WO2018096726A1 - Polymère à cristaux liquides photoréticulable, et procédé de fabrication de polymère à cristaux liquides photoréticulable - Google Patents

Polymère à cristaux liquides photoréticulable, et procédé de fabrication de polymère à cristaux liquides photoréticulable Download PDF

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WO2018096726A1
WO2018096726A1 PCT/JP2017/025651 JP2017025651W WO2018096726A1 WO 2018096726 A1 WO2018096726 A1 WO 2018096726A1 JP 2017025651 W JP2017025651 W JP 2017025651W WO 2018096726 A1 WO2018096726 A1 WO 2018096726A1
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liquid crystalline
crystalline polymer
containing compound
photocrosslinkable
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PCT/JP2017/025651
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Japanese (ja)
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井関　清治
彰則 佐藤
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東洋ゴム工業株式会社
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Priority to JP2018552403A priority Critical patent/JP7112332B2/ja
Publication of WO2018096726A1 publication Critical patent/WO2018096726A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen

Definitions

  • the present invention relates to a photocrosslinkable liquid crystalline polymer and a method for producing a photocrosslinkable liquid crystalline polymer.
  • a liquid crystalline polymer having a mesogenic group in the molecular structure changes in physical properties with a change in the degree of orientation of the liquid crystal (mesogenic group). Paying attention to such properties, attempts have been made to use liquid crystalline polymers as elastomers in various applications.
  • liquid crystalline polyurethane elastomer obtained by a reaction of a diisocyanate component, a high molecular weight polyol component, and a mesogenic diol (see, for example, Patent Document 1).
  • the liquid crystalline polyurethane elastomer of Patent Document 1 was developed by the present applicant and has rubber elasticity in the liquid crystal expression temperature range. This liquid crystalline polyurethane elastomer has a lower liquid crystal expression temperature than conventional liquid crystalline polyurethane.
  • liquid crystalline polymer In order to obtain a liquid crystalline polymer, it is necessary to cure (crosslink) the raw material of the liquid crystalline polymer in the liquid crystal expression temperature range (liquid crystal phase). Moreover, in order to make a liquid crystalline polymer easy to use industrially, it is required that it can be processed into various shapes while maintaining a liquid crystal phase.
  • the liquid crystalline polymer of Patent Document 1 is designed to lower the liquid crystal expression temperature, and as a means therefor, using a trifunctional or higher functional isocyanate as the isocyanate component, A high molecular weight polyol component having 3 or more hydroxyl groups is used as the high molecular weight polyol component.
  • a cross-linking reaction proceeds between the raw materials while maintaining a liquid crystal phase during thermoforming, and a liquid crystalline polymer (liquid crystalline elastomer having rubber elasticity) ) Can be obtained.
  • thermosetting method the melt viscosity of the polymer increases with the progress of crosslinking, so that the reaction is difficult to control.
  • the liquid crystal polymer raw material may be cured at an early stage inside the molding machine. For this reason, in industrial production of liquid crystalline polymers, there is a need for an improvement measure that does not hinder continuous production due to an increase in the melt viscosity of the polymer or early curing of raw materials.
  • the liquid crystalline polymer of the above-mentioned Patent Document 1 is one in which molding and curing (crosslinking) of raw materials are performed simultaneously inside the molding machine. However, if molding and curing (crosslinking) can be performed separately, It is considered that there is no risk of increasing the melt viscosity of the polymer inside and curing of the raw materials, and it can be applied to industrial continuous production.
  • An object of the present invention is to provide a new liquid crystalline polymer produced by separating molding and curing (crosslinking). Moreover, it aims at providing the manufacturing method of such a new liquid crystalline polymer.
  • the characteristic constitution of the photocrosslinkable liquid crystalline polymer according to the present invention for solving the above problems is as follows:
  • the object is to include a reaction product of a mesogen group-containing compound having an active hydrogen group, an isocyanate compound, a photopolymerizable group-containing compound, and a photocuring initiator.
