JP2006265527A - Heat-releasing member and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-releasing member having low water permeability, water absorbability and gas permeability as well as having high thermal conductivity, and having excellent properties including chemical stability, heat resistance, hardness and mechanical strength. <P>SOLUTION: The heat-releasing member consists of a liquid crystalline polymer that is obtained by polymerizing a liquid crystal composition containing a polymerizable group-terminated polymerizable liquid crystal compound through aligning control of the mesogenic site of the liquid crystal compound by aligned film, alignment-controlling additive, rubbing treatment or the autologous alignment-controlling potential of the composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a heat dissipating member made of a polymer obtained by polymerizing a liquid crystal composition by controlling the alignment with an alignment control additive, a rubbing treatment method, or the like, and a method for producing the same.

  In recent years, electronic information devices such as personal computers, mobile phones, and PDAs (Personal Data Assistants) have become highly functional. In order to achieve this higher functionality, improvements such as higher integration and higher speed of LSI and higher capacity of battery are indispensable. However, with such improvements, the amount of heat generated from electronic material components increases, and problems such as malfunction due to heat accumulation have occurred. Therefore, in order to achieve higher functionality of electronic information equipment, it is necessary to solve the heat dissipation problem immediately.

  As a method for solving such a heat dissipation problem, there is a method of dissipating heat by providing a highly heat conductive material (heat dissipating member) at a heat generating portion. Examples of materials having high thermal conductivity include inorganic materials such as metals and metal oxides. However, such an inorganic material has a problem in insulation, workability, and the like, and there is a limitation in providing it especially around the electronic material component. Therefore, development of a heat radiating member made of a resin having high thermal conductivity has been performed.

  Generally, high thermal conductivity of a resin has been performed by adding a large amount of a metal filler or an inorganic filler to a general-purpose resin such as a polyethylene resin, a polyamide resin, a polystyrene resin, an acrylic resin, or an epoxy resin. However, in such a method, the filling operation of the filler is complicated, and it is difficult to satisfy recently required characteristics such as processability, improvement in mechanical strength and weight reduction of the obtained resin material.

Among these, as a resin material exhibiting excellent thermal conductivity, a liquid crystalline resin (for example, see Patent Documents 1 and 2) in which a liquid crystal phase is expressed by polymerizing a resin composition containing a monomer having a mesogenic group, Liquid crystalline resins aligned by a magnetic field (see, for example, Patent Documents 3 to 6) have been proposed. However, a heat radiating member that can cope with higher requirements is desired.
JP-A-11-323162 JP 2003-268070 A JP 2004-149722 A JP 2004-149723 A JP 2004-175926 A JP 2004-256687 A

  An object of the present invention is to provide a heat dissipating member having excellent properties such as chemical stability, heat resistance, hardness and mechanical strength, in addition to high thermal conductivity, low water permeability, water absorption and gas permeability. It is in.

The inventors of the present invention have made it possible to use a heat dissipation element made of a polymer with a fixed molecular arrangement obtained by orienting mesogenic sites of a polymerizable compound having liquid crystallinity in a certain direction and polymerizing the element of heat conduction. It was found that the transmission loss of phonon, which is one of them, is suppressed, and that high thermal conductivity of the resin can be expected. As an aspect of the heat radiating member which concerns on this invention, and its manufacturing method, it is as having described below.

  [1] A liquid crystal composition containing a polymerizable liquid crystal compound having a polymerizable group at the end is aligned with a mesogenic portion of the liquid crystal compound by an alignment film, an alignment control additive, a rubbing treatment, or a self-alignment regulating force of the composition. A heat radiating member comprising a liquid crystal polymer obtained by controlling and polymerizing.

[2] The heat dissipation member according to [1], wherein the polymerizable liquid crystal compound is at least one compound represented by the following formula (1-1).
R ^a1 -Z- (AZ) _m1 -R ^a1 (1-1)
In the formula (1-1), R ^a1 is independently a polymerizable group represented by the following formulas (2-1) to (2-6), hydrogen, halogen, cyano, —CF ₃ , —CF ₂ H, _{-CFH 2, -OCF 3, -OCF 2} H,
—N═C═O, —N═C═S, or alkyl having 1 to 20 carbons, in which arbitrary —CH ₂ — represents —O—, —S—, —SO ₂ —, — CO—, —COO—, —OCO—, —CH═CH—, —CF═CF— or —C≡C— may be replaced, and any hydrogen may be replaced with halogen or cyano, At least one of R ^a1 is a polymerizable group represented by formulas (2-1) to (2-6);
A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] Octo-1,4-diyl, bicyclo [3.1.0] hex-3,6-diyl or divalent compounds represented by the following formulas (3-1) to (3-10) In these rings, any —CH ₂ — may be replaced by —O—, any —CH═ may be replaced by —N═, and any hydrogen may be halogen, The alkyl may be substituted with an alkyl having 1 to 10 carbon atoms or an alkyl halide having 1 to 10 carbon atoms, and in the alkyl, any —CH ₂ — may be —O—, —CO—, —COO—, —OCO. -, -C
May be replaced by H═CH— or —C≡C—;
Z is independently a single bond or alkylene having 1 to 20 carbon atoms, and in the alkylene, arbitrary —CH ₂ — is —O—, —S—, —CO—, —COO—, —OCO—, -CH = C
H—, —CF═CF—, —CH═N—, —N═CH—, —N═N—, —N (O) ═N— or —C≡C— Hydrogen may be replaced by halogen;
m1 is an integer of 1-6.

In formulas (2-1) to (2-6), R ^b is hydrogen, halogen, —CF _3, or alkyl having 1 to 5 carbons, and q is 0 or 1.

[3] In the formula (1-1), at least one of R ^a1 is a polymerizable group represented by the formula (2-1), (2-5) or (2-6). The heat dissipating member according to [2].

[4] In the formula (1-1), at least one of R ^a1 is a polymerizable group represented by the formula (2-1), (2-5) or (2-6); 1,4-cyclohexylene, 1,4-cyclohexylene in which arbitrary hydrogen is replaced with halogen, 1,4-phenylene, 1,4-phenylene in which arbitrary hydrogen is replaced with halogen or methyl, fluorene-2 , 7-diyl or fluorene-2,7-diyl in which arbitrary hydrogen is replaced by halogen or methyl, The heat radiating member according to [2].

[5] In the formula (1-1), at least one of R ^a1 is a polymerizable group represented by the formula (2-1), (2-5) or (2-6); 1,4-cyclohexylene, 1,4-cyclohexylene in which arbitrary hydrogen is replaced with halogen, 1,4-phenylene, 1,4-phenylene in which arbitrary hydrogen is replaced with halogen or methyl, fluorene-2 , 7-diyl or fluorene-2,7-diyl in which any hydrogen is replaced by halogen or methyl; Z is a single bond, — (CH ₂ ) _a —, —O (CH ₂ ) _a —, — (CH ₂ ) _a O—, —O (CH ₂ ) _a O—, —CH═CH—, —C≡C—, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH _{= CH -, - CH 2 CH} 2 -COO -, - OCO-CH 2 CH 2 -, -CH = N -, - N = CH -, - N = N -, - OCF 2 - or -C
F ₂ is O-, the heat radiation member according to [2], wherein the said a is an integer from 1 to 20.

[6] In the formula (1-1), at least one of R ^a1 is a polymerizable group represented by the formula (2-2), (2-3) or (2-4). The heat dissipating member according to [2].

[7] In the formula (1-1), at least one of R ^a1 is a polymerizable group represented by the formula (2-2), (2-3) or (2-4); 1,4-cyclohexylene, 1,4-cyclohexylene in which arbitrary hydrogen is replaced with halogen, 1,4-phenylene, 1,4-phenylene in which arbitrary hydrogen is replaced with halogen or methyl, fluorene-2 , 7-diyl or fluorene-2,7-diyl in which arbitrary hydrogen is replaced by halogen or methyl, The heat radiating member according to [2].

[8] In the formula (1-1), at least one of R ^a1 is a polymerizable group represented by the formula (2-2), (2-3) or (2-4); 1,4-cyclohexylene, 1,4-cyclohexylene in which arbitrary hydrogen is replaced with halogen, 1,4-phenylene, 1,4-phenylene in which arbitrary hydrogen is replaced with halogen or methyl, fluorene-2 , 7-diyl or fluorene-2,7-diyl in which any hydrogen is replaced by halogen or methyl; Z is a single bond, — (CH ₂ ) _a —, —O (CH ₂ ) _a —, — (CH ₂ ) _a O—, —O (CH ₂ ) _a O—, —CH═CH—, —C≡C—, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH _{= CH -, - CH 2 CH} 2 -COO -, - OCO-CH 2 CH 2 -, -CH = N -, - N = CH -, - N = N -, - OCF 2 - or -C
F ₂ is O-, the heat radiation member according to [2], wherein the said a is an integer from 1 to 20.

[9] In the formula (1-1), at least one of R ^a1 is a polymerizable group represented by the formula (2-1), (2-5), or (2-6); 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene, fluorene-2,7-diyl or any hydrogen replaced with halogen or methyl, or halogen or methyl replaced with any hydrogen Fluorene-2,7-diyl; Z is a single bond, —COO—, —OCO—, — (CH ₂ ) _a —, —CH═CH—COO—, —OCO—CH═CH—, —CH _{2 CH 2 -COO -, - OCO} -CH 2 CH 2 -, - O (CH 2) a -, - (CH 2) a O- or -O (CH _{2) a} a O-, said a is 1 It is an integer of -20, The heat radiating member as described in [2] characterized by the above-mentioned.

[10] In the formula (1-1), at least one of R ^a1 is a polymerizable group represented by the formula (2-1), (2-5), or (2-6); 1,4-phenylene, 1,4-phenylene, fluorene-2,7-diyl in which any hydrogen is replaced with Cl, F or methyl, or fluorene-2,7 in which any hydrogen is replaced with F or methyl - it is diyl; Z is, -COO -, - OCO -, - (CH 2) a -, - O (CH 2) a -, - (CH 2) a O- or -O (CH _{2) a} O -, And a is an integer of 1 to 20, the heat dissipating member according to [2].

