JP2007002065A - Liquid crystal material, method for producing the same and display device containing the liquid crystal material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal material excellent in response and contrast and obtained by regularly arranging the molecules of a polymer liquid crystal compound, to provide a simple and easy method for producing the liquid crystal material, and to provide a display device using the material. <P>SOLUTION: The liquid crystal material has a liquid crystal layer on a substrate, which layer is obtained by directly combining a polymerizable group-containing liquid crystal compound with the substrate. The liquid crystal material can be produced by contacting the liquid crystal compound having a polymerizable group to a substrate containing a polymerization initiator and giving energy to directly combine the liquid compound with the substrate surface by graft polymerization. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a liquid crystal material realizing high-speed response and high contrast, a method for producing the liquid crystal material, and a display element including the liquid crystal material.

Liquid crystal compounds have been used in the field of optoelectronics, particularly in the fields of display elements, optical recording media, nonlinear optical elements and the like. In the case of using a liquid crystal compound as a display material, a low molecular liquid crystal compound is usually used by being held between two glass substrates arranged at a micron order interval. In a liquid crystal layer made of a low-molecular liquid crystal compound, since the uniformity of the film thickness greatly affects the performance of the liquid crystal layer, it is important that the gap width between the substrates is uniform throughout the liquid crystal layer. However, on large screens and curved screens, it is difficult to uniformly adjust such a small interval between two glass plates. For this reason, a large screen display device or the like is configured using a low-molecular liquid crystal compound. There is a problem that it is difficult to manufacture.
In order to solve this problem, attempts have been made to polymerize a liquid crystal compound and use it as a display material (see, for example, Patent Documents 1, 2, and 3). Due to the physical properties of polymer liquid crystal compounds, the uniformity of the thickness of the liquid crystal layer does not depend greatly on the distance between the substrates that sandwich the liquid crystal layer, so it can be applied to large and curved screen display devices. It is suitable for. However, since the polymer liquid crystal compound is viscous, it has a problem that it is difficult to fill the device and to arrange the molecules in the device.

As a method of aligning a polymer liquid crystal compound in a desired state, a thin alignment layer (organic alignment layer and inorganic alignment layer) is deposited, and the surface is rubbed with a cloth (rubbing treatment). It is common to use a method of depositing and automatically arranging molecules in the rubbing direction, or using mechanical techniques such as shearing, but the former method uses a surface shape that is lower than that of low-molecular liquid crystal molecular compounds. It is difficult to achieve a uniform alignment of a polymer liquid crystal compound having poor followability. Further, the latter method has a problem in that it is not suitable for a hard base material such as glass because mechanical shearing is preferably used only for a soft base material, and lacks versatility. Furthermore, in order to arrange such a polymer liquid crystal compound in a molecular arrangement, very slow cooling is required, but as a result, it is affected by a temperature gradient and the uniformity of the molecular arrangement is also reduced.
Thus, the liquid crystal molecules with reduced alignment uniformity cannot achieve the high-speed response and high contrast that are normally required for devices, and can easily align the molecules of the polymer liquid crystal compound. The method was anxious.
Japanese Patent Laid-Open No. 5-125116 JP-A-6-56939 Japanese Patent Laid-Open No. 8-20641

  An object of the present invention in consideration of the above problems is to provide a liquid crystal material having excellent responsiveness and contrast by regularly arranging molecules of a polymer liquid crystal compound. Another object of the present invention is to provide a display element which is a liquid crystal device including the liquid crystal material capable of regularly performing molecular alignment, and a simple method for producing such a liquid crystal material.

As a result of intensive studies, the present inventor has found that the above object can be achieved by directly bonding a liquid crystal compound having a polymerizable group to a substrate, and has completed the present invention.
That is, the liquid crystal material of the present invention is characterized in that a liquid crystal layer formed by directly bonding a liquid crystal compound having a polymerizable group to a base material is provided on the base material.
Here, the substrate to be used is preferably a substrate containing a polymerization initiator, and further, a polymer having a functional group having a polymerization initiating ability on a side chain and a polymer having a crosslinkable group is formed on the support surface by a crosslinking reaction. More preferably, it is a substrate having a polymerization initiation layer formed by immobilization.

According to a fourth aspect of the present invention, there is provided a method for producing a liquid crystal material according to the present invention, wherein a liquid crystal compound having a polymerizable group is brought into contact with a substrate, and the liquid compound is applied to the substrate surface by graft polymerization by applying energy. It is characterized by direct coupling.
Also in this production method, the substrate to be used preferably contains a polymerization initiator, and a polymer having a functional group having a polymerization initiation ability and a crosslinkable group in the side chain is immobilized on a support by a crosslinking reaction. It is more preferable that the substrate has a polymerization initiation layer.
A display element according to a seventh aspect of the present invention includes the liquid crystal material according to the present invention.

In the present invention, a polymer liquid crystal compound having a regularly aligned molecular arrangement can be obtained by graft polymerization of a low molecular weight liquid crystal molecule having a polymerizable group, and the base point of this graft polymerization is present on the substrate surface. Alternatively, since it is an active point generated on the surface of the base material, the generated polymer liquid crystal compound is firmly bonded to the surface of the base material.
The low molecular weight liquid crystal molecules used for the graft polymerization have a lower viscosity than the high molecular liquid crystal compound, and therefore are easily arranged regularly and can be more easily filled into the device. The liquid crystal monomer can be present in any of the existing liquid crystal phases including nematic, cholesteric or smectic. In the present invention, a liquid crystal layer having a more uniform molecular arrangement can be produced by performing graft polymerization, and the above-described problems of the polymer liquid crystal compound have been solved.

ADVANTAGE OF THE INVENTION According to this invention, the liquid crystal material excellent in the responsiveness and contrast which the molecule | numerator of a high molecular liquid crystal compound arranges regularly can be provided, and its simple manufacturing method.
In addition, according to the present invention, it is possible to provide a display element including the liquid crystal material capable of regularly arranging molecules.

The liquid crystal material of the present invention has a liquid crystal layer formed by directly bonding a liquid crystal compound having a polymerizable group on a base material.
Since the liquid crystal compound is immobilized on the base material by graft polymerization starting from the active sites generated on the base material, the base material used in the present invention may be a base material containing a polymerization initiator. It is preferable from the viewpoint of efficient formation. The polymerization initiator may be contained in the substrate itself, or may be contained in a form having a layer containing the polymerization initiator on the support. In the present invention, a substrate having a polymerization initiating layer formed by immobilizing a polymer having a functional group having a polymerization initiating ability on a side chain and a polymer having a crosslinkable group by a crosslinking reaction on the surface of the support is selected for the support substrate. Since the degree of freedom is high and a commercially available support can be used, it is preferable in terms of cost.

  The production method for forming the liquid crystal material of the present invention will be described in detail. A low molecular liquid crystal compound having a polymerizable group is brought into contact with a substrate surface capable of generating an active site by applying energy such as exposure, and then the group. Energy is imparted to the material, and starting from the active sites generated on the substrate surface, a low-molecular liquid crystal compound having a polymerizable group such as a polymerizable unsaturated double bond is graft-polymerized and directly bonded to the substrate. A graft polymer which is a molecular liquid crystal compound is produced. Thus, by using a low molecular weight liquid crystal compound as a raw material, a liquid crystal polymer is formed on the base material by graft polymerization, whereby a liquid crystal layer in which high molecular liquid crystal compounds are regularly arranged can be formed on the base material surface.

<Liquid crystal compound having a polymerizable group>
The liquid crystal compound having a polymerizable group used in the present invention has an ethylene addition polymerizable unsaturated group such as a vinyl group, an allyl group or a (meth) acryl group introduced into the molecule, and has a liquid crystalline functional group. From the viewpoint of handleability, liquid crystal monomers and oligomers are preferable. For example, liquid crystal macromonomers, liquid crystal oligomers, and known liquid crystal monomers having a molecular weight of 500 to 2000 can be used.
In the present invention, for example, a liquid crystal compound represented by the following general formula (I) can be given as a preferred example.

In the general formula (I), R ¹ represents a hydrogen atom, a halogen atom, or an alkyl group having a linear or branched chain having 1 to 16 carbon atoms. X represents —C (O) O—, —OC (O) —, —CONH—, —O—, —CH ₂ — or a phenylene group, and Y represents a single bond, —O—, —C (O) O. -Or -OC (O)-is represented.
n represents an integer of 0 to 20, and m represents 1 or 2.
Here, the structure other than the mesogen represented by the general formula (I) represents a polymerizable group for graft polymerization of a mesogen, which is a partial structure that exhibits liquid crystallinity, and is connected from the terminal double bond portion to the mesogen. By controlling the structure of the group [—X— (CH ₂ ) _n —Y—], the behavior of the mesogenic site after graft polymerization can be controlled.
In general formula (I), n is preferably about 2 to 12, more preferably in the range of 6 to 8, and m is preferably 1 from the viewpoint of improving the mobility and orientation of the mesogen.
R ¹ is preferably a hydrogen atom or a methyl group.

