CN111040775B

CN111040775B - Wide temperature range liquid crystal composition, wide temperature range polymer dispersed liquid crystal composition and wide temperature range polymer dispersed liquid crystal film

Info

Publication number: CN111040775B
Application number: CN201811183595.3A
Authority: CN
Inventors: 祝春才; 杨亚非
Original assignee: Jiangsu Hecheng Display Technology Co Ltd
Current assignee: Jiangsu Hecheng Display Technology Co Ltd
Priority date: 2018-10-11
Filing date: 2018-10-11
Publication date: 2023-09-08
Anticipated expiration: 2038-10-11
Also published as: CN111040775A

Abstract

The invention provides a wide-temperature liquid crystal composition for polymer dispersed liquid crystal, a wide-temperature polymer dispersed liquid crystal composition and a wide-temperature polymer dispersed liquid crystal film, wherein the liquid crystal composition consists of at least two liquid crystal molecules, and the wide-temperature polymer dispersed liquid crystal film prepared from the wide-temperature liquid crystal composition has the advantages of low driving voltage, quick response, good optical performance, high reliability, wide use temperature range and the like, and solves the problems of poor reliability and narrow working temperature range of a PDLC product in the prior art.

Description

Wide temperature range liquid crystal composition, wide temperature range polymer dispersed liquid crystal composition and wide temperature range polymer dispersed liquid crystal film

Technical Field

The invention belongs to the technical field of liquid crystal materials and liquid crystal display devices, relates to a liquid crystal composition, in particular to a wide-temperature liquid crystal composition, a wide-temperature polymer dispersed liquid crystal composition and a wide-temperature polymer dispersed liquid crystal film.

Background

Polymer dispersed liquid crystal (Polymer Dispersed Liquid Crystal, PDLC) is a novel composite liquid crystal material with electro-optical properties, which was discovered by accident several decades ago, which is a two-phase system consisting of liquid crystal and polymer, in which small-molecule liquid crystals are dispersed in a transparent polymer system by UV or heating methods, forming micro-or nano-sized liquid crystal droplets, the polymer system providing a stable network structure for the small-molecule liquid crystals. The application of PDLC is strongly dependent on the composition, morphology, size, nature of the phase interface, particle size control, matching of the two-phase properties, etc. of the two-phase system.

Under the condition of no external voltage, a regular electric field cannot be formed between the PDLC films, the optical axes of the liquid crystal molecules are randomly oriented and present a disordered state, the effective refractive index of the liquid crystal molecules is not matched with the refractive index of the polymer, the incident light is strongly scattered, and the PDLC films are opaque or semitransparent; after external voltage is applied, the optical axis of the liquid crystal molecules is arranged perpendicular to the surface of the film, namely, the direction of the electric field is consistent, the effective refractive index of the liquid crystal molecules is basically matched with the refractive index of the polymer, no obvious interface exists, a basically uniform medium is formed, incident light is basically not scattered, and the PDLC film is transparent. Therefore, the PDLC film has an optical switching characteristic by the applied electric field. Specifically, the PDLC film can be used as intelligent glass, and can form shielding property under voltage drive through the induction of polymer materials to light and/or heat, so that the purpose of controlling room temperature is achieved, and meanwhile, the PDLC film has the effects of energy conservation and environmental protection and is widely applied to products such as automobile window films, curtains, screens and the like.

Since the liquid crystal molecules have optical anisotropy and dielectric anisotropy, the PDLC film has remarkable optical characteristics, and the indexes for measuring the photoelectric performance of the PDLC film include driving voltage, response time, transmittance and the like. The above properties are significantly dependent on the materials selected, the method of preparation, and the process. In addition, the structure and application properties of the PDLC film are also subject to process conditions, and subtle differences in the process conditions may have a non-negligible effect on the degree of phase separation, the speed of phase separation, the structure and morphology of the two phases, and the structure and properties of the phase interface, thereby affecting the parameters of the PDLC film such as driving voltage, response time, haze, viewing angle, transmittance, and the like.

The prior PDLC product has larger improvement and disclosure in the aspect of reliability, and the defects of increased power consumption, yellowing, poor optical switching characteristics and the like of the product are easy to occur in long-time high-temperature and sunlight environments; in addition, the off-state haze may be deteriorated under a high temperature environment (particularly, at 60 ℃ or higher), the shielding property may be lost, and the characteristics of the optical switch may be lost.