[11] In the formula (1-1), at least one of R ^a1 is a polymerizable group represented by the formula (2-2), (2-3) or (2-4); 1,4-cyclohexylene, 1,4-cyclohexylene in which arbitrary hydrogen is replaced with halogen, 1,4-phenylene, 1,4-phenylene in which arbitrary hydrogen is replaced with halogen or methyl, fluorene-2 , 7-diyl or fluorene-2,7-diyl in which any hydrogen is replaced by halogen or methyl; Z is a single bond, —COO—, —OCO—, — (CH ₂ ) _a —, —O _{(CH 2) a -, -} (CH 2) a O- or -O (CH _{2) a} is O-, heat dissipation according to, characterized in that said a is an integer from 1 to 20 [2] Element.

[12] In the formula (1-1), at least one of R ^a1 is a polymerizable group represented by the formula (2-2), (2-3) or (2-4); 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene, fluorene-2,7-diyl or any hydrogen replaced with halogen or methyl, or halogen or methyl replaced with any hydrogen Fluorene-2,7-diyl; Z is —COO—, —OCO—, — (CH ₂ ) _a —, —O (CH ₂ ) _a —, — (CH ₂ ) _a O— or —O ( CH _{2) a} is O-, the heat radiation member according to [2], wherein the said a is an integer from 1 to 20.

[13] In the formula (1-1), at least one of R ^a1 is a polymerizable group represented by the formula (2-2), (2-3) or (2-4); 1,4-phenylene, 1,4-phenylene, fluorene-2,7-diyl in which any hydrogen is replaced with Cl, F or methyl, or fluorene-2,7 in which any hydrogen is replaced with F or methyl - it is diyl; Z is, -COO -, - OCO -, - (CH 2) a -, - O (CH 2) a -, - (CH 2) a O- or -O (CH _{2) a} O -, And a is an integer of 1 to 20, the heat dissipating member according to [2].

  [14] The heat dissipation member according to [1], wherein the polymerizable liquid crystal compound is at least one compound represented by the following formula (1-2).

In formula (1-2), R ^a2 is independently hydrogen, halogen, cyano, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, —N═C═O, — N = C = S or alkyl having 1 to 20 carbon atoms, in which arbitrary —CH ₂ — represents —O—, —S—, —SO ₂ —, —CO—, —COO—, —OCO. —, —CH═CH—, —CF═CF— or —C≡C— may be substituted, and any hydrogen may be substituted with halogen or cyano; R ^a3 is as described in [2] A polymerizable group represented by any one of formulas (2-1) to (2-5);
A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl. , Bicyclo [2.2.2] oct-1,4-diyl, bicyclo [3.1.0] hex-3,6-diyl or formulas (3-1) to (3-10) described in [2] In these rings, any —CH ₂ — may be replaced by —O—, and any —CH═ may be replaced by —N═, Arbitrary hydrogen may be replaced by halogen, alkyl having 1 to 10 carbons or halogenated alkyl having 1 to 10 carbons, and in the alkyl, any —CH ₂ — may be —O—, —CO—, -COO-,-
May be replaced by OCO-, -CH = CH- or -C≡C-;
Z is independently a single bond or alkylene having 1 to 20 carbon atoms,
In the alkylene, arbitrary —CH ₂ — represents —O—, —S—, —CO—, —COO—, —
OCO-, -CH = CH-, -CF = CF-, -CH = N-, -N = CH-, -N = N-, -N (O) = N- or -C≡C- Any hydrogen may be replaced by halogen;
Y is a single bond or alkylene having 1 to 20 carbon atoms, and in the alkylene,
CH ₂ — may be replaced with —O—, —S—, —CO—, —COO—, —OCO— or —CH═CH—, and any hydrogen may be replaced with halogen;
m2 and n2 are each an integer of 0 to 5.

[15] In the formula (1-2), R ^a3 is a polymerizable group represented by the formula (2-1), (2-5) or (2-6) described in [2] [14 ] The compound of description.
[16] The compound according to [14], wherein in formula (1-2), m2 + n2 is an integer of 1 to 3.

[17] The compound according to [14], wherein m2 + n2 is 2 in the formula (1-2).
[18] In the formula (1-2), R ^a2 is independently alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and these arbitrary hydrogens are R ^a3 is a polymerizable group represented by the formula (2-1), (2-5) or (2-6) described in [2]; A is independently 1,4-cyclohexylene, 1,4-phenylene, pyridine-2,5-diyl, pyridazine-3,6-diyl or pyrimidine-2,5-diyl, and these optional hydrogens include chlorine, fluorine May be replaced by alkyl having 1 to 3 carbons or fluoroalkyl having 1 to 3 carbons; Z is independently a single bond, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—. , -CH = CH-,-(CH ₂
) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═CH—COO—, —OCO—CH═CH
- or -C≡C-; Y is a single bond or alkylene having 1 to 10 carbon atoms, any -CH ₂ - in the alkylene - is -O -, - COO- or -OCO- in replaced The compound according to [14].

[19] In the formula (1-2), R ^a2 is independently alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons; R ^a3 is represented by the formula (2- 1) a polymerizable group represented by (2-5) or (2-6); A is independently 1,4-cyclohexylene or 1,4-phenylene; Z is independently Bond, —COO—, —OCO—, —CH═CH—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═CH—COO—, —OCO—CH═CH— or a -C≡C-; Y is a single bond or alkylene having 1 to 10 carbon atoms, -CH ₂ adjacent to the ring in the alkylene - is -O -, - COO- or -
The compound according to [14], which may be replaced by OCO-.

[20] The heat radiating member according to any one of [1] to [19], wherein the liquid crystal composition contains a non-polymerizable liquid crystal compound.
[21] The heat dissipation member according to any one of [1] to [20], wherein the liquid crystal composition is optically active.

  [22] The liquid crystal composition contains a polymerizable optically active compound other than the liquid crystal compound represented by the formula (1-1) described in [2] or the formula (1-2) described in [14]. The heat dissipating member according to any one of [1] to [21].

  [23] The liquid crystal composition contains a non-polymerizable optically active compound other than the liquid crystal compound represented by the formula (1-1) described in [2] or the formula (1-2) described in [14]. The heat radiating member according to any one of [1] to [22].

[24] The heat radiating member according to any one of [1] to [23], wherein the liquid crystal composition contains an inorganic filler.
[25] The heat dissipation member according to any one of [1] to [23], wherein the liquid crystal composition contains a metal filler.

  [26] The liquid crystal polymer according to [1] to [25], wherein the liquid crystal polymer is obtained by polymerizing the liquid crystal composition by homogeneous, twist, homeotropic, hybrid, bend or spray alignment. The heat radiating member in any one.

  [27] The liquid crystal polymer is obtained by polymerizing the liquid crystal composition by homogenous, twist, homeotropic, hybrid or spray alignment with an alignment control additive. 25] The heat radiating member in any one of.

  [28] Any one of [1] to [25], wherein the liquid crystal polymer is obtained by polymerizing the liquid crystal composition by subjecting the liquid crystal composition to homogeneous, twist, hybrid or spray alignment by rubbing treatment. The heat radiating member of description.

[29] The heat radiating member according to any one of [1] to [28], which is a polymer molded body.
[30] The heat dissipation member according to any one of [1] to [28], which is a sheet.

[31] The heat dissipation member according to any one of [1] to [28], which is a film.
[32] The heat dissipation member according to any one of [1] to [28], which is a thin film.

[33] The heat radiation member according to any one of [1] to [32], wherein the thermal conductivity is 0.3 W / (K · m) or more.
[34] A liquid crystal composition containing a polymerizable liquid crystal compound having a polymerizable group at the terminal is aligned on a mesogen site of the liquid crystal compound by an alignment film, an alignment control additive, a rubbing treatment, or a self-alignment regulating force of the composition. A method for producing a heat radiating member, wherein polymerization is performed under control.

  In addition to high thermal conductivity, the heat dissipation member of the present invention has low water permeability, water absorption and gas permeability, and has excellent characteristics such as chemical stability, heat resistance, hardness and mechanical strength. Suitable for heat sinks, heat dissipation sheets, heat dissipation coatings, heat dissipation adhesives, etc.

Hereinafter, the heat radiating member and the manufacturing method thereof of the present invention will be described in detail. The terminology used in this specification is as follows.
“Liquid crystal compound” is a generic term for a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and a compound having no liquid crystal phase but useful as a component of a liquid crystal composition. Further, “(meth) acryloyloxy” means acryloyloxy or methacryloyloxy, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylic acid” means acrylic acid or methacrylic acid. means.

The meaning of a phrase such as “any —CH ₂ — in alkyl may be replaced by —O—, —CH═CH—, etc.” is shown by way of example. For example, the group in which any —CH ₂ — in C ₄ H ₉ — is replaced by —O— or —CH═CH— includes C ₃ H ₇ O—, CH ₃ —O—.
(CH ₂ ) ₂ —, CH ₃ —O—CH ₂ —O—, H ₂ C═CH— (CH ₂ ) ₃ —, CH ₃ —CH═CH— (CH ₂ ) ₂ —, CH ₃ —CH═ CH—CH ₂ —O— and the like. Thus, the term “arbitrary” means “at least one selected without distinction”. In consideration of the stability of the compound, CH ₃ —O—CH ₂ —O— in which oxygen and oxygen are not adjacent to each other than CH ₃ —O—O—CH ₂ — in which oxygen and oxygen are adjacent to each other. Is preferred.

“Compound (1-1)” means a liquid crystal compound represented by the above formula (1-1), and may mean at least one compound represented by the above formula (1-1). The same applies to “compound (1-2)”, and compound (1-1) and compound (1-2) are collectively referred to as “compound (1)”. “Composition (1)” means a liquid crystal composition containing at least one compound selected from the compound (1). “Polymer (1)” means a liquid crystal polymer obtained by polymerizing the composition (1). When one compound (1) has a plurality of A, any two A may be the same or different. When two or more compounds (1) have A, arbitrary two A may be same or different. This rule also applies to other symbols and groups such as R ^a1 and Z.