The mesogen in the general formula (I) is preferably a group represented by the following general formula (II) or general formula (III).
Specifically, JP-A-5-51378, JP-A-5-239052, JP-A-5-255309, JP-A-5-255309, JP-A-5-301869, JP-A-5-301687, JP-A-5-320651, JP-A-5-320651. And mesogens described in JP-A-3-339575, JP-A-5-339576, JP-A-6-1979, JP-A-6-9959, and JP-A-6-9961.

In the general formulas (II) and (III), A ¹ , A ² and A ³ each independently represent a divalent group shown below, wherein R ² is a hydrogen atom, a methyl group, a halogen atom, or Represents a cyano group.

In the general formulas (II) and (III), Q ¹ and Q ² are each independently a single bond, —O—, —C (O) O—, —OC (O) —, —CH ₂ CH ₂ —, —CH ₂ O— or —OCH ₂ — is represented, and Q ³ is a hydrogen atom, a cyano group, a halogen atom, a hydroxyl group, —CO ₂ H, —CF ₃ , —R, —OR, or —CO ₂ R. Or -OCOR, wherein R represents a linear or branched alkyl group having 1 to 16 carbon atoms, and may be chiral.

  Specific examples of the polymerizable liquid crystal compound having a liquid crystal functional group particularly useful in the present invention include the following compounds [Exemplary compounds (I-1) to (I-44)], but are not limited thereto. Is not to be done.

As the liquid crystal monomer used in the present invention, a chiral smectic C phase (Sc ^* phase) compound is preferable from the viewpoint of high-speed response, and a ferroelectric smectic liquid crystal material corresponds to this.
In the present invention, a liquid crystal layer is formed using a liquid crystal monomer having such a polymerizable group.
As the substrate for the liquid crystal material, a substrate having a polymerization initiating ability is used, but a substrate containing a polymerization initiator is preferable, and among them, a substrate having a polymerization initiating layer on the surface of the support is preferably used. First, a substrate having a polymerization initiation layer which is a preferred embodiment of the present invention will be described.

<Polymerization initiation layer formed by immobilizing a polymer having a functional group having a polymerization initiating ability in a side chain and a crosslinkable group by a crosslinking reaction>
First, a polymer having a functional group having a polymerization initiating ability and a crosslinkable group in the side chain used in the present invention (hereinafter, a specific polymerization initiating polymer as appropriate) will be described.
The specific polymerization initiating polymer is a copolymer including a copolymer component having a functional group having a polymerization initiating ability (hereinafter, appropriately referred to as a polymerization initiating group) and a copolymer component having a crosslinkable group. It is preferable.

[Copolymerization component having functional group capable of initiating polymerization]
The copolymer component having a polymerization initiating group constituting the specific polymerization initiating polymer is preferably composed of a radical, anion, or cationic polymerizable group in which a structure having the following polymerization initiating ability is pendant. That is, this copolymer component has a structure in which both a polymerizable group capable of polymerization and a functional group capable of initiating polymerization exist in the molecule.
The structure having the ability to initiate polymerization includes (a) aromatic ketones, (b) onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiimidazole compounds, (f) Examples thereof include ketoxime ester compounds, (g) borate compounds, (h) azinium compounds, (i) active ester compounds, (j) compounds having a carbon halogen bond, and (k) pyridinium compounds. Specific examples of the above (a) to (k) are given below, but the present invention is not limited to these.

(A) Aromatic ketones In the present invention, (a) aromatic ketones preferable as a structure having a polymerization initiating ability include “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY” P. Fouassier, J. et al. F. Examples include compounds having a benzophenone skeleton or a thioxanthone skeleton described in Rabek (1993), p77-117. For example, the following compounds are mentioned.

Among these, particularly preferred examples of (a) aromatic ketones are listed below.
The α-thiobenzophenone compound described in JP-B-47-6416 and the benzoin ether compound described in JP-B-47-3981 include, for example, the following compounds.

  Examples of the α-substituted benzoin compounds described in JP-B-47-22326 include the following compounds.

  Examples thereof include benzoin derivatives described in JP-B-47-23664, aroylphosphonic acid esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, for example, the following compounds.

  Examples of the benzoin ethers described in JP-B-60-26403 and JP-A-62-181345 include the following compounds.

  Examples of the α-aminobenzophenones described in JP-B-1-34242, US Pat. No. 4,318,791, and European Patent 0284561A1, such as the following compounds.

  P-Di (dimethylaminobenzoyl) benzene described in JP-A-2-211452, for example, the following compounds may be mentioned.

  Examples of the thio-substituted aromatic ketone described in JP-A-61-194062 include the following compounds.

  The acylphosphine sulfide described in JP-B-2-9597, for example, the following compounds may be mentioned.

  Examples of the acylphosphine described in JP-B-2-9596 include the following compounds.

  Further, thioxanthones described in JP-B-63-61950, coumarins described in JP-B-59-42864, and the like can also be mentioned.

(B) Onium Salt Compound In the present invention, examples of the preferable (b) onium salt compound as a structure having polymerization initiating ability include compounds represented by the following general formulas (1) to (3).

In general formula (1), Ar ¹ and Ar ² each independently represent an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred substituents when this aryl group has a substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or a carbon atom having 12 or less carbon atoms. An aryloxy group is mentioned. (Z ² ) ⁻ represents a counter ion selected from the group consisting of halogen ion, perchlorate ion, carboxylate ion, tetrafluoroborate ion, hexafluorophosphate ion, and sulfonate ion, preferably perchloric acid Ions, hexafluorophosphate ions, and aryl sulfonate ions.

In General Formula (2), Ar ³ represents an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred examples of the substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an aryloxy group having 12 or less carbon atoms, and 12 or less carbon atoms. Examples thereof include an alkylamino group, a dialkylamino group having 12 or less carbon atoms, an arylamino group having 12 or less carbon atoms, or a diarylamino group having 12 or less carbon atoms. (Z ³ ) ⁻ represents a counter ion having the same meaning as (Z ² ) ⁻ .

In general formula (3), R ²³ , R ²⁴ and R ²⁵ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferable substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms. (Z ⁴ ) ⁻ represents a counter ion having the same meaning as (Z ² ) ⁻ .

  Specific examples of the (b) onium salt compound that can be suitably used in the present invention include paragraph numbers [0030] to [0033] of JP-A No. 2001-133969 and paragraph numbers of JP-A No. 2001-305734. Examples include [0048] to [0052] and those described in paragraph numbers [0015] to [0046] of JP-A-2001-343742.

(C) Organic peroxide In the present invention, (c) the organic peroxide preferable as the structure having a polymerization initiating ability includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. Examples thereof include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tertiary butyl peroxy) -3,3 , 5-trimethylcyclohexane, 1,1-bis (tertiary butyl peroxy) cyclohexane, 2,2-bis (tertiary butyl peroxy) butane, tertiary butyl hydroperoxide, cumene hydroperoxide, diisopropylben Zen hydroperoxide, paraffin hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary Butylcumyl peroxide, dicumyl peroxide, bis (tertiarybutylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane, 2,5-xanoyl peroxide, Succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxide Sidicarbonate, dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tertiary butyl peroxyacetate, tertiary butyl peroxypivalate, tertiary butyl peroxyneodecanoate, Tertiary butyl peroxyoctanoate, tertiary butyl peroxy-3,5,5-trimethylhexanoate, tertiary butyl peroxylaurate, tertiary carbonate, 3,3'4,4'-tetra- ( t-butylperoxycarbonyl) benzophenone, 3,3′4,4′-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3′4,4′-tetra- (t-hexylperoxycarbonyl) benzophenone 3, 3'4, 4 ' -Tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (cumylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (p-isopropylcumylperoxy) Carbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

  Among these, 3,3′4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3′4,4′-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3 ′ 4,4′-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3′4,4′-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3′4,4′-tetra- ( Peroxide esters such as (cumylperoxycarbonyl) benzophenone, 3,3′4,4′-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, di-t-butyldiperoxyisophthalate are preferably used.

(D) Thio compound In the present invention, examples of the preferable (d) thio compound as a structure having polymerization initiating ability include compounds having a structure represented by the following general formula (4).

(In the general formula (4), R ²⁶ represents an alkyl group, an aryl group or a substituted aryl group, R ²⁷ represents a hydrogen atom or an alkyl group, and R ²⁶ and R ²⁷ are bonded to each other to form oxygen, sulfur, And a group of nonmetallic atoms necessary to form a 5- to 7-membered ring that may contain a heteroatom selected from nitrogen atoms.
As an alkyl group in the said General formula (4), a C1-C4 thing is preferable. The aryl group is preferably one having 6 to 10 carbon atoms such as phenyl or naphthyl, and the substituted aryl group may be a halogen atom such as a chlorine atom or a methyl group as described above. Those substituted with an alkoxy group such as an alkyl group, a methoxy group, and an ethoxy group are included. R ²⁷ is preferably an alkyl group having 1 to 4 carbon atoms. Specific examples of the thio compound represented by the general formula (4) include the following compounds.

