KR101688436B1 - Polymerizable liquid crystal composition, and cholesteric reflective film using the same, and reflection type polarizing plate - Google Patents

Abstract

로 표시되는 액정 화합물을 1종 또는 2종 이상 함유하고, b) 중합성 관능기를 1개만 갖는 액정 화합물을 1종 또는 2종 이상 함유하고, c) 중합성 관능기를 2개 이상 갖는 액정 화합물을 1종 또는 2종 이상 함유하고, d) 중합성 관능기를 1개 이상 갖는 키랄 화합물을 1종 또는 2종 이상 함유하고, e) 중합 개시제를 1종 또는 2종 이상 함유하는 것을 특징으로 하는 중합성 액정 조성물 및 당해 중합성 액정 조성물에 의해 구성되는 콜레스테릭 반사 필름을 제공한다.[PROBLEMS] To provide a polymerizable liquid crystal composition which easily expands a wavelength range of selective reflection of a cholesteric reflective film and is excellent in productivity, and also provides a cholesteric reflective film having excellent appearance using the polymerizable liquid crystal composition And a reflection type polarizing plate.
[MEANS FOR SOLVING PROBLEMS] a)

And b) one or two or more liquid crystal compounds having only one polymerizable functional group, and c) a liquid crystal compound having two or more polymerizable functional groups is referred to as 1 Or d) at least one chiral compound having at least one polymerizable functional group, and e) at least one kind of polymerization initiator, A composition and a cholesteric reflective film constituted by the polymerizable liquid crystal composition are provided.

Description

TECHNICAL FIELD [0001] The present invention relates to a polymerizable liquid crystal composition, a cholesteric reflective film using the polymerizable liquid crystal composition, and a reflective type polarizing plate using the same,

The present invention relates to a polymerizable liquid crystal composition useful as a liquid crystal device, a display, an optical component, a coloring agent, a mark for security, a member for laser emission, etc., and a cholesteric polarizing film and a reflective polarizing plate obtainable from the polymerized liquid crystal composition will be.

The development of polarizing plates using selective reflection properties of cholesteric liquid crystals has been actively carried out since the 1990s. In order to use a cholesteric liquid crystal as a polarizing plate, it is necessary to set the wavelength region of the selective reflection to be the visible light region, and the polarization characteristic can be obtained by setting the pitch of the cholesteric liquid crystal to a predetermined value. However, when a chiral compound is added to a nematic liquid crystal, the pitch thereof is generally maintained at a constant pitch, and only a selective reflection of a specific narrow wavelength region corresponding thereto can be obtained. Therefore, attempts have been made to expand the wavelength range of selective reflection by devising a cholesteric liquid crystal composition.

As one of such methods, a method of controlling the pitch of the pitch by controlling the polymerization rate on the light-irradiated surface and the non-irradiated surface in the polymerizable cholesteric liquid crystal (see Patent Document 1) . This method is effective in suppressing the absorption of the photoinitiator contained in the cholesteric liquid crystal composition by adding a dye having an absorption wavelength overlapping with the absorption wavelength of the photoinitiator in the polymerizable cholesteric liquid crystal composition, And the pitch is controlled by the difference in polymerization rate between the surface and the non-alignment surface. However, in this method, it takes a long time to obtain a cholesteric reflective film in which the wavelength region of the selective reflection is enlarged, and there is a problem in productivity. Further, since the dye is not a liquid crystal compound, there has been a problem that defects such as coloring on a film and occurrence of alignment defects tend to occur as the amount of addition increases. It is also known that a polymerizable cholesteric liquid crystal composition is composed of only a polymerizable liquid crystal composition without adding a dye having an absorption wavelength overlapping with the absorption wavelength of the photoinitiator (see Patent Document 2). However, a composition capable of obtaining a sufficient reflection area without using a dye is limited to a combination of a very narrow range of polymerizable liquid crystal compounds, so that the degree of freedom in designing a composition is low, .

As another method, there can be mentioned a method in which the chiral compound in the cholesteric liquid crystal composition is made to be a non-polymerized type, thereby causing a change in pitch easily (Non-Patent Document 1). In this method, weak light is irradiated onto the irradiation surface, and the pitch is dispersed by photopolymerizing the cholesteric liquid crystal composition little by little from the irradiation surface.

However, when enlarging the wavelength region of the selective reflection, it took a long time to produce the cholesteric reflective film in these methods, and there was a problem in productivity.

Japanese Patent No. 3224467 Japanese Patent No. 4271729 (Example 8 on page 29)

Liquid Crystal, Vol. 34, No. 9, 1009-1018 (2007)

A problem to be solved by the present invention is to provide a polymerizable liquid crystal composition which easily expands a wavelength range of selective reflection of a cholesteric reflective film and is excellent in productivity, And an excellent cholesteric reflective film and a reflective polarizer.

The inventors of the present invention have found that alignment dyes are generated in the dyes disclosed in the prior art because of the increase in the amount of the dyes, and therefore, even if the amount of the compound capable of becoming a liquid crystal increases, The present invention has been completed.

According to the present invention,

a) a compound represented by the general formula (1)

(Wherein R ₁ and R ₂ each independently represent a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms, Or more thereof may be substituted with a fluorine atom, and Z ₁ is a single bond, -O-, -S-, -COO-, -OCO-, -OCH ₂ -, -CH═CH-, -CH═CH-COO- Or -OCO-CH = CH-, and Z ₂ represents a single bond, -O-, -S-, -COO-, -OCO-, -CH ₂ O-, -CH = CH-, COO- or -OCO-CH = CH-, A represents -C≡C-, -C═N-, -N═N- or -C═NN═C-, or a ring structure of any of the following

R ₃ represents a fluorine atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group, and B represents a cyclic structure

And R ₄ represents a fluorine atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group, and b) C) at least one liquid crystal compound having at least two polymerizable functional groups, and d) at least one polymerizable functional group, wherein the liquid crystal compound contains at least one polymerizable functional group, , And e) one or two or more polymerization initiators. The polymerizable liquid crystal composition according to any one of < RTI ID = 0.0 >

A cholesteric reflective film constituted by a cured product of a planar alignment polymerizable liquid crystal composition, wherein the polymerizable liquid crystal composition comprises the cholesteric reflective film as the polymerizable liquid crystal composition,

A reflection type polarizing plate in which a substrate, a cholesteric reflecting film and a retardation film are sequentially laminated, wherein the retardation film is the retardation film,

A reflective polarizing plate comprising a substrate, a cholesteric reflective film, a retardation film and a linear polarizing film sequentially laminated, wherein the retardation film is the retardation film.