[Liquid crystal compound]
The compound (1) used in the present invention has a liquid crystal skeleton and a polymerizable group, and has high polymerization reactivity, a wide liquid crystal phase temperature range, good miscibility, and the like. When this compound (1) is mixed with other liquid crystal compounds or polymerizable compounds, it tends to be uniform easily.

By appropriately selecting the terminal group R ^a1 or R ^a2 (hereinafter collectively referred to as “terminal group R ^a ”), the ring structure A, and the bonding group Z of the compound (1), Physical properties can be adjusted arbitrarily. The effects of the terminal group R ^a , the ring structure A and the bonding group Z on the physical properties of the compound (1) and preferred examples thereof will be described below.

<Terminal group R ^a >
When R ^a of the compound (1) is ^a linear alkyl, the temperature range of the liquid crystal phase is wide and the viscosity is small. On the other hand, when R ^a is branched alkyl, compatibility with other liquid crystal compounds is good. Even in the case where R ^a is cyano, halogen, —CF ₃ , or —OCF ₃ , the liquid crystal phase temperature range is good, the dielectric anisotropy is high, and the compatibility is appropriate.

Preferred R ^a is hydrogen, fluorine, chlorine, cyano, —N═C═O, —N═C═S,
Examples include alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkylthio, alkylthioalkoxy, alkenyl, alkenyloxy, alkenyloxyalkyl, alkoxyalkenyl, alkynyl, alkynyloxy and the like. Among these groups, a group in which at least one hydrogen is replaced with a halogen is also preferable. Preferred halogens are fluorine and chlorine, more preferably fluorine. Specific examples include monofluoroalkyl, polyfluoroalkyl, perfluoroalkyl, monofluoroalkoxy, polyfluoroalkoxy, perfluoroalkoxy and the like. These groups are preferably linear rather than branched, but branched ^Ra is preferred for obtaining the optically active compound (1).

More preferable R ^a is hydrogen, fluorine, chlorine, cyano, —CF ₃ , —CF ₂ H, —
_{CFH 2, -OCF 3, -OCF 2} H, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, and alkoxyalkyl having 2 to 10 carbon atoms. Examples of the alkyl, alkoxy and alkoxyalkyl include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, Examples include octyloxy, nonyloxy, decyloxy, methoxymethyl, methoxyethyl and the like. Particularly preferred R ^a is alkyl having 1 to 10 carbons and alkoxy having 1 to 10 carbons.

<Ring structure A>
When at least one ring in the ring structure A of the compound (1) is 1,4-phenylene, the orientational order parameter and the magnetic anisotropy are large. When at least two rings are 1,4-phenylene, the temperature range of the liquid crystal phase is wide and the clearing point is high. When at least one hydrogen on the 1,4-phenylene ring is substituted with cyano, halogen, —CF ₃ or —OCF ₃ , the dielectric anisotropy is high. When at least two rings are 1,4-cyclohexylene, the clearing point is high and the viscosity is low. When compound (1) has groups (3-1) to (3-10) as ring structure A, the twist-inducing force is large.

  As preferred A, 1,4-cyclohexylene, 1,4-cyclohexenylene, 2,2-difluoro-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4 -Phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2 , 3,5-trifluoro-1,4-phenylene, pyridine-2,5-diyl, 3-fluoropyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, naphthalene -2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methylfluorene-2,7-diyl, 9,9-dimethylfluorene-2,7- , 9-ethylfluorene-2,7-diyl, 9-fluorofluorene-2,7-diyl, 9,9-difluorofluorene-2,7-diyl, formulas (3-1), (3-2), And divalent groups represented by (3-6), (3-8) or (3-10).

  The configuration of 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl is preferably trans rather than cis. Since 2-fluoro-1,4-phenylene and 3-fluoro-1,4-phenylene are structurally identical, the latter is not illustrated. This rule also applies to the relationship between 2,5-difluoro-1,4-phenylene and 3,6-difluoro-1,4-phenylene.

  More preferable A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene and the like. Particularly preferred A is 1,4-cyclohexylene and 1,4-phenylene.

<Binding group Z>
The linking group Z of the compound (1) is a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, When —CF═CF— or — (CH ₂ ) ₄ —, in particular, a single bond, — (CH ₂ ) ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH— or — (CH _{2) 4} -, the viscosity is reduced. Further, when the bonding group Z is —CH═CH—, —CH═N—, —N═CH—, —N═N— or —CF═CF—, the temperature range of the liquid crystal phase is wide. Further, when the bonding group Z is alkyl having about 4 to 10 carbon atoms, the melting point is lowered.

Preferred Z is a single bond, — (CH ₂ ) ₂ —, — (CF ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, — OCF ₂ —, —CH═CH—, —CF═CF—, —C≡C—, — (CH ₂ ) ₄ —, — (CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ —, — ( CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═CH—COO—, —OCO—CH═CH— and the like.

More preferable Z is a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═. CH—, —C≡C— and the like can be mentioned. Particularly preferred Z is a single bond, — (CH ₂ ) ₂ —, —COO— or —OCO—.

  When the compound (1) has 3 or less rings, the viscosity is low, and when it has 3 or more rings, the clearing point is high. In the present specification, basically, a 6-membered ring and a condensed ring including a 6-membered ring are regarded as a ring, and for example, a 3-membered ring, a 4-membered ring or a 5-membered ring alone is not regarded as a ring. A condensed ring such as a naphthalene ring or a fluorene ring is regarded as one ring.

The compound (1) may be optically active or optically inactive. When the compound (1) is optically active, the compound (1) may have an asymmetric carbon or an axial asymmetry. The configuration of the asymmetric carbon may be R or S. The asymmetric carbon may be located at either R ^a or A. When the asymmetric carbon is present, the compatibility of the compound (1) is good. When the compound (1) has axial asymmetry, the twist-inducing force is large. In addition, the light application property may be any.
As described above, a compound having desired physical properties can be obtained by appropriately selecting the terminal group R ^a , the type of the ring structure A and the bonding group Z, and the number of rings.

<Compound (1-1)>
Compound (1-1) can also be represented by the following formula (1-a) or (1-b). PY- (AZ) _m -R ^a (1-a)
PY- (AZ) _m -YP (1-b)

In the above formulas (1-a) and (1-b), A, Z and R ^a are A defined in the above formula (1-1).
, Z, and R ^a1 , P represents a polymerizable group represented by the above formulas (2-1) to (2-6), Y represents a single bond or alkylene having 1 to 20 carbon atoms, preferably represents alkylene having 1 to 10 carbon atoms, in the alkylene, arbitrary -CH ₂ -, -O -, - S -, - CO -, -
It may be replaced by COO-, -OCO- or -CH = CH-. Particularly preferred Y is alkylene in which —CH ₂ — at one or both ends of alkylene having 1 to 10 carbon atoms is replaced by —O—. m is an integer of 1-6, preferably an integer of 2-6, more preferably an integer of 2-4.

  Examples of preferred compound (1-1) include compounds (a-1) to (g-20) shown below.

In the above chemical formula, R ^a , P and Y are as defined in the above formulas (1-a) and (1-b).
Z ¹ is a single bond, — (CH ₂ ) ₂ —, — (CF ₂ ) ₂ —, — (CH ₂ ) ₄ —, —CH ₂ O—, —OCH ₂ —, — (CH ₂ ) ₃ O— _{, -O (CH 2) 3 -} , - COO -, - OCO -, - CH =
CH—, —CF═CF—, —CH═CHCOO—, —OCOCH═CH—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —C≡C—, —C≡C— COO—, —OCO—C≡C—, —C≡C—CH═CH—, —CH═CH—C≡C—, —CH═N—, —N═CH—, —N═N—, — OCF ₂ — or —CF ₂ O—. The plurality of Z ¹ may be the same or different.

Z ² represents — (CH ₂ ) ₂ —, — (CF ₂ ) ₂ —, — (CH ₂ ) ₄ —, —CH ₂ O—, —OCH _{2.
-, - (CH 2) 3} O -, - O (CH 2) 3 -, - COO -, - OCO -, - CH = CH -, - CF = CF -, - CH = CHCOO -, - OCOCH = CH _{-, - (CH 2) 2} COO -, - OCO (CH 2) 2 -, - C≡C -, - C≡C-COO -, - OCO-C≡C -, - C≡C-CH = CH —, —CH═CH—C≡C—, —CH═N—, —N═CH—, —N═N—, —OCF ₂ — or —CF ₂ O—.

Z ³ is a single bond, alkyl having 1 to 10 carbon atoms, — (CH ₂ ) _a —, —O (CH ₂ ) _a O—,
—CH ₂ O—, —OCH ₂ —, —O (CH ₂ ) ₃ —, — (CH ₂ ) ₃ O—, —COO—, —OCO—, —CH═CH—, —CH═CHCOO—, — OCOCH═CH—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CF═CF—, —C≡C—, —CH═N—, —N═CH—, —N═ N—, —OCF ₂ — or —CF ₂ O—, and a plurality of Z ³ may be the same or different.

  X is a substituent of 1,4-phenylene and fluorene-2,7-diyl in which arbitrary hydrogen may be replaced by halogen, alkyl or fluorinated alkyl, and represents halogen, alkyl or fluorinated alkyl.

The more preferable aspect of the said compound (1-1) is demonstrated. More preferable compound (1-1) can be represented by the following formula (1-c) or (1-d).
P ¹ —Y— (AZ) _m —R ^a (1-c)
P ¹ -Y- (AZ) _m -YP ¹ (1-d)
In the above formula, A, Y, Z, ^Ra and m are as defined above, and P ¹ represents a polymerizable group represented by the following formulas (4-1) to (4-14). In the case of the above formula (1-d), two P ¹
Represents the same polymerizable groups (4-1) to (4-14), two Ys represent the same group, and two Ys are bonded so as to be symmetrical.

  More preferred specific examples of the compound (1-1) are shown below.

<Compound (1-2)>
Next, an example of the compound (1-2) is shown below. Examples of preferred compound (1-2) include compounds (h-1) to (h-5) shown below.

In the above chemical formula, R ^a has the same meaning as R ^a2 defined in the above formula (1-2), and X, Y
, Z ³ and P are as described above.
More preferred specific examples of the compound (1-2) are shown below.