  • the present inventors examined a photocrosslinkable (photocurable) liquid crystalline polymer as a new liquid crystalline polymer produced without using the thermosetting method. If it is a photocrosslinkable liquid crystalline polymer, the molding of the raw material and the photocrosslinking (curing) can be carried out as separate steps, so the melt viscosity of the polymer increases inside the molding machine or the raw material is cured. Is prevented. Therefore, it becomes possible to continuously produce the liquid crystalline polymer, and it is possible to cope with industrial production.
  • the photocrosslinkable liquid crystalline polymer of this configuration is a reaction of a mesogen group-containing compound having an active hydrogen group, an isocyanate compound, a photopolymerizable group-containing compound, and a photocuring initiator, the applicable range is It is obtained as a wide liquid crystalline polyurethane and can be easily molded even in a low temperature region including normal temperature, and the whole polymer is cured uniformly.
  • the raw material can be cured in a state where the temperature after molding is sufficiently lowered (that is, in a state where a liquid crystal phase is expressed), it becomes easy to form a monodomain, and the resulting photocrosslinkable liquid crystalline polymer
  • the temperature range of the liquid crystal phase is a relatively low temperature range including normal temperature.
  • Such a photocrosslinkable liquid crystalline polymer having low-temperature liquid crystal developability can be suitably used, for example, as a heat-responsive material utilizing a phase transition between a liquid crystal phase and an isotropic phase.
  • the mesogenic group-containing compound having an active hydrogen group is represented by the following general formula (1): (Wherein X is an active hydrogen group, R 1 is a single bond that forms part of an adjacent linking group, —N ⁇ N—, —CO—, —CO—O—, or —CH ⁇ N— R 2 is a single bond that forms part of an adjacent linking group, or —O—, and R 3 is a single bond that forms part of an adjacent linking group, or an alkylene group having 1 to 20 carbon atoms. (However, the case where R 2 is —O— and R 3 is a single bond forming a part of the adjacent linking group is excluded.) It is preferable that it is a compound represented by these.
  • the photocrosslinkable liquid crystalline polymer of this configuration since the compound having the appropriate structure described above is used as the mesogenic group-containing compound having an active hydrogen group, the practicality of having liquid crystallinity in a low temperature region including normal temperature High photocrosslinkable liquid crystalline polymer can be prepared.
  • the photopolymerizable group-containing compound is preferably at least one selected from the group consisting of acryloyl group-containing compounds, methacryloyl group-containing compounds, and allyl group-containing compounds.
  • the above-mentioned appropriate compound is used as the photopolymerizable group-containing compound, so that the photocrosslinking reaction by light irradiation proceeds quickly and reliably, and low temperature liquid crystal expression
  • a photocrosslinkable liquid crystalline polymer having both properties and rubber elasticity can be produced.
  • the photocrosslinkable liquid crystalline polymer according to the present invention It is preferable to contain 1 to 10% by weight of the photopolymerizable group-containing compound.
  • photocrosslinkable liquid crystalline polymer of this configuration by containing 1 to 10% by weight of the photopolymerizable group-containing compound, a photocrosslinkable liquid crystalline polymer having an excellent balance between low temperature liquid crystal developability and rubber elasticity is obtained. Can be produced.
  • the characteristic configuration of the method for producing a photocrosslinkable liquid crystalline polymer according to the present invention is as follows: A mixing step of mixing a mesogenic group-containing compound having an active hydrogen group, an isocyanate compound, a photopolymerizable group-containing compound, and a photocuring initiator; An irradiation step of irradiating the mixture obtained in the mixing step with light having a wavelength of 200 to 600 nm; It is to include.
  • the mixture can be easily molded even in a low temperature region including normal temperature, and the whole polymer can be cured uniformly. Moreover, since the mixture can be cured by irradiating the mixture with light in a state where the temperature is sufficiently lowered after forming (ie, a state in which a liquid crystal phase is developed), it becomes easy to make a monodomain, and the resulting photocrosslinking
  • the temperature range of the liquid crystal phase of the liquid crystalline polymer is a relatively low temperature range including normal temperature.
  • the isocyanate compound is contained in the raw material, a liquid crystalline polyurethane with a wide application range as a liquid crystalline polymer can be produced.
  • the irradiation step is performed in a state where the mesogen groups contained in the mesogen group-containing compound are aligned in the stretching direction by the stretching step, so that the orientation is maintained.