Disclosure of Invention

In order to solve the technical problems in the prior art, the invention provides a wide-temperature liquid crystal composition, a wide-temperature polymer dispersed liquid crystal composition and a wide-temperature polymer dispersed liquid crystal film, which have the advantages of low driving voltage, quick response, good optical performance, high reliability, wide use temperature range and the like, and solve the problems of poor reliability and narrow working temperature range of a PDLC product in the prior art.

One of the purposes of the present invention is to provide a wide temperature range liquid crystal composition of a polymer dispersed liquid crystal, the composition comprises a component A and a component B, wherein the component A comprises a compound shown as a formula I-1 and/or a formula I-2, and the component B comprises any one compound or a combination of at least two compounds in a formula II-1, a formula II-2 or a formula II-3;

wherein R is ₁ 、R ₂ 、R ₃ 、R ₅ And R is ₇ Each independently C1-C10 chain alkyl or alkoxy, ring A, ring B, ring C, ring D, ring E, ring F, ring G, ring H and ring I are each independently at least one of 1, 4-cyclohexylene, 1, 4-phenylene, 1, 4-cyclohexylene, -CH ₂ -a group substituted by-O-, a group in which at least one carbon-carbon single bond in 1, 4-cyclohexylene is replaced by a carbon-carbon double bond, a group in which at least one-H in 1, 4-phenylene is replaced by-CN, -F or-Cl, or a group in at least one-ch=in 1, 4-phenylene is replaced by-n=z ₁ 、Z ₂ 、Z ₃ 、Z ₄ 、Z ₅ Or Z is ₆ Each independently is a single bond or-COO-, X ₁ ～X ₄ Y is as follows ₁ ～Y ₆ Each independently is-H or-F, R ₄ 、R ₆ And R is ₈ Each independently is halogen, haloalkyl or haloalkoxy having 1 to 5 carbon atoms, haloalkenyl or haloalkenoxy having 2 to 5 carbon atoms, preferably R ₄ 、R ₆ And R is ₈ Are each independently-F, -CF ₃ or-OCF ₃ Any one of the following.

In the invention, the combination of the liquid crystal molecules in the component A and the component B ensures that the liquid crystal composition has large dielectric anisotropy, high clearing point, large refractive index anisotropy, good low-temperature storage performance and good intersolubility with a high-molecular UV polymer.

As a preferable technical scheme of the invention, the clear point of the wide-temperature liquid crystal composition is more than or equal to 100 ℃, and the refractive index is more than or equal to 0.18.

In the invention, the wide temperature liquid crystal composition can ensure that the working temperature range of the film is wide, the optical performance is good and the contrast ratio is good.

Preferably, the composition comprises 50 to 90wt% of component A and 10 to 50wt% of component B, preferably 55 to 85wt% of component A and 15 to 45wt% of component B, further preferably 60 to 85wt% of component A and 15 to 40wt% of component B.

Wherein the mass fraction of component A may be 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt% or 90wt% etc. and the mass fraction of component B may be 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt% or 50wt% etc. but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In the present invention, the content of component A is less than 50% or the content of component B is more than 50%, and the liquid crystal composition has a small dielectric anisotropy, resulting in a high driving voltage.

As a preferable technical scheme of the invention, the compound shown in the formula I-1 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula I-1 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula I-1-2 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula I-1-3 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula I-1-4 is selected from any one or a combination of at least two of the following compounds:

wherein R is ₁ ' is C1-C10 chain alkyl.

Preferably, the compound shown in the formula I-1-5 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula I-1 is any one or at least two of the compounds shown in the formula I-1-1-1, the formula I-1-4-2, the formula I-1-5-1 or the formula I-1-2-1. Wherein typical but non-limiting examples of such combinations are: a combination of CPN and CGN, a combination of CEPN and PEGN, a combination of CPN, CGN and PPN, a combination of CPN, CGN, PPN and OPPN, a combination of CGN, PPN, OPPN, PEPN and CEPN, a combination of CPN, PPN, OPPN, PEPN and CEPN, a combination of CPN, CGN, PPN, PEGN, PEUN and CEUN, a combination of CPN, CGN, PPN, OPPN, PEPN, CEPN, PEGN, PEUN, CEUN, CUN and DUN, and the like.

Preferably, the compound shown in the formula I-2 is selected from any one or a combination of at least two of the following compounds:

the X is ₅ And X ₆ Are each independently-H or-F, and X ₅ And X is ₆ At most one of them is-F.