(E) Hexaarylbiimidazole compound In the present invention, preferred (e) hexaarylbiimidazole compounds as a structure having a polymerization initiating ability include lophine dimers described in JP-B Nos. 45-37377 and 44-86516, For example, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5 '-Tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4, 4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (o, o′-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimi Sol, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

(F) Ketooxime ester compound In the present invention, preferable (f) ketoxime ester compound as a structure having a polymerization initiating ability includes 3-benzoyloxyiminobutane-2-one and 3-acetoxyiminobutane-2-one. 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1- ON, 3-p-toluenesulfonyloxyiminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

(G) Borate Compound In the present invention, examples of the preferable (g) borate compound as a structure having a polymerization initiating ability include compounds represented by the following general formula (5).

(In the general formula (5), R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ may be the same or different from each other, and each is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group. Represents an alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted heterocyclic group, and R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ are bonded to form a cyclic structure. Provided that at least one of R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ is a substituted or unsubstituted alkyl group, wherein (Z ⁵ ) ⁺ is an alkali metal cation or a quaternary ammonium cation. Is shown.)

Examples of the alkyl group for R ^{28 to} R ³¹ include straight-chain, branched, and cyclic groups, and those having 1 to 18 carbon atoms are preferable. Specifically, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl, cyclohexyl and the like are included. As the substituted alkyl group, a halogen atom (for example, —Cl, —Br, etc.), a cyano group, a nitro group, an aryl group (preferably a phenyl group), a hydroxy group, —COOR ^{32, etc.} (Wherein R ³² represents a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group), —OCOR ³³ or —OR ³⁴ (where R ³³ and R ³⁴ are alkyl groups having 1 to 14 carbon atoms) Or an aryl group) and those having the following formula as a substituent.

(Wherein R ³⁵ and R ³⁶ independently represent a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group)

The aryl group of R ^{28 to} R ³¹ includes 1 to 3 ring aryl groups such as a phenyl group and a naphthyl group, and the substituted aryl group is a substitution of the above substituted alkyl group with the above aryl group. Those having a group or an alkyl group having 1 to 14 carbon atoms are included. Examples of the alkenyl group of R ^{28 to} R ³¹ include straight chain, branched, and cyclic groups having 2 to 18 carbon atoms, and examples of the substituent of the substituted alkenyl group include those described above as the substituent of the substituted alkyl group. Is included. Examples of the alkynyl group of R ^{28 to} R ³¹ include straight chain or branched groups having 2 to 28 carbon atoms, and examples of the substituent of the substituted alkynyl group include those listed as the substituents of the substituted alkyl group. included. In addition, examples of the heterocyclic group of R ^{28 to} R ³¹ include a 5-membered ring or more, preferably a 5- to 7-membered heterocyclic group containing at least one of N, S, and O. May contain a condensed ring. Furthermore, you may have what was mentioned as a substituent of the above-mentioned substituted aryl group as a substituent. Specific examples of the compound represented by the general formula (5) are described in US Pat. Nos. 3,567,453 and 4,343,891, European Patents 109,772 and 109,773. Compounds and those shown below are mentioned.

(H) Azinium Compound In the present invention, preferable (h) azinium salt compounds as a structure having a polymerization initiating ability include JP-A-63-138345, JP-A-63-142345, JP-A-63-142346, Listed are compounds having an N—O bond described in JP-A-63-143537 and JP-B-46-42363.

(I) Active ester compound In the present invention, (i) an active ester compound preferable as a structure having a polymerization initiating ability includes an imide sulfonate compound described in JP-B-62-2223, JP-B-63-14340, JP-A-59- And active sulfonates described in No. 174831.

(J) Compound having a carbon halogen bond In the present invention, preferred compounds having a carbon halogen bond as a structure having a polymerization initiating ability include those represented by the following general formulas (6) to (12). .

The compound represented by the said General formula (6).
(In the general formula (6), X ² represents a halogen atom, and Y ¹ represents —C (X ² ) ₃ , —NH ₂ , —NHR ³⁸ , —NR ³⁸ , —OR ³⁸ , where R ³⁸ represents alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group. Further, R ³⁷ represents -C (X ²⁾ _3, alkyl group, substituted alkyl group, an aryl group, a substituted aryl group, a substituted alkenyl group.)

The compound represented by the said General formula (7).
(In the general formula (7), R ³⁹ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxyl group, a nitro group or a cyano group. X ³ is a halogen atom, and n is an integer of 1 to ^3. )

The compound represented by the said General formula (8).
(In the general formula (8), R ⁴⁰ is an aryl group or a substituted aryl group, R ⁴¹ is a group or halogen shown below, and Z ⁶ is —C (═O) —, —C (═S ) — Or —SO ₂ —, X ³ is a halogen atom, and m is 1 or 2.)

(Wherein R ⁴² and R ⁴³ are an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group, and R ⁴⁴ is the same as R ³⁸ in formula (6)). )

The compound represented by the said General formula (9).
(In the general formula (9), R ⁴⁵ is an optionally substituted aryl group or heterocyclic group, R ⁴⁶ is a trihaloalkyl group or trihaloalkenyl group having 1 to 3 carbon atoms, and p is 1, 2, or 3.)

A carbonylmethylene heterocyclic compound having a trihalogenomethyl group represented by the general formula (10).
(In the general formula (10), L ⁷ represents a hydrogen atom or the _{^{formula: CO- (R 47) q (}} C (X 4) 3) is a substituent _r, Q ² represents a sulfur, selenium or oxygen atom, dialkylmethylene A group, an alkene-1,2-ylene group, a 1,2-phenylene group or an N—R group, and M ⁴ is a substituted or unsubstituted alkylene group or alkenylene group, or a 1,2-arylene group. R ⁴⁸ is an alkyl group, an aralkyl group or an alkoxyalkyl group, R ⁴⁷ is a carbocyclic or heterocyclic divalent aromatic group, X ⁴ is a chlorine, bromine or iodine atom, q = 0 and r = 1, or q = 1 and r = 1 or 2.)

4-halogeno-5- (halogenomethyl-phenyl) -oxazole derivative represented by the above general formula (11).
(In General Formula (11), X ⁵ is a halogen atom, t is an integer of 1 to 3, s is an integer of 1 to 4, and R ⁴⁹ is a hydrogen atom or a CH ₃ -tX ⁵ t group. And R ⁵⁰ is an s-valent optionally substituted unsaturated organic group)

A 2- (halogenomethyl-phenyl) -4-halogeno-oxazole derivative represented by the general formula (12).
(In the general formula (12), X ⁶ is a halogen atom, v is an integer of 1 to 3, u is an integer of 1 to 4, and R ⁵¹ is a hydrogen atom or a CH ₃ -vX ⁶ v group. And R ⁵² represents an u-valent unsaturated organic group which may be substituted.)

  Specific examples of such a compound having a carbon-halogen bond include, for example, Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), for example, 2-phenyl 4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2 -(2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6 -Bis (trichloromethyl) -S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α, α, β-trichloroethyl) -4,6- Scan (trichloromethyl) -S- triazine. In addition, compounds described in British Patent 1388492, for example, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-S-triazine, etc. And compounds described in JP-A No. 53-133428, such as 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphtho) 1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloro Til-S-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine), 2- (acenaphtho-5-yl) -4,6- Examples include compounds described in German Patent No. 3333724, such as bis-trichloromethyl-S-triazine, and the like.

  F.F. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), for example, 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-tris (tribromomethyl) -S-triazine, 2, 4,6-tris (dibromomethyl) -S-triazine, 2-amino-4-methyl-6-tribromomethyl-S-triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine, etc. be able to. Furthermore, for example, the following compounds described in JP-A-62-258241 can be exemplified.

  Furthermore, for example, the following compounds described in JP-A-5-281728 can be exemplified.

  Alternatively, M.M. P. Hutt, E .; F. Elslager and L. M.M. The following compounds that can be easily synthesized by those skilled in the art according to the synthesis method described in “Journalof Heterocyclic Chemistry”, Volume 7 (No. 3) by Herbel, page 511 et seq. (1970) Examples of the group include the following compounds.

(K) Pyridium compounds In the present invention, examples of the (k) pyridium compounds that are preferable as a structure having a polymerization initiating ability include compounds represented by the following general formula (13).

(In Formula (13), preferably, R ⁵ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, or a substituted alkynyl group, R ^{6 , R 7, R 8, R} 9, R 10 may be different even in the same, represent a hydrogen atom, an organic residue of a halogen atom or a monovalent, at least one of the following general formula ( 14) R ⁵ and R ⁶ , R ⁵ and R ¹⁰ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ And may be bonded to each other to form a ring, and X represents a counter anion, and m represents an integer of 1 to 4.)

(In the general formula (14), R ¹² and R ¹³ are each independently a hydrogen atom, halogen atom, alkyl group, substituted alkyl group, aryl group, substituted aryl group, alkenyl group, substituted alkenyl group, alkynyl group or substituted alkynyl. It represents a group, R ¹¹ is a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, substituted alkynyl group, hydroxyl group, substituted oxy group, a mercapto group, a substituted thio Represents a group, an amino group or a substituted amino group, and R ¹² and R ¹³ , R ¹¹ and R ¹² , or R ¹¹ and R ¹³ may be bonded to each other to form a ring. Represents a valent linking group.)