<Synthesis Method of Compound (1)>
The compound (1) can be synthesized by combining known methods in organic synthetic chemistry. Methods for introducing the desired end groups, ring structures and linking groups into the starting materials are described, for example, by Houben-Wyle, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, Organic Syntheses, John Books such as Wily & Sons, Inc., Organic Reactions, John Wily & Sons Inc., Comprehensive Organic Synthesis, Pergamon Press, New Experimental Chemistry Course (Maruzen) It is described in.

A method for introducing the bonding group Z will be described in the following schemes 1 to 12. In these schemes, MSG ¹ and MSG ² represent a monovalent organic group having at least one ring, and Hal represents a halogen. A plurality of MSG ¹ (or MSG ² ) used in the following scheme may be the same or different. Compounds (1A) to (1M) in the following scheme correspond to the compound (1). These methods can be applied to the synthesis of the optically active compound (1) and the optically inactive compound (1).

(Scheme 1) Compound in which Z is a single bond As shown below, an arylboric acid (S1) and a compound (S2) synthesized by a known method are mixed with an aqueous carbonate solution and tetrakis (triphenylphosphine) palladium. By reacting in the presence of a catalyst, a compound (1A) in which a single bond is introduced between MSG ¹ and MSG ² can be synthesized. This compound (1A) is obtained by reacting compound (S3) synthesized by a known method with n-butyllithium and then zinc chloride, and then in the presence of a catalyst such as dichlorobis (triphenylphosphine) palladium. It can also be synthesized by further reacting (S2).

(Scheme 2) Compound in which Z is —CH═CH— As shown below, phosphorus ylide generated by the action of a base such as potassium t-butoxide on a phosphonium salt (S5) synthesized by a known method, and an aldehyde By reacting with (S4), a compound (1B) in which —CH═CH— is introduced between MSG ¹ and MSG ² can be synthesized. Since a cis isomer is generated depending on the reaction conditions and the substrate, the cis isomer is isomerized to a trans isomer by a known method as necessary.

(Scheme 3) Compound in which Z is — (CH ₂ ) ₂ — As shown below, MSG is obtained by hydrogenating the compound (1B) obtained as described above in the presence of a catalyst such as palladium carbon. A compound (1C) having — (CH ₂ ) ₂ — between ¹ and MSG ² can be synthesized.

(Scheme 4) Compound in which Z is — (CF ₂ ) ₂ — As shown below, in the presence of a hydrogen fluoride catalyst according to the method described in J. Am. Chem. Soc., 2001, 123, 5414 The compound (1D) having — (CF ₂ ) ₂ — between MSG ¹ and MSG ² can be synthesized by fluorinating the diketone (S6) with sulfur tetrafluoride.

(Scheme 5) Compound in which Z is — (CH ₂ ) ₄ — As shown below, according to the method of Scheme 2, using phosphonium salt (S7) instead of phosphonium salt (S5), — (CH ₂ ) ₂ — A compound having CH = CH— was synthesized, and this was catalytically hydrogenated in the same manner as in Scheme 3 above, whereby a compound in which — (CH ₂ ) ₄ — was introduced between MSG ¹ and MSG ² (1E ) Can be synthesized.

(Scheme 6) Compound in which Z is —CH ₂ O— or —OCH ₂ — As shown below, compound (S4) is reduced with a reducing agent such as sodium borohydride to obtain compound (S8). This is halogenated with hydrobromic acid or the like to obtain compound (S9). By reacting this compound (S9) and compound (S10) in the presence of potassium carbonate or the like, —OCH ₂ — (or —CH ₂ O—) was introduced between MSG ¹ and MSG ² . Compound (1F) can be synthesized.

(Scheme 7) Compound in which Z is —COO— or —OCO— As shown below, compound (S3) is reacted with n-butyllithium and then carbon dioxide to obtain carboxylic acid (S11). This compound (S11) and phenol (S10) are subjected to a dehydration reaction in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine), so that MSG ¹ and MSG ² are mixed. A compound (1G) into which —COO— (or —OCO—) is introduced can be synthesized.

(Scheme 8) Compound in which Z is —CF═CF— As shown below, compound (S3) is treated with n-butyllithium and then reacted with tetrafluoroethylene to obtain compound (S12). Next, the compound (S2) is treated with n-butyllithium and then reacted with the compound (S12) to synthesize a compound (1H) in which —CF═CF— is introduced between MSG ¹ and MSG ^2. can do. It is also possible to produce a cis compound by selecting the synthesis conditions.

(Scheme 9) Compound in which Z is —C≡C— As shown below, MSG ¹ and MSG are reacted by reacting Compound (S13) with Compound (S2) in the presence of a catalyst of dichloropalladium and copper halide. A compound (1J) in which —C≡C— is introduced between ² and ² can be synthesized.

(Scheme 10) Compound in which Z is —C≡C—COO— or —OCO—C≡C— As shown below, after lithiation of compound (S13) with n-butyllithium, carbon dioxide is allowed to act on Carboxylic acid (S14) is obtained. Subsequently, carboxylic acid (S14) and phenol (S10) are subjected to a dehydration reaction in the presence of DCC and DMAP, whereby -C≡C-COO- (or -OCO-C) between MSG ¹ and MSG ^2. A compound (1K) into which ≡C-) is introduced can be synthesized.

(Scheme 11) Compound in which Z is —C≡C—CH═CH— or —CH═CH—C≡C— As shown below, by a cross-coupling reaction between compound (S13) and vinyl bromide (S15) A compound (1L) in which —C≡C—CH═CH— (or —CH═CH—C≡C—) is introduced between MSG ¹ and MSG ² can be synthesized. Cis compound (
If S15) is used, a cis-form compound (1L) can be synthesized.

(Scheme 12) Compound in which Z is —CF ₂ O— or —OCF ₂ — As shown below, the compound (1G) obtained by the method such as Scheme 7 is treated with a sulfurizing agent such as Lawesson's reagent. Thus, compound (S16) is obtained. This compound (S16) is fluorinated with a hydrogen fluoride pyridine complex and N-bromosuccinimide (NBS) to have —CF ₂ O— (or —OCF ₂ —) between MSG ¹ and MSG ^2. Compound (1M) can be synthesized. Compound (1M) can also be synthesized by fluorinating compound (S16) with (diethylamino) sulfur trifluoride (DAST). These linking groups can also be generated by the method described in P. Kirsch et al., Angew. Chem. Int. Ed. 2001, 40, 1480.

[Liquid crystal composition]
The composition (1) in the present invention comprises at least one compound (1) and comprises two or more compounds. That is, the composition (1) may be composed of two or more compounds (1), and at least one compound (1) and at least one compound other than the compound (1). You may be comprised by the combination. The constituent elements other than the compound (1) are not particularly limited. For example, polymerizable compounds other than the compound (1) (hereinafter also referred to as “other polymerizable compounds”), non-polymerizable liquid crystal compounds. , Optically active compounds, polymerization initiators, solvents and fillers.

<Other polymerizable compounds>
The composition (1) may contain other polymerizable compound as a constituent element. As such a polymerizable compound, a compound that does not lower the film formability and the mechanical strength is preferable. This polymerizable compound is classified into a compound having no liquid crystallinity and a compound having liquid crystallinity. Examples of the polymerizable compound having no liquid crystallinity include vinyl derivatives, styrene derivatives, (meth) acrylic acid derivatives, sorbic acid derivatives, fumaric acid derivatives, itaconic acid derivatives, and the like. Preferred examples of these derivatives are shown below.

  Preferred vinyl derivatives include, for example, vinyl chloride, vinyl fluoride, vinyl acetate, vinyl pivalate, vinyl 2,2-dimethylbutanoate, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butanoate, Vinyl propionate, vinyl stearate, vinyl 2-ethyl-2-methylbutanoate, N-vinylacetamide, vinyl tert-butylbenzoate, vinyl N, N-dimethylaminobenzoate, vinyl benzoate, ethyl vinyl ether, hydroxy Examples thereof include butyl monovinyl ether, t-amyl vinyl ether, cyclohexanedimethanol methyl vinyl ether, α, β-vinyl naphthalene, methyl vinyl ketone, and isobutyl vinyl ketone.

  Preferred styrene derivatives include, for example, styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, α-methylstyrene, and the like. It is done.

  Preferred (meth) acrylic acid derivatives include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, and 1,4-butanediol. Diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate , Trimethylolpropane triacrylate, trimethylol EO addition triacrylate, pentaerythritol triacrylate, trisacryloyloxyethyl phospho Feto, bisphenol A EO addition diacrylate, bisphenol A glycidyl Jijiru diacrylate (trade name: manufactured by Osaka Organic Chemical Co., Ltd. "Viscoat 700"), and polyethylene glycol diacrylate dimethyl itaconate and the like.

  Preferred sorbic acid derivatives include, for example, sodium sorbate, potassium sorbate, lithium sorbate, 1-naphthylmethylammonium sorbate, benzylammonium sorbate, dodecylammonium sorbate, octadecylammonium sorbate, methyl sorbate, sorbic acid Ethyl, propyl sorbate, isopropyl sorbate, butyl sorbate, t-butyl sorbate, hexyl sorbate, octyl sorbate, octadecyl sorbate, cyclopentyl sorbate, cyclohexyl sorbate, vinyl sorbate, allyl sorbate, sorbic acid For example, propargyl.

  Preferable fumaric acid derivatives include, for example, dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, dibutyl fumarate, dicyclopentyl fumarate, dicyclohexyl fumarate and the like.

Preferable itaconic acid derivatives include, for example, diethyl itaconate, dibutyl itaconate, diisopropyl itaconate and the like.
In addition to these, many polymerizable compounds such as butadiene, isoprene, and maleimide can be used.

<Non-polymerizable liquid crystalline compound>
The composition (1) may contain a liquid crystal compound having no polymerizable group as a constituent element. Examples of such non-polymerizable liquid crystal compounds are described in Licris, a database of liquid crystal compounds (LiqCryst, LCI Publisher GmbH, Hamburg, Germany). By polymerizing the composition (1) containing a non-polymerizable liquid crystal compound, a composite material of the polymer of the compound (1) and the liquid crystal compound can be obtained. In such a composite material, for example, a non-polymerizable liquid crystal compound exists in a polymer network such as a polymer dispersed liquid crystal.