The polymerizable liquid crystal composition of the present invention has a function close to that of a dye and contains a compound capable of becoming a liquid crystal so that alignment defects are hardly generated and the wavelength region of selective reflection can be easily expanded . Further, the polymerizable liquid crystal composition of the present invention can produce a cholesteric reflective film by a simple method, and is also excellent in productivity. Therefore, the polymerizable liquid crystal composition, the cholesteric reflective film, and the reflective polarizing plate of the present invention can be applied to a liquid crystal device, a display, an optical component, a coloring agent, a marking for security, and a member for laser emission.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a polarized reflection band of a cholesteric reflective film produced in Example 1. Fig.
2 is a view showing a polarization reflection band of the cholesteric reflective film produced in Example 17. Fig.

Hereinafter, the present invention will be described in detail.

a) (liquid crystal compound represented by the general formula (1)

The liquid crystal compound represented by the general formula (1) is used in the polymerizable liquid crystal composition of the present invention. However, by adding a dye having an absorption wavelength overlapping with the absorption wavelength of the photoinitiator, the photoinitiator contained in the cholesteric liquid crystal composition From the viewpoint of suppressing the absorption of the liquid crystal compound.

In this respect, in the liquid crystal compound represented by the general formula (1), R ₁ and R ₂ are each independently a fluorine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms , Particularly a fluorine atom, an alkyl group having 3 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms.

Z ₁ is preferably a single bond, -O-, -S-, -COO-, -OCO- or -OCH ₂ -, particularly preferably a single bond, -O-, -COO- or -OCO-. Z ₂ is preferably a single bond, -O-, -S-, -COO-, -OCO- or -OCH ₂ -, particularly preferably a single bond, -O-, -COO- or -OCO-.

A is -C≡C-, -C═N-, -N═N-, -C═N-N═C-

Particularly preferably -C? C-, -C = N-N = C-

. R ₃ is preferably a fluorine atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group, particularly preferably a fluorine atom or an alkyl group having 1 to 6 carbon atoms.

B of the liquid crystal compound represented by the general formula (1)

Is preferable, and in particular,

. R ₄ is preferably a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a cyano group, and particularly preferably a fluorine atom or an alkyl group having 1 to 6 carbon atoms.

Specific examples of the general formula (1) include the following liquid crystal compounds, but the present invention is not limited thereto.

(Wherein m and n each independently represent an integer of 0 to 7, and R represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms)

The content of the compound represented by the general formula (1) is preferably from 0.1 to 20 mass%, more preferably from 0.5 to 10 mass%.

b) (a liquid crystal compound having only one polymerizable functional group)

The liquid crystal compound having only one polymerizable functional group, which is used in the polymerizable liquid crystal composition of the present invention, exhibits liquid crystallinity in the composition alone or in combination with other liquid crystal compounds. Is not particularly limited as long as it is a compound having only one polymerizable functional group, and those known in the art can be used.

For example, Handbook of Liquid Crystals (D.Demus, J.W. Goodby, G.W.Gray, H. W. Sapess, edited by V. Vill, published by Wiley-VCH, 1998); 22, liquid crystal chemistry (Japanese Chemical Society, 1994), or Japanese Patent Application Laid-Open No. 7-294735, Japanese Patent Application Laid-Open No. 8-3111, Japanese Patent Application Laid-Open No. 8-29618, Phenylene group and 1,4-cyclohexylene group as described in JP-A-11-80090, JP-A-11-116538 and JP-A-11-148079 A roughened polymerizable liquid crystal compound having a polymerizable functional group such as a methacryloyl group, a vinyloxy group and a glycidyl group, or a polymeric liquid crystal compound having a polymerizable functional group such as a methacryloyl group, And a rod-like polymerizable liquid crystal compound having a maleimide group as described in JP-A-2004-99446. Among them, a rod-like liquid crystal compound having a polymerizable group is preferable because it can easily form a liquid crystal temperature range including a low temperature before and after room temperature.

The polymerizable functional group may be a vinyl group, a vinyloxy group, an acryloyl group, a (meth) acryloyl group, a glycidyl group, a glycidyl ether group, an oxetanyl group or a maleimide group. , An acryloyl group or a (meth) acryloyl group is preferable.

Specific examples of the liquid crystal compound having only one polymerizable functional group used in the polymerizable liquid crystal composition of the present invention include, but are not limited to, the following liquid crystal compounds.

(Wherein l and m each independently represent an integer of 1 to 9 and n represents an integer of 0 to 10)

These liquid crystal compounds may be used alone or in combination of two or more.

When the liquid crystal compound having only one polymerizable functional group is represented by the general formula (2)

(Wherein L represents a hydrogen atom or a methyl group, Sp represents a single bond or an alkyl group having 1 to 10 carbon atoms, X represents a single bond, -O-, -S-, -COO-, -OCO-, -OCH ₂ , -CH = CH-, -CH = CH-COO- or -OCO-CH = CH-, G ₁ represents a single bond, a 1,4-phenylene group, a naphthalene- , And a cyclohexylene group, but one or two or more hydrogen atoms present in these groups may be substituted with a fluorine atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group M is a single bond, -O-, -S-, -COO-, -OCO-, -OCH ₂ -, -CH = CH-, -CH = CH-COO- or -OCO-CH = CH -, when G ₁ represents a single bond, M represents a single bond, and when G ₁ represents a 1,4-phenylene group, a naphthalene-2,6-diyl group or a 1,4-cyclohexylene group , -O-, -S-, -COO-, -OCO-, -OCH ₂ -, -CH = CH-, -CH = CH-COO- or -OCO-CH = CH-, G ₂ represents hydrogen Atoms, phenyl groups, Cyclohexyl group or naphthyl group in the phenyl, cyclohexyl or naphthyl group, the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, the carboxy group, the carbamoyl group, the cyano group, the nitro group or the halogen atom, The atom may be unsubstituted or substituted with one or two or more halogen atoms, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group, and hydrogen in the carboxyl group or carbamoyl group Y ₁ and Y ₂ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms An alkoxy group) is particularly preferable because the wavelength region of the selective reflection can be further enlarged.

L of the liquid crystal compound represented by the general formula (2) is preferably a hydrogen atom.

The Sp of the liquid crystal compound represented by the general formula (2) is preferably a single bond or an alkyl group having 3 to 6 carbon atoms, particularly preferably an alkyl group having 3 to 6 carbon atoms.

X in the liquid crystal compound represented by the general formula (2) is preferably a single bond, -O-, -COO-, -OCO- or -OCO-CH = CH- and is preferably a single bond, -O- or -OCO- Is particularly preferable.