R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the general formula (13) are more preferably each independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, Alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group, hydroxyl group, substituted oxy group, mercapto group, substituted thio group, amino group, substituted amino group, substituted carbonyl group, sulfo group, sulfonate group, substituted sulfinyl group, substituted A sulfonyl group, a phosphono group, a substituted phosphono group, a phosphonate group, a cyano group, a nitro group, or a silyl group can be used. R ⁵ and R ⁶ , R ⁵ and R ¹⁰ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ may be bonded to each other to form a ring.

Subsequently, in the general formula (13) will be described in detail for preferred embodiments of R ^5. Preferred examples of the alkyl group, substituted alkyl group, aryl group, substituted aryl group, alkenyl group, substituted alkenyl group, alkynyl group, or substituted alkynyl group are shown below.

  Examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, An isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-norbornyl group and the like can be mentioned. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

The substituted alkyl group is composed of a bond between a substituent and an alkylene group. As the substituent, a monovalent non-metallic atomic group other than hydrogen is used. Preferred examples include halogen atoms (—F, —Br, — Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N -Arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyl Oxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-aryl Rubamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkyl Ureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N -Alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N -Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-dia Reel-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, Acyl group, carboxyl group and its conjugate base group (hereinafter referred to as carboxylate), alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group N, N-diarylcarbamo Yl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group) , Alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N -Alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N- Sils sulfamoyl group and its conjugated base group, N- alkylsulfonylsulfamoyl group _{(-SO 2 NHSO 2 (alkyl)} ) and its conjugated base group, N- aryl sulfonylsulfamoyl group (-SO ₂ NHSO ₂ (allyl )) And its conjugate base group, N-alkylsulfonylcarbamoyl group (—CONHSO ₂ (alkyl)) and its conjugate base group, N-arylsulfonylcarbamoyl group (—CONHSO ₂ (allyl)) and its conjugate base group, alkoxysilyl Group (—Si (Oalkyl) ₃ ), aryloxysilyl group (—Si (Oallyl) ₃ ), hydroxysilyl group (—Si (OH) ₃ ) and its conjugate base group, phosphono group (—PO ₃ H ₂ ) and Its conjugate base group (hereinafter referred to as phosphonate group), dialkylphosphono group (-P ₃ (alkyl) _2), diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (-PO ₃ H (alkyl )) And conjugated base groups thereof (hereinafter referred to as alkylphosphonate groups), monoarylphosphono groups (—PO ₃ H (aryl)) and conjugated base groups thereof (hereinafter referred to as arylphosphonate groups), phosphonooxy groups (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ) , Alkylarylphosphonooxy group (—OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy group (—OPO ₃ H ( alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonatoxy group), monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonatoxy group). ), Cyano group, nitro group, aryl group, alkenyl group, alkynyl group.

  Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, and a cumenyl group. , Fluorophenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl Group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, phenoxycarbonylphenyl group, N-phenylcarbamoyl group Group, a phenyl group, nitrophenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, and the like phosphonium Hona preparative phenyl group. Examples of the alkenyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like. Examples of alkynyl group include ethynyl group, 1- Examples include propynyl group, 1-butynyl group, trimethylsilylethynyl group, phenylethynyl group and the like.

The above-described acyl group (R ⁴ CO-), R ⁴ can be exemplified hydrogen atom and the above alkyl group, an aryl group, an alkenyl group, an alkynyl group.

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

  Specific examples of preferred substituted alkyl groups include chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, methylthiomethyl, Ruthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N- Methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, methoxycarbonylmethyl group, methoxycarbonylbutyl group, ethoxycarbonyl Bonylmethyl group, butoxycarbonylmethyl group, allyloxycarbonylmethyl group, benzyloxycarbonylmethyl group, methoxycarbonylphenylmethyl group, trichloromethylcarbonylmethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N- Methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfopropyl group, sulfobutyl group, sulfonatobutyl group, sulfur Famoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphono Eniru) sulfamoyl-octyl group,

Phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, Phosphonatooxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group , 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group and the like.

  Examples of the aryl group include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, naphthyl Groups, anthryl groups, phenanthryl groups, indenyl groups, acenaphthenyl groups, fluorenyl groups, and the like. Among these, phenyl groups and naphthyl groups are more preferable.

  The substituted aryl group is a group in which the substituent is bonded to the aryl group, and those having a monovalent non-metallic atomic group excluding hydrogen as a substituent on the ring-forming carbon atom of the aryl group described above are used. Examples of preferred substituents include the aforementioned alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group.

  Preferred examples of these substituted aryl groups include biphenyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl, trifluoromethylphenyl, hydroxy Phenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, phenylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxy Phenyl group, benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoyla Nophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) ) Carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfa Moylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenyl Ruphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

  Examples of the alkenyl group include those described above. The substituted alkenyl group is a group in which the substituent is replaced and bonded to a hydrogen atom of the alkenyl group, and as the substituent, the substituent in the above-mentioned substituted alkyl group is used, while the alkenyl group uses the above-mentioned alkenyl group. Can do. The following compounds etc. can be mentioned as an example of a preferable substituted alkenyl group.

  Examples of the alkynyl group include those described above. The substituted alkynyl group is a group in which the substituent is replaced with a hydrogen atom of the alkynyl group, and the substituent in the above-described substituted alkyl group is used as this substituent, while the alkynyl group uses the above-described alkynyl group. be able to.

Next, preferable examples other than the structure represented by the general formula (14) among R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ in the general formula (13) will be described in detail. The halogen atom is preferably a fluorine, chlorine, bromine or iodine atom. Preferable examples of the alkyl group, the substituted alkyl group, the aryl group, the substituted aryl group, the alkenyl group, and the substituted alkenyl group include those exemplified as the aforementioned examples of R ⁵ .

As the substituted oxy group (R ¹⁴ O—), those in which R ¹⁴ is a monovalent nonmetallic atomic group excluding hydrogen can be used. Preferred substituted oxy groups include alkoxy groups, aryloxy groups, acyloxy groups, carbamoyloxy groups, N-alkylcarbamoyloxy groups, N-arylcarbamoyloxy groups, N, N-dialkylcarbamoyloxy groups, N, N-diarylcarbamoyloxy groups. Groups, N-alkyl-N-arylcarbamoyloxy groups, alkylsulfoxy groups, arylsulfoxy groups, phosphonooxy groups, and phosphonatoxy groups. Examples of the alkyl group and aryl group in these include the alkyl groups, substituted alkyl groups, aryl groups, and substituted aryl groups described above. Examples of the acyl group (R ¹⁵ CO—) in the acyloxy group include those in which R ¹⁵ is the alkyl group, substituted alkyl group, aryl group, and substituted aryl group described above. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferable.

  Specific examples of preferred substituted oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, Carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, Phenoxy, tolyloxy, xylyloxy, mesityloxy, cumyloxy, methoxyphenyloxy, ethoxyphenyloxy, chlorophenyloxy, bromo Niruokishi group, acetyloxy group, benzoyloxy group, naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group, phosphonatoxy group, and the like.

As the substituted thio group (R ¹⁶ S—), those in which R ¹⁶ is a monovalent nonmetallic atomic group excluding a hydrogen atom can be used. Examples of preferred substituted thio groups include alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups, and acylthio groups. Alkyl group in these alkyl groups described above as the aryl group, a substituted alkyl group, and aryl group include those shown as the substituted aryl group, R ¹⁵ of the acyl group (R ¹⁵ CO-) in the acylthio group is As described above. Among these, an alkylthio group and an arylthio group are more preferable. Specific examples of preferable substituted thio groups include a methylthio group, an ethylthio group, a phenylthio group, an ethoxyethylthio group, a carboxyethylthio group, and a methoxycarbonylthio group.

As the substituted amino group (R ¹⁷ NH—, (R ¹⁸ ) (R ¹⁹ ) N—), those in which R ¹⁷ , R ¹⁸ , and R ¹⁹ are monovalent nonmetallic atomic groups excluding hydrogen atoms can be used. Preferred examples of the substituted amino group include an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, an N, N-diarylamino group, an N-alkyl-N-arylamino group, an acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group, N′-a Reel-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido Group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino Group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group. Examples of the alkyl group and aryl group in these include the alkyl groups, substituted alkyl groups, aryl groups, and substituted aryl groups described above, such as acylamino group, N-alkylacylamino group, and N-arylacylamino. R ¹⁵ of the acyl group (R ¹⁵ CO-) in the group is as previously described.

  Of these, more preferred are an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an acylamino group. Specific examples of preferred substituted amino groups include methylamino group, ethylamino group, diethylamino group, morpholino group, piperidino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.

As the substituted carbonyl group (R ²⁰ —CO—), those in which R ²⁰ is a monovalent nonmetallic atomic group can be used. Preferred examples of the substituted carbonyl group include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, NN-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group may be mentioned. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group.