  • a photocrosslinking reaction proceeds between raw materials, and a liquid crystalline polymer having both low-temperature liquid crystal developability and elasticity can be obtained.
  • the orientation of the liquid crystal is increased by the stretching process, the phase transition between the liquid crystal phase and the isotropic phase becomes clear, and a material having excellent thermal response can be manufactured.
  • the photocrosslinkable liquid crystalline polymer of the present invention includes a mesogen group-containing compound having an active hydrogen group (hereinafter simply referred to as “mesogen group-containing compound”), an isocyanate compound, a photopolymerizable group-containing compound, and a photocuring initiator. Is a liquid crystalline polyurethane elastomer obtained by reacting these four raw materials.
  • the photocrosslinkable liquid crystalline polymer (liquid crystalline polyurethane elastomer) of the present invention has liquid crystallinity generated from a mesogen group-containing compound and elasticity generated due to a reaction between the mesogen group-containing compound, an isocyanate compound, and a photopolymerizable group-containing compound. And the physical properties change due to the phase transition of the liquid crystal, and the temperature range where the liquid crystal phase appears is a relatively low temperature range including normal temperature.
  • Such a liquid crystalline polymer having a low-temperature liquid crystal display property exhibits a specific behavior in which the physical properties change due to the phase transition of the liquid crystal, for example, utilizing the phase transition between the liquid crystal phase and the isotropic phase. It can be suitably used as a thermoresponsive material.
  • the photocrosslinkable liquid crystalline polymer (liquid crystalline polyurethane elastomer) of the present invention and the mesogen group-containing compound, isocyanate compound, photopolymerizable group-containing compound, and photocuring initiator that are raw materials thereof will be described. .
  • mesogenic group-containing compound for example, a compound represented by the following general formula (1) is used.
  • X is an active hydrogen group
  • R 1 is a single bond that forms part of an adjacent linking group, —N ⁇ N—, —CO—, —CO—O—, or —CH ⁇ .
  • N— is a single bond that forms part of an adjacent linking group, or —O—
  • R 3 is a single bond that forms part of an adjacent linking group, or alkylene having 1 to 20 carbon atoms. It is a group. However, the case where R 2 is —O— and R 3 is a single bond forming a part of the adjacent linking group is excluded.
  • the “single bond forming a part of the adjacent linking group” means a state in which the single bond is shared with a part of the adjacent linking group.
  • R 1 when R 1 is a single bond forming part of the coupling group adjacent, R 1 is a single bond in a state of being shared with both sides of the benzene ring, of the sides benzene A biphenyl structure is formed with the ring.
  • X include OH, SH, NH 2 , COOH, secondary amine and the like.
  • the blending amount of the mesogen group-containing compound is adjusted so as to be 30 to 80% by weight, preferably 40 to 70% by weight, based on the total raw material of the photocrosslinkable liquid crystalline polymer.
  • the blending amount of the mesogen group-containing compound is less than 30% by weight, liquid crystallinity is hardly exhibited in the produced polymer.
  • the phase transition temperature (Ti) between the liquid crystal phase and the isotropic phase becomes high, and it becomes difficult to mold the polymer in a low temperature region including normal temperature.
  • alkylene oxide and / or styrene oxide in combination with the mesogenic group-containing compound. Since the alkylene oxide and / or styrene oxide functions to lower the liquid crystallinity expression temperature in the photocrosslinkable liquid crystalline polymer, the photocrosslinkability produced by using the alkylene oxide and / or styrene oxide in combination with the mesogen group-containing compound.
  • the liquid crystalline polymer can be a product excellent in practicality at room temperature.
  • the alkylene oxide for example, ethylene oxide, propylene oxide, or butylene oxide can be used.
  • the above alkylene oxides may be used alone or in combination of two or more.
  • styrene oxide you may have substituents, such as an alkyl group, an alkoxy group, and a halogen, in a benzene ring.
  • alkylene oxide a mixture of the above-mentioned alkylene oxide and the above-mentioned styrene oxide can be used.
  • the blending amount of alkylene oxide and / or styrene oxide is adjusted so that 1 to 10 mol, preferably 2 to 6 mol, of alkylene oxide and / or styrene oxide is added to 1 mol of the mesogen group-containing compound.