M in the liquid crystal compound represented by the general formula (2) is preferably a group represented by -O-, -COO (1) when G ₁ represents a 1,4-phenylene group, a naphthalene-2,6-diyl group or a 1,4- -, -OCO-, -CH = CH-, -CH = CH-COO- or -OCO-CH = CH- is preferable, and -O-, -COO- and -OCO- are particularly preferable.

G ₂ of the liquid crystal compound represented by the general formula (2) represents a hydrogen atom, a phenyl group, a cyclohexyl group, a naphthyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a carboxyl group, a carbamoyl group, A fluorine atom or a chlorine atom is preferable, and an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group or a fluorine atom is particularly preferable.

Y ₁ of the liquid crystal compound represented by the general formula (2) is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, An alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms is particularly preferable.

Y ₂ of the liquid crystal compound represented by the general formula (2) is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, An alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms is particularly preferable.

The content of the liquid crystal compound represented by the general formula (2) is preferably 5 to 80% by mass, and particularly preferably 10 to 70% by mass. The liquid crystal compounds represented by the general formula (2) may be used alone or in combination of two or more.

Specific examples of the liquid crystal compound represented by the general formula (2) include the following liquid crystal compounds, but are not limited thereto.

(Wherein m represents an integer of 1 to 6, and R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a carboxyl group, a carbamoyl group, a halogen atom, a cyano group or a nitro group , And when these groups are carboxy or carbamoyl groups, the hydrogen atom at the terminal may be unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms)

When the liquid crystal compound having only one polymerizable functional group is represented by the general formula (3)

(Wherein L ₁ represents a hydrogen atom or a methyl group, Sp ₁ represents a single bond or an alkyl group having 1 to 10 carbon atoms, X ₁ and X ₂ each independently represent a single bond, -O-, -S-, _{COO-, -OCO-, -OCH 2 -,} -CH = CH-, denotes a -CH = CH-COO- or _{-OCO-CH = CH-, Y 3} , Y 4, Y 5 and Y ₆ are each independently A halogen atom, a cyano group, a nitro group or a halogen atom, but the hydrogen atom in the alkyl or alkoxy group may be substituted by 1 or 2 groups selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, a carbamoyl group, Or a hydrogen atom in the carboxyl group or carbamoyl group may be unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms)

Is particularly preferable because the wavelength region of the selective reflection can be further enlarged.

L ₁ of the liquid crystal compound represented by the general formula (3) is preferably a hydrogen atom.

Sp ₁ of the liquid crystal compound represented by the general formula (3) is preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably an alkyl group having 2 to 6 carbon atoms.

X ₁ of the liquid crystal compound represented by the general formula (3) is preferably -O-, -COO-, -OCO-, -CH = CH-, -CH = CH-COO- or -OCO-CH = CH- , -O-, -COO- or -OCO-.

X ₂ of the liquid crystal compound represented by the general formula (3) is preferably -O-, -COO-, -OCO-, -CH = CH-, -CH = CH-COO- or -OCO-CH = CH- , -COO-, -OCO-, -CH = CH- or -O-.

Y ₃ , Y ₄ , Y ₅ and Y ₆ of the liquid crystal compound represented by the general formula (3) are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group, A cyano group or a fluorine atom is preferable, and a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group is particularly preferable.

These liquid crystal compounds may be used alone or in combination of two or more.

Specific examples of the liquid crystal compound represented by the general formula (3) include the following liquid crystal compounds, but are not limited thereto.

(Wherein m represents an integer of 1 to 10 and R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, a carbamoyl group, a cyano group, a nitro group or a halogen atom Provided that when these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, all of them may be unsubstituted or substituted by one or two or more halogen atoms, , The terminal hydrogen atom may be unsubstituted or may be substituted with an alkyl group having 1 to 10 carbon atoms)

In these formulas, R preferably represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group.

These liquid crystal compounds may be used alone or in combination of two or more.

c) (liquid crystal compound having two or more polymerizable functional groups)

The liquid crystal compound having two or more polymerizable functional groups, which is used in the polymerizable liquid crystal composition of the present invention, exhibits liquid crystallinity in the composition alone or in combination with other liquid crystal compounds. The compound having two or more polymerizable functional groups is not particularly limited, and a known compound can be used.

For example, Handbook of Liquid Crystals (D.Demus, J.W. Goodby, G.W.Gray, H. W. Sapess, edited by V. Vill, published by Wiley-VCH, 1998); 22, liquid crystal chemistry (Japanese Chemical Society, 1994), or Japanese Patent Application Laid-Open No. 4-227684, Japanese Patent Application Laid-Open No. 11-80090, Japanese Laid-Open Patent Application No. 11-116538, As described in JP-A-11-148079, JP-A-2000-178233, JP-A-2002-308831, JP-A-2002-145830, JP-A-2004-125842, , A 4-phenylene group, a 1,4-cyclohexylene group and the like, and a polymer such as an acryloyl group, a (meth) acryloyl group, a vinyloxy group and a glycidyl group A rod-like polymerizable liquid crystal compound having a malfunctioning group, or a rod-like polymerizable liquid crystal compound having a maleimide group as described in JP-A-2004-2373 and JP-A-2004-99446. Among them, a rod-like liquid crystal compound having a polymerizable group is preferable because it can easily form a liquid crystal temperature range including a low temperature before and after room temperature.

The polymerizable functional group may be a vinyl group, a vinyloxy group, an acryloyl group, a (meth) acryloyl group, a glycidyl group, a glycidyl ether group, an oxetanyl group or a maleimide group. , An acryloyl group or a (meth) acryloyl group is preferable.

Specific examples of the liquid crystal compound having two or more polymerizable functional groups used in the polymerizable liquid crystal composition of the present invention include the following liquid crystal compounds.

(Wherein m and n each independently represent an integer of 1 to 10, and R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, a carbamoyl group, Or a halogen atom. When these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, all of them may be unsubstituted or substituted with one or two or more halogen atoms. A carboxyl group or a carbamoyl group, the terminal hydrogen atom may be unsubstituted or may be substituted with an alkyl group having 1 to 10 carbon atoms)

R is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group.

These liquid crystal compounds may be used alone or in combination of two or more.

d) (chiral compound having at least one polymerizable functional group)

The chiral compound having at least one polymerizable functional group, which is used in the polymerizable liquid crystal composition of the present invention, is not particularly limited and may be a known one.