  Among these, more preferred substituents are formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N ′, N-dialkylcarbamoyl group, N-ary. Examples include a rucarbamoyl group, and more preferable examples include a formyl group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Specific examples of preferred substituted carbonyl groups include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, allyloxycarbonyl group, N-methylcarbamoyl group, N-phenylcarbamoyl group, N, N-diethylcarbamoyl group. And a morpholinocarbonyl group.

As the substituted sulfinyl group (R ²¹ —SO—), those in which R ²¹ is a monovalent nonmetallic atomic group can be used. Preferable examples include alkylsulfinyl group, arylsulfinyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl. Group, N-alkyl-N-arylsulfinamoyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Of these, more preferred examples include an alkylsulfinyl group and an arylsulfinyl group. Specific examples of such a substituted sulfinyl group include a hexylsulfinyl group, a benzylsulfinyl group, and a tolylsulfinyl group.

As the substituted sulfonyl group (R ²⁵ —SO ₂ —), those in which R ²⁵ is a monovalent nonmetallic atomic group can be used. More preferable examples include an alkylsulfonyl group and an arylsulfonyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Specific examples of such a substituted sulfonyl group include a butylsulfonyl group and a chlorophenylsulfonyl group.

Sulfonato group (SO ₃ ^-) are as described above, means a conjugate base anion group of a sulfo group (-SO ₃ H), it is usually used preferably in combination with a counter cation. Such counter cations include those generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , Ca). ²⁺ , Zn ^2+, etc.).

  The substituted phosphono group means a group in which one or two hydroxyl groups on the phosphono group are substituted with other organic oxo groups. Preferred examples thereof include the above-mentioned dialkylphosphono group, diarylphosphono group, alkylarylphospho group. Group, monoalkylphosphono group and monoarylphosphono group. Of these, dialkylphosphono groups and diarylphosphono groups are more preferred. Specific examples thereof include a diethyl phosphono group, a dibutyl phosphono group, a diphenyl phosphono group, and the like.

As described above, the phosphonate group (—PO ₃ ²⁻ , —PO ₃ H ⁻ ) is a conjugated base anion group derived from the acid first dissociation or acid second dissociation of the phosphono group (—PO ₃ H ₂ ). Means. Usually, it is preferable to use it with a counter cation. Such counter cations include those generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , Ca). ²⁺ , Zn ^2+, etc.).

The substituted phosphonato group is a conjugated base anion group obtained by substituting one organic oxo group in the above-described substituted phosphono group. As a specific example, the above-described monoalkylphosphono group (—PO ₃ H ( alk)), and a conjugate base of a monoarylphosphono group (—PO ₃ H (aryl), which is usually preferably used together with a counter cation. In other words, various oniums (ammonium, sulfonium, phosphonium, iodonium, azinium, etc.) and metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.) .

As the silyl group ((R ²³ ) (R ²⁴ ) (R ²⁵ ) Si—), those in which R ²³ , R ²⁴ and R ²⁵ are monovalent nonmetallic atomic groups can be used. Examples include an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. Examples of preferred silyl groups include trimethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, dimethylphenylsilyl group and the like.

Among the examples of R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ listed above, more preferred are a hydrogen atom, a halogen atom (—F, —Cl, —Br, —I), alkyl Groups, substituted alkyl groups, aryl groups, substituted aryl groups, substituted oxy groups, substituted thio groups, substituted amino groups, substituted carbonyl groups, sulfo groups, sulfonate groups, and cyano groups, and even more preferably hydrogen atoms, halogen atoms Examples thereof include an atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted carbonyl group.

Next, R ⁵ and R ⁶ , R ⁵ and R ¹⁰ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ are bonded to each other to form a ring. Indicates. Examples of such are R ⁵ and R ⁶ , R ⁵ and R ¹⁰ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ bonded together and saturated, or Examples of unsaturated aliphatic rings may be mentioned, and preferably, 5-membered, 6-membered, 7-membered and 8-membered aliphatic rings in combination with the carbon atom to which they are bonded. Can be mentioned. More preferred examples include 5-membered and 6-membered aliphatic rings. In addition, these may further have a substituent on the carbon atom constituting them (as examples of the substituent, the substituents in the substituted alkyl group described above as examples of R ⁸ and R ¹¹ ). In addition, a part of the ring carbon may be substituted with a hetero atom (oxygen atom, sulfur atom, nitrogen atom, etc.). Furthermore, a part of the aliphatic ring may form a part of the aromatic ring. Preferred examples of these include cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclo-1,3-dioxapentane ring, cyclopentene ring, cyclohexene ring, cycloheptene ring, cyclooctene ring, cyclo-1 , 3-dioxapentene ring, cyclo-1,3-dioxahexene ring, cyclohexadiene ring, benzocyclohexene ring, benzocyclohexacene ring, tetrahydropyranone ring and the like.

Next, R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ are bonded to each other to form an aromatic ring. In cooperation with the ring, examples include a quinoline ring, an isoquinoline ring, an acridine ring, a phenanthridine ring, a benzquinoline ring, and a benzisoquinoline ring, and more preferably a quinoline ring. Moreover, these may have a substituent on the carbon atom which comprises (As an example of a substituent, the substituent on the above-mentioned substituted alkyl group can be mentioned).

Next, the preferable example of R <^12> , R < ¹³ > in General formula (14) is explained in full detail. The halogen atom is preferably a fluorine, chlorine, bromine or iodine atom. Preferable examples of the alkyl group, the substituted alkyl group, the aryl group, the substituted aryl group, the alkenyl group, the substituted alkenyl group, the alkynyl group, and the substituted alkynyl group include those exemplified as the aforementioned examples of R ⁵ . R ¹² and R ¹³ are more preferably a hydrogen atom or an alkyl group.

Next, it will be described in detail preferable examples of R ¹¹ in the general formula (14). Alkyl group, substituted alkyl group, aryl group, substituted aryl group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group, hydroxyl group, substituted oxy group, mercapto group, substituted thio group, amino group, and substituted amino group Preferable examples include those mentioned as examples of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ described above. More preferred R ¹¹ is an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or an alkenyl group.

R ¹² and R ¹³ , R ¹¹ and R ¹² , R ¹¹ and R ¹³ may be bonded to each other to form a saturated or unsaturated aliphatic ring, and preferably a carbon atom to which they are bonded A group which forms a 5-membered ring, a 6-membered ring, a 7-membered ring and an 8-membered aliphatic ring jointly can be mentioned. More preferred examples include 5-membered and 6-membered aliphatic rings. In addition, these may further have a substituent on the carbon atom constituting them (examples of the substituent include the examples of the substituent in the substituted alkyl group described above). In addition, a part of the ring carbon may be substituted with a hetero atom (oxygen atom, sulfur atom, nitrogen atom, etc.). Furthermore, a part of the aliphatic ring may form a part of the aromatic ring. Preferred examples of these include cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclo-1,3-dioxapentane ring, cyclopentene ring, cyclohexene ring, cycloheptene ring, cyclooctene ring, cyclo-1 , 3-dioxapentene ring, cyclo-1,3-dioxahexene ring, cyclohexadiene ring, benzocyclohexene ring, benzocyclohexadiene ring, perhydropyranone ring and the like.

  Next, L in the general formula (14) will be described. L represents a divalent linking group containing a hetero atom, and specifically has the following partial structure.

  Here, “having the following partial structure” means that L as a linking group or terminal group has at least one of the partial structures, and may have a plurality of the partial structures. Therefore, L may be the partial structure itself, or may be a group in which a plurality of these are connected, or a group in which the partial structure is connected to another hydrocarbon group or the like. Specific examples of particularly preferred L ′ include the structures shown below.

Next, pairs in the general formula (13) the anion X _m ^- will be described in detail preferable examples. Preferred examples of X _m ⁻ include halide ions (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), sulfonate ions, organic boron anions, perchlorate ions (ClO ₄ ⁻ ), and general formula (a) or An anion represented by (b) is mentioned.

MX _r (a)
MX _r-1 (OH) (b)
(In general formulas (a) and (b), M represents a boron atom, a phosphorus atom, an arsenic atom, or an antimony atom, X represents a halogen atom, and r represents an integer of 4 to 6.)

Preferred examples of the sulfonate ion include methanesulfonate ion, benzenesulfonate ion, p-toluenesulfonate ion (TsO ⁻ ), p-styrenesulfonate ion, β-naphthoquinone-4-sulfonate ion, and anthraquinone-1. , 5-disulfonic acid ion, anthraquinone-1,8-disulfonic acid ion, anthraquinone-1-sulfonic acid ion, anthraquinone-2-sulfonic acid ion, quinoline-8-sulfonic acid ion, hydroquinonesulfonic acid ion, 1,5- Naphthalene disulfonate ion, 1-naphthalenesulfonate ion, 2-naphthalenesulfonate ion, 2-amino-1-naphthalenesulfonate ion, 2-naphthol-6-sulfonate ion, dibutylnaphthalenesulfonate ion, naphthalene-1, 3, -Trisulfonic acid ion, m-benzenedisulfonic acid ion, p-phenolsulfonic acid ion, dodecylbenzenesulfonic acid ion, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid ion, 4-acetylbenzenesulfonic acid ion, 4 -Nitrotoluene-2-sulfonic acid ion, o-benzaldehyde sulfonic acid ion, diphenylamine-4-sulfonic acid ion, benzaldehyde-2,4-disulfonic acid ion, mesitylene sulfonic acid ion, trifluoromethanesulfonic acid ion, chlorosulfonic acid ion, Examples thereof include fluorosulfonic acid ions and 9,10-dimethoxyanthracene-2-sulfonic acid ions.