<Optically active compound>
The composition (1) may contain an optically active compound as a constituent element. A composition containing an appropriate amount of the optically active compound (1) or an optically active composition obtained by adding an appropriate amount of an optically active compound to the optically active compound (1) The film on which the liquid crystal molecules exhibit a helical structure (twist structure) is obtained by coating and polymerizing on the substrate. This helical structure is fixed by the polymerization of the compound (1). The helical pitch length can be adjusted by the type and amount of the optically active compound. One optically active compound may be added, but a plurality of optically active compounds may be used for the purpose of offsetting the temperature dependence of the helical pitch. In addition, since the compound (1) having optical activity has a high twist-inducing force, it is useful for adjusting the helical pitch of the composition (1).

  The optically active compound to be added may be any optically active compound as long as it induces a helical structure and can be appropriately mixed with the base polymerizable liquid crystal composition. For example, the following chemical formulas (Op-1) to (Op- The optically active compound represented by 13) is preferred.

In the above formula, R ^c represents an alkyl group having 1 to 10 carbon atoms, and the carbon provided with * is an asymmetric carbon.
The optically active compound may be either a polymerizable compound or a non-polymerizable compound, and may be appropriately selected according to the purpose. For example, in view of heat resistance and solvent resistance, a polymerizable compound is preferable. In addition, it is preferable that the optically active compound has a larger twisting force (HTP: helical twisting power) in order to shorten the helical pitch. A representative example of a compound having a large twisting force is disclosed in DE10221751. Particularly preferred compounds include compounds represented by the following chemical formulas (Op-14) to (Op-19).

The compounds represented by the above formulas (Op-14) to (Op-16) are polymerizable compounds, and the compounds represented by the above formulas (Op-17) to (Op-19) are non-polymerizable compounds. . Here, if a polymerizable group is introduced into —C ₃ H ₇ at the terminal of the compounds represented by the above formulas (Op-17) to (Op-19), an optically active compound having useful polymerizability is obtained.

<Polymerization initiator>
The composition (1) may contain a polymerization initiator as a constituent element. As the polymerization initiator, for example, a radical photopolymerization initiator, a cationic photopolymerization initiator, a thermal radical polymerization initiator, or the like may be used depending on the polymerization method of the composition (1).

The radical photopolymerization initiator is not particularly limited, and known ones can be used,
For example, 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10 Benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyldimethyl ketal, 2-methyl-1 -[4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate, benzophenone / methyltriethanolamine mixture, and the like. Examples of commercially available products include “Darocur Series 1173, 4265” and “Irgacure Series 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850, manufactured by Ciba Specialty Co., Ltd. , 2959 ".

The photo-cationic polymerization initiator is not particularly limited, and known ones can be used. For example, “Cyracure UVI-6990, 6974” manufactured by UCC Corporation, “Adekaopt” manufactured by Asahi Denka Co., Ltd. Mar SP-150, 152, 170, 172 "," Photoinitiator 2074 "manufactured by Rhodia Co., Ltd.," Irgacure 2 "manufactured by Ciba Specialty Co., Ltd.
50 ”,“ DTS-102 ”manufactured by Midori Chemical Co., Ltd., and the like.

  Preferred initiators for thermal radical polymerization include, for example, benzoyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, di-t-butylperoxide. Oxide (DTBPO), t-butylperoxydiisobutyrate, lauroyl peroxide, dimethyl 2,2′-azobisisobutyrate (MAIB), azobisisobutyronitrile (AIBN), azobiscyclohexanecarbonitrile (ACN), etc. Can be mentioned.

The anionic polymerization, preferred initiators for coordination polymerization and living polymerization, for _{example, n-C 4 H 9 Li} , alkali metal alkyl compound, such as _{t-C 4 H 9 Li-} R 3 Al, an aluminum compound, a transition metal Compound etc. are mentioned.

<Curing agent>
When the composition (1) includes a compound having a cyclic ether group as a constituent element, a curing agent may be included as a constituent element. Examples of preferred curing agents are shown below.

  Diaminetriamine, triethylenetetramine, tetraethylenepentamine, o-xylenediamine, m-xylenediamine, p-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine, isophoronediamine as amine curing agents 1,3-bisaminomethylcyclohexane, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, 3,9-dipropanamine- 2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-diaminodiphenylmethane, 4,4′-diamino-1,2-diphenylethane, o-phenylenediamine, m-phenyle Diamines, p- phenylenediamine, 4,4'-diaminodiphenyl sulfone, polyoxypropylene diamine, polyoxypropylene triamine, poly cyclohexyl polyamine, such as N- aminoethyl piperazine.

Acid anhydride curing agents include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, hydrogenated methylnadic acid anhydride, trialkyltetrahydrophthalic anhydride Acid, methylcyclohexene tetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, ethylene glycol bisanhydrotrimethylate, glycerin bis (anhydrotrimellitate) ) Monoacetate, dedecenyl succinic anhydride, chlorendic anhydride and the like.

As phenolic curing agents, phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, m-ethylphenol, p-ethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, o-isopropylphenol, p-tert-butylphenol, o-sec-butylphenol, p-octylphenol, 2 , 6-di-tert-butylphenol, resorcinol, 1-naphthol, 2-naphthol, bisphenol A, phenol novolak, xylylene novolak, bisphenol A novolak, and the like.
In addition to the above, curing agents described in JP-A Nos. 2004-256687 and 2002-226550 can also be used.

<Filler>
The composition (1) may contain a heat conductive filler as a constituent element. Examples include diamond, graphite, silicon carbide, silicon, beryllia, magnesium oxide, aluminum oxide, zinc oxide, silicon oxide, copper oxide, titanium oxide, cerium oxide, yttrium oxide, tin oxide, holmium oxide, bismuth oxide, cobalt oxide. , Inorganic filling such as calcium oxide, aluminum nitride, boron nitride, silicon nitride, magnesium hydroxide, aluminum hydroxide, gold, silver, copper, platinum, iron, tin, lead, nickel, aluminum, magnesium, tungsten, molybdenum, stainless steel Agents and metal fillers. Examples of the shape of the filler include a spherical shape, an amorphous shape, a fiber shape, a rod shape, and a tubular shape. The type, shape, size, addition amount, and the like of the filler can be appropriately selected depending on the purpose. When the obtained heat radiating member requires insulation, a conductive filler may be used as long as the desired insulation is maintained.

<Solvent>
The composition (1) may contain a solvent. The polymerization of the composition (1) may be performed in a solvent or without a solvent. The composition (1) containing a solvent may be applied onto a substrate by, for example, a spin coating method, and then photopolymerized after removing the solvent. Further, after photocuring, it may be heated to an appropriate temperature and post-treated by heat curing.

Preferred solvents include, for example, benzene, toluene, xylene, mesitylene, hexane, heptane, octane, nonane, decane, tetrahydrofuran, γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, cyclohexane, methylcyclohexane, cyclopentanone. , Cyclohexanone, PGMEA and the like. The said solvent may be used individually by 1 type, or may mix and use 2 or more types.
In addition, there is not much meaning in limiting the use ratio of the solvent at the time of polymerization, and it may be determined for each case in consideration of polymerization efficiency, solvent cost, energy cost, and the like.

<Others>
Since the compound (1) and the composition (1) have high polymerizability, a stabilizer may be added for easy handling. As such a stabilizer, known ones can be used without limitation, and examples thereof include hydroquinone, 4-ethoxyphenol and 3,5-di-t-butyl-4-hydroxytoluene (BHT).

[Liquid Crystal Polymer]
The polymer (1) in the present invention is obtained by polymerizing the composition (1) containing at least one compound (1) while controlling the orientation. This polymer (1) has high thermal conductivity, low water permeability, water absorption and gas permeability, and is excellent in chemical stability, heat resistance, hardness, mechanical strength and the like. The mechanical strength includes Young's modulus, tensile strength, tear strength, bending strength, bending elastic modulus, impact strength, and the like.

  The polymer (1) is a thermoplastic resin or a thermosetting resin. When the compound (1) having a polymerizable group at one end is used, a thermoplastic resin is easily obtained, and when the compound (1) having both ends is a polymerizable group, a thermosetting resin is easily obtained.

  The weight average molecular weight of the thermoplastic resin is preferably in the range of 500 to 1,000,000, more preferably 1,000 to 500,000, and particularly preferably 5,000 to 100,000. Since such a polymer (1) is soluble in a solvent, it can be easily formed into a shape suitable for the application.

  The thermosetting resin has a three-dimensional crosslinked structure. Since such a polymer (1) is insoluble in a solvent, the molecular weight cannot be measured. However, in the case where the composition (1) is applied onto the substrate and the heat radiation member is obtained by polymerizing with the molecular orientation fixed, no further processing is performed, so the size of the molecular weight is not a problem. It is sufficient to satisfy the conditions in the usage environment. In order to further increase the molecular weight, a crosslinking agent may be added. Thereby, the polymer (1) extremely excellent in chemical resistance and heat resistance can be obtained. As such a cross-linking agent, known ones can be used without limitation, and examples thereof include tris (3-mercaptopropionate).

  As described above, the polymer (1) has a feature that the molecular orientation is fixed in an arbitrary direction. Thus, the polymer (1) to which high thermal conductivity is imparted in the certain direction can be obtained by fixing the mesogenic portion of the liquid crystal molecule by aligning it as uniformly as possible in the certain direction. This direction can be arbitrarily controlled by aligning liquid crystal molecules before polymerization.

  Further, by imparting a helical structure or the like to the alignment of liquid crystal molecules, high thermal conductivity can be achieved in all directions. When fixing such a helical structure, torsional inversion can be suppressed and the helical pitch can be adjusted by adding a small amount of an optically active compound. The addition amount of the optically active compound is usually 0.01 to 50% by weight, preferably 1 to 30% by weight.

