KR20110110012A - 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.[Problem] A cholesteric reflective film that easily expands the wavelength region of selective reflection of the cholesteric reflective film and provides a polymerizable liquid crystal composition having excellent productivity, and also has an excellent appearance using the polymerizable liquid crystal composition. And a reflective polarizing plate.
[Solution] a) General formula (1)

1 or 2 or more types of liquid crystal compounds represented by (b), b) 1 or 2 or more types of liquid crystal compounds having only one polymerizable functional group, and c) 1 or more liquid crystal compounds having two or more polymerizable functional groups. Species or two or more kinds, d) one or two or more kinds of chiral compounds having one or more polymerizable functional groups, and e) one or two or more kinds of polymerization initiators. Provided are a cholesteric reflective film composed of the composition and the polymerizable liquid crystal composition.

Description

Polymeric liquid crystal composition and cholesteric reflective film and reflective polarizing plate using the same {POLYMERIZABLE LIQUID CRYSTAL COMPOSITION, AND CHOLESTERIC REFLECTIVE FILM USING THE SAME, AND REFLECTION TYPE POLARIZING PLATE}

The present invention relates to a polymerizable liquid crystal composition useful as a liquid crystal device, a display, an optical component, a colorant, a marking for security, a member for laser light emission, a cholesteric polarizing film obtained from a polymerized liquid crystal composition, and a reflective polarizing plate. will be.

The development of the polarizing plate using the selective reflection characteristic of a cholesteric liquid crystal has been performed vigorously since the 1990s. In order to use a cholesteric liquid crystal as a polarizing plate, it is necessary to make wavelength range of selective reflection into a visible light region, and polarization characteristic can be acquired by making the pitch of a cholesteric liquid crystal into a predetermined value. However, when the chiral compound is added to the nematic liquid crystal, the pitch is generally maintained at a constant pitch, and only selective reflection of a specific narrow wavelength region corresponding thereto can be obtained. For this reason, an attempt has been made to widen the wavelength range of selective reflection by devising a cholesteric liquid crystal composition.

As one of them, in the polymerizable cholesteric liquid crystal, a method of sequentially controlling the width of the pitch by controlling the polymerization rate on the irradiated surface and the non-irradiated surface (see Patent Literature 1) is disclosed. It is. This method suppresses absorption of the photoinitiator contained in a cholesteric liquid crystal composition by adding the dye which has an absorption wavelength which overlaps with the absorption wavelength of a photoinitiator in a polymeric cholesteric liquid crystal composition, and irradiates the light generate | occur | produced accordingly. Pitch is controlled by the difference of the superposition | polymerization rate in a surface and a non-irradiation surface. However, in this method, it took a long time to obtain the cholesteric reflective film which enlarged the wavelength range of selective reflection, and there existed a problem in productivity. Moreover, since dye is not a liquid crystal compound, there existed a problem that defects, such as coloring to a film and generation of an orientation defect, are easy to generate | occur | produce with increase of the addition amount. Moreover, it is also known to comprise only a polymeric liquid crystal composition without adding the dye which has an absorption wavelength which overlaps with the absorption wavelength of a photoinitiator in a polymeric cholesteric liquid crystal composition (refer patent document 2). However, the composition which can obtain sufficient reflection area | region without using dye is limited to the combination of the polymerizable liquid crystal compound of a very narrow range, and the freedom of composition design is low, and most compositions cannot obtain sufficient reflection area | region. There was.

As another method, the method which makes it easy to produce a change of pitch by making a chiral compound in a cholesteric liquid crystal composition into a non-polymerization type is mentioned (nonpatent literature 1). In this method, the light is irradiated to the irradiated surface, and the pitch is dispersed by photopolymerizing the cholesteric liquid crystal composition little by little from the irradiated surface.