  • the added mole number of alkylene oxide and / or styrene oxide is less than 1 mole, it is difficult to sufficiently reduce the temperature range in which the liquid crystallinity of the photocrosslinkable liquid crystalline polymer is exhibited. It becomes difficult to continuously mold a liquid crystalline polymer (liquid crystalline polyurethane) in a state where the above has developed.
  • the added mole number of alkylene oxide and / or styrene oxide exceeds 10 moles, the liquid crystallinity of the photocrosslinkable liquid crystalline polymer may be difficult to be exhibited.
  • isocyanate compound for example, a diisocyanate compound or a trifunctional or higher functional isocyanate compound can be used.
  • diisocyanate compounds include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate.
  • Aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylylene diisocyanate, and m-xylylene diisocyanate, ethylene diisocyanate, 2,2,4-trimethylhexamethylene-1,6-diisocyanate, 2, Aliphatic diisocyanates such as 4,4-trimethylhexamethylene-1,6-diisocyanate and 1,6-hexamethylene diisocyanate; B hexane diisocyanate, cyclohexane diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, isophorone diisocyanate, and include alicyclic diisocyanates such as norbornane diisocyanate.
  • diisocyanate compounds may be used alone or in combination of two or more.
  • trifunctional or higher functional isocyanate compounds include triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, lysine ester triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,6,11-undecane triisocyanate, Examples thereof include triisocyanates such as 1,8-diisocyanate-4-isocyanate methyloctane and bicycloheptane triisocyanate, and tetraisocyanates such as tetraisocyanate silane.
  • the above trifunctional or higher functional isocyanate compounds may be used singly or as a mixture of plural kinds.
  • As the isocyanate compound it is possible to use a mixture of the above-mentioned diisocyanate compound and the above-described trifunctional or higher isocyanate compound.
  • the compounding amount of the isocyanate compound is adjusted so as to be 10 to 40% by weight, preferably 15 to 30% by weight in the whole raw material of the photocrosslinkable liquid crystalline polymer. When the blending amount of the isocyanate compound is less than 10% by weight, the polymerization by the urethane reaction becomes insufficient, so that it becomes difficult to continuously mold the liquid crystalline polymer (liquid crystalline polyurethane).
  • the blending amount of the isocyanate compound exceeds 40% by weight, the blending amount of the mesogen group-containing compound in the entire raw material of the photocrosslinkable liquid crystalline polymer becomes relatively small, so that the liquid crystallinity of the liquid crystalline polymer (liquid crystalline polyurethane) Decreases.
  • Photopolymerizable group-containing compound for example, an acryloyl group-containing compound, a methacryloyl group-containing compound, or an allyl group-containing compound can be used.
  • acryloyl group-containing compounds examples include propylene glycol diglycidyl ether acrylic acid adduct, ethylene glycol diglycidyl ether methacrylic acid adduct, tripropylene glycol diglycidyl ether acrylic acid adduct, glycerin diglycidyl ether acrylic acid adduct, bisphenol A PO 2 mol adduct diglycidyl ether acrylic acid adduct, 2-acryloyloxyethyl succinate, ⁇ -carboxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxy-3-phenoxy Propyl acrylate, 2-acryloyloxyethyl-succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acrylo Rokishiechiru - phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl
  • methacryloyl group-containing compounds examples include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloic acid.
  • allyl group-containing compounds include glycerin monoallyl ether, trimethylolpropane diallyl ether, pentaerythritol triallyl ether and the like.
  • the blending amount of the photopolymerizable group-containing compound is adjusted so as to be 0.1 to 10% by weight, preferably 0.3 to 7% by weight, in the whole raw material of the photocrosslinkable liquid crystalline polymer.
  • the blending amount of the photopolymerizable group-containing compound is less than 0.1% by weight, the raw material is not sufficiently cured even when irradiated with light, and thus the produced polymer is less likely to exhibit thermal responsiveness.
  • the blending amount of the photopolymerizable group-containing compound exceeds 10% by weight, the crosslink density in the polymer after light irradiation becomes too high, so that also in this case, the produced polymer is difficult to exhibit thermal responsiveness.