  Moreover, high heat conductivity in all directions can be achieved by laminating films arranged in a certain direction in each direction. Such a laminated structure can also be formed by repeating the process of “application of composition → polymerization → application of composition → polymerization”. Forming a laminated structure in this way is also useful in reducing the anisotropy of the mechanical strength of the resulting heat dissipation member.

  As a method for controlling the alignment of the mesogenic sites of the liquid crystal molecules in the composition (1), a method using an alignment film, a method of adding an alignment control agent to the composition (1), a rubbing treatment method, a composition (1) Examples thereof include a method of aligning by self-orientation regulating force possessed by itself. These methods may be performed singly or in combination of two or more. Examples of the alignment state controlled by such an alignment control method include homogeneous, twist, homeotropic, hybrid, bend, and spray alignment, and can be appropriately determined according to the application and the alignment control method.

As a method for controlling the orientation by the self-orientation force of the composition (1) itself, a method of heat-treating the composition (1) can be mentioned. The heat treatment of the composition (1) is performed at or above the clearing point of the composition (1). As an example of the heat treatment method, there is a method in which the composition (1) is heated to a temperature at which a liquid crystal phase is exhibited to form an orientation in the composition (1). In addition, the orientation may be formed by changing the temperature within the temperature range in which the composition (1) exhibits a liquid crystal phase. In this method, the orientation of the composition (1) is substantially completed by heating the composition (1) to a high temperature range of the temperature range showing the liquid crystal phase, and then the order is further ordered by lowering the temperature. To do. The liquid crystal phase expressed by the composition (1) may be a nematic, smectic, or cholesteric phase.

  The heat treatment temperature ranges from room temperature to 150 ° C, preferably from room temperature to 100 ° C, more preferably from room temperature to 70 ° C. The heat treatment time is in the range of 5 seconds to 2 hours, preferably 10 seconds to 60 minutes, more preferably 20 seconds to 30 minutes. When the heat treatment time is shorter than the above range, the temperature of the layer made of the composition (1) may not be raised to a predetermined temperature, and when it is longer than the above range, the productivity may be lowered. In addition, since the said heat processing conditions change with the kind and composition ratio of a compound used for a composition (1), the presence or absence, content of a polymerization initiator, etc., they show the approximate range to the last.

  Examples of the polymerization method of the composition (1) include radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization. In order to fix a molecular arrangement or a helical structure, an electron beam, Thermal polymerization or photopolymerization using light or heat such as ultraviolet rays, visible rays or infrared rays (heat rays) is suitable. The thermal polymerization is preferably performed in the presence of a radical polymerization initiator, and the photopolymerization is preferably performed in the presence of a radical photopolymerization initiator. For example, a polymer in which the alignment of liquid crystal molecules is fixed is obtained by a polymerization method in which ultraviolet rays or electron beams are irradiated in the presence of a radical photopolymerization initiator. The obtained polymer (1) may be any of a homopolymer, a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer, and may be appropriately selected depending on the use. .

  When fixing the orientation of the composition (1) by photopolymerization, ultraviolet rays or visible rays are usually used. The wavelength of light used for light irradiation is in the range of 150 to 500 nm, preferably 250 to 450 nm, more preferably 300 to 400 nm. Light sources for light irradiation include, for example, low-pressure mercury lamps (sterilization lamps, fluorescent chemical lamps, black lights), high-pressure discharge lamps (high-pressure mercury lamps, metal halide lamps), and short arc discharge lamps (extra-high pressure mercury lamps, xenon lamps, mercury). Xenon lamp). Of these, metal halide lamps, xenon lamps and high-pressure mercury lamps are preferred.

You may select the wavelength range of an irradiation light source by installing a filter etc. between the said light source and a composition (1), and letting only a specific wavelength range pass. The amount of light radiated from a light source, 2~5000mJ / cm ^2, preferably in the range 10~3000mJ / cm ^2, more preferably 100 to 2000 mJ / cm ^2. The temperature condition at the time of light irradiation is preferably set similarly to the heat treatment temperature described above.

  As conditions for fixing the orientation of the composition (1) by thermal polymerization, the thermosetting temperature is in the range of room temperature to 350 ° C, preferably room temperature to 250 ° C, more preferably 50 ° C to 200 ° C, and the curing time. Is in the range of 5 seconds to 10 hours, preferably 1 minute to 5 hours, more preferably 5 minutes to 1 hour. After the polymerization, it is preferable to slowly cool in order to suppress stress strain and the like. In addition, reheating treatment may be performed to reduce strain and the like.

The polymer whose orientation is controlled as described above or the polymer in the polymerization process may be further controlled in an arbitrary direction by a mechanical operation such as stretching.
The isolated polymer (1) may be dissolved in a solvent and oriented on an orientation-treated substrate and processed into a film or the like, or two polymers may be mixed and processed, or a plurality of polymers may be laminated. You may let them. Examples of the solvent include N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylacetamide dimethyl acetal, tetrahydrofuran, chloroform, 1,4-dioxane. Bis (methoxyethyl) ether, γ-butyrolactone, tetramethylurea, trifluoroacetic acid, ethyl trifluoroacetate, hexafluoro-2-propanol, 2-methoxyethyl acetate, methyl ethyl ketone, cyclopentanone, cyclohexanone and the like are preferable. These may be used by mixing with common organic solvents such as acetone, benzene, toluene, heptane, methylene chloride.

(Heat dissipation member)
The heat radiating member of this invention consists of said polymer (1), and uses it in shapes, such as a sheet | seat, a film, a thin film, a fiber, a molded object. Preferred shapes are films and thin films. A film and a thin film are obtained by polymerizing the composition (1) applied to the substrate or sandwiched between the substrates. It can also be obtained by applying a composition (1) containing a solvent to an alignment-treated substrate and removing the solvent. Further, the film can be obtained by press-molding a polymer. In addition, the film thickness of the sheet | seat in this specification is 1 mm or more, The film thickness of a film is 5 micrometers or more, Preferably it is 10-500 micrometers, More preferably, it is 20-300 micrometers, The film thickness of a thin film is less than 5 micrometers.

Hereinafter, a method for producing a film as a heat radiating member using the composition (1) containing a solvent will be specifically described.
First, the composition (1) is applied onto a substrate, and the solvent is removed by drying to form a coating layer having a uniform film thickness. Examples of the coating method include spin coating, roll coating, caten coating, flow coating, printing, micro gravure coating, gravure coating, wire barcode, dip coating, spray coating, meniscus coating method, and the like.

  The solvent can be removed by drying, for example, by air drying at room temperature, drying on a hot plate, drying in a drying furnace, blowing hot air or hot air, and the like. The conditions for removing the solvent are not particularly limited, and it may be dried until the solvent is almost removed and the fluidity of the coating layer is lost. Depending on the type and composition ratio of the compound used in the composition (1), the molecular orientation of the liquid crystal molecules in the coating layer may be completed in the process of drying the coating layer. In such a case, the coating layer that has undergone the drying step can be subjected to the polymerization step without going through the heat treatment step described above. However, in order to make the alignment of the liquid crystal molecules in the coating layer more uniform, it is preferable to heat-treat the coating layer that has undergone the drying step, and then to fix the alignment by photopolymerization.

  Moreover, it is also preferable to orient the substrate surface before applying the composition (1). As an alignment treatment method, for example, an alignment film may be formed only on a substrate, or after an alignment film is formed on a substrate, a rubbing treatment with a rayon cloth or the like, or a substrate is directly rubbed with a rayon cloth or the like. And a method of oblique deposition of silicon oxide, a rubbing-free orientation method using a stretched film, a photo-alignment film, an ion beam, or the like. In some cases, a desired alignment state can be formed without processing the substrate surface. For example, when homeotropic alignment is formed, surface treatment such as rubbing is often not performed, but rubbing may be performed in order to prevent alignment defects.

  The alignment film is not particularly limited as long as it can control the alignment of the composition (1), and a known alignment film can be used, for example, polyimide, polyamide, polyvinyl alcohol, alkylsilane, alkylamine. Or a lecithin-type oriented film is suitable.

  Any method can be adopted for the rubbing treatment. Usually, a rubbing cloth made of materials such as rayon, cotton, and polyamide is applied to a metal roll or the like, and the roll is rotated while being in contact with the substrate or the alignment film. A method of moving the substrate while moving it, a method of moving the substrate side while fixing the roll, and the like are employed.

  Moreover, in order to obtain a more uniform orientation, an orientation control additive may be contained in the composition (1). Examples of such alignment control additives include imidazoline, quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol and esters thereof, sodium lauryl sulfate, ammonium lauryl sulfate, and lauryl. Amine sulfates, alkyl-substituted aromatic sulfonates, alkyl phosphates, aliphatic or aromatic sulfonic acid formalin condensates, laurylamidopropylbetaine, laurylaminoacetic acid betaine, polyethylene glycol fatty acid esters, polyoxyethylene alkylamines, Perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl trimethyl ammonium Salt, oligomer having perfluoroalkyl group and hydrophilic group, oligomer having perfluoroalkyl group and lipophilic group, urethane having perfluoroalkyl group, and organosilicon compound having primary amino group (for example, , Alkoxysilane type, linear siloxane type, and three-dimensional condensed silsesquioxane type organosilicon compounds).

  By appropriately selecting a substrate subjected to the alignment treatment as described above and sandwiching the composition between the substrates, alignment such as homogeneous, homeotropic, twist, spray, and hybrid can be obtained. In addition to the above method, the orientation may be arbitrarily controlled by applying an electric field or a magnetic field.

  Examples of the substrate include glass substrates such as alkali glass, borosilicate glass and flint glass; metal substrates such as aluminum, iron and copper; inorganic substrates such as silicon; polyimide, polyamideimide, polyamide, polyetherimide and polyether Ether ketone, polyether ketone, polyketone sulfide, polyether sulfone, polysulfone, polyphenylene sulfide, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol, polypropylene, cellulose , Triacetyl cellulose or partially saponified product thereof, epoxy resin, phenol resin, norbornene tree Like plastic film substrate such as.