  Although the preferable specific example of a compound represented by General formula (13) below is shown, this invention is not limited to these.

  Among these structures having polymerization initiating ability, aromatic ketones and triazines having the following structure are preferably pendant to the polymerizable group.

  Moreover, as for the structure which has such a polymerization initiating ability, only 1 type may be pendant to the polymeric group, and 2 or more types may be pendant.

  Examples of the polymerizable group pendant with such a structure having a polymerization initiating ability include a polymerizable group capable of undergoing radical, anionic, and cationic polymerization such as an acryl group, a methacryl group, an acrylamide group, a methacrylamide group, and a vinyl group. Among these, an acrylic group and a methacryl group are particularly preferable because of ease of synthesis.

  Specific examples of the copolymer component having a functional group having a polymerization initiating ability in the present invention include monomers having the following structures.

[Copolymerization component having crosslinkable group]
As the copolymer component having a crosslinkable group constituting the specific polymerization initiating polymer in the present invention, for example, a conventionally known crosslinkable group (used in a crosslink reaction) as described in Shinji Yamashita “Crosslinker Handbook” is used. The functional group having a structure) is preferably composed of a radical, anion, or cationic polymerizable group capable of being polymerized. That is, this copolymerization component has a structure in which a polymerizable group and a crosslinkable group are both present in the molecule.

Among these conventionally known crosslinkable groups, a carboxylic acid group (—COOH), a hydroxyl group (—OH), an amino group (—NH ₂ ), and an isocyanate group (—NCO) are preferably pendant to a polymerizable group. .
Moreover, as for such a crosslinkable group, only 1 type may be pendant by the polymeric group, and 2 or more types may be pendant.

  Examples of the polymerizable group pendant with these crosslinkable groups include a polymerizable group capable of undergoing radical, anionic, and cationic polymerization such as an acryl group, a methacryl group, an acrylamide group, a methacrylamide group, and a vinyl group. Among these, an acrylic group and a methacryl group are particularly preferable because of ease of synthesis.

  Specific examples of the copolymer component having a crosslinkable group in the present invention include monomers having the following structures.

[Other copolymer components]
In the specific polymerization initiating polymer in the present invention, a third copolymer component as shown below may be used for controlling the hydrophilicity / hydrophobicity of the polymerization initiating layer.
As the third copolymer component, any compound can be used as long as it is a radical, anion, or cationic polymerizable compound. In addition, in a system where polymerization is initiated by hydrogen abstraction such as benzophenones as an initiator component, the initiation efficiency increases when isopropyl methacrylate is added as a copolymerizable component. Two or more kinds of the third copolymer component may be used.

  In the specific polymerization initiating polymer in the present invention, as the copolymerization molar ratio of the copolymer component (A) having a polymerization initiating group and the copolymer component (B) having a crosslinkable group, (A) is 5 mol%. More preferably, (B) is 10 mol% or more, (A) is 5 to 50 mol%, and (B) is preferably 30 to 70 mol%, and (A) is 10 mol%. More preferably, it is -20 mol% and (B) 30-40 mol%. Here, if the polymerization initiation group is less than 5 mol%, the polymerization initiation function is limited, and the polymerizability may be lowered. Moreover, when there are few crosslinkable groups than 10 mol%, a polymerization start layer may become easy to melt | dissolve in a monomer solution.

  The weight average molecular weight of the specific polymerization initiating polymer in the present invention is preferably 10,000 to 10,000,000, more preferably 10,000 to 5,000,000, and further preferably 100,000 to 1,000,000. When the weight average molecular weight of the specific polymerization initiating polymer in the present invention is less than 10,000, the polymerization initiating layer may be easily dissolved in the monomer solution.

The specific polymerization initiating polymer in the present invention can be synthesized by copolymerizing these above-described copolymer components.
The specific polymerization initiating polymer in the present invention has been described above, but the specific polymerization initiating polymer is not limited to being synthesized by copolymerization. For example, a polymer having a polymerization initiating group in the side chain is synthesized, and then The specific polymerization initiating polymer in the present invention may be synthesized by introducing an appropriate amount of a crosslinkable group into the polymer.

[Polymerization initiation layer formed by immobilizing a specific polymerization initiation polymer by a crosslinking reaction]
In the present invention, as a method for immobilizing a specific polymerization initiating polymer by a crosslinking reaction, there are a method of using a self-condensation reaction of a specific polymerization initiating polymer and a method of using a crosslinking agent together, and it is preferable to use a crosslinking agent. . As a method of using the self-condensation reaction of the specific polymerization initiating polymer, for example, when the crosslinkable group is -NCO, the property that the self-condensation reaction proceeds by applying heat is used. As this self-condensation reaction proceeds, a crosslinked structure can be formed.

In addition, as a crosslinking agent used in the method of using a crosslinking agent in combination, conventionally known as described in “Crosslinking Agent Handbook” edited by Shinji Yamashita, considering the combination with a crosslinking group in a specific polymerization initiating polymer. Can be used.
Preferred combinations of the crosslinkable group and the crosslinker in the specific polymerization initiating polymer include (crosslinkable group, crosslinker) = (— COOH, polyvalent amine), (—COOH, polyvalent aziridine), (—COOH, (Polyvalent isocyanate), (—COOH, polyvalent epoxy), (—NH ₂ , polyvalent isocyanate), (—NH ₂ , aldehydes), (—NCO, polyvalent amine), (—NCO, polyvalent isocyanate) ), (—NCO, polyhydric alcohol), (—NCO, polyhydric epoxy), (—OH, polyhydric alcohol), (—OH, polyhalogenated compound), (—OH, polyhydric amine), ( -OH, acid anhydride). Among these, (functional group, cross-linking agent) = (— OH, polyvalent isocyanate) is a more preferable combination in that a urethane bond is formed after the cross-linking and a high-strength cross-linking can be formed.

  Specific examples of the crosslinking agent in the present invention include the structures shown below.

  Such a crosslinking agent is added to the coating solution containing the above-mentioned specific polymerization initiating polymer when the polymerization initiating layer is formed. Thereafter, the crosslinking reaction proceeds by the heat during the drying of the coating film, and a strong crosslinked structure can be formed. More specifically, the following ex1. Or the dehydration reaction indicated by ex2. The cross-linking reaction proceeds by the addition reaction represented by the above, and a cross-linked structure is formed.

  The amount of the crosslinking agent in the coating solution varies depending on the amount of the crosslinkable group introduced into the specific polymerization initiating polymer, but is usually 0.01 to 50 with respect to the number of moles of the crosslinkable group. It is preferably an equivalent, more preferably 0.01 to 10 equivalent, and still more preferably 0.5 to 3 equivalent. When the addition amount of the crosslinking agent is less than this upper limit value, the degree of crosslinking becomes low and the polymerization initiating layer is easily dissolved in the monomer solution. On the other hand, when the addition amount of the crosslinking agent is larger than the upper limit value, the unreacted crosslinking component remains in the polymerization initiation layer and is eluted into the monomer solution, thereby adversely affecting the polymerization reaction.

[Deposition of polymerization initiation layer]
In the present invention, the polymerization initiation layer is selected from the base materials described later according to the intended use as a support, and the specific polymerization initiation polymer is dissolved in an appropriate solvent on the surface, and the prepared coating solution is applied. For example, the film is formed by removing the solvent and proceeding with the crosslinking reaction.

(solvent)
The solvent used when applying the polymerization initiation layer is not particularly limited as long as the above-mentioned specific polymerization initiation polymer is dissolved. From the viewpoint of easy drying and workability, a solvent having a boiling point that is not too high is preferable. Specifically, a solvent having a boiling point of about 40 ° C to 150 ° C may be selected.
Specifically, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, methanol, Ethanol, 1-methoxy-2-propanol, 3-methoxypropanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, - such as methoxypropyl acetate.
These solvents can be used alone or in combination. The solid content in the coating solution is suitably 2 to 50% by weight.

The coating amount of the polymerization initiation layer is a weight after drying is preferably 0.1 to 20 g / m ^2, further, 1 to 15 g / m ² is preferred. If the coating amount is less than 0.1 g / m ² , sufficient polymerization initiating ability cannot be exhibited, graft polymerization becomes insufficient, and there is a concern that a desired strong graft structure cannot be obtained, and the coating amount exceeds 20 g / m ² . However, the film properties tend to deteriorate, and film peeling tends to occur.