  • photocuring initiator examples include 1-hydroxy-cyclohexyl-phenyl-ketone, bis (2,4,6-trimethylbenzoyl) -phenylphosphonic oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone / benzophenone, 1- [ 4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) ) -Benzyl] -phenyl ⁇ -2-methyl-propan-1-one, oxy-phenyl-acetic Cyd 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester
  • the blending amount of the photocuring initiator is adjusted so as to be 0.5 to 10% by weight, preferably 1 to 8% by weight in the whole raw material of the photocrosslinkable liquid crystalline polymer.
  • the blending amount of the photocuring initiator is less than 0.5% by weight, the polymerization reaction does not proceed uniformly at the time of light irradiation or the curing becomes insufficient, so that the produced polymer is less likely to exhibit thermal responsiveness.
  • the blending amount of the photocuring initiator exceeds 10% by weight, the content of mesogenic groups in the produced polymer is decreased, so that liquid crystal properties are hardly exhibited.
  • the photocuring initiator preferably has an absorption wavelength of 200 to 600 nm.
  • the photocuring initiator has an absorption wavelength in the above range, the photocuring initiator emits light even if the photocrosslinkable liquid crystalline polymer or its raw material has low transparency (transmittance of visible light). It can absorb and reliably advance the photocrosslinking reaction.
  • the photocrosslinkable liquid crystalline polymer is produced by irradiating a raw material containing a mesogen group-containing compound, an isocyanate compound, a photopolymerizable group-containing compound, and a photocuring initiator with light. Specifically, the raw material is kneaded and heated, formed into a predetermined shape using an extruder, and then irradiated with light to cause a photocrosslinking reaction between the raw materials to be cured.
  • the light applied to the raw material is preferably ultraviolet light or visible light having a wavelength of 200 to 600 nm.
  • the raw material can be kneaded and heated, then stretched and molded, and then cured in a state where the temperature is sufficiently lowered by cooling. That is, molding and photocrosslinking (curing) can be performed as separate steps. Accordingly, it is possible to obtain a photocrosslinkable liquid crystalline polymer in which a liquid crystal phase is surely developed in a low temperature region.
  • the photocrosslinkable liquid crystalline polymer of the present invention can be easily molded even in a low temperature region including normal temperature, and the entire polymer can be uniformly cured.
  • the raw material can be cured in a state where the temperature is sufficiently lowered after molding (that is, in a state where a liquid crystal phase is expressed), it becomes easy to make a monodomain, and the generated photocrosslinkable liquid crystalline polymer
  • the expression temperature range of the liquid crystal phase is a relatively low temperature range including normal temperature.
  • the kneading and heating of the raw material of the photocrosslinkable liquid crystalline polymer can be performed simultaneously with the molding in an extruder.
  • raw materials are put into an extruder and sufficiently kneaded and heated.
  • the kneaded melt is extruded while being stretched in a temperature range in which liquid crystallinity develops (that is, a glass transition temperature (T g ) or more and a phase transition temperature (T i ) or less).
  • T g glass transition temperature
  • T i phase transition temperature
  • the stretched kneaded melt is formed into an appropriate shape, cooled, and irradiated with light having a wavelength of 200 to 600 nm while maintaining the stretched state, the crosslinking reaction proceeds between the raw materials while maintaining the orientation, and the low temperature liquid crystal A photocrosslinkable liquid crystalline polymer having both expression and elasticity is completed. This is a continuous manufacturing method.
  • the raw material of the photocrosslinkable liquid crystalline polymer is previously kneaded and heated to be formed into a pellet, and after the pelletized raw material is molded into a predetermined shape using an extruder, the temperature at which liquid crystallinity is manifested Stretching in the region (that is, not less than the glass transition temperature (T g ) and not more than the phase transition temperature (T i )) and irradiating with light having a wavelength of 200 to 600 nm while maintaining the stretched state produces a photocrosslinkable liquid crystalline polymer. It is also possible. This is a batch manufacturing method.