The film substrate may be a uniaxially stretched film or a biaxially stretched film. The film substrate may be subjected to surface treatment such as saponification treatment, corona treatment, or plasma treatment in advance. A protective layer that is not affected by the solvent contained in the composition (1) may be formed on these film substrates. Examples of the material used as the protective layer include polyvinyl alcohol. Furthermore, an anchor coat layer may be formed in order to improve the adhesion between the protective layer and the substrate. Such an anchor coat layer may be any inorganic or organic material as long as it improves the adhesion between the protective layer and the substrate.
The heat radiating member of the present invention is useful for a heat radiating plate, a heat radiating sheet, a heat radiating film, a heat radiating adhesive, a heat radiating molded product and the like.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not restrict | limited by these Examples.

In the following examples, the thermal conductivity (λ) was calculated according to the following formula by measuring the thermal diffusivity (α) using a half-time method of laser flash measurement at room temperature in accordance with JIS R1611.
Formula: λ = α ・ ρ ・ c
In the formula, ρ represents specific gravity, and c represents specific heat.

<Example 1>
An alignment film made of polyvinyl alcohol was formed, and a homogeneous alignment cell was prepared using a glass substrate on which the alignment film was rubbed and a 200 μm spacer. 1-wt% of 2,2-dimethoxy-2-phenylacetophenone was mixed with the composition consisting of the following composition example 1. This composition was injected into the cell at 120 ° C. The liquid crystal phase of the composition at the same temperature was a nematic phase. The polymer was held at the same temperature for 60 minutes and irradiated with 30 mW / cm ² (center wavelength 365 nm) of UV light for 5 minutes for polymerization. After irradiation, the film was gradually cooled, and a 200 μm film was taken out from the cell. As a result of observing the film with a polarizing microscope, uniform orientation was observed, and when the polarizer and analyzer were rotated, extinction positions were observed at 45 ° intervals. From this, it was confirmed that the obtained film was a homogeneous homogeneously oriented film. The heat conductivity (λ) of the homogeneously oriented film with respect to the molecular long axis direction was λ = 0.63 W / (K · m).

<Example 2>
In Example 1, instead of the composition of Composition Example 1, the composition of Composition Example 2 below was used, injected into the cell in an isotropic liquid state at 140 ° C., cooled to 90 ° C., and the nematic phase state A homogeneous alignment film was produced in the same manner as in Example 1 except that the polymerization was carried out. The resulting film had a thermal conductivity of λ = 0.71 W / (K · m) with respect to the molecular major axis direction.

<Example 3>
An alignment film made of polyvinyl alcohol was formed, and a twist alignment cell in which the rubbing directions of the glass substrate were orthogonal to each other was produced using a glass substrate on which the alignment film was rubbed and a 250 μm spacer. Diphenyl (p-phenylthiophenyl) sulfonium hexafluorophosphate 0.3 wt% was mixed with the composition consisting of the following composition example 3. When this composition was poured into a cell at 90 ° C. and cooled to 50 ° C., the liquid crystal phase of the composition was a nematic phase. Hold at the same temperature for 30 minutes, UV of 30mW / cm ² (center wavelength 365nm)
Polymerization was performed by irradiation with light for 5 minutes. After irradiation, the film was gradually cooled, and a 250 μm film was taken out from the cell. As a result of observing the film with a polarizing microscope, uniform orientation was observed, and when the polarizer and analyzer were rotated, no extinction position was observed at any angle. From this, it was confirmed that the obtained film was a film with uniform twist orientation. The twisted oriented film had a thermal conductivity in the molecular major axis direction of λ = 0.55 W / (K · m).

<Example 4>
A homeotropic alignment cell was prepared using a glass substrate on which an alignment film made of n-octadecylethoxysilane was formed and a spacer of 100 μm. 1,2-dimethoxy-2-phenylacetophenone 1 wt% was mixed with the composition consisting of the following composition example 4. When this composition was poured into a cell at 70 ° C. and cooled to room temperature, the liquid crystal phase of the composition was a nematic phase. The polymer was held at the same temperature for 50 minutes and polymerized by irradiation with UV light of 30 mW / cm ² (center wavelength 365 nm) for 5 minutes. After irradiation, the film was gradually cooled, and a 100 μm film was taken out from the cell. When the film was observed with a polarizing microscope, transmitted light was not observed even when the polarizer and analyzer were rotated, and black crosshairs were observed by conoscopic observation. From this, it was confirmed that the obtained film was a uniform homeotropically oriented film. The thermal conductivity in the molecular major axis direction of this homeotropic alignment film was λ = 0.68 W / (K · m).

  Below, the composition examples 5-23 which can form the heat radiating member of this invention similarly to the said composition examples 1-4 are shown.

<Comparative Example 1>
An alignment film made of polyvinyl alcohol was formed, and a cell was produced using a glass substrate on which the alignment film was not rubbed and a 200 μm spacer. 1,2-dimethoxy-2-phenylacetophenone 1 wt% was mixed with the composition of Composition Example 1 above. This composition was injected into the cell at 180 ° C. The composition at the same temperature was isotropic. It was held at the same temperature for 3 minutes and polymerized by irradiation with UV light of 30 mW / cm ² (center wavelength 365 nm) for 5 minutes. After irradiation, the film was gradually cooled, and a 200 μm film was taken out from the cell. As a result of observing the film with a polarizing microscope, the structure was not observed even when the polarizer and the analyzer were rotated, and the film was always in a dark state. From this, it was confirmed that the obtained film was an isotropically oriented film. The thermal conductivity (λ) of this isotropically oriented film was λ = 0.18 W / (K · m).

Claims (34)

  A liquid crystal composition containing a polymerizable liquid crystal compound having a polymerizable group at the end is subjected to orientation control of the mesogenic portion of the liquid crystal compound by an alignment film, an alignment control additive, a rubbing treatment, or the self-alignment regulating force of the composition. A heat dissipating member comprising a liquid crystal polymer obtained by polymerization. The heat radiating member according to claim 1, wherein the polymerizable liquid crystal compound is at least one compound represented by the following formula (1-1).
R ^a1 -Z- (AZ) _m1 -R ^a1 (1-1)
[In Formula (1-1),
R ^a1 is independently a polymerizable group represented by the following formulas (2-1) to (2-6), hydrogen, halogen, cyano, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , _{-OCF 2 H, -N = C =} O, -N
= C = S or alkyl having 1 to 20 carbon atoms,
In the alkyl, arbitrary —CH ₂ — represents —O—, —S—, —SO ₂ —, —CO—, —COO—, —OCO—, —CH═CH—, —CF═CF— or — C≡C— may be replaced, and any hydrogen may be replaced with halogen or cyano,
At least one of R ^a1 is a polymerizable group represented by formulas (2-1) to (2-6);
A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] Octo-1,4-diyl, bicyclo [3.1.0] hex-3,6-diyl or divalent compounds represented by the following formulas (3-1) to (3-10) The basis of
In these rings, any —CH ₂ — may be replaced by —O—, and any —CH ₂ —
= May be replaced by -N =, and any hydrogen may be replaced by halogen, alkyl having 1 to 10 carbon atoms or halogenated alkyl having 1 to 10 carbon atoms,
In the alkyl, arbitrary —CH ₂ — represents —O—, —CO—, —COO—, —OCO—.
, -CH = CH- or -C≡C-;
Z is independently a single bond or alkylene having 1 to 20 carbon atoms,
In the alkylene, arbitrary —CH ₂ — represents —O—, —S—, —CO—, —COO—,
-OCO-, -CH = CH-, -CF = CF-, -CH = N-, -N = CH-, -N = N-, -N (O) = N- or -C≡C- Any hydrogen may be replaced with a halogen;
m1 is an integer of 1-6. ]

[In the formulas (2-1) to (2-6), R ^b is hydrogen, halogen, —CF _3, or alkyl having 1 to 5 carbon atoms, and q is 0 or 1. ]