For example, Japanese Patent Application Laid-Open No. 11-193287, Japanese Patent Application Laid-Open Nos. 2001-158788, 2006-52669, 2007-269639, 2007-269640, 2009 -84178 or the like, chiral saccharides such as isosorbide, isomannide, glucoside, etc., and also include rigorous substances such as 1,4-phenylene group and 1,4-cyclohexylene group, A polymerizable chiral compound having a polymerizable functional group such as a (meth) acryloyl group, a vinyloxy group and a glycidyl group, a terpenoid (meth) acrylate as described in JP-A-8-239666 terpenoid derivatives, as described in NATURE VOL 35 467-469 (published on November 30, 1995), NATURE VOL 392 476-479 (published on Apr. 2, 1998) A polymeric chiral compound comprising a spacer having a tile and a chiral moiety, Include polymeric chiral compounds containing a non-naphthyl group as described in JP-A-2004-504285 and JP-A-2007-248945. Among them, a chiral compound having a high helical twisting force (HTP) is preferable because the polymerizable liquid crystal composition of the present invention is easily produced.

Specific examples of the chiral compound having at least one polymerizable functional group which is used in the polymerizable liquid crystal composition of the present invention include the following liquid crystal compounds, but are not limited thereto.

(Wherein m and n each independently represent an integer of 1 to 10, and R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, a carbamoyl group, , And halogen atoms. When these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, all of these groups may be unsubstituted or substituted with one or two or more halogen atoms. A carboxyl group or a carbamoyl group, the terminal hydrogen atom may be unsubstituted or may be substituted with an alkyl group having 1 to 10 carbon atoms)

These chiral compounds may be used alone or in combination of two or more.

e) (polymerization initiator)

The polymerization initiator used in the polymerizable liquid crystal composition of the present invention is used for polymerizing the polymerizable liquid crystal composition of the present invention. As the photopolymerization initiator used when polymerization is carried out by light irradiation, known photopolymerization initiators can be used.

For example, 2-hydroxy-2-methyl-1-phenylpropan-1-one ("Darocure 1173" manufactured by Merck), 1-hydroxycyclohexyl phenyl ketone ("Irgacure 184" Methyl-1 - [(methylthio) phenyl] - (2-methylphenyl) 2-benzyl-2-dimethylamino-1- (4-methylphenyl) propane-1 (Irgacure 907, manufactured by Ciba Specialty Chemicals), benzyl methyl ketal (Irgacure 651, manufactured by Ciba Specialty Chemicals) -Morpholinophenyl) -butanone (Irgacure 369 from Ciba Specialty Chemicals), 2-dimethylamino-2- (4-methylbenzyl) Butane-1-one (Irgacure 379, manufactured by Ciba Specialty Chemicals), 2,2-dimethoxy-1,2-diphenylethan-1-one, bis (2,4,6-trimethylbenzoyl) -phenyl Phosphine oxide (Darocure TPO), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide 1- (4- (phenylthio) -, 2- (O-benzoyloxime)] ("Irgacure OXE01" manufactured by Ciba Specialty Chemicals, Inc.) , 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime) (Irgacure OXE02 manufactured by Ciba Specialty Chemicals) ), A mixture of 2,4-diethylthioxanthone ("Kayacure DETX" manufactured by Nippon Kayaku Co., Ltd.) and ethyl p-dimethylaminobenzoate ("Kayacure EPA" manufactured by Nippon Kayaku Co., Ltd.), isopropylthioxanthone And a mixture of ethyl p-dimethylaminobenzoate, acylphosphine oxide ("Lucirin TPO" available from BASF), and the like.

The content of the photopolymerization initiator is preferably from 1 to 10 mass%, particularly preferably from 2 to 7 mass%. These may be used alone or in combination of two or more.

As the thermal polymerization initiator to be used for thermal polymerization, known ones can be used, and examples thereof include methyl acetoacetate peroxide, cumene hydroperoxide, benzoyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarboxylic acid Butyl peroxybenzoate, methyl ethyl ketone peroxide, 1,1-bis (t-hexyl peroxy) 3,3,5-trimethyl cyclohexane, p-pentahydro peroxide, t- Organic peroxides such as roper oxide, dicumyl peroxide, isobutyl peroxide, di (3-methyl-3-methoxybutyl) peroxydicarbonate and 1,1-bis (t-butylperoxy) cyclohexane, , Azo compounds such as 2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile), azo compounds such as 2,2'-azobis (2-methyl- -Amidine) dihydrochloride, azomethine compounds such as 2,2 'azobis {2-methyl-N- [1,1-bis Hydroxymethyl) Oh, such as 2-hydroxyethyl] propionamide} tighten imide compound, 2,2 'azobis (2,4,4-trimethylpentane) and the like can be used azo compounds such as alkyl. The content of the thermal polymerization initiator is preferably from 1 to 10 mass%, particularly preferably from 2 to 6 mass%. These may be used alone or in combination of two or more.

The photopolymerization initiator and the thermopolymerization initiator may be used in combination in accordance with the application or production method.

f) (solvent)

The composition of the present invention contains the above-mentioned polymerizable liquid crystal composition and a solvent, but the solvent used in the composition is not completely dissolved in the base material or the alignment film formed on the base material, As long as the composition can be aligned without defects, the solvent to be used is not particularly limited, but a solvent in which the polymerizable liquid crystal compound exhibits good solubility is preferable.

Examples of such a solvent include aromatic hydrocarbons such as toluene, xylene, cumene and mesitylene, ester solvents such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, Ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane and anisole; amide solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone; Glycol monomethyl ether acetate, diethyl glycol monomethyl ether acetate,? -Butyrolactone, and chlorobenzene. These may be used alone or in combination of two or more.

The proportion of the solvent is not particularly limited as long as the polymerizable liquid crystal composition to be used in the present invention is usually applied by coating, so long as it does not significantly impair the applied state. The ratio of the solid content and the solvent in the polymerizable liquid crystal composition is preferably 0.1: Preferably 99.9 to 80:20, and more preferably 1:99 to 60:40 in view of coating properties.

g) (Surfactant or polymer promoting planar orientation)

In order to polymerize the polymerizable liquid crystal composition of the present invention in the planar orientation, a surfactant or polymer that promotes the planar orientation is used as needed.

The surfactant for promoting the planar orientation used in the polymerizable liquid crystal composition of the present invention is soluble in the polymerized liquid crystal composition and is not segregated (segregated) at the air interface on the side opposite to the substrate during application and drying of the polymerizable liquid crystal composition ), The surfactant to be used is not particularly limited, but a surfactant having a lower surface tension than a liquid crystal compound having a polymerizable functional group is preferable. Examples of such a surfactant include a fluorine-containing nonionic surfactant, an organosilane surfactant, and a polyacrylate ester surfactant. The surfactant may have a polymerizable group in order to obtain a film that is stronger than when it was polymerized.