  • the mesogenic group is oriented in the stretching direction in the low temperature region, but when heated and exceeds the phase transition temperature (T i ), the orientation of the mesogenic group collapses. When it shrinks (roughly) in the stretching direction, cools and falls below the phase transition temperature (T i ), the orientation of the mesogenic group is restored and exhibits a specific thermal responsive behavior in which it stretches in the stretching direction.
  • the orientation of the photocrosslinkable liquid crystalline polymer can be evaluated by the degree of orientation of the mesogenic group.
  • the degree of orientation was determined by one-time total reflection measurement (ATR) using a Fourier transform infrared spectrophotometer (FT-IR), the absorbance (0 °, 90 °) of the antisymmetric stretching vibration of the aromatic ether, and methyl Absorbance (0 °, 90 °) of the symmetrical bending vibration of the group is measured, and is calculated based on the following calculation formula using these absorbances as parameters.
  • ATR one-time total reflection measurement
  • FT-IR Fourier transform infrared spectrophotometer
  • the degree of orientation of the mesogenic group is preferably 0.05 or more, and more preferably 0.1 or more.
  • the photocrosslinkable liquid crystalline polymer (liquid crystalline polyurethane elastomer) of the present invention was prepared and its characteristics were confirmed.
  • the unit of the blending amount of each raw material is “g”, but the present invention can be scaled up at an arbitrary magnification. That is, the unit of the blending amount of each raw material can be read as “parts by weight”.
  • Example 1 In a reaction vessel, BH6 (500 g) in which R 1 of formula (1) is a single bond as a mesogen group-containing compound having an active hydrogen group, potassium hydroxide (19 g), and N, N-dimethylformamide (3000 ml) as a solvent
  • R 1 of formula (1) is a single bond as a mesogen group-containing compound having an active hydrogen group
  • potassium hydroxide (19 g) potassium hydroxide (19 g)
  • N, N-dimethylformamide (3000 ml) as a solvent
  • 5 equivalents of propylene oxide as alkylene oxide with respect to 2 moles of BH6 that is, 2.5 equivalents with respect to 1 mole of BH6
  • Reacted at 120 ° C. for 2 hours (addition reaction).
  • mesogenic diol A A synthesis scheme of mesogenic diol A is shown in Formula (2).
  • the mesogen diol A shown in Formula (2) is typical, and may contain various structural isomers.
  • mesogenic diol A 100 g
  • 2-hydroxyethyl acrylate (2 g) as a photopolymerizable group-containing compound
  • propylene glycol diglycidyl ether acrylic acid adduct 1 g
  • 2,4,6- Trimethylbenzoyl-diphenyl-phosphine oxide 3 g
  • 1,6-hexamethylene diisocyanate 35 g
  • the resin was pulverized with a plastic pulverizer (product name: ZI-420, manufactured by Horai Co., Ltd.) to be pelletized. Subsequently, the resin pellets were put into a single-screw extruder (product name: SZW25GT-24MG-STD, manufactured by Technobell Co., Ltd.) set at 80 to 120 ° C., and molded into a resin sheet having a thickness of 1.0 mm. The resin sheet was passed through a cooling roll set at 15 ° C., cooled to a glass transition temperature (Tg) or higher and a phase transition temperature (Ti) or lower, and taken up with a take-up roll.
  • Tg glass transition temperature
  • Ti phase transition temperature
  • the resin sheet was stretched 1.5 to 10 times by providing a rotational difference between the cooling roll and the take-up roll. Further, a desktop UV curing device (product name: imini grantage (ESC-1511U), manufactured by iGraphics Co., Ltd.) is installed between the cooling roll and the take-up roll, and the stretched resin sheet has a wavelength of 200 to The photocrosslinkable liquid crystalline polymer of Example 1 was obtained by being irradiated with light of 600 nm and photocrosslinked (cured).
  • a desktop UV curing device product name: imini grantage (ESC-1511U), manufactured by iGraphics Co., Ltd.
  • Example 2 In preparing the raw material of the photocrosslinkable liquid crystalline polymer, 2-hydroxyethyl acrylate (1.5 g) and propylene glycol diglycidyl ether acrylic acid adduct (6 g) as the photopolymerizable group-containing compound, and 1, 6-hexamethylene diisocyanate (38 g) was blended. Other raw materials, blending amounts, and production conditions were the same as in Example 1, and the photocrosslinkable liquid crystalline polymer of Example 2 was obtained.