In the formula (1-1), at least one of R ^a1 is a polymerizable group represented by the formula (2-1), (2-5) or (2-6). Item 3. A heat dissipating member according to Item 2. In the formula (1-1),
At least one of R ^a1 is a polymerizable group represented by the formula (2-1), (2-5) or (2-6);
A is 1,4-cyclohexylene, 1,4-cyclohexylene in which arbitrary hydrogen is replaced with halogen, 1,4-phenylene, 1,4-phenylene in which arbitrary hydrogen is replaced with halogen or methyl, fluorene The heat radiating member according to claim 2, which is fluorene-2,7-diyl in which −2,7-diyl or any hydrogen is replaced by halogen or methyl. In the formula (1-1),
At least one of R ^a1 is a polymerizable group represented by the formula (2-1), (2-5) or (2-6);
A is 1,4-cyclohexylene, 1,4-cyclohexylene in which arbitrary hydrogen is replaced with halogen, 1,4-phenylene, 1,4-phenylene in which arbitrary hydrogen is replaced with halogen or methyl, fluorene -2,7-diyl or fluorene-2,7-diyl in which any hydrogen is replaced by halogen or methyl;
Z is a single bond, — (CH ₂ ) _a —, —O (CH ₂ ) _a —, — (CH ₂ ) _a O—, —O (CH ₂ ) _a O—, —CH═CH—, —C ≡C—, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —CH ₂ CH ₂ —COO—, —OCO—CH ₂ CH ₂ —, —CH═N -, - N = CH -, - N = N -, - OCF 2 - or -CF ₂ is O-, the a is 1
It is an integer of 20, The heat radiating member of Claim 2 characterized by the above-mentioned. In the formula (1-1), at least one of R ^a1 is a polymerizable group represented by the formula (2-2), (2-3) or (2-4). Item 3. A heat dissipating member according to Item 2. In the formula (1-1),
At least one of R ^a1 is a polymerizable group represented by the formula (2-2), (2-3) or (2-4);
A is 1,4-cyclohexylene, 1,4-cyclohexylene in which arbitrary hydrogen is replaced with halogen, 1,4-phenylene, 1,4-phenylene in which arbitrary hydrogen is replaced with halogen or methyl, fluorene The heat radiating member according to claim 2, which is fluorene-2,7-diyl in which −2,7-diyl or any hydrogen is replaced by halogen or methyl. In the formula (1-1),
At least one of R ^a1 is a polymerizable group represented by the formula (2-2), (2-3) or (2-4);
A is 1,4-cyclohexylene, 1,4-cyclohexylene in which arbitrary hydrogen is replaced with halogen, 1,4-phenylene, 1,4-phenylene in which arbitrary hydrogen is replaced with halogen or methyl, fluorene -2,7-diyl or fluorene-2,7-diyl in which any hydrogen is replaced by halogen or methyl;
Z is a single bond, — (CH ₂ ) _a —, —O (CH ₂ ) _a —, — (CH ₂ ) _a O—, —O (CH ₂ ) _a O—, —CH═CH—, —C ≡C—, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —CH ₂ CH ₂ —COO—, —OCO—CH ₂ CH ₂ —, —CH═N -, - N = CH -, - N = N -, - OCF 2 - or -CF ₂ is O-, the heat radiation member according to claim 2, wherein said a is an integer from 1 to 20 . In the formula (1-1),
At least one of R ^a1 is a polymerizable group represented by the formula (2-1), (2-5) or (2-6);
A is 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which arbitrary hydrogen is replaced by halogen or methyl, fluorene-2,7-diyl, or arbitrary hydrogen is replaced by halogen or methyl Fluorene-2,7-diyl produced;
Z is a single bond, —COO—, —OCO—, — (CH ₂ ) _a —, —CH═CH—COO—, —OCO—CH═CH—, —CH ₂ CH ₂ —COO—, —OCO—. _{CH 2 CH 2 -, - O} (CH 2) a -, - (CH 2) a O- or -O (CH _{2) a} is O-, and wherein the said a is an integer from 1 to 20 The heat radiating member according to claim 2. In the formula (1-1),
At least one of R ^a1 is a polymerizable group represented by the formula (2-1), (2-5) or (2-6);
A is 1,4-phenylene, 1,4-phenylene, fluorene-2,7-diyl in which any hydrogen is replaced with Cl, F or methyl, or fluorene-2 in which any hydrogen is replaced with F or methyl 7-diyl;
Z is, -COO -, - OCO -, - (CH 2) a -, - O (CH 2) a -, - (CH 2) a O- or -O (CH _{2) a} a O-, said a is an integer of 1-20, The heat radiating member of Claim 2 characterized by the above-mentioned. In the formula (1-1),
At least one of R ^a1 is a polymerizable group represented by the formula (2-2), (2-3) or (2-4);
A is 1,4-cyclohexylene, 1,4-cyclohexylene in which arbitrary hydrogen is replaced with halogen, 1,4-phenylene, 1,4-phenylene in which arbitrary hydrogen is replaced with halogen or methyl, fluorene -2,7-diyl or fluorene-2,7-diyl in which any hydrogen is replaced by halogen or methyl;
Z is a single bond, -COO -, - OCO -, - (CH 2) a -, - O (CH 2) a -, - (CH 2) a O- or -O (CH _{2) a} O- in The heat-radiating member according to claim 2, wherein a is an integer of 1 to 20. In the formula (1-1),
At least one of R ^a1 is a polymerizable group represented by the formula (2-2), (2-3) or (2-4);
A is 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which arbitrary hydrogen is replaced by halogen or methyl, fluorene-2,7-diyl, or arbitrary hydrogen is replaced by halogen or methyl Fluorene-2,7-diyl produced;
Z is, -COO -, - OCO -, - (CH 2) a -, - O (CH 2) a -, - (CH 2) a O- or -O (CH _{2) a} a O-, said a is an integer of 1-20, The heat radiating member of Claim 2 characterized by the above-mentioned. In the formula (1-1),
At least one of R ^a1 is a polymerizable group represented by the formula (2-2), (2-3) or (2-4);
A is 1,4-phenylene, 1,4-phenylene, fluorene-2,7-diyl in which any hydrogen is replaced with Cl, F or methyl, or fluorene-2 in which any hydrogen is replaced with F or methyl 7-diyl;
Z is, -COO -, - OCO -, - (CH 2) a -, - O (CH 2) a -, - (CH 2) a O- or -O (CH _{2) a} a O-, said a is an integer of 1-20, The heat radiating member of Claim 2 characterized by the above-mentioned. The heat-radiating member according to claim 1, wherein the polymerizable liquid crystal compound is at least one compound represented by the following formula (1-2).

[In the formula (1-2),
R ^a2 is independently hydrogen, halogen, cyano, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, —N═C═O, —N═C═S or carbon number 1-20 alkyl,
In the alkyl, arbitrary —CH ₂ — represents —O—, —S—, —SO ₂ —, —CO—, —COO—, —OCO—, —CH═CH—, —CF═CF— or —C. May be replaced with ≡C-, and any hydrogen may be replaced with halogen or cyano;
R ^a3 is a polymerizable group represented by any one of formulas (2-1) to (2-6) according to claim 2;
A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl. , Bicyclo [2.2.2] oct-1,4-diyl, bicyclo [3.1.0] hex-3,6-diyl or formulas (3-1) to (3-10) according to claim 2. )
A divalent group represented by:
In these rings, any —CH ₂ — may be replaced by —O—, and any —CH ₂ —
= May be replaced by -N =, and any hydrogen may be replaced by halogen, alkyl having 1 to 10 carbon atoms or halogenated alkyl having 1 to 10 carbon atoms,
In the alkyl, arbitrary —CH ₂ — represents —O—, —CO—, —COO—, —OCO—.
, -CH = CH- or -C≡C-;
Z is independently a single bond or alkylene having 1 to 20 carbon atoms,
In the alkylene, arbitrary —CH ₂ — represents —O—, —S—, —CO—, —COO—, —
OCO-, -CH = CH-, -CF = CF-, -CH = N-, -N = CH-, -N = N-, -N (O) = N- or -C≡C- Any hydrogen may be replaced by halogen;
Y is a single bond or alkylene having 1 to 20 carbon atoms,
In the alkylene, arbitrary —CH ₂ — represents —O—, —S—, —CO—, —COO—, —
OCO— or —CH═CH— may be replaced, and any hydrogen may be replaced with halogen;
m2 and n2 are each an integer of 0 to 5. ] The formula (1-2), wherein R ^a3 is a polymerizable group represented by the formula (2-1), (2-5) or (2-6) according to claim 2. Compound.   The compound according to claim 14, wherein m2 + n2 is an integer of 1 to 3 in the formula (1-2).   The compound according to claim 14, wherein m2 + n2 is 2 in the formula (1-2). In the formula (1-2),
R ^a2 is independently alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and these optional hydrogens may be replaced by fluorine;
R ^a3 is a polymerizable group represented by the formula (2-1), (2-5) or (2-6) according to claim 2;
A is independently 1,4-cyclohexylene, 1,4-phenylene, pyridine-2,5-diyl, pyridazine-3,6-diyl or pyrimidine-2,5-diyl, and these optional hydrogens are , Chlorine, fluorine, alkyl having 1 to 3 carbons or fluoroalkyl having 1 to 3 carbons may be substituted;
Z is independently a single bond, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CH═CH—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —. , -CH = CH-COO-, -OCO-CH = CH-, or -C≡C-;
The compound according to claim 14, wherein Y is a single bond or alkylene having 1 to 10 carbon atoms, and in the alkylene, arbitrary —CH ₂ — may be replaced by —O—, —COO— or —OCO—. In the formula (1-2),
R ^a2 is independently alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons;
R ^a3 is a polymerizable group represented by the formula (2-1), (2-5) or (2-6) according to claim 2;
A is independently 1,4-cyclohexylene or 1,4-phenylene;
Z is independently a single bond, —COO—, —OCO—, —CH═CH—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═CH—COO—, —OCO -CH = CH- or -C≡C-;
15. Y is a single bond or alkylene having 1 to 10 carbon atoms, and —CH ₂ — adjacent to the ring in the alkylene may be replaced by —O—, —COO— or —OCO—.
Compound described in 1.   The heat dissipation member according to claim 1, wherein the liquid crystal composition contains a non-polymerizable liquid crystal compound.   The heat radiating member according to claim 1, wherein the liquid crystal composition is optically active.   The liquid crystal composition contains a polymerizable optically active compound other than the liquid crystal compound represented by formula (1-1) according to claim 2 or formula (1-2) according to claim 14. The heat radiating member according to claim 1.   The liquid crystal composition contains a non-polymerizable optically active compound other than the liquid crystal compound represented by formula (1-1) according to claim 2 or formula (1-2) according to claim 14. The heat radiating member according to any one of claims 1 to 22.   The heat dissipation member according to any one of claims 1 to 23, wherein the liquid crystal composition contains an inorganic filler.   The heat dissipation member according to any one of claims 1 to 23, wherein the liquid crystal composition contains a metal filler.   26. The liquid crystal polymer according to any one of claims 1 to 25, wherein the liquid crystal polymer is obtained by polymerizing the liquid crystal composition in a homogeneous, twist, homeotropic, hybrid, bend or spray orientation. Heat dissipation member.   26. The liquid crystal polymer according to claim 1, wherein the liquid crystal polymer is obtained by polymerizing the liquid crystal composition by homogeneous, twist, homeotropic, hybrid or spray alignment with an alignment control additive. The heat radiating member of description.   The heat-radiating member according to any one of claims 1 to 25, wherein the liquid crystal polymer is obtained by polymerizing the liquid crystal composition by subjecting the liquid crystal composition to homogeneous, twist, hybrid, or spray alignment by rubbing treatment. .   It is a polymer molded object, The heat radiating member in any one of Claims 1-28 characterized by the above-mentioned.   It is a sheet | seat, The heat radiating member in any one of Claims 1-28 characterized by the above-mentioned.   It is a film, The heat radiating member in any one of Claims 1-28 characterized by the above-mentioned.   It is a thin film, The heat radiating member in any one of Claims 1-28 characterized by the above-mentioned.   The heat radiating member according to claim 1, wherein the heat conductivity is 0.3 W / (K · m) or more.   A liquid crystal composition containing a polymerizable liquid crystal compound having a polymerizable group at the end is subjected to orientation control of the mesogenic portion of the liquid crystal compound by an alignment film, an alignment control additive, a rubbing treatment, or the self-alignment regulating force of the composition. A method for producing a heat radiating member comprising polymerizing.