<Base material (support)>
The substrate used for the liquid crystalline material of the present invention is preferably a dimensionally stable plate-like material, for example, glass, paper, plastic (for example, polyethylene, polypropylene, polystyrene, etc.) laminated. Paper, metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene , Polycarbonate, polyvinyl acetal, polyimide, etc.).
By using the base material as a support and forming the polymerization initiation layer, a base material that can be suitably used in the present invention is obtained.
Moreover, what is necessary is just to use what contains the polymerization initiator which has a polymerization start group shown by said (a)-(k) in this base material, when using the base material which does not have a polymerization start layer. In addition, the aspect in which a part of the base material is constituted by the polymerization initiating group by the organic material constituting these base materials having the above-described polymerization initiating group as a partial structure is also referred to as “polymerization initiator” in the present invention. Are included.
When a substrate containing a polymerization initiator is used as the substrate, the amount of the polymerization initiator added to the substrate is preferably 0.1% by mass to 50% by weight, more preferably 5% by weight to 20% by weight. It is a range.
The substrate or support used in the present invention is preferably made of glass or light transmissive plastic in terms of transparency.

<Liquid crystal layer formed by directly bonding a liquid crystal compound having a polymerizable group to a substrate or a polymerization initiation layer>
First, a method for producing a liquid crystal layer formed by directly bonding a liquid crystal compound having a polymerizable group to the polymerization initiation layer formed on the substrate or support will be described.
(Graft polymerization)
In preparing the liquid crystal layer according to the present invention, a means generally called surface graft polymerization is used. Graft polymerization is a method in which an active species is provided on a polymer compound chain, whereby another monomer that initiates polymerization is further bound and polymerized to synthesize a graft (grafting) polymer, and in particular, an active species is provided. When a polymer compound forms a solid surface, it is called surface graft polymerization. The graft polymerization in the present invention includes a method of synthesizing a graft polymer (liquid crystal polymer) obtained by bonding the liquid crystal polymer to an active species on a polymer compound chain. In the present invention, a polymer compound to which an active species is given is a base material or the above-mentioned specific polymerization initiating polymer.

  Graft polymerization usually involves treating the surface of a polymer such as PET constituting the substrate directly with plasma or electron beam to generate radicals on the surface to express the ability to initiate polymerization. A graft polymer surface layer can be obtained by reacting with a monomer having various functional groups. In the present invention, preferably, a base material having a polymerization initiating ability is used or a base material in which a polymerization initiating layer is previously formed on the surface of the support is used. The liquid crystal layer can be formed by a simple method because it can be easily carried out and many active points are generated.

[Energization to give active species to substrate or polymerization initiation layer]
There is no particular limitation on the method of applying energy to give the active species to the substrate or the polymerization initiating layer, and a liquid crystal having a polymerizable group in the active species by activating the polymerization initiating group in the substrate or the polymerization initiating layer. Any method can be used as long as it can impart energy capable of bonding (and polymerizing) the compound, for example, heating by a thermal head, writing by actinic ray irradiation such as exposure, etc., but from the viewpoint of cost and simplicity of the apparatus. It is preferable to use means for irradiating actinic rays.
That is, examples of actinic rays that can be used for energy application include ultraviolet rays, visible light, and infrared light. Among these actinic rays, ultraviolet rays and visible light are preferable, and ultraviolet rays are particularly preferable from the viewpoint of excellent polymerization rate. preferable. It is preferable that the main wavelength of the actinic ray is 250 nm or more and 800 nm or less.
Examples of the light source include a low-pressure mercury lamp, a high-pressure mercury lamp, a fluorescent lamp, a xenon lamp, a carbon arc lamp, a tungsten incandescent lamp, and sunlight.
The time required for irradiation with actinic rays varies depending on the intended liquid crystal phase formation and the light source used, but is usually several seconds to 24 hours.

In the method for producing a liquid crystal layer using graft polymerization in the present invention, a liquid crystal compound having a polymerizable group is placed on the above-described base material or polymerization initiation layer, and the liquid crystal is irradiated on the base material or polymerization initiation layer. It is a method of bonding and polymerizing compounds.
The above-mentioned liquid crystal monomer is brought into contact with the polymerization initiation layer formed on the surface of the substrate or the support and irradiated with actinic rays to generate active species on the surface of the substrate (polymerization initiation layer). As a starting point, graft polymerization of the liquid crystal monomer occurs and proceeds, and a liquid crystal polymer formed by directly bonding to the substrate (polymerization initiation layer) is grafted.

In order to bring the liquid crystal monomer into contact with the base material, the liquid crystal monomer may be filled between two substrates for forming a liquid crystal layer, which are produced by a conventional method. Since the liquid crystal monomer is a low molecular weight component, this filling can be easily performed.
Here, when the actinic ray is irradiated, the graft polymerization of the liquid crystal monomer proceeds, but the liquid crystal monomer is graft-polymerized to form a liquid crystal graft polymer layer. Therefore, the liquid crystal graft polymer corresponds to a branch portion of the trunk polymer. Since a plurality of mesogens are bonded to a portion in a direction parallel to the substrate, it is considered that uniform alignment of the partial structure exhibiting liquid crystallinity is achieved. In addition, since the exposure is performed uniformly over the entire surface of the substrate, a liquid crystal graft polymer layer having uniform physical properties over the entire surface of the substrate is formed.

In the liquid crystal graft polymer, in a member containing a liquid crystal material such as a display element, when the liquid crystal layer is directly formed on the surface of the insulating film, the insulating film corresponds to the base material of the present invention. A polymerization initiator may be contained therein, or a polymerization initiator layer may be formed on the surface of the insulating layer.
In the present invention, since the alignment of the liquid crystal compound is achieved by forming the liquid crystal graft polymer layer as described above, the alignment film is not always necessary, but the substrate or the polymerization initiating layer can also serve as the alignment film. . In that case, it has the same function as the alignment film by rubbing the surface of the substrate or the polymerization initiation layer.
In the present invention, since a liquid crystal graft polymer layer having a uniform film thickness and good alignment obtained by directly bonding to an arbitrary substrate surface such as an insulating layer can be used as a liquid crystal layer as it is, it is easy to form and has high alignment. Excellent response and high contrast are realized, and its application range is wide, including application to display elements. In addition, the liquid crystal material of the present invention achieves high adhesion to a base material such as an insulating layer, and is therefore excellent in fields such as optical switching elements and nonlinear optical elements that have been difficult to apply in the past. It can be applied as a liquid crystal material.

Next, an example of a liquid crystal display element using the liquid crystal material of the present invention will be described.
FIG. 1 is a cross-sectional view schematically showing the main part of the liquid crystal display element of the present invention. In FIG. 1, a liquid crystal display element 1 includes a transparent electrode 3 provided on a substrate 2, an insulating layer 4 provided thereon, and an alignment film 5 provided thereon. An electrode 7 is provided, an insulating layer 8 is provided thereon, an alignment film 9 is further provided thereon, the substrate 2 and the substrate 6 face the alignment film 5 and the alignment film 9, and a gap is formed between them. The liquid crystal material 10 of the present invention is enclosed in the gap.
In the liquid crystal display element 1, the alignment films 5 and 9 have a specific tilt angle, the insulating layers 4 and 8 have a specific dielectric constant, and the liquid crystal 10 is the liquid crystal material of the present invention. This is the same as a conventionally known liquid crystal display element.
That is, a glass substrate, a transparent heat-resistant resin substrate or the like can be used as the substrate 2 and the substrate 6, and an ITO film, a SnO ₂ film, an In ₂ O ₃ film or the like is used as the transparent electrodes 3 and 7. can do.

The insulating layer 4 and the insulating layer 8 are not particularly limited as long as they have a dielectric constant of 5 or more, preferably 8 or more. For example, Ta ₂ O ₅ , Al ₂ O ₃ , HfO ₂ , Y ₂ Those having a film thickness of 30 nm to 300 nm formed from O ₃ , Nd ₂ O ₃ , ZrO ₂ , TiO ₂ or the like are preferable. Such an insulating layer can be formed by a conventionally known film formation method, for example, a vacuum evaporation method by resistance heating, a vacuum evaporation method by electron beam (EB) heating, a sputtering method, an ion plating method, or the like. Only one of the insulating layers 4 and 8 may be provided.
The alignment film 5 and the alignment film 9 are not particularly limited, and can be formed by a known method. Specifically, a rubbed polyimide film or the like can be used. The polyimide alignment film is, for example, a polyamic acid obtained from a diamine such as the following (III-1) to (III-3) and a tetracarboxylic dianhydride such as the following (IV-1) to (IV-4): Is formed by preparing a coating solution for forming an alignment film, applying the coating solution to the surface of the insulating layer 4 or the insulating layer 8, drying, heating, and then rubbing. Can do. In the present invention, the base material or the polymerization initiating layer can also serve as an alignment film, and can be used as an alignment film by performing a rubbing treatment. In addition, since the liquid crystal material of the present invention exhibits excellent alignment, such an alignment film is not always necessary. If the insulating layer 4 or 8 has a polymerization initiating ability, the liquid crystal 10 is directly applied to the surface. Can also be applied.