  • Example 3 In preparing the raw material of the photocrosslinkable liquid crystalline polymer, 2-hydroxyethyl acrylate (1 g) and propylene glycol diglycidyl ether acrylic acid adduct (3 g) as the photopolymerizable group-containing compound, and 1,6- Hexamethylene diisocyanate (36 g) was blended. Other raw materials, blending amounts, and production conditions were the same as in Example 1, and the photocrosslinkable liquid crystalline polymer of Example 3 was obtained.
  • Example 4 In preparing the raw material of the photocrosslinkable liquid crystalline polymer, propylene glycol diglycidyl ether acrylic acid adduct (8 g) and 2-hydroxyethyl methacrylate (2 g) as the photopolymerizable group-containing compound, and 1,6- Hexamethylene diisocyanate (39 g) was blended. Other raw materials, blending amounts, and production conditions were the same as in Example 1, and the photocrosslinkable liquid crystalline polymer of Example 4 was obtained.
  • Example 5 In preparing the raw material of the photocrosslinkable liquid crystalline polymer, 2-hydroxyethyl acrylate (0.5 g) and glyceryl monoallyl ether (2 g) as the photopolymerizable group-containing compound and 1,6-hexamethylene diisocyanate as the isocyanate compound (36 g) was blended. Other raw materials, blending amounts, and production conditions were the same as in Example 1, and the photocrosslinkable liquid crystalline polymer of Example 5 was obtained.
  • Example 6 In a reaction vessel, BH6 (500 g) in which R 1 of formula (1) is a single bond as a mesogen group-containing compound having an active hydrogen group, potassium hydroxide (19 g), and N, N-dimethylformamide (3000 ml) as a solvent
  • R 1 of formula (1) is a single bond as a mesogen group-containing compound having an active hydrogen group
  • potassium hydroxide (19 g) potassium hydroxide (19 g)
  • N, N-dimethylformamide (3000 ml) as a solvent
  • 5 equivalents of propylene oxide as alkylene oxide with respect to 4 moles of BH6 ie, 1.25 equivalents with respect to 1 mole of BH6 were added.
  • Reacted at 120 ° C. for 2 hours (addition reaction).
  • mesogenic diol B A synthesis scheme of mesogenic diol B is shown in Formula (3).
  • the mesogen diol B shown in Formula (3) is typical, and may contain various structural isomers.
  • mesogenic diol B 100 g
  • 2-hydroxyethyl acrylate 1.5 g
  • propylene glycol diglycidyl ether acrylic acid adduct 2 g
  • 2,4,4 as a photocuring initiator
  • 6-Trimethylbenzoyl-diphenyl-phosphine oxide 3 g
  • 1,6-hexamethylene diisocyanate 41 g
  • Example 7 In a reaction vessel, BH6 (500 g) in which R 1 of formula (1) is a single bond as a mesogen group-containing compound having an active hydrogen group, potassium hydroxide (19 g), and N, N-dimethylformamide (3000 ml) as a solvent
  • R 1 of formula (1) is a single bond as a mesogen group-containing compound having an active hydrogen group
  • potassium hydroxide (19 g) potassium hydroxide (19 g)
  • N, N-dimethylformamide (3000 ml) as a solvent
  • 3 equivalents of propylene oxide as alkylene oxide with respect to 4 moles of BH6 ie, 0.75 equivalent with respect to 1 mole of BH6 were added, and these mixtures were subjected to pressure conditions. , Reacted at 120 ° C. for 2 hours (addition reaction).
  • mesogenic diol C A synthesis scheme of mesogenic diol C is shown in Formula (4).
  • the mesogen diol C shown in Formula (4) is typical, and may contain various structural isomers.
  • Example 8 In a reaction vessel, BHBA6 (500 g) in which R 1 in formula (1) is —CH ⁇ N—, potassium hydroxide (19 g) as a mesogen group-containing compound having an active hydrogen group, and N, N-dimethylformamide as a solvent (3000 ml) is added and mixed, and further 5 equivalents of propylene oxide as alkylene oxide to 2 moles of BHBA6 (that is, 2.5 equivalents to 1 mole of BHBA6) are added, and the mixture is added. The reaction was carried out at 120 ° C. for 2 hours under pressure (addition reaction).