However, when enlarging the wavelength range of selective reflection, in these said methods, it took a long time to produce a cholesteric reflective film, and there existed 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)

The problem to be solved by the present invention is to easily expand the wavelength region of selective reflection of the cholesteric reflective film, to provide a polymerizable liquid crystal composition excellent in productivity, and also to provide an appearance using the polymerizable liquid crystal composition. An excellent cholesteric reflective film and a reflective polarizing plate are provided.

The inventors of the present invention, in the dye as disclosed in the prior art, since the alignment defect occurs with the increase in the amount of addition, the orientation defect is maintained even if the compound having a function close to the dye and the amount of the compound which can be a liquid crystal increases the addition amount In view of the difficulty of occurrence, the present invention has been reached.

The present invention,

a) general formula (1)

(In formula, R <_1> and R <_2> respectively independently represents a fluorine atom, a chlorine atom, a cyano group, a C1-C12 alkyl group, or a C2-C12 alkenyl group, and one of the hydrogen atoms contained in these groups Or more 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-, Z ₂ is a single bond, -O-, -S-, -COO-, -OCO-, -CH ₂ O-, -CH = CH-, -CH = CH- COO- or -OCO-CH = CH-, where A is -C≡C-, -C = N-, -N = N- or -C = NN = C- or any of the following structures:

R <_3> represents a fluorine atom, a chlorine atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a cyano group, B is the following ring structure

Represents a, R ₄ is 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 represents a cyano group), a liquid crystal compound of two or more kinds represented by and, b) One or two or more liquid crystal compounds having only one polymerizable functional group, c) one or two or more liquid crystal compounds having two or more polymerizable functional groups, and d) one or more polymerizable functional groups. Provides 1 type (s) or 2 or more types of chiral compounds which have, and e) 1 type (s) or 2 or more types of polymerization initiators, The polymerizable liquid crystal composition characterized by the above-mentioned,

A cholesteric reflective film composed of a cured product of a planar-oriented polymerizable liquid crystal composition, wherein the polymerizable liquid crystal composition provides a cholesteric reflective film that is the polymerizable liquid crystal composition,

A reflective polarizing plate in which a substrate, a cholesteric reflective film, and a retardation film are sequentially stacked, and the retardation film is the retardation film, and a reflective polarizing plate is provided.

Provided is a reflective polarizing plate in which a substrate, a cholesteric reflective film, a retardation film, and a linear polarizing film are sequentially stacked, and the retardation film is the retardation film.

The polymerizable liquid crystal composition of the present invention has a function close to a dye and contains a compound capable of becoming a liquid crystal, whereby an orientation defect is less likely to occur, and has a feature of easily expanding the wavelength region of selective reflection. . Moreover, the polymeric liquid crystal composition of this invention can manufacture a cholesteric reflective film by a simple method, and is excellent also in productivity. Therefore, the polymeric liquid crystal composition of this invention, a cholesteric reflective film, and a reflective polarizing plate can be applied to a liquid crystal device, a display, an optical component, a coloring agent, security marking, and a laser light emitting member.

BRIEF DESCRIPTION OF THE DRAWINGS The figure which shows the polarization reflection band of the cholesteric reflection film produced in Example 1. FIG.
2 is a view showing a polarization reflection band of the cholesteric reflection film produced in Example 17. FIG.

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail.

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

Although the liquid crystal compound represented by General formula (1) is used for the polymeric liquid crystal composition of this invention, the photoinitiator contained in a cholesteric liquid crystal composition by adding the dye which has an absorption wavelength which overlaps with the absorption wavelength of a photoinitiator. From the viewpoint of suppressing the absorption of the compound, a compound having many overlapping conjugated bonds of the liquid crystal compound is preferable.

From such a viewpoint, in the liquid crystal compound represented by the general formula (1), R ₁ and R ₂ are each independently preferably 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, Especially a fluorine atom, a C3-C8 alkyl group, or a C2-C8 alkenyl group is preferable.

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-

Preference is given, in particular -C≡C-, -C = N-N = C-

Is preferred. 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, and a cyano group, and particularly preferably a fluorine atom and an alkyl group having 1 to 6 carbon atoms.

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

Is preferred, in particular,

Is preferred. 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.