The polymer for promoting the planar orientation used in the polymerizable liquid crystal composition of the present invention is also usable in the polymerized liquid crystal composition and is a material segregated at the air interface on the side opposite to the substrate at the time of application and drying of the polymerizable liquid crystal composition The polymer to be used is not particularly limited, but a polymer having a lower surface tension than a liquid crystal compound having a polymerizable functional group is preferable. Examples of such a polymer include polyethylene, polypropylene, polyisobutylene, paraffin, liquid paraffin, chlorinated polypropylene, chlorinated paraffin, chlorinated liquid paraffin, and polyvinylidene fluoride.

The mass average molecular weight of the polymer is preferably 200 to 1,000,000, more preferably 300 to 100,000, and particularly preferably 400 to 10,000.

The content of the surfactant or polymer that promotes the planar orientation is preferably from 0.01 to 3% by mass, and particularly preferably from 0.05 to 1.0% by mass.

h) (stabilizer)

In order to uniformly coat the polymerizable liquid crystal composition of the present invention, a general purpose additive may be used for obtaining a cholesteric reflective film having a uniform film thickness or for each purpose. Additives such as a leveling agent, a tin agent, a surfactant, an ultraviolet absorber, an infrared absorber, an antioxidant, a surface treatment agent and a polymerization inhibitor may be added to such an extent as not to remarkably lower the aligning ability of the liquid crystal.

(Cholesteric reflective film)

INDUSTRIAL APPLICABILITY The cholesteric reflective film of the present invention is a cholesteric reflective film constituted by a cured product of a planar-oriented polymerizable liquid crystal composition,

a) a compound represented by the general formula (1)

(Wherein R ₁ and R ₂ each independently represent a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms, Or more thereof may be substituted with a fluorine atom, and Z ₁ is a single bond, -O-, -S-, -COO-, -OCO-, -OCH ₂ -, -CH═CH-, -CH═CH-COO- Or -OCO-CH = CH-, and Z ₂ represents a single bond, -O-, -S-, -COO-, -OCO-, -CH ₂ O-, -CH = CH-, COO- or -OCO-CH = CH-, A represents -C≡C-, -C═N-, -N═N- or -C═NN═C-, or a ring structure of any of the following

. R ₃ represents F, Cl, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group. B is

And R ₄ represents a fluorine atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group, and b) C) at least one liquid crystal compound having at least two polymerizable functional groups, and d) at least one polymerizable functional group, wherein the liquid crystal compound contains at least one polymerizable functional group, , And e) one or two or more polymerization initiators.

The cholesteric reflective film of the present invention is preferably a cholesteric reflective film having a polarization reflection band of 300 nm or more.

(Preparation of cholesteric reflective film)

(materials)

The substrate used in the cholesteric reflective film of the present invention is a substrate usually used for a liquid crystal device, a display, an optical component, or an optical film, and can be used as a substrate after application of the polymerizable liquid crystal composition of the present invention, It is not particularly limited as long as it is a material having heat resistance capable of withstanding the heating in Examples of such a substrate include an organic material such as a glass substrate, a metal substrate, a ceramic substrate, and a plastic substrate. Particularly, when the base material is an organic material, it is possible to use a cellulose derivative, a polyolefin, a polyester, a polyolefin, a polycarbonate, a polyacrylate, a polyarylate, a polyether sulfone, a polyimide, a polyphenylsulfide, a polyphenylene ether, And the like.

Of these, plastic substrates such as polyester, polystyrene, polyolefin, cellulose derivatives, polyarylate, and polycarbonate are preferable.

In order to improve the coatability and adhesion of the polymerizable liquid crystal composition of the present invention, surface treatment of these substrates may be performed. Examples of the surface treatment include ozone treatment, plasma treatment, corona treatment, and silane coupling treatment. In order to control the transmittance and reflectance of light, an organic thin film, an inorganic oxide thin film, a metal thin film, or the like is provided on the surface of the substrate by vapor deposition or the like, or in order to attach an optical added value, A lens, an optical disk, a phase difference film, a light diffusion film, a color filter, or the like. Among them, a pickup lens, a retardation film, a light diffusion film, and a color filter which have higher added value are preferable.

In addition, the substrate may be subjected to a usual alignment treatment or may be provided with an alignment film so that the polymerizable liquid crystal composition of the present invention is oriented when the polymerizable liquid crystal composition is applied and dried. Examples of the orientation treatment include a stretching treatment, a rubbing treatment, a polarized ultraviolet visible light irradiation treatment, and an ion beam treatment. When an alignment film is used, a known alignment film can be used. Examples of such an orientation film include a film made of an organic material such as polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, Compounds, chalcone compounds, cinnamate compounds, peptidic compounds, anthraquinone compounds, azo compounds, and arylethene compounds. The compound which is subjected to orientation treatment by rubbing is preferably accelerated in crystallization of the material by applying an orientation treatment or a heating process after the orientation treatment. Among the compounds that are subjected to the orientation treatment other than rubbing, it is preferable to use a photo-alignment material.

(apply)

Examples of a coating method for obtaining the cholesteric reflective film of the present invention include an applicator method, a bar coating method, a spin coating method, a gravure printing method, a flexo printing method, an ink jet method, a die coating method, a cap coating method, A publicly known method can be performed. Normally, since the polymerizable liquid crystal composition diluted with a solvent is applied, it is dried after application.

(Polymerization step)

The polymerization operation of the polymerizable liquid crystal composition of the present invention is generally carried out by irradiation with light such as ultraviolet rays or heating by removing the solvent in the polymerizable liquid crystal composition by drying or the like and then planar alignment. When the polymerization is carried out by light irradiation, concretely, ultraviolet light of 390 nm or less is preferably irradiated, and it is most preferable to irradiate light of a wavelength of 250 to 370 nm. However, when the polymerizable liquid crystal composition causes decomposition or the like due to ultraviolet light of 390 nm or less, it is preferable that the polymerization treatment is performed with ultraviolet light of 390 nm or more. It is preferable that this light is diffused light and is not polarized light.

On the other hand, the polymerization by heating is preferably carried out at a temperature at which the polymerizable liquid crystal composition exhibits a liquid crystal phase or at a lower temperature, and in particular, when a thermal polymerization initiator which releases radicals by heating is used, It is preferable to use the one that is within the temperature range of. When the thermal polymerization initiator and the photopolymerization initiator are used in combination, it is preferable to select the polymerization temperature and the respective initiator so that the polymerization rate of the both layers of the photo-alignment film and the polymerizable liquid crystal film do not differ greatly with the above-described temperature range limitation. The heating temperature is preferably lower than the temperature at which the heterogeneous polymerization due to heat is induced (induced) depending on the transition temperature to the isotropic phase on the liquid crystal of the polymerizable liquid crystal composition. However, when the glass transition point of the substrate made of an organic material is exceeded, the glass transition temperature is preferably from room temperature to the substrate, since thermal deformation of the substrate becomes remarkable. For example, when the polymerizable group is a methacryloyl group, it is preferably carried out at a temperature lower than 90 ° C.