Preferably, the compound shown in the formula I-2-1 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula I-2-2 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula I-2-3 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula I-2-4 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula I-2-5 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula I-2-6 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula I-2-7 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula I-2 is any one or a combination of at least two of the compounds shown in the general formula I-2-2-1, the general formula I-2-3-1, the general formula I-2-4-1, the general formula I-2-2-2, the general formula I-2-7-2, the general formula I-2-6-2 or the general formula I-2-3-2. Wherein typical but non-limiting examples of such combinations are: a combination of CPPN and PPPN, a combination of PPPN and CEPPN, a combination of CCEPN, CCEGN and CPEGN, a combination of CPPN, PPPN, CEPPN and CCEPN, a combination of CCUN, CPUN, PEPPN, CPEPN and PGPN, a combination of CPPN, PPPN, CEPPN, CCEPN, CCEGN and NPGP, a combination of CPPN, PPPN, CEPPN, NPGP, CPGN, CPEGN, CCEGN and PGPN, and the like.

As a preferred technical scheme of the invention, the compound shown in the formula II-1 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula II-1-1 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula II-1-2 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula II-1-3 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula II-1-4 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula II-1 is any one or at least two of compounds shown in the general formula II-1-1-1 or general formula II-1-3-3;

preferably, the compound shown in the formula II-2 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula II-2-1 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula II-2-2 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula II-2-3 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula II-2-4 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula II-2-5 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula II-2-6 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula II-2-7 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula II-2 is any one or at least two of the compounds shown in the general formula II-2-1-4, the general formula II-2-3-4, the general formula II-2-5-1, the general formula II-2-5-3 or the general formula II-2-5-4. Wherein typical but non-limiting examples of such combinations are: a combination of CCGF and CCUF, a combination of CPUF and PPUF, a combination of PGUF, PGPF and CPGF, a combination of CCEGF, CPEGF, CCPOCF and CPPCF 3, a combination of CCUF, CPUF, PGUF, PPUF and PGPF, a combination of CCEUF, CPEUF, CCEPF, CPEPF, CDUF and DPUF, and the like.

Preferably, the compound shown in the formula II-3 is selected from any one or a combination of at least two of the following compounds:

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the Y is ₇ ～Y ₁₀ Each independently is-H or-F.

Preferably, the compound shown in the formula II-3-1 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula II-3-2 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula II-3-3 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula II-3-4 is selected from any one or a combination of at least two of the following compounds:

preferably, the compound shown in the formula II-3 is any one or at least two of the compounds shown in the general formula II-3-1-3, the general formula II-3-1-4 or the general formula II-3-3. Wherein typical but non-limiting examples of such combinations are: ccpff and CCPGF, CCGUF and CPGUF, CDPUF and DPGUF, ccpff, CCPGF and CCGUF, ccpff, CCGUF and CPGUF, CCPUF, CCPGF, CDPUF and DPGUF, CCPUF, CCPGF, CCGUF, CPGUF, CDPUF and DPGUF, etc.

As a preferred embodiment of the present invention, the wide temperature range liquid crystal composition includes a compound represented by formula III:

wherein R is ₉ And R is ₁₀ Straight-chain alkyl or alkoxy of C1-C10, J and K are each independently 1, 4-cyclohexylene or 1, 4-phenylene, Y ₁₁ And Y ₁₂ Each independently-H or-F, a is 0 or 1, and if a is 1, J and K are not simultaneously 1, 4-phenylene.

Preferably, the compound represented by formula III is selected from any one or a combination of at least two of the following compounds:

wherein typical but non-limiting examples of such combinations are: a combination of CPPC and PGPC, a combination of CPGP and CGPC, a combination of CGPC and PGP, a combination of CPPC, PGPC and CPGP, a combination of CPGP, CGPC, PGP, and CPP, a combination of CPPC, PGPC, CPGP, CGPC and PGP, or a combination of CPPC, PGPC, CPGP, CGPC, PGP and CPP, etc.

Preferably, the mass fraction of the compound shown in formula III in the wide temperature range liquid crystal composition is 0 to 20wt%, such as 0wt%, 1wt%, 2wt%, 5wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt%, or 20wt%, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In the invention, the addition of the compound shown in the formula III can increase the clearing point of the liquid crystal composition, and the low-temperature storage performance of the liquid crystal composition is better.