Although the following liquid crystal compound is illustrated specifically, General formula (1) is not limited to this.

(In formula, m and n respectively independently represent the integer of 0-7, R represents a hydrogen atom, a fluorine atom, or a C1-C6 alkyl group.)

0.1-20 mass% is preferable, and, as for the content rate of the compound represented by General formula (1), 0.5-10 mass% is more preferable.

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

The liquid crystal compound which has only one polymerizable functional group used for the polymeric liquid crystal composition of this invention shows liquid crystallinity in a composition with single or another liquid crystal compound. There is no restriction | limiting in particular if it is a compound which has only one polymerizable functional group, A well-known conventional thing can be used.

For example, Handbook of Liquid Crystals (D.Demus, J.W.Goodby, G.W.Gray, H.W.Spiess, V.Vill Edit, published by Wiley-VCH, 1998), Quarterly Chemistry No. 22, chemistry of liquid crystal (Japanese Chemical Society, 1994) or JP-A-7-294735, JP-A-8-3111, JP-A-8-29618, JP-A 1,4-phenylene group, 1,4-cyclohexylene group, etc. as described in Unexamined-Japanese-Patent No. 11-80090, Unexamined-Japanese-Patent No. 11-116538, Unexamined-Japanese-Patent No. 11-148079, etc. Rod-shaped polymerizable liquid crystal compound having a rigid site called mesogen having a plurality of structures and a polymerizable functional group such as methacryloyl group, vinyloxy group and glycidyl group, or JP 2004-2373 A The rod-like polymerizable liquid crystal compound which has a maleimide group as described in Unexamined-Japanese-Patent No. 2004-99446 is mentioned. Especially, it is preferable that the rod-shaped liquid crystal compound which has a polymeric group makes it easy to produce what contains the low temperature before and behind room temperature as a liquid crystal temperature range.

The polymerizable functional group may be a vinyl group, vinyloxy group, acryloyl group, (meth) acryloyl group, glycidyl group, glycidyl ether group, oxetanyl group or maleimide group, and the like. , Acryloyl group or (meth) acryloyl group is preferable.

Although the liquid crystal compound which shows only one polymerizable functional group used for the polymeric liquid crystal composition of this invention specifically, as shown below is illustrated, it is not limited to these.

(In formula, l and m represent the integer of 1-9 each independently, n represents the integer of 0-10.)

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

In addition, a liquid crystal compound having only one polymerizable functional group is represented by 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- denotes a, G ₁ represents a single bond, 1,4-phenylene group, naphthalene-2,6-diyl or 1 Although a 4-cyclohexylene group is shown, 1 or 2 or more hydrogen atoms which exist in these groups are substituted by a fluorine atom, a chlorine atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a cyano group M may be 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 Atom, phenyl group, cycle Hexyl group, naphthyl group, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, carboxyl group, carbamoyl group, cyano group, nitro group or halogen atom, but hydrogen in the phenyl group, cyclohexyl group or naphthyl group 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 in the carboxy group or carbamoyl group. The atom may be unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms, and 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 a 1 to 6 carbon group. In the case of a compound represented by an alkoxy group), the wavelength region of selective reflection can be further enlarged, which is particularly preferable.

As for L of the liquid crystal compound represented by General formula (2), a hydrogen atom is preferable.

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

As for X of the liquid crystal compound represented by General formula (2), a single bond, -O-, -COO-, -OCO-, or -OCO-CH = CH- is preferable, A single bond, -O-, or -OCO- Is particularly preferred.

M of the liquid crystal compound represented by General Formula (2) is -O-, -COO when G ₁ represents a 1,4-phenylene group, a naphthalene-2,6-diyl group or a 1,4-cyclohexylene group -, -OCO-, -CH = CH-, -CH = CH-COO- or -OCO-CH = CH- is preferred, and -O-, -COO- and -OCO- are particularly preferred.