In order to stabilize the content property and heat resistance of the resulting cholesteric reflective film, the cholesteric reflective film may be subjected to heat treatment. In this case, it is preferable to heat the polymerizable liquid crystal film to the glass transition point or higher. In general, heating in a range not exceeding the glass transition point of a substrate made of an organic material is preferable. For the above purpose, light irradiation treatment may also be performed. In this case, it is preferable that the amount of the liquid crystal compound in the cholesteric reflective film is not photodegraded by light irradiation.

(Reflective polarizer)

The reflection type polarizing plate of the present invention is a reflection type polarizing plate in which a reflective type polarizing plate or substrate in which a substrate, a cholesteric reflecting film and a retardation film are sequentially laminated, a cholesteric reflecting film, a retardation film and a linearly polarizing film are sequentially laminated, The cholesteric reflective film uses the cholesteric reflective film of the present invention.

It is also preferable that the retardation film has two or more retardation films in the reflection type polarizing plate, and the retardation film has a retardation film having a different retardation.

The lamination of the substrate and the cholesteric reflective film is the same as described for the production of the cholesteric reflective film. Examples of the lamination of the retardation film include the following methods.

(When laminated directly on a cholesteric reflective film)

Can be obtained by forming an orientation film on the cholesteric reflective film of the present invention, applying and drying a solution containing the liquid crystal compound on the orientation film, and polymerizing the liquid crystal compound in a uniaxially oriented state. When the liquid crystal compound is uniaxially oriented without forming an alignment film, it can be obtained by applying a solution containing the liquid crystal compound directly on the cholesteric film of the present invention, followed by drying and polymerization. When an alignment film is used, a known alignment film can be used as the alignment film as described in the above section.

(When bonding to a cholesteric reflective film)

The above substrate is coated and dried by the above-mentioned coating method, and a retardation film is obtained in the same manner as in the above-mentioned polymerization process. Bonding the resulting retardation film with an adhesive or an adhesive film, and then bonding the cholesteric reflective film of the present invention and the retardation film via an adhesive or an adhesive film. When an adhesive or an adhesive film is used, known adhesives for optical films may be used as the adhesive and the adhesive film.

Further, the retardation film may be provided with two other retardation films. As for the combination of the other two retardation films, the orientation of the liquid crystal compound is preferably selected from homogeneous (positive A plate), homogeneous (positive A plate), homogeneous (positive A plate), homeotropic (positive C plate) Positive A plate) and a hybrid (O plate).

When a linearly polarizing film is provided on the retardation film, the retardation film is usually laminated by a bonding method.

The lamination method is the same as the method of laminating the retardation film on the cholesteric reflective film.

When the cholesteric reflective film of the present invention is subjected to X-ray irradiation treatment or electron beam irradiation treatment, adhesion between the substrate and the polymerizable liquid crystal composition of the present invention is improved. The X-ray is an electromagnetic wave having a wavelength of 0.1 to 100 Å (angstrom) and an energy of about 0.1 to 100 keV, and a commercially available X-ray irradiator can be used. The energy of the X-rays is not particularly limited so long as the cholesteric reflective film of the present invention does not decompose by the X-ray irradiation treatment, and specifically, it is preferably 1 to 100 kGy (gray). On the other hand, the electron beam EB is a flow of accelerated electrons which is given a large energy by an accelerator, and usually, a commercially available electron beam irradiation apparatus can be used. The output of the electron beam may be such that the cholesteric reflective film of the present invention does not decompose by the electron beam irradiation treatment, and specifically, it is preferably 10 to 200 kGy.

[Example]

Hereinafter, the present invention will be described with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these. Unless otherwise specified, "parts" and "%" are on a mass basis.

(Preparation of Polymerizable Liquid Crystal Composition (1)) [

The liquid crystal compound represented by the formula (A-1), the liquid crystal compound represented by the formula (B-1), the liquid crystal compound represented by the formula (C-1), the liquid crystal compound represented by the formula (C- 1), 0.5 part of a polymerization initiator represented by the formula (E-1), a polymerization initiator represented by the formula (E-2) and liquid paraffin (G-1) To obtain liquid crystal composition (1). To the obtained polymerizable liquid crystal composition was added 0.07 part of 4-methoxy-1-naphthol (H-1) and 60 parts of siloxhexanone (F-1) and dissolved at 60 캜 to obtain the polymerizable liquid crystal composition ).

(Preparation of Polymerizable Liquid Crystal Compositions (3) to (25)) [

The polymerizable liquid crystal compositions (3) to (21) of the present invention and the polymerizable liquid crystal compositions (22) to (25) of the comparative examples were obtained in the same manner as the preparation of the polymerizable liquid crystal composition (2) of the present invention. Tables 1 to 6 show specific compositions of the polymerizable liquid crystal compositions (1) to (21) of the present invention and the polymerizable liquid crystal compositions (22) to (25) of the comparative examples.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

The compounds shown in Tables 1 to 6 are as follows.

Cyclopentanone (F-2)

Toluene (F-3)

Polypropylene (G-2) having a weight average molecular weight of 2200

4-methoxyphenol (H-2)

(Example 1)

The polyimide solution for alignment film was applied to a glass substrate having a thickness of 0.7 mm by spin coating, dried at 100 占 폚 for 10 minutes and then baked at 200 占 폚 for 60 minutes to obtain a coating film. The obtained coating film was subjected to rubbing treatment to obtain a substrate for a cholesteric reflective film of the present invention. The rubbing treatment was carried out using a commercially available rubbing apparatus.

The polymerizable liquid crystal composition (2) of the present invention was coated on a rubbed substrate by spin coating and dried at 80 DEG C for 2 minutes. The resultant coating film was placed on a hot plate at 60 ° C and a UV light was irradiated for 10 seconds at an intensity of 15 mW / cm 2 using a high-pressure mercury lamp adjusted to obtain ultraviolet light (UV light) of only 365 nm with a band- I investigated. Next, the band-pass filter was removed and UV light was irradiated for 20 seconds at an intensity of 70 mW / cm 2 to obtain the cholesteric reflective film of the present invention.

The selective reflection wavelength of the obtained cholesteric reflective film was measured by using a spectrophotometer (U-4100, Hitachi, Ltd.), as shown in Fig. 1, and the polarization reflection band was approximately 350 nm.