  • mesogenic diol D A synthesis scheme of mesogenic diol D is shown in Formula (5).
  • the mesogen diol D shown in Formula (5) is typical, and may contain various structural isomers.
  • mesogendiol D 100 g
  • 2-hydroxyethyl acrylate (1 g) as a photopolymerizable group-containing compound
  • propylene glycol diglycidyl ether acrylic acid adduct 3 g
  • 2,4,6- Trimethylbenzoyl-diphenyl-phosphine oxide 3 g
  • 1,6-hexamethylene diisocyanate 34 g
  • the photocrosslinkable liquid crystalline polymers of Examples 1 to 8 had good extrudability of the liquid crystalline polymer even in a low temperature region including normal temperature. Therefore, it was possible to uniformly cure the entire liquid crystalline polymer by performing light irradiation after extrusion molding.
  • the liquid crystalline polymer after irradiation with light has a glass transition temperature (Tg) and a phase transition temperature (Ti) with room temperature (about 20 to 30 ° C.) interposed therebetween, and thus is an excellent material for usability.
  • Tg glass transition temperature
  • Ti phase transition temperature
  • room temperature about 20 to 30 ° C.
  • the liquid crystalline polymer of Comparative Example 2 was hardened in the extruder and could not be discharged to the outside.
  • the photocrosslinkable liquid crystalline polymer of the present invention can be formed and cured (crosslinked) separately, and as a result, there is no risk of the raw material being cured inside the molding machine. It is a highly practical material.
  • the photocrosslinkable liquid crystalline polymer of the present invention may be used in the fields of clothing products (fibers), actuators, filters and the like.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention fournit un nouveau polymère à cristaux liquides élaboré en séparant le moulage et le durcissement (réticulation). Plus précisément, l'invention concerne un polymère à cristaux liquides photoréticulable qui contient un produit de réaction d'un composé à teneur en groupe mésogène possédant un groupe hydrogène actif, d'un composé isocyanate, d'un composé à teneur en groupe photopolymérisable et d'un initiateur de photodurcissement. Le composé à teneur en groupe mésogène possédant un groupe hydrogène actif consiste en un composé représenté par la formule générale (1) (Dans la formule, X représente le groupe hydrogène actif, Ｒ１ représente －Ｎ＝Ｎ－, －ＣＯ－, －ＣＯ－Ｏ－, －ＣＨ＝Ｎ－ ou une liaison simple formant une partie d'un groupe de liaison adjacent, Ｒ２ représente －Ｏ－ ou une liaison simple formant une partie d'un groupe de liaison adjacent, et Ｒ３ représente une liaison simple formant une partie d'un groupe de liaison adjacent ou un groupe alkylène de 1 à 20 atomes de carbone. Cependant, le cas où Ｒ２ représente －Ｏ－, et Ｒ３ représente une liaison simple formant une partie d'un groupe de liaison adjacent, est exclu).
PCT/JP2017/025651 2016-11-28 2017-07-14 Polymère à cristaux liquides photoréticulable, et procédé de fabrication de polymère à cristaux liquides photoréticulable WO2018096726A1 (fr)

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JP2019112605A (ja) * 2017-12-22 2019-07-11 Ｔｏｙｏ Ｔｉｒｅ株式会社 液晶性ポリマー、及び液晶性ポリマーの製造方法
JP2019112606A (ja) * 2017-12-22 2019-07-11 Ｔｏｙｏ Ｔｉｒｅ株式会社 シリコーン含有液晶性ポリマー、及びシリコーン含有液晶性ポリマーの製造方法
JP7425595B2 (ja) 2019-12-23 2024-01-31 Ｔｏｙｏ Ｔｉｒｅ株式会社 光架橋性液晶ポリマー組成物、架橋型液晶ポリマーおよびその製造方法

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JP7425595B2 (ja) 2019-12-23 2024-01-31 Ｔｏｙｏ Ｔｉｒｅ株式会社 光架橋性液晶ポリマー組成物、架橋型液晶ポリマーおよびその製造方法

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