G ₂ of the liquid crystal compound represented by General Formula (2) represents a hydrogen atom, a phenyl group, a cyclohexyl group, a naphthyl group, a C1-C10 alkyl group, a C1-C10 alkoxy group, a carboxyl group, a carbamoyl group, a cyano group, A fluorine atom or a chlorine atom is preferable, and a C1-C6 alkyl group, a C1-C6 alkoxy group, a cyano group, or a fluorine atom is especially 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, and a hydrogen atom, a fluorine atom, or a carbon number Particularly preferred is an alkyl group of 1 to 3 or an alkoxy group of 1 to 3 carbon atoms.

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, and a hydrogen atom, a fluorine atom, or a carbon number Particularly preferred is an alkyl group of 1 to 3 or an alkoxy group of 1 to 3 carbon atoms.

5-80 mass% is preferable, and, as for the content rate of the liquid crystal compound represented by General formula (2), 10-70 mass% is especially preferable. In addition, the liquid crystal compound represented by General formula (2) may be used independently, and may mix and use two or more types.

Although the following liquid crystal compounds are specifically, the liquid crystal compound represented by General formula (2) is not limited to these.

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

In addition, a liquid crystal compound having only one polymerizable functional group is represented by 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 are each independently a single bond, -O-, -S-,- COO-, -OCO-, -OCH _2- , -CH = CH-, -CH = CH-COO- or -OCO-CH = CH-, and Y _3, Y ₄ , Y ₅ and Y ₆ are each independently To represent 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, but the hydrogen atom in the alkyl group or alkoxy group is one or two. May be substituted with at least one halogen atom, and the hydrogen atom in the carboxy group or carbamoyl group may be unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms)

Also in the case of the liquid crystal compound represented by, since the wavelength region of selective reflection can be further enlarged, it is especially preferable.

As for L <_1> of the liquid crystal compound represented by General formula (3), a hydrogen atom is preferable.

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

X ₁ of the liquid crystal compound represented by General Formula (3) is preferably -O-, -COO-, -OCO-, -CH = CH-, -CH = CH-COO- or -OCO-CH = CH-. , -O-, -COO- or -OCO- are particularly preferred.

X ₂ of the liquid crystal compound represented by General Formula (3) is preferably -O-, -COO-, -OCO-, -CH = CH-, -CH = CH-COO- or -OCO-CH = CH-. , -COO-, -OCO-, -CH = CH- or -O- are particularly preferred.

Y ₃ , Y ₄ , Y ₅ and Y ₆ of the liquid crystal compound represented by 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 carboxyl group, a carbamoyl 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 kinds thereof.

Although the following liquid crystal compounds are specifically, the liquid crystal compound represented by General formula (3) is not limited to these.

(Wherein m represents an integer of 1 to 10, R represents a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, a carboxyl group, a carbamoyl group, a cyano group, a nitro group, or a halogen atom) However, when these groups are a C1-C6 alkyl group or a C1-C6 alkoxy group, all may be unsubstituted or may be substituted by 1 or 2 or more halogen atoms. In the case of a group, the terminal hydrogen atom may be unsubstituted or 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 kinds thereof.

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

The liquid crystal compound which has two or more polymerizable functional groups used for the polymeric liquid crystal composition of this invention shows liquid crystallinity in the composition with single or another liquid crystal compound. There is no restriction | limiting in particular if it is a compound which has 2 or more of polymerizable functional groups, A well-known conventional thing can be used.