(Examples 2 to 16)

The cholesteric reflective films of Examples 2 to 16 were obtained in the same manner as in Example 1. The polarization reflection band of the obtained cholesteric reflection film was 300 nm or more as shown in Table 7. Therefore, the cholesteric reflective film produced using the polymerizable liquid crystal composition of the present invention can be said to be an excellent cholesteric reflective film capable of reflecting the entire visible light. In addition, coating, drying and irradiation at the time of producing the cholesteric reflective film can be performed in a shorter time than in the prior art, and the productivity is also excellent.

[Table 7]

(Comparative Examples 1 to 3)

Cholesteric reflective films of Comparative Examples 1 to 3 were obtained in the same manner as in Example 1 except that the polymerizable liquid crystal compositions (21) to (23) were used. As shown in Table 8, the polarizing reflection band of the obtained reflective film was all 150 nm or less.

[Table 8]

(Comparative Examples 4 to 5)

It was attempted to obtain the cholesteric reflective films of Comparative Examples 4 and 5 by using the polymerizable liquid crystal compositions (24) and (25) in the same manner as in Example 1, but many appearance defects were generated, A steric reflective film could not be obtained.

(Example 17)

The polymerizable liquid crystal composition (4) of the present invention was applied to a rubbed PET film by a bar coater and dried at 90 DEG C for 2 minutes. The obtained coating film was maintained at 60 占 폚 and UV light was irradiated for 10 seconds at an intensity of 15 mW / cm2 using a high-pressure mercury lamp adjusted to obtain UV light of only 365 nm by a band-pass filter. Next, the band-pass filter was removed, and the cholesteric reflective film of Example 17 was obtained by irradiating UV light for 20 seconds at an intensity of 70 mW / cm 2. The selective reflection wavelength of the obtained cholesteric reflection film was measured. As shown in Fig. 2, the polarization reflection band was approximately 360 nm as in Example 2. Fig.

(Examples 18 to 32)

The cholesteric reflective films of Examples 18 to 32 were obtained in the same manner as in Example 17. [ As shown in Table 9, the cholesteric reflection film obtained had a polarization reflection band of 300 nm or more.

[Table 9]

(Example 33)

And 2 parts of polyvinyl butyral (product name: Esque BM-2, manufactured by Sekisui Chemical Co., Ltd.) were dissolved in 49 parts of ethanol and 49 parts of 2-butoxyethanol. The resulting polyvinyl butyral solution was applied to the cholesteric reflective film obtained in Example 1 by spin coating and dried at 80 DEG C for 2 minutes. The obtained coating film was rubbed. The rubbing treatment was carried out using a commercially available rubbing apparatus.

Next, a toluene solution (solid content ratio: 20%) of a polymerizable liquid crystal composition for a retardation film (trade name: UV curable liquid crystal "UCL-017" manufactured by DIC Corporation) was applied onto the rubbed substrate by spin coating And dried at 80 DEG C for 2 minutes. The obtained coating film was irradiated with UV light for 15 seconds at a strength of 30 mW / cm < 2 > using a high-pressure mercury lamp to obtain a reflective polarizer of Example 33. [

The spectroscopic characteristics of the obtained reflection type polarizing plate were measured using a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.). The measurement was carried out in the same manner as in Example 33 except that a linear polarizer commercially available between the reflective polarizer and the detector of Example 33 was used and the polarizing directions of the reflective polarizer and the commercially available linear polarizer were parallel (Cross Nicol), the transmittance was measured. In the case of parallel Nicole, the transmittance was more than 90% in the visible light region. In the case of Cross-Nicol, the transmittance was almost 0% in the visible light region.

(Example 34)

A toluene solution of UCL-017 used in Example 33 was applied to a surface rubbed polyacetylcellulose film and dried at 60 DEG C for 3 minutes. The resultant coating film was irradiated with UV light for 15 seconds at an intensity of 30 mW / cm 2 using a high-pressure mercury lamp to obtain a retardation film made of a polymerizable liquid crystal composition. One of the release layers of the commercially available transparent double-faced pressure-sensitive adhesive tape was peeled off, and the obtained release film was peeled off from the obtained retardation film and then laminated on the cholesteric reflective film of Example 17 to obtain Example 34 Reflective polarizer was obtained. When the spectroscopic characteristics of the obtained reflection type polarizing plate were evaluated in the same manner as in Example 33, good polarization characteristics were obtained as in Example 33. [

(Example 35)

The polyvinyl butyral solution of Example 33 was coated on the reflective polarizer of Example 33 by spin coating and dried at 80 DEG C for 2 minutes.

Next, a xylene solution (solid content ratio: 25%) of a polymerizable liquid crystal composition for a retardation film (trade name: UV curable liquid crystal "UCL-018" manufactured by DIC Corporation) was applied to the reflection type polarizing plate by spin coating , And dried at 80 DEG C for 2 minutes. The resultant coating film was irradiated with UV light for 20 seconds at an intensity of 30 mW / cm < 2 > using a high-pressure mercury lamp to obtain a reflective polarizer of Example 35. [

(Example 36)

The xylene solution of UCL-018 used in Example 35 was applied to a surface-treated polyacetylcellulose film and dried at 60 DEG C for 3 minutes. The resultant coating film was irradiated with UV light for 20 seconds at an intensity of 30 mW / cm 2 using a high-pressure mercury lamp to obtain a retardation film made of a polymerizable liquid crystal composition. One of the release layers of the commercially available transparent double-faced pressure-sensitive adhesive tape was peeled off, and the resultant was adhered on the obtained retardation film and the other release layer was peeled off, and then the resultant was applied onto the reflection type polarizing plate of Example 34 to obtain a reflection type polarizing plate of Example 36 .

(Example 37)

The cholesteric reflective film of Example 17 was stuck on one cholesteric reflective film of the commercially available transparent double-faced pressure-sensitive adhesive tape, and the other cholesteric reflective film was peeled off, 37 cholesteric reflective film was obtained.

The selective reflection wavelength of the cholesteric reflective film of Example 37 was measured. As in Example 2, the polarization reflection band was approximately 400 nm. The transmittance was almost 50% or less over the entire visible light.

(Example 38)

A cholesteric reflective film of Example 38 was obtained by irradiating X-ray of 5 kGy at room temperature to a cholesteric reflective film of Example 17 using a commercially available X-ray irradiator.

The adhesion of the obtained cholesteric reflective film was evaluated by a cross-cut test described in JIS-K5400. In the cross-cut test, a cutter was used to make a 25-inch grid by making a sheath longitudinally and horizontally at intervals of 2 mm. The tape was pasted onto the grid on the grid, and the grid at the time of peeling was divided into 24 squares.

(Example 39)

The cholesteric reflective film of Example 17 was irradiated with an electron beam of 10 kGy at room temperature using a commercially available electron beam irradiation apparatus to obtain a cholesteric reflective film of Example 39. [

When the adhesion was evaluated in the same manner as in Example 38, 20 squares remained.

Claims (19)

a) a compound represented by the general formula (1)

(Wherein R ₁ and R ₂ each independently represent a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms, Or more thereof may be substituted with a fluorine atom and Z ₁ is a single bond, -O-, -S-, -OCH ₂ -, -CH═CH-, -CH═CH-COO- or -OCO-CH═CH- It represents a, Z ₂ is a single _{bond, -O-, -S-, -CH 2 O-} , -CH = CH-, denotes a -CH = CH-COO- or -OCO-CH = CH-, a is - C = C-, -C = N-, -N = N- or -C = NN = C- or a cyclic structure

R ₃ represents a fluorine atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group, and B represents a cyclic structure

And R ₄ represents a fluorine atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group, and b) C) at least one liquid crystal compound having at least two polymerizable functional groups, and d) at least one polymerizable functional group, wherein the liquid crystal compound contains at least one polymerizable functional group, , And e) one or two or more polymerization initiators. The polymerizable liquid crystal composition according to claim 1, The method according to claim 1,
Wherein the content of the compound represented by the general formula (1) is 0.1 to 20% by mass. 3. The method according to claim 1 or 2,
1. A polymerizable liquid crystal composition comprising a) at least two kinds of liquid crystal compounds having only one polymerizable functional group. 3. The method according to claim 1 or 2,
A polymerizable liquid crystal composition comprising two or more liquid crystal compounds having two polymerizable functional groups. 3. The method according to claim 1 or 2,
When the liquid crystal compound having only one polymerizable functional group is represented by the general formula (2)

(Wherein L represents a hydrogen atom or a methyl group, Sp represents a single bond or an alkyl group having 1 to 10 carbon atoms, X represents a single bond, -O-, -S-, -COO-, -OCO-, -OCH ₂ , -CH = CH-, -CH = CH-COO- or -OCO-CH = CH-, G ₁ represents a single bond, a 1,4-phenylene group, a naphthalene- , And a cyclohexylene group, but one or two or more hydrogen atoms present in these groups may be substituted with a fluorine atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group M is a single bond, -O-, -S-, -COO-, -OCO-, -OCH ₂ -, -CH = CH-, -CH = CH-COO- or -OCO- CH-, when G ₁ represents a single bond, M represents a single bond and G ₁ represents a 1,4-phenylene group, a naphthalene-2,6-diyl group or a 1,4-cyclohexylene group If, -O-, -S-, -COO-, -OCO- , -OCH 2 -, -CH = CH-, denotes a -CH = CH-COO- or -OCO-CH = CH-, G ₂ is A hydrogen atom, a phenyl group, Cyclohexyl group or naphthyl group in the phenyl, cyclohexyl or naphthyl group, the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, the carboxy group, the carbamoyl group, the cyano group, the nitro group or the halogen atom, The atom may be unsubstituted or substituted with one or two or more halogen atoms, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group, and the hydrogen atom in the carboxyl group or the carbamoyl group Y ₁ and Y ₂ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, which may be substituted or substituted with an alkyl group having 1 to 10 carbon atoms ). ≪ / RTI > 6. The method of claim 5,
Wherein the content of the compound represented by the general formula (2) is 5 to 80% by mass. 3. The method according to claim 1 or 2,
When the liquid crystal compound having only one polymerizable functional group is represented by the general formula (3)

(Wherein L ₁ represents a hydrogen atom or a methyl group, Sp ₁ represents a single bond or an alkyl group having 1 to 10 carbon atoms, X ₁ and X ₂ each independently represent a single bond, -O-, -S-, _{COO-, -OCO-, -OCH 2 -,} -CH = CH-, denotes a -CH = CH-COO- or _{-OCO-CH = CH-, Y 3} , Y 4, Y 5 and Y ₆ are each independently A halogen atom, a cyano group, a nitro group or a halogen atom, the hydrogen atom in the alkyl group or alkoxy group may be substituted with one or two hydrogen atoms, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, a carbamoyl group, Or a hydrogen atom in the carboxyl group or carbamoyl group may be unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms). 3. The method according to claim 1 or 2,
Wherein the content of the polymerization initiator is 1 to 10% by mass. 3. The method according to claim 1 or 2,
A surfactant for promoting planar alignment, or a polymerizable liquid crystal composition containing at least one kind of polymer. 10. The method of claim 9,
A surfactant for promoting planar alignment, or a polymerizable liquid crystal composition having a content of a polymer of 0.01 to 3 mass%. A composition comprising at least one of the polymerizable liquid crystal composition and the solvent according to any one of claims 1 to 12. Wherein the polymerizable liquid crystal composition is a cholesteric reflective film constituted by a cured product (cured product) of a polymerizable liquid crystal composition oriented in a planar direction,
a) a compound represented by the general formula (1)

(Wherein R ₁ and R ₂ each independently represent a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms, Or more thereof may be substituted with a fluorine atom and Z ₁ is a single bond, -O-, -S-, -OCH ₂ -, -CH═CH-, -CH═CH-COO- or -OCO-CH═CH- It represents a, Z ₂ is a single _{bond, -O-, -S-, -CH 2 O-} , -CH = CH-, denotes a -CH = CH-COO- or -OCO-CH = CH-, a is - C = C-, -C = N-, -N = N- or -C = NN = C- or a ring structure

R ₃ represents a fluorine atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group, and B represents a cyclic structure

And R ₄ represents a fluorine atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group, and b) C) at least one liquid crystal compound having at least two polymerizable functional groups, and d) at least one polymerizable functional group, wherein the liquid crystal compound contains at least one polymerizable functional group, , And e) one or two or more polymerization initiators. The cholesteric reflective film according to claim 1, 13. The method of claim 12,
A cholesteric reflective film having a polarized reflection band of 300 nm or more. The method according to claim 12 or 13,
A cholesteric reflective film having a substrate, wherein the substrate is a plastic film. A reflective polarizer comprising a substrate, a cholesteric reflective film and a retardation film laminated in this order, wherein the cholesteric reflective film is the cholesteric reflective film according to claim 12 or claim 13. A reflective polarizing plate comprising a substrate, a cholesteric reflective film, a retardation film and a linear polarizing film sequentially laminated, wherein the cholesteric reflective film is a cholesteric reflective film according to claim 12 or claim 13, Type polarizer. 16. The method of claim 15,
A reflection type polarizing plate having two or more retardation films in a reflection type polarizing plate, wherein the retardation film has a retardation film having a different retardation. The method according to claim 12 or 13,
An X-ray irradiation treatment, or an electron beam irradiation treatment is applied to the cholesteric reflective film. 16. The method of claim 15,
Wherein the base material is a light-diffusing film.

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