The thickness of the gap (cell gap) enclosing the liquid crystal of the liquid crystal display element 1 is generally 1 to 6 μm, preferably 1 to 2 μm. Even in such a thin cell gap liquid crystal display element, the present invention is applied. The liquid crystal display element using the liquid crystal material exhibits excellent high-speed response.
Although it is the filling point of the liquid crystal compound having a polymerizable group into the cell, a smectic phase is preferable from the viewpoint of high-speed response, but this phase is viscous, so it can be performed in an isotropic phase or a nematic phase. preferable. Therefore, in order to use a liquid crystal material having a smectic phase, the material is heated to a nematic phase or an isotropic phase, and this is slowly cooled to a molecularly aligned smectic state.
When such a technique is applied to a liquid crystal polymer, the cooling time is usually extremely long due to the promotion of the molecular alignment, and the molecular alignment is often insufficient. In the present invention, this problem is filled in a cell as a liquid crystal monomer, and then a graft polymerization is carried out to form a liquid crystal polymer. Therefore, the problem of orientation deterioration due to the cooling time is also solved.

  In the said aspect, although the general purpose polyimide was used as a base material (insulating layer), it is also possible to use a specific polyimide containing a polymerization initiation site in the molecule, which the applicant of the present application previously proposed as Japanese Patent Application No. 2004-87980. it can. According to the polyimide base material having such a polymerization initiating ability, it is possible to efficiently form the liquid crystal layer according to the present invention directly on the surface thereof without adding a heavy initiator or forming a polymerization initiating layer. ,preferable.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
[Example 1]
(Preparation of liquid crystal composition)
A liquid crystal composition comprising 32% by weight of compound (I-3), 32% by weight of compound (I-4), 20% by weight of compound (I-5) and 16% by weight of compound (I-11) was prepared. This liquid crystal composition was sandwiched between two glass plates, and the phase structure pattern was observed with a deflection microscope. As a result, the phase transition temperature was confirmed as follows.
Sc ^* phase → S _A phase transition temperature: 65.6 ℃
S _A phase → N ^* phase Phase transition temperature: 83.3 ° C
N ^* phase → Iso phase Phase transition temperature: 92.6 ° C

(Production of display element)
An ITO transparent electrode (film thickness: 150 nm) is formed on a glass substrate (thickness: 1.1 mm), and an insulating layer (film thickness: 100 nm) made of Ta ₂ O ₅ is formed on the transparent electrode by electron beam vacuum deposition. Formed by the method. The dielectric constant of this insulating layer was 22.
On this insulating layer, a 10 wt% N-methylpyrrolidone solution of polyamic acid obtained by dehydration condensation from equimolar amounts of the diamine (III-1) and tetracarboxylic dianhydride (IV-1) 20 Parts by weight, 0.2 parts by weight of a polymerization initiator represented by the following structural formula (A), diluent for coating solution (20% by weight of N-methylpyrrolidone, 40% by weight of ethylene glycol monobutyl ether and 40% of diethylene glycol monoethyl ether 40) A coating solution for alignment film obtained by mixing 80 parts by weight of a mixture (weight% mixture) was applied using a spinner, and the coating film was dried to form a polyimide film. The surface of the polyimide film was rubbed with nylon brushed cloth.

The two substrates thus obtained, which have a transparent electrode, an insulating layer and an alignment film, face each other inward so that the rubbing surface of the alignment film is parallel to the rubbing direction, and a 2 μm spacer is mixed. The liquid crystal display element cell having a cell gap of 1.9 μm was prepared by using the adhesive.
Into this cell, the liquid crystal composition prepared above was injected, slowly cooled, and aligned. This was irradiated with light for 5 minutes using a 1.5 kW high pressure mercury lamp, graft polymerization was performed to form the liquid crystal material of the present invention between cells, and the liquid crystal display element of Example 1 containing this liquid crystal material was obtained. .

(Evaluation of liquid crystal display elements)
1. Response time When the obtained display element is sandwiched between two orthogonal deflection plates and a square wave of ± 10 V, 50 Hz is applied, the time required for the transmitted light intensity to change from 0% to 90% (response Time τ) was measured. As a result, τ at 35 ° C. was 79 μsec.
2. Contrast ratio When the obtained display element is held at 45 ° C., an electric field having a waveform (Vs = ± 42 V, τs = 5 to 30 μsec) shown in FIG. 2 is applied, and a switching state is observed using a deflection microscope A clear switching operation with a high contrast ratio was observed in the range of τs = 9 to 13 μsec. The resulting contrast ratio was 200: 1.

[Example 2]
(Synthesis of specific polymerization initiation polymer)
30 g of propylene glycol monomethyl ether (MFG) was added to a 300 ml three-necked flask and heated to 75 degrees. 5.7 g of the following polymerization initiator (B), 9.9 g of 2-hydroxyethyl methacrylate, 13.5 g of isopropyl methacrylate, 0.43 g of dimethyl-2,2′-azobis (2-methylpropionate), and propylene glycol A solution of 30 g of monomethyl ether (MFG) was added dropwise over 2.5 hours.

  Thereafter, the reaction temperature was raised to 80 ° C., and the reaction was further continued for 2 hours to obtain the following specific polymerization initiating polymer A.

特定重合開始ポリマーＡ

Specific polymerization initiating polymer A

(Formation of polymerization initiation layer)
Instead of the alignment film in Example 1, the following polymerization initiation layer coating solution was applied using a spinner, and dried and crosslinked at 110 ° C. for 10 minutes. The surface was rubbed with a nylon brushed cloth.

(Polymerization initiation layer coating solution)
・ 0.4 g of the above specific polymerization initiating polymer A
・ TDI (Tolylene-2,4-diisocyanate) 0.16g
・ Propylene glycol monomethyl ether (MFG) 1.6g

The production of the liquid crystal display element cell and the liquid crystal display element, the graft polymerization method, the response time and the contrast were evaluated in the same manner as in Example 1.
As a result, τ at 35 ° C. was 75 μsec. The contrast ratio was 200: 1.

[Comparative Example 1]
A liquid crystal composition having the following composition was prepared. The phase transition temperature was as follows.
Sc ^* phase → S _A phase transition temperature: 56.9 ℃
S _A phase → Iso phase transition temperature: 87.8 ℃

Using this liquid crystal composition, a display device of Comparative Example 1 was obtained in the same manner as in Example 1 except that graft polymerization was not performed, and the same evaluation as in Example 1 was performed.
As a result, τ at 35 ° C. was 2 msec. The contrast ratio was 30: 1.

[Comparative Example 2]
A display device of Comparative Example 2 was obtained in the same manner as in Comparative Example 1 except that the following liquid crystal polymer (C) was used instead of the liquid crystal composition in Comparative Example 1, and evaluation was performed in the same manner as in Example 1. It was.
As a result, τ at 35 ° C. was 10 msec. The contrast ratio was 15: 1.

  From the above results, the display element of the present invention was obtained by forming Example 1 in which a polyimide layer having a polymerization initiator as a base material was formed on the insulating layer surface, and forming a polymerization initiating layer having a crosslinked structure on the insulating layer surface. All of Examples 2 were found to be excellent in responsiveness and contrast. On the other hand, Comparative Example 1 having a liquid crystal layer formed without graft polymerization with a low molecular weight liquid crystal compound even when a liquid crystal composition having a mesogenic structure similar to or similar to that in the liquid crystal composition used in the examples was used. The display device of Comparative Example 2 having a liquid crystal layer formed using a polymer liquid crystal compound having a mesogen in the side chain was significantly inferior to each of the examples in terms of both responsiveness and contrast.

It is sectional drawing which shows typically the principal part in the one aspect | mode of the display element of this invention. It is a graph which shows the waveform (Vs = ± 42V, (tau) = 5-30microsec) of the electric field applied in order to evaluate the contrast ratio of the liquid crystal display element of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Liquid crystal display element 2, 6 Substrate 3, 7 Transparent electrode 4, 8 Insulating layer 5, 9 Alignment film 10 Liquid crystal material

Claims (7)

  A liquid crystal material comprising a liquid crystal layer formed by directly bonding a liquid crystal compound having a polymerizable group to a base material on the base material.   The liquid crystal material according to claim 1, wherein the substrate is a substrate containing a polymerization initiator.   The substrate containing the polymerization initiator is a substrate having a polymerization initiating layer formed by immobilizing a polymer having a functional group having a polymerization initiating ability and a crosslinkable group in a side chain by a crosslinking reaction. The liquid crystal material according to claim 2.   A method for producing a liquid crystal material, comprising: bringing a liquid crystal compound having a polymerizable group into contact with a substrate and applying energy to bond the liquid compound directly to the substrate surface by graft polymerization.   The method for producing a liquid crystal material according to claim 4, wherein the substrate contains a polymerization initiator.   The substrate containing the polymerization initiator is a substrate having a polymerization initiating layer formed by immobilizing a polymer having a functional group having a polymerization initiating ability and a crosslinkable group in a side chain by a crosslinking reaction. The manufacturing method of the liquid-crystal material of Claim 5.   A display element comprising the liquid crystal material according to claim 1.

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