For example, Handbook of Liquid Crystals (D.Demus, J.W.Goodby, G.W.Gray, H.W.Spiess, V.Vill Edit, published by Wiley-VCH, 1998), Quarterly Chemistry No. 22, chemistry of liquid crystal (Japanese Chemical Society, 1994) or JP-A 4-227684, JP-A 11-80090, JP-A 11-116538, JP As described in Japanese Patent Application Laid-Open No. 11-148079, Japanese Laid-Open Patent Publication No. 2000-178233, Japanese Laid-Open Patent Publication No. 2002-308831, Japanese Laid-Open Patent Publication No. 2002-145830, Japanese Laid-Open Patent Publication No. 2004-125842, and the like. A rigid site such as a mesogen having a plurality of structures such as a, 4-phenylene group, a 1,4-cyclohexylene group, and acryloyl group, a (meth) acryloyl group, a vinyloxy group, and a glycidyl group The rod-like polymerizable liquid crystal compound which has a functional group, or the rod-like polymerizable liquid crystal compound which has a maleimide group as described in Unexamined-Japanese-Patent No. 2004-2373 and 2004-99446 is mentioned. Especially, it is preferable that the rod-shaped liquid crystal compound which has a polymeric group makes it easy to produce what contains the low temperature before and behind room temperature as a liquid crystal temperature range.

The polymerizable functional group may be a vinyl group, vinyloxy group, acryloyl group, (meth) acryloyl group, glycidyl group, glycidyl ether group, oxetanyl group or maleimide group, and the like. , Acryloyl group or (meth) acryloyl group is preferable.

As for the liquid crystal compound which has two or more polymerizable functional groups used for the polymeric liquid crystal composition of this invention, the liquid crystal compound as shown below is illustrated specifically.

(In formula, m and n respectively independently represent the integer of 1-10, R is a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a carboxy group, a carbamoyl group, a cyano group, a nitro group. Or although a halogen atom is represented, when these groups are a C1-C6 alkyl group or a C1-C6 alkoxy group, all may be unsubstituted or may be substituted by 1 or 2 or more halogen atoms. In the case of a carboxyl group or a carbamoyl group, the terminal hydrogen atom may be unsubstituted or 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 kinds thereof.

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

There is no restriction | limiting in particular if it is a chiral compound which has at least 1 or more polymerizable functional groups used for the polymeric liquid crystal composition of this invention, A well-known conventional thing can be used.

For example, Japanese Patent Laid-Open No. 11-193287, Japanese Patent Laid-Open No. 2001-158788, Japanese Patent Laid-Open No. 2006-52669, Japanese Patent Laid-Open No. 2007-269639, Japanese Patent Laid-Open No. 2007-269640, 2009 It contains the chiral saccharides, such as isosorbide, isomannide, and glucoside, as described in Unexamined-Japanese-Patent No. 8484, and also it is rigid, such as a 1, 4- phenylene group and a 1, 4- cyclohexylene group. A polymerizable chiral compound having a site | part and a polymerizable functional group, such as a (meth) acryloyl group, a vinyloxy group, and a glycidyl group, a terpenoid (as described in Unexamined-Japanese-Patent No. 8-239666) ( polymerizable chiral compounds composed of terpenoid) derivatives, mesogens as described in NATURE VOL35 pages 467 to 469 (published on November 30, 1995) and NATURE VOL392 pages 476 to 479 (published on April 2, 1998) and the like. A polymerizable chiral compound comprising a spacer having a group and a chiral moiety, or The polymerizable chiral compound containing a vinaphthyl group as described in Unexamined-Japanese-Patent No. 2004-504285 and Unexamined-Japanese-Patent No. 2007-248945 is mentioned. Especially, the chiral compound with a large spiral torsion force (HTP) is preferable because the polymerizable liquid crystal composition of the present invention is easy to make.

Although the chiral compound which has at least 1 or more polymerizable functional group used for the polymeric liquid crystal composition of this invention specifically shows the liquid crystal compound shown below, it is not limited to these.

(In formula, m and n respectively independently represent the integer of 1-10, R is a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a carboxy group, a carbamoyl group, a cyano group, a nitro group. Although a halogen atom is represented, when these groups are a C1-C6 alkyl group or a C1-C6 alkoxy group, all may be unsubstituted or may be substituted by 1 or 2 or more halogen atoms. In the case of a carboxyl group or a carbamoyl group, the terminal hydrogen atom may be unsubstituted or 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 thereof.

e) (polymerization initiator)

The polymerization initiator used in the polymerizable liquid crystal composition of the present invention is used to polymerize the polymerizable liquid crystal composition of the present invention. As a photoinitiator used when superposing | polymerizing is performed by light irradiation, a well-known conventional thing can be used.

For example, 2-hydroxy-2-methyl-1-phenylpropan-1-one ("Darcure 1173" made by Merck Corporation), 1-hydroxycyclohexylphenyl ketone ("irgacure 184" made by Chiba Specialty Chemical Co., Ltd.) ), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one ("Tarocure 1116" by Merck Co., Ltd.), 2-methyl-1-[(methylthio) phenyl]- 2-morpholino propane-1 ("irgacure 907" by Chiba specialty chemical company), benzyl methyl ketal ("irgacure 651" by Chiba specialty chemical company), 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butanone ("irgacure 369" by Chiba Specialty Chemical Co., Ltd.), 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) Butan-1-one ("irgacure 379" by Chiba Specialty Chemical Co., Ltd.), 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 "Irgacure 819" made by specialty chemical company), 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyl oxime)] ("irgacure OXE01" made by Chiba specialty chemical company) , Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyl oxime) ("Irucure OXE02" made by Chiba Specialty Chemical Co., Ltd.) ), Mixture of 2,4-diethyl thioxanthone ("kayakure DETX" by Nihon Kayaku Co., Ltd.) and ethyl p-dimethylaminobenzoate ("kayakure EPA" by Nihon Kayaku Co., Ltd.), isopropyl thioxanthone ( The mixture of "Cantacure-ITX" by Wado Frecking Sop Co., Ltd., and ethyl p-dimethylaminobenzoate, "Acyl phosphine oxide (" Lucirine TPO "by BASF Corporation), etc. are mentioned.

1-10 mass% is preferable, and, as for the content rate of a photoinitiator, 2-7 mass% is especially preferable. These may be used independently and may be used in mixture of 2 or more types.

In addition, as a thermal polymerization initiator used at the time of thermal polymerization, a well-known conventional thing can be used, For example, methyl acetoacetate peroxide, cumene hydroperoxide, benzoyl peroxide, bis (4-t- butylcyclohexyl) peroxy dica Carbonate, t-butylperoxybenzoate, methylethylketone peroxide, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, p-pentahydroperoxide, t-butylhydride Organic peroxides such as loperoxide, dicumyl peroxide, isobutyl peroxide, di (3-methyl-3-methoxybutyl) peroxydicarbonate, 1,1-bis (t-butylperoxy) cyclohexane, 2 Azonitrile compounds, such as 2,2'- azobisisobutyronitrile and 2,2'- azobis (2, 4- dimethylvaleronitrile), and 2,2'- azobis (2-methyl- N-phenylpropion Azoamidine compounds such as -amidine) dihydrochloride, 2,2'azobis {2-methyl-N- [1,1-bis (hi) 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. 1-10 mass% is preferable, and, as for content of a thermal polymerization initiator, 2-6 mass% is especially preferable. These may be used independently and may be used in mixture of 2 or more types.

You may use together the said photoinitiator and the said thermal polymerization initiator according to a use and a manufacturing method, respectively.

f) (solvent)

Although the composition of this invention contains the said polymeric liquid crystal composition and a solvent, the solvent used for a composition does not make a base material or the alignment film formed on a base material, when apply | coated on a base material, but the polymerizable liquid crystal of this invention. Although it will not specifically limit as a solvent to use if a composition can be oriented without a defect, The solvent in which a polymeric liquid crystal compound shows favorable solubility is preferable.

Examples of such solvents include aromatic hydrocarbons such as toluene, xylene, cumene, mesitylene, ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketone solvents such as these, ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane and anisole, amide solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone, and propylene Glycol monomethyl ether acetate, diethyl glycol monomethyl ether acetate, γ-butyrolactone, chlorobenzene and the like. These may be used independently and may be used in mixture of 2 or more types.

The ratio of the solvent is not particularly limited as long as the polymerizable liquid crystal composition used in the present invention is usually applied by application, so long as the applied state is not significantly impaired. However, the ratio of the solid content of the polymerizable liquid crystal composition and the solvent is 0.1: 99.9-80: 20 are preferable and when considering applicability, 1: 99-60: 40 is more preferable.

g) (surfactants, or polymers that promote planar orientation)

In order to superpose | polymerize in the planar orientation state, the polymeric liquid crystal composition of this invention uses surfactant or polymer which promotes planar orientation as needed.

The surfactant which promotes planar alignment, which is used in the polymerizable liquid crystal composition of the present invention, is soluble in the polymerized liquid crystal composition, and segregates at the air interface opposite to the substrate at the time of application drying of the polymerizable liquid crystal composition. Although it does not specifically limit as surfactant to be used if it is a material used), Surfactant whose surface tension is smaller than the liquid crystal compound which has a polymeric functional group is preferable. As such surfactant, a fluorine-containing nonionic surfactant, organosilane type surfactant, polyacrylic acid ester type surfactant etc. are mentioned, for example. The surfactant may have a polymerizable group in order to obtain a film that is stronger than when polymerized.

The polymer which promotes planar alignment, which is used in the polymerizable liquid crystal composition of the present invention, is also a material that is soluble in the polymerized liquid crystal composition and that is segregated at the air interface opposite to the substrate at the time of application drying of the polymerizable liquid crystal composition. Although there is no limitation in particular as a polymer to be used, The polymer whose surface tension is smaller than the liquid crystal compound which has a polymerizable functional group is preferable. Examples of such polymers include polyethylene, polypropylene, polyisobutylene, paraffin, liquid paraffin, chlorinated polypropylene, chlorinated paraffin, chlorinated liquid paraffin, polyvinylidene fluoride, and the like.

It is preferable that the mass mean molecular weight of the said polymer is 200-1 million, It is more preferable that it is 300-100000, It is especially preferable that it is 400-10000.

0.01-3 mass% of surfactant or a polymer which promotes planar orientation is preferable, and 0.05-1.0 mass% is especially preferable.

h) (stabilizer)

In order to apply | coat uniformly the polymeric liquid crystal composition of this invention, in order to obtain the uniform cholesteric reflective film of a film thickness, you may use a general purpose additive according to each objective. For example, additives, such as a leveling agent, a thixo agent, surfactant, a ultraviolet absorber, an infrared absorber, an antioxidant, a surface treating agent, and a polymerization inhibitor, can be added to the extent which does not significantly reduce the orientation ability of a liquid crystal.

(Cholesteric reflective film)

The cholesteric reflective film of this invention is a cholesteric reflective film comprised by the hardened | cured material of the planar orientation polymerizable liquid crystal composition, The said polymeric liquid crystal composition,

a) general formula (1)

(In formula, R <_1> and R <_2> respectively independently represents a fluorine atom, a chlorine atom, a cyano group, a C1-C12 alkyl group, or a C2-C12 alkenyl group, and one of the hydrogen atoms contained in these groups Or more 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-, Z ₂ is a single bond, -O-, -S-, -COO-, -OCO-, -CH ₂ O-, -CH = CH-, -CH = CH- COO- or -OCO-CH = CH-, A represents -C≡C-, -C = N-, -N = N- or -C = NN = C- or any of the following ring structures

Indicates. R <_3> represents F, Cl, a C1-C6 alkyl group, a C1-C6 alkoxy group, and a cyano group. B is

Represents a, R ₄ is 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 represents a cyano group), a liquid crystal compound of two or more kinds represented by and, b) One or two or more liquid crystal compounds having only one polymerizable functional group, c) one or two or more liquid crystal compounds having two or more polymerizable functional groups, and d) one or more polymerizable functional groups. It is characterized by containing 1 type (s) or 2 or more types of chiral compounds which it has, and e) 1 type (s) or 2 or more types of polymerization initiators.

As for the cholesteric reflective film of this invention, the cholesteric reflective film whose polarization reflection band is 300 nm or more is preferable.

(The manