mol), acrylic acid 108 g
(1.5 mol), 150 mg of p-methoxyphenol and 1.31 g of N, N-dimethylbenzylamine as a catalyst
And stirred at 80 ° C. Next, the temperature of the reaction solution was slowly raised to 110 ° C., and the mixture was stirred for 10 hours while maintaining the temperature to complete the reaction. Next, the reaction mixture was washed with 300 ml of a 5% sodium hydroxide solution, further washed with pure water and saturated saline, and the organic layer was dried over anhydrous sodium sulfate. A light brown transparent liquid product having an acid value of 1.5 was obtained.

Next, the liquid product 2 was placed in a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube, and a thermometer.
8.0 g, p-methoxyphenol 20 mg, 4-dimethylaminopyridine 3.1 g, sebacic acid 10.1 g
(0.05 mol) and 500 ml of tetrahydrofuran were added, and the mixture was kept at 5 ° C. using a water-ice bath under a nitrogen stream. Next, 20.6 g of dicyclohexylcarbodiimide (0.
(1 mol) in 100 ml of tetrahydrofuran was slowly added dropwise over 1 hour. The following operations were performed in the same manner as in Example 16,

[0188]

Embedded image

15 g of a transparent liquid side-chain type radically polymerizable compound (A-17) represented by the following formula was obtained. The Rf value is 0.
It was 5. Further, from the infrared absorption spectrum (IR), it was confirmed that the absorption of the hydroxyl group at 3200 to 3600 cm ^-1 disappeared, and that the esterification was completed.

<Physical properties> ¹ H-NMR (solvent deuterated chloroform) δ: 6.46 (2H), 6.14 (2H), 5.88 (2H), 5.14 (2H), 4.35 (2H)
H), 4.27 (2H), 2.32 (4H), 1.59 (4H), 1.51 (4H), 1.34-
1.25 (42H), 0.85 (6H)

¹³ C-NMR (solvent deuterated chloroform) δ: 173.6, 173.3, 171.3, 165.7, 165.4, 131.3, 131.
2, 128.2, 128.1, 71.5, 63.1, 35.4, 31.9, 31.0-29.
0, 25.8, 24.9, 22.6, 14.1

IR (KBr) cm ^-1 : 2925, 2854, 1738, 1651-1624, 807.5

Example 18 A four-necked flask equipped with a stirrer, a condenser and a thermometer was charged with 326 g (1.0 mol) of stearyl glycidyl ether and 108 g of acrylic acid.
(1.5 mol), 150 mg of p-methoxyphenol and 1.31 g of N, N-dimethylbenzylamine as a catalyst
And stirred at 80 ° C. Next, the temperature of the reaction solution was slowly raised to 110 ° C., and the mixture was stirred for 10 hours while maintaining the temperature to complete the reaction. Next, the reaction mixture was washed with 300 ml of a 5% sodium hydroxide solution, further washed with pure water and saturated saline, and the organic layer was dried over anhydrous sodium sulfate. A light brown transparent liquid product having an acid value of 1.1 was obtained.

Next, the liquid product 4 was placed in a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube, and a thermometer.
0.0 g, p-methoxyphenol 20 mg, 4-dimethylaminopyridine 3.1 g, dimer acid 25.0 g
(0.05 mol) and 500 ml of tetrahydrofuran were added, and the mixture was kept at 5 ° C. using a water-ice bath under a nitrogen stream. Next, 20.6 g of dicyclohexylcarbodiimide (0.
(1 mol) in 100 ml of tetrahydrofuran was slowly added dropwise over 1 hour. The following operations were performed in the same manner as in Example 16,

[0195]

Embedded image

35 g (A-18) of a transparent liquid side-chain type radically polymerizable compound represented by the following formula: was obtained. The Rf value is 0.
It was 6. Further, from the infrared absorption spectrum (IR), it was confirmed that the absorption of the hydroxyl group at 3200 to 3600 cm ^-1 disappeared, and that the esterification was completed.

<Physical properties> ¹ H-NMR (solvent deuterated chloroform) δ: 6.46 (2H), 6.14 (2H), 5.88 (2H), 5.33 (2H), 4.35 (2H)
H), 4.27 (2H), 3.57 (4H), 3.45 (4H), 2.32 (4H), 2.28 (4
H), 1.62 (4H), 1.59 (4H), 1.48 (4H), 1.42-1.25 (96
H), 0.85 (12H)

¹³ C-NMR (solvent deuterated chloroform) δ: 173.6, 173.3, 171.3, 165.7, 165.4, 131.3, 131.
2, 128.2, 128.1, 71.5, 70.5, 63.1, 35.4, 31.9, 35.
0-26.0, 25.8, 24.9, 22.6, 15.4, 14.1

IR (KBr) cm ^-1 : 2926, 2857, 1738, 1651 to 1624, 1176, 807.5

<Examples 19 to 40> (Liquid crystal device) Using the side chain type radically polymerizable compounds obtained in Examples 1 to 18, the respective raw materials were blended according to the compositions shown in Tables 2 to 4. ,
A light modulating layer forming material for an example was prepared. These dimming layer forming materials are sandwiched between two ITO electrode glass substrates coated with a 11.0 μm glass fiber spacer, and the entire substrate is temperature-controlled so as to keep the dimming layer forming material in a uniform solution state. Then, an ultraviolet ray of 40 mW / cm ² was irradiated for 60 seconds to cure the radically polymerizable compound, thereby obtaining a liquid crystal device having a light modulating layer having a thickness of about 11 μm and comprising a transparent polymer material and a liquid crystal material. .

Tables 2 to 4 collectively show the measurement results of the relationship between the applied voltage and the light transmittance of the obtained liquid crystal device.

Table 5 shows the results of measuring the liquid crystal device manufactured in Example 20 at measurement temperatures of 0 ° C., 25 ° C., and 50 ° C.

Comparative Example 1 As a radical polymerizable compound, 1,6 having no side chain between radical polymerizable double bonds was used.
-Except for using hexanediol diacrylate (trade name "HDDA" manufactured by Nippon Kayaku Co., Ltd.), a liquid crystal device was manufactured in the same manner as in the example, and evaluation was performed in the same manner as in the example. The results are shown in FIG.

<Comparative Example 2> A liquid crystal was prepared in the same manner as in the Examples using diacrylate (trade name “M210” manufactured by Toagosei Chemical Co., Ltd.) as an average of 4 moles of ethylene oxide adduct of bisphenol A as a radical polymerizable compound. The device was manufactured and evaluated in the same manner as in the examples, and the results are shown in Table 4.

Comparative Example 3 As a radical polymerizable compound, epichlorohydrin-modified 1,6-hexanediol diacrylate (trade name “R-16” manufactured by Nippon Kayaku Co., Ltd.)
7)), a liquid crystal device was manufactured in the same manner as in the example, and evaluation was performed in the same manner as in the example. The results are shown in Table 4.

Comparative Example 4 A liquid crystal device was manufactured in the same manner as in the example using 3,3-dimethylol heptane diacrylate (trade name “C9A” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as a radical polymerizable compound. Then, evaluation was performed in the same manner as in the examples, and the results are shown in Table 4.

[0207]

[Table 2]

[0208]

[Table 3]

[0209]

[Table 4]

In the table, the liquid crystal material "PN-005" is a nematic liquid crystal material manufactured by Roddick Co., Ltd., and "Irgacure 651" is a photopolymerizable material comprising 2,2-dimethoxy-2-phenylacetophenone manufactured by Ciba-Geigy. The initiator, “HDDA” is 1,6-hexanediol diacrylate manufactured by Nippon Kayaku Co., Ltd., and “M210” is
It is a diacrylate of an average of 4 moles of ethylene oxide adduct of bisphenol A manufactured by Toa Gosei Chemical Co., Ltd.
167 "is an epichlorohydrin-modified 1,6-hexanediol diacrylate manufactured by Nippon Kayaku Co., Ltd.
9A "is 3,3-dimethylol heptane diacrylate manufactured by Daiichi Kogyo Seiyaku.

Example 41 The relationship between the applied voltage and the light transmittance of the liquid crystal device manufactured in Example 19 was measured one day after the manufacture and left for one week at 80 ° C., and the result was as follows.

One day after production: V ₉₀ = 10.2 V, T ₀ = 3.0, T ₁₀₀ = 88.0

80 ° C. (after one week) V ₉₀ = 9.9 V, T ₀ = 3.2, T ₁₀₀ = 88.0

Comparative Example 5 As a radical polymerizable compound, 12.2 parts by weight of 3,3-dimethylol heptane diacrylate (trade name “C9A” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 13.0 parts by weight of lauryl acrylate were used. A liquid crystal device was manufactured in the same manner as in Comparative Example 4 except that was used, and the relationship between the applied voltage and the light transmittance was measured one day after the manufacture and left at 80 ° C. for one week, and the results were as follows. .

One day after production: V ₉₀ = 14.6 V, T ₀ = 15.8, T ₁₀₀ = 88.0

80 ° C. (after one week) V ₉₀ = 10.2 V, T ₀ = 12.2, T ₁₀₀ = 87.5

Example 42 The liquid crystal device manufactured in Example 20 was evaluated at measurement temperatures of 0 ° C., 25 ° C. and 50 ° C. The results are shown in Table 5.

Comparative Example 6 In a four-necked flask equipped with a stirrer, a condenser and a thermometer, 174 g of ethylene glycol glycol diglycidyl ether (trade name "Epiol E-100" manufactured by NOF Corporation) and acrylic acid 180 g (2.
5 mol), 180 mg of p-methoxyphenol and 1.61 g of N, N-dimethylbenzylamine as a catalyst were stirred at 80 ° C. until a homogeneous solution was obtained. Next, slowly raise the temperature of the reaction solution to 110 ° C., and while maintaining the same temperature,
After stirring was continued for 10 hours, the reaction was terminated. The reaction mixture was washed with 300 ml of a 5% sodium hydroxide solution, further washed with pure water and a saturated saline solution, and the organic layer was dried over anhydrous sodium sulfate. 1.8, a pale brown transparent liquid product having a hydroxyl value of 335 was obtained.

Next, the liquid product 1 was placed in a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube and a thermometer.
5.8 g, 10 mg of p-methoxyphenol, 15.1 g (0.15 mol) of triethylamine and 500 ml of tetrahydrofuran were added, and 21.9 g of lauroyl chloride (0.0 g) was added under a nitrogen stream while maintaining the temperature at 5 ° C using a water-ice bath. .1
Mol) was slowly added dropwise over 1 hour. After dropping,
After removing the water-ice bath and refluxing for 5 hours, the reaction was terminated. After completion of the reaction, the precipitated hydrochloride was separated by filtration and concentrated.
The concentrate was dissolved in 200 ml of toluene, washed with 300 ml of a 0.1N hydrochloric acid solution, further washed with pure water and a saturated saline solution, and then the organic layer was dried over anhydrous sodium sulfate. The solvent of the organic layer was distilled off under reduced pressure, and the concentrated solution was purified by silica gel chromatography (using 40 times the amount of silica gel with respect to the concentrated solution),

[0220]

Embedded image

13 g of a transparent liquid side-chain type radically polymerizable compound (A-19) represented by the following formula was obtained. The Rf value of the thin plate was 0.3. Further, from the infrared absorption spectrum (IR), it was confirmed that the absorption of the hydroxyl group at 3200 to 3600 cm ^-1 disappeared, and that the esterification was completed.

<Physical properties> ¹ H-NMR (solvent deuterated chloroform) δ: 6.42 (2H), 6.10 (2H), 5.86 (2H), 5.64 (2H), 4.24 (4
H), 3.71 (4H), 3.55 (4H), 2.33 (4H), 1.55 (4H), 1.3-
1.24 (32H), 0.88 (6H)

¹³ C-NMR (solvent deuterated chloroform) δ: 173.7, 173.5, 165.5, 165.3, 131.5, 131.3, 128.
4, 128.1, 81.2, 70.63, 70.56, 70.22, 34.3, 29.6-2
9.0, 25.8, 24.9, 14.6

IR (KBr) cm ^-1 : 2925, 2854, 1742, 1652 to 1620, 1176, 807.9

Elemental analysis: C = 66.22% (66.49%), H =
10.32% (10.19)

Next, Example 1 was prepared using the synthesized compound.
A liquid crystal device was manufactured in the same manner as in Examples 9 to 40, and evaluated at the same three kinds of measurement temperatures as in Example 42. The results are shown in Table 5.

[0227]

[Table 5]

[0228]

The side chain type radically polymerizable compound of the present invention can be used as a polarizing plate when it is used as a constituent material of a transparent polymer material of a liquid crystal device having a light control layer composed of a liquid crystal material and a transparent polymer material. This makes it possible to manufacture a large-area thin liquid crystal device having a bright display screen, high steepness, high contrast, low-voltage driving of 10 Vrms or less, and little change in characteristics due to temperature. Further, since the resistance is high, the voltage holding ratio can be improved and flickering of the screen can be eliminated.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 14, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Embedded image (Wherein R ₁ is —CH ₂ — or —CH ₂ CH ₂ COOCH ₂
- a represents, R ₂ and R ₃ are each independently an aliphatic group, cyclic aliphatic group, an aromatic group or substituted versions thereof, R ₄
And R ₅ represents -H or -CH _3, X is -CH
_2- represents an ether bond or an ester bond, Y represents an ether bond or an ester bond, n represents an integer of 2 to 4, and p and q represent 0 or 1. ) A side chain type radical polymerizable compound represented by the formula:

Embedded image(Where R₁Is -CH_Two-Or -CH_TwoCH_TwoCOOCH_Two
-Represents R_TwoAnd R _ThreeAre each independently an aliphatic group, a ring
An aliphatic group, an aromatic group or a substituted product thereof,
_FourAnd R_FiveIs -H or -CH_ThreeX is -CH
_Two-Represents an ether bond or an ester bond, and Y is
Represents an ether bond or an ester bond, and n is 2 to 4
Represents an integer. P) in the general formula (I) represented by
=0And q =1The side-chain type radical weight according to claim 1, which is
Compatible compounds.

Embedded image(Where R₁Is -CH_Two-Or -CH_TwoCH_TwoCOOCH_Two
-Represents R_TwoAnd R _ThreeAre each independently an aliphatic group, a ring
An aliphatic group, an aromatic group or a substituted product thereof,
_FourAnd R_FiveIs -H or -CH_ThreeX is -CH
_Two-Represents an ether bond or an ester bond, and Y is
Represents an ether bond or an ester bond, and n is 2 to 4
Represents an integer. P) in the general formula (I) represented by
=1And q =0The side-chain type radical weight according to claim 1, which is
Compatible compounds.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction contents]

(Where R₁Is -CH_Two-Or -CH_TwoCH
_TwoCOOCH_Two-Represents R_TwoAnd R _ThreeAre each independently
Aliphatic group, cycloaliphatic group, aromatic group or a substituted product thereof
And R_FourAnd R_FiveIs -H or -CH_ThreeAnd X
Is -CH_Two-Represents an ether bond or an ester bond.
Y represents an ether bond or an ester bond, and n represents
Represents an integer of 2 to 4. To the general formula (I)
Wherein p = 0 and q = 1 in the side chain type according to the above (1).
Radical polymerizable compound,

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction contents]

(Where R₁Is -CH_Two-Or -CH_TwoCH
_TwoCOOCH_Two-Represents R_TwoAnd R _ThreeAre each independently
Aliphatic group, cycloaliphatic group, aromatic group or a substituted product thereof
And R_FourAnd R_FiveIs -H or -CH_ThreeAnd X
Is -CH_Two-Represents an ether bond or an ester bond.
Y represents an ether bond or an ester bond, and n represents
Represents an integer of 2 to 4. To the general formula (I)
Wherein p = 1 and q = 0 in the side chain type according to the above (1).
Radical polymerizable compound,

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction contents]

(1) In the general formula (I), p = 0 and q
= 1 The compound of the general formula (II) wherein the side chain type polymerizable compound represented by the general formula (II) is, for example, a compound (a) having a polyvalent epoxy group and an active hydrogen capable of reacting with the epoxy group. It can be easily synthesized by reacting a radical polymerizable compound (b) having the same with a generated hydroxyl group and a compound (c) having a group capable of reacting with the hydroxyl group. Is
It is as follows.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0032

[Correction method] Change

[Correction contents]

(2) In the general formula (I), p = 1 and q
The compound of the general formula (III) wherein = 0 The side chain type radical polymerizable compound represented by the general formula (III) has a compound (a ′) having a monoepoxy group and an active hydrogen capable of reacting with the epoxy group. The compound can be easily produced by reacting a radical polymerizable compound (b) with a compound (c ') having two or more groups capable of reacting with a hydroxyl group formed in a molecule, and further reacting the resulting hydroxyl group. It is possible, but specifically, as follows.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0218

[Correction method] Change

[Correction contents]

Comparative Example 6 In a four-necked flask equipped with a stirrer, a condenser and a thermometer, 17.4 g of ethylene glycol glycol diglycidyl ether (trade name “Epiol E-100” manufactured by NOF Corporation) was added. 40 g of lauric acid, p-
0.1 g of methoxyphenol and 2 g of N, N-dimethylbenzylamine as a catalyst were added and stirred at 80 ° C. until a homogeneous solution was obtained. Next, the reaction solution was added to the solution over 1 hour.
C., and the reaction was continued for 2 hours while stirring at the same temperature. Further, the reaction was continued for 2 hours while stirring at 140 ° C., and then the reaction was terminated to give a brown liquid product (having a hydroxyl value of 28).
(0 KOH mg / g) 57 g was obtained.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0219

[Correction method] Change

[Correction contents]

Next, the liquid product 1 was placed in a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube and a thermometer.
5.8 g, 10 mg of p-methoxyphenol, 15.1 g (0.15 mol) of triethylamine and 500 ml of tetrahydrofuran were added, and 10 g of acrylic acid chloride was maintained under a nitrogen stream at 5 ° C. using a water-ice bath.
(0.1 mol) was slowly added dropwise over 1 hour. After the completion of the dropwise addition, the water-ice bath was removed, the mixture was refluxed for 5 hours, and the reaction was terminated. After completion of the reaction, the precipitated hydrochloride was filtered off,
Concentrated. Dissolve the concentrate in 200 ml of toluene,
After washing with 300 ml of 0.1N hydrochloric acid solution and further with pure water and saturated saline, the organic layer was dried over anhydrous sodium sulfate. The solvent of the organic layer was distilled off under reduced pressure, and the concentrated solution was purified by silica gel chromatography (using 40 times the amount of silica gel with respect to the concentrated solution),

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0221

[Correction method] Change

[Correction contents]

About 16 g of a transparent liquid side-chain type radically polymerizable compound (A-19) represented by the following formula was obtained. From the infrared absorption spectrum (IR), it was confirmed that the absorption of hydroxyl groups at 3200 to 3600 cm ^-1 had disappeared.

Claims (7)

[Claims] 1. A compound of the general formula (I) (Wherein R ₁ is —CH ₂ — or —CH ₂ CH ₂ COOCH ₂
- a represents, R ₂ and R ₃ are each independently an aliphatic group, cyclic aliphatic group, an aromatic group or substituted versions thereof, R ₄
And R ₅ represents -H or -CH _3, X is -CH
_2- represents an ether bond or an ester bond, Y represents an ether bond or an ester bond, n represents an integer of 2 to 4, and p and q represent 0 or 1. ) A side chain type radical polymerizable compound represented by the formula: 2. A compound of the general formula (II)(Where R₁Is -CH_Two-Or -CH_TwoCH_TwoCOOCH_Two
-Represents R_TwoAnd R _ThreeAre each independently an aliphatic group, a ring
An aliphatic group, an aromatic group or a substituted product thereof,
_FourAnd R_FiveIs -H or -CH_ThreeX is -CH
_Two-Represents an ether bond or an ester bond, and Y is
Represents an ether bond or an ester bond, and n is 2 to 4
Represents an integer. P) in the general formula (I) represented by
= 1 and q = 0, the side-chain type radical weight according to claim 1.
Compatible compounds. 3. A compound of the general formula (III)(Where R₁Is -CH_Two-Or -CH_TwoCH_TwoCOOCH_Two
-Represents R_TwoAnd R _ThreeAre each independently an aliphatic group, a ring
An aliphatic group, an aromatic group or a substituted product thereof,
_FourAnd R_FiveIs -H or -CH_ThreeX is -CH
_Two-Represents an ether bond or an ester bond, and Y is
Represents an ether bond or an ester bond, and n is 2 to 4
Represents an integer. P) in the general formula (I) represented by
2. The side chain type radical weight according to claim 1, wherein = 0 and q = 1.
Compatible compounds. 4. The side chain according to claim 1, which is a reaction product of an epoxy acrylate comprising a compound having an epoxy group, a carboxylic acid having a (meth) acryloyl group, and carboxylic acid or carboxylic acid chloride. Type radical polymerizable compound. 5. The side chain type radical polymerizable compound according to claim 1, wherein R ₂ is a saturated alkyl group having 4 to 20 carbon atoms. 6. A liquid crystal device comprising two substrates having electrode layers, at least one of which is transparent, and a light modulating layer comprising a liquid crystal material and a transparent polymer material supported between these substrates, has a high transparency. A liquid crystal device, wherein the molecular substance is a polymer substance obtained by polymerizing a polymerizable composition containing the side-chain type radically polymerizable compound according to claim 1. 7. The liquid crystal device according to claim 6, wherein a light modulating layer made of a three-dimensional network transparent polymer is provided in the continuous layer of the liquid crystal material.