Preferably, the wide temperature range liquid crystal composition comprises a compound represented by formula IV:

wherein R is ₁₁ Is H, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C5 cycloalkyl or more than 2-CH not adjacent to 1 or non-adjacent of the substituted or unsubstituted C1-C10 chain alkyl ₂ -groups each independently replaced by-ch=ch-, -c≡c-, -O-, -CO-O-, or-O-CO-, said substituents being-F or-Cl;

ring L and ring M are each independently At least one of-CH ₂ -a group or group substituted by-O-At least one single carbon-carbon bondGroups substituted by carbon-carbon double bondsA group or group in which at least one of-H is substituted by-CN, -F or-ClAt least one of-ch=substituted by-n=group;

Z ₇ represents a single bond, -CH ₂ CH ₂ -、-CF ₂ CF ₂ -、-CF ₂ O-、-OCF ₂ -、-CO-O-、-O-CO-、-O-CO-O-、-CH＝CH-、-C≡C-、-CF＝CF-、-CH ₂ O-or-OCH ₂ -any one of the following;

b represents 0, 1, 2 or 3, when b=2 or 3, each ring L is the same or different, each Z ₇ The same or different;

x is any one of halogen, C1-C5 haloalkyl, C1-C5 haloalkoxy, C2-C5 haloalkenyl or C2-C5 haloalkenoxy.

Preferably, the halogen is any one of F, cl, br or I.

Preferably, the compound represented by formula IV is selected from any one or a combination of at least two of the following compounds:

typical but non-limiting examples of such combinations are: a combination of PUQUF and PGUQUF, a combination of PGUQUF and PGUQPOCF3, a combination of PGUQPOCF3 and CCQUF, a combination of PUQUF, PGUQUF and PGUQPOCF3, a combination of PGUQUF, PGUQPOCF3 and CCQUF or PUQUF, PGUQUF, PGUQPOCF and CCQUF, and the like.

Preferably, the mass fraction of the compound shown in formula IV in the wide temperature range liquid crystal composition is 0 to 15wt%, such as 0wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In the present invention, the addition of the compound represented by formula IV can increase the dielectric anisotropy of the liquid crystal composition and reduce the driving voltage.

In the present invention, the C1-C10 linear or branched alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, 3-hexyl, n-heptyl, 2-heptyl, n-octyl, 2-octyl, n-nonyl, n-decyl or the like; the concept of the alkoxy of C1-C10 is similar to that of the straight-chain or branched-chain alkyl of C1-C10, namely, the straight-chain or branched-chain alkyl of C1-C10 is connected with a compound main body through an oxygen atom; the concept of a C1-C10 linear or branched alkylene group is similar to that of a C1-C10 linear or branched alkyl group, i.e., the C1-C10 linear or branched alkyl group has another free end attached to the other group.

In the invention, the C1-C5 haloalkyl is a straight-chain or branched-chain alkyl with at least one hydrogen atom substituted by halogen atom of C1-C5; the haloalkoxy of C1-C5 is that at least one hydrogen atom is substituted by halogen atom on straight-chain or branched-chain alkoxy of C1-C5; the C2-C5 halogenated alkenyl is that at least one hydrogen atom on the C2-C5 alkenyl is replaced by halogen atom; the C2-C5 halogenated alkenyloxy is C2-C5 alkenyloxy with at least one hydrogen atom replaced by halogen atom. The concept of the C1-C5 linear or branched alkyl group and the C1-C5 linear or branched alkoxy group is the same as that of the C1-C10 linear or branched alkyl group, and will not be described here again. The C2-C5 haloalkenyl and C2-C5 haloalkenyloxy are C1-C5 straight-chain or branched alkyl and alpha carbon and beta carbon in the C1-C5 straight-chain or branched alkoxy are connected through carbon-carbon double bonds.

The second object of the present invention is to provide a wide temperature range polymer dispersed liquid crystal composition comprising 15 to 70wt% of the wide temperature range liquid crystal composition and 30 to 85wt% of the high molecular UV polymer.

The mass fraction of the wide temperature range liquid crystal composition may be 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, or 70wt%, and the mass fraction of the polymer UV polymer may be 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, or 85wt%, etc., but is not limited to the recited values, and other non-recited values within the above ranges are equally applicable.

Preferably, the invention adopts a mode of UV polymerization to polymerize, and the wide temperature polymer dispersed liquid crystal composition contains 40-60 wt% of the wide temperature liquid crystal composition and 40-60 wt% of the high molecular UV polymer.

As a preferred embodiment of the present invention, the high molecular UV polymer contains 20 to 80wt% of prepolymer, 20 to 80wt% of reactive diluent and 1 to 6wt% of photoinitiator, wherein the mass fraction of prepolymer may be 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt% or 80wt%, the mass fraction of reactive diluent may be 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt% or 80wt%, and the mass fraction of photoinitiator may be 1wt%, 2wt%, 3wt%, 4wt%, 5wt% or 6wt%, etc., but the present invention is not limited to the above-mentioned values, and other non-mentioned values within the above-mentioned ranges are applicable.

Preferably, the prepolymer comprises any one or a combination of at least two of urethane acrylate, epoxy acrylate, acrylic prepolymer, polyester acrylate, polyether acrylate, polybutadiene acrylate, or polyamide, typical but non-limiting examples of which are: a combination of urethane acrylate and epoxy acrylate, a combination of epoxy acrylate and acrylic prepolymer, a combination of acrylic prepolymer and polyester acrylate, a combination of polyester acrylate and polyether acrylate, a combination of polyether acrylate and polybutadiene acrylate, a combination of polybutadiene acrylate and polyamide, or a combination of urethane acrylate, epoxy acrylate and acrylic prepolymer, etc.

Preferably, the reactive diluent is any one or a combination of at least two of hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxypropyl methacrylate, ethyl methacrylate, N-octyl methacrylate, dodecyl 2-acrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, isobornyl acrylate, isobornyl methacrylate, hydroxy dicyclopentene, or N-acryloylmorpholine, typical but non-limiting examples of such combinations being: a combination of hydroxyethyl methacrylate and 4-hydroxybutyl acrylate, a combination of 4-hydroxybutyl acrylate and 2-hydroxypropyl methacrylate, a combination of 2-hydroxypropyl methacrylate and ethyl methacrylate, a combination of N-octyl methacrylate and dodecyl 2-acrylate, a combination of dodecyl 2-acrylate and 1, 6-hexanediol diacrylate, a combination of trimethylolpropane triacrylate and isobornyl acrylate, a combination of isobornyl methacrylate and hydroxy dicyclopentene, a combination of hydroxy dicyclopentene and N-acryloylmorpholine, a combination of hydroxyethyl methacrylate, 4-hydroxybutyl acrylate and 2-hydroxypropyl methacrylate, and the like.

Preferably, the photoinitiator is any one or a combination of at least two of 1-hydroxycyclohexylphenyl ketone, (2, 4, 6-trimethylbenzoyl) -diphenyl phosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholin-1-one or 2-isopropylthioxanthone, typical but non-limiting examples of such combinations are: a combination of 1-hydroxycyclohexylphenyl ketone and (2, 4, 6-trimethylbenzoyl) -diphenylphosphine oxide, a combination of (2, 4, 6-trimethylbenzoyl) -diphenylphosphine oxide and 2-methyl-1- (4-methylthiophenyl) -2-morpholin-1-one, a combination of 2-methyl-1- (4-methylthiophenyl) -2-morpholin-1-one and 2-isopropylthioxanthone, a combination of 1-hydroxycyclohexylphenyl ketone and 2-isopropylthioxanthone or a combination of 1-hydroxycyclohexylphenyl ketone, (2, 4, 6-trimethylbenzoyl) -diphenylphosphine oxide and 2-methyl-1- (4-methylthiophenyl) -2-morpholin-1-one, and the like.

As a preferred embodiment of the present invention, the wide temperature range polymer dispersed liquid crystal composition contains 0.1 to 5wt% of dye, such as 0.1wt%, 0.2wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt% and 5wt%, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.

It is a further object of the present invention to provide a wide temperature polymer dispersed liquid crystal film comprising two conductive films, and a liquid crystal layer between the conductive films, the liquid crystal layer comprising the wide temperature polymer dispersed liquid crystal composition according to any one of claims 6 to 8 and spacer particles.

As a preferable technical scheme of the invention, the conductive film is a PET-ITO conductive film.

Preferably, the thickness of the conductive film is any one or a combination of at least two of 0.060 mm-0.180 mm,0.060mm, 0.070mm, 0.080mm, 0.100mm, 0.120mm, 0.150mm or 0.180 mm. But are not limited to, the recited values, and other non-recited values within the range of values are equally applicable.

Preferably, the mass ratio of the wide temperature range polymer dispersed liquid crystal composition to the spacer is 1:0.0002 to 0.005, such as 1:0.0002, 1:0.0005, 1:0.001, 1:0.002, 1:0.003, 1:0.004, or 1:0.005, etc., but not limited to the recited values, other non-recited values within the range of values are equally applicable.

Preferably, the spacer particles have a particle diameter of 10 to 30. Mu.m, such as 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 22 μm,25 μm, 28 μm or 30 μm, etc., but are not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable, preferably 10 to 20. Mu.m.

Preferably, the thickness of the liquid crystal layer is 10 to 20 μm, such as 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm or 20 μm, etc., but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.

In the present invention, specific meanings of codes in each liquid crystal molecule are shown in table 1.

TABLE 1

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Compared with the prior art, the invention has at least the following beneficial effects:

(1) The invention aims to provide a wide-temperature liquid crystal composition, which has high clear point (Cp is more than or equal to 100 ℃), large refractive index anisotropy (Deltan is more than or equal to 0.18) and large dielectric anisotropy; meanwhile, the wide-temperature liquid crystal composition has good solubility in a polymer;

(2) The invention provides a wide-temperature polymer dispersed liquid crystal composition, which has the characteristics of low uniform phase temperature, high polymerization speed, moderate viscosity and the like;

(3) The invention provides a wide-temperature polymer dispersed liquid crystal film which has the advantages of low driving voltage, quick response, good optical performance, high reliability, wide use temperature range, good weather resistance and the like, and solves the problems of poor reliability and narrow working temperature range of a PDLC product in the prior art.

Detailed Description

To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.

The structural code is illustrated by way of example for a compound of the formula:

the structural formula can be expressed as nCPPM if represented by the code shown in Table 1, wherein n in the code represents the number of carbon atoms of the left-end alkyl group, for example, n is 3, that is, the alkyl group is-C ₃ H ₇ In the code, C represents a cyclohexenyl group, P represents a phenyl group, m represents the number of carbon atoms of the right-end alkyl group, e.g., m is 2, i.e., the alkyl group is-C ₂ H ₅ 。

In the following examples, shorthand numbers of performance test items are shown in table 2.

Table 2 abbreviated code for performance test items

Code number of test item	Meaning of
		Δn：	Optical anisotropy (589 nm,25 ℃ C.)
Δε：	Dielectric anisotropy (1 KHz,25 ℃ C.)
		Cp：	Clearing point (nematic-isotropic phase transition temperature, DEG C)
LTS	Low temperature stability

The components used in the liquid crystal compositions of the following examples were synthesized by a known method or obtained commercially, and the components of the obtained liquid crystal compositions were tested to meet the electronic compound standards.

The liquid crystal compositions in the following examples were prepared in accordance with the proportions of the respective components (the formulas of the components belonging to the brackets at the ends of the components in the examples) and were mixed by a conventional preparation method such as heating, ultrasonic wave, suspension and the like to obtain liquid crystal compositions.

The compositions of the wide temperature range liquid crystal compositions used in the specific examples of the present invention are shown in tables 3 to 5.

TABLE 3 Table 3

TABLE 4 Table 4

Liquid crystal B	Mass fraction/%
				3CCEPC3	2	Cp	117
5CCEPC5	2	△n	0.184
				2CEPPN	4	△ε	13.0
3CEPPN	4	LTS	-40℃
				3CCEGN	4
3CPPN	3
				3CGN	7
5CPGN	5
				3CCUF	6
5CCUF	7
				3CCPUF	3
2CCPUF	2
				4CCPUF	3
2PPN	3
				3PPN	5
4PPN	4
				5PPN	8
2OPPN	4
				3OPPN	6
5OPPN	6
				NPGP3	12

TABLE 5

The compositions of the high molecular UV polymers in the specific examples of the present invention are shown in tables 6 and 7.

TABLE 6

TABLE 7

In Table 6 and Table 7, MM8209, MM8610, and MPB110 are prepolymers produced by Shanghai Feiki photovoltaic materials Co., ltd.

Example 1

Material	Model number	Parts by mass
			Liquid crystal material	Liquid crystal A	55
Polymer	High molecular UV Polymer 1	45
			Spacer particles	20μm	0.5

Example 2

Material	Model number	Parts by mass
			Liquid crystal material	Liquid crystal A	50
Polymer	High molecular UV Polymer 2	50
			Spacer particles	20μm	0.5

Example 3

Material	Model number	Parts by mass
			Liquid crystal material	Liquid crystal B	55
Polymer	High molecular UV Polymer 1	45
			Spacer particles	20μm	0.5

Example 4

Material	Model number	Parts by mass
			Liquid crystal material	Liquid crystal B	55
Polymer	High molecular UV Polymer 2	45
			Spacer particles	20μm	0.5

Example 5

Material	Model number	Parts by mass
			Liquid crystal material	Liquid crystal C	60
Polymer	High molecular UV Polymer 1	40
			Spacer particles	20μm	0.5

Example 6

Material	Model number	Parts by mass
			Liquid crystal material	Liquid crystal C	60
Polymer	High molecular UV Polymer 2	40
			Spacer particles	20μm	0.5

The above examples 1-6 were weighed according to the mass ratio in the table and stirred at room temperature for 30min to allow them to be sufficiently and uniformly stirred, the well-mixed mixture was uniformly coated between two pieces of ITO-PET, and the mixture was subjected to ultraviolet light of 365nm and 5mW/cm ² The light intensity is irradiated for 5min at the temperature of 25-35 ℃ to obtain the 220mm multiplied by 180mm polymer dispersed liquid crystal film.

Examples 1-6 photovoltaic performance test a WGT-S light transmittance/haze tester manufactured by Shanghai Shen Guang instruments and meters limited. The off-state optical data are measured when the PDLC applies 0V, and the on-state optical data are measured when the PDLC applies corresponding driving voltage. The test results are shown in tables 8 and 9.

TABLE 8

TABLE 9

From the above test data, it can be seen that the PDLC films fabricated according to examples 1-6 have large off-state haze, good shielding, small on-state haze, good transparency, and low driving voltage. The haze change is small in the high-temperature environment of 80 ℃, the shielding performance is good, and the use requirements of vehicles, outdoors and other high-temperature environments can be met. Meanwhile, the optical performance change is small after high-temperature aging and sunlight aging, and the weather resistance is good.

The applicant states that the detailed process equipment and process flows of the present invention are described by the above examples, but the present invention is not limited to, i.e., does not mean that the present invention must be practiced in dependence upon, the above detailed process equipment and process flows. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims

1. A wide temperature polymer dispersed liquid crystal composition, which is characterized in that the wide temperature polymer dispersed liquid crystal composition contains 50-60 wt% of the wide temperature liquid crystal composition and 40-50 wt% of high molecular UV polymer, the wide temperature liquid crystal composition comprises a component A and a component B, the component A comprises compounds shown in formulas I-1 and I-2, the component B comprises any one compound or a combination of at least two compounds in formulas II-2 or II-3, and the component B comprises at least one compound shown in formula II-2;

the compound shown in the formula I-1 is selected from any one or a combination of at least two of the following compounds:

the compound shown in the formula I-1 comprises at least one compound shown in the formula I-1-4-2

The compound shown in the formula I-2 is selected from any one or a combination of at least two of the following compounds:

the compound shown in the formula I-2 comprises at least one compound shown in the formula I-2-4 and at least one compound shown in the formula I-2-6;

wherein R is ₁ 、R ₂ 、R ₅ And R is ₇ Each independently C1-C10 chain alkyl or alkoxy, and each of ring E, ring F, ring G, ring H and ring I is independently at least one-CH of 1, 4-cyclohexylene, 1, 4-phenylene, 1, 4-cyclohexylene ₂ -a group substituted by-O-or a group in which at least one carbon-carbon single bond in 1, 4-cyclohexylene is replaced by a carbon-carbon double bond or a group in 1, 4-phenylene in which at least one-H is replaced by-CN, -F or-Cl or a group in 1, 4-phenylene in which at least one-ch=is replaced by-n=z ₅ Or Z is ₆ Each independently is a single bond or-COO-, X ₁ ～X ₄ Y is as follows ₃ ～Y ₆ Are each independently-H or-F, X ₅ And X ₆ Are each independently-H or-F, and X ₅ And X is ₆ At most one of them is-F, R ₆ And R is ₈ Each independently-F;

R ₁ ' is C1-C10 chain alkyl;

the composition comprises 60-85 wt% of component A and 15-40 wt% of component B;

the clear point of the wide-temperature liquid crystal composition is more than or equal to 100 ℃, and the refractive index anisotropy is more than or equal to 0.18.

2. The broad temperature polymer dispersed liquid crystal composition according to claim 1, wherein the compound of formula I-1-1 is selected from any one or a combination of at least two of the following compounds:

the compounds shown in the formula I-1-4 are also selected from any one or a combination of at least two of the following compounds:

3. the broad temperature polymer dispersed liquid crystal composition according to claim 1, wherein the compound of formula I-2-2 is selected from any one or a combination of at least two of the following compounds:

the compound shown in the formula I-2-3 is selected from any one or a combination of at least two of the following compounds:

the compound shown in the formula I-2-4 is selected from any one or a combination of at least two of the following compounds:

the compound shown in the formula I-2-6 is selected from any one or a combination of at least two of the following compounds:

the compound shown in the formula I-2-7 is selected from any one or a combination of at least two of the following compounds:

4. the broad temperature polymer dispersed liquid crystal composition according to claim 1, wherein the compound of formula II-2 is selected from any one or a combination of at least two of the following compounds:

wherein Y is ₇ is-H or-F.

5. The broad temperature polymer dispersed liquid crystal composition according to claim 4, wherein the compound represented by formula II-2-1 is selected from any one or a combination of at least two of the following compounds:

the compound shown in the formula II-2-2 is selected from any one or a combination of at least two of the following compounds:

the compound shown in the formula II-2-3 is selected from any one or a combination of at least two of the following compounds:

the compound shown in the formula II-2-4 is selected from any one or a combination of at least two of the following compounds:

the compound shown in the formula II-2-5 is selected from any one or a combination of at least two of the following compounds:

the compound shown in the formula II-2-6 is selected from any one or a combination of at least two of the following compounds:

the compound shown in the formula II-2-7 is selected from any one or a combination of at least two of the following compounds:

6. the broad temperature polymer dispersed liquid crystal composition according to claim 1, wherein the compound of formula II-3 is selected from any one or a combination of at least two of the following compounds:

the Y is ₈ ～Y ₁₀ Each independently is-H or-F.

7. The broad temperature polymer dispersed liquid crystal composition according to claim 6, wherein the compound of formula II-3-1 is selected from any one or a combination of at least two of the following compounds:

the compound shown in the formula II-3-2 is selected from any one or a combination of at least two of the following compounds:

the compound shown in the formula II-3-3 is selected from any one or a combination of at least two of the following compounds:

the compound shown in the formula II-3-4 is selected from any one or a combination of at least two of the following compounds:

8. the broad temperature polymer dispersed liquid crystal composition of claim 1, wherein the broad temperature liquid crystal composition comprises a compound of formula III:

wherein R is ₉ And R is ₁₀ C1-C10-chain alkyl or alkoxy, and rings J and K are each independently 1, 4-cyclohexylene or 1, 4-phenylene, Y ₁₁ And Y ₁₂ Each independently-H or-F, a is 0 or 1, and if a is 1, J and K are not simultaneously 1, 4-phenylene.

9. The broad temperature polymer dispersed liquid crystal composition according to claim 8, wherein the compound of formula III is selected from any one or a combination of at least two of the following compounds:

10. the broad temperature polymer dispersed liquid crystal composition according to claim 8, wherein the mass fraction of the compound represented by formula III in the broad temperature liquid crystal composition is 0 to 20wt%.

11. The broad temperature polymer dispersed liquid crystal composition according to claim 1, wherein the broad temperature liquid crystal composition comprises a compound of formula IV selected from any one or a combination of at least two of the following compounds:

wherein, the liquid crystal display device comprises a liquid crystal display device,

R ₁₁ is H, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C5 cycloalkyl or more than 2-CH not adjacent to 1 or non-adjacent of the substituted or unsubstituted C1-C10 chain alkyl ₂ -groups each independently replaced by-ch=ch-, -c≡c-, -O-, -CO-O-, or-O-CO-, said substituents being-F or-Cl.

12. The broad temperature polymer dispersed liquid crystal composition according to claim 11, wherein the mass fraction of the compound represented by formula IV in the broad temperature liquid crystal composition is 0 to 15wt%.

13. The broad temperature polymer dispersed liquid crystal composition according to claim 1, wherein the high molecular UV polymer contains 20 to 80wt% prepolymer, 20 to 80wt% reactive diluent and 1 to 6wt% photoinitiator.

14. The broad temperature polymer dispersed liquid crystal composition of claim 13, wherein the prepolymer comprises any one or a combination of at least two of urethane acrylate, epoxy acrylate, acrylic prepolymer, polyester acrylate, polyether acrylate, polybutadiene acrylate, or polyamide;

the reactive diluent is any one or a combination of at least two of hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxypropyl methacrylate, ethyl methacrylate, N-octyl methacrylate, 2-dodecyl acrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, isobornyl acrylate, isobornyl methacrylate, hydroxy dicyclopentene or N-acryloylmorpholine;

the photoinitiator is any one or a combination of at least two of 1-hydroxycyclohexyl phenyl ketone, (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholin-1-acetone or 2-isopropylthioxanthone.

15. The broad temperature polymer dispersed liquid crystal composition as claimed in claim 14, wherein the broad temperature polymer dispersed liquid crystal composition contains 0.1 to 5wt% of the dye.

16. A wide temperature polymer dispersed liquid crystal film comprising two conductive films, and a liquid crystal layer between the conductive films, the liquid crystal layer comprising the wide temperature polymer dispersed liquid crystal composition of any one of claims 1-15 and spacer particles.

17. The liquid crystal film according to claim 16, wherein the conductive film is a PET-ITO conductive film;

the thickness of the conductive film is 0.060 mm-0.180 mm;

the mass ratio of the wide-temperature polymer dispersed liquid crystal composition to the spacer is 1:0.0002-0.005;

the thickness of the liquid crystal layer is 10-20 mu m;

the particle size of the spacer is 10-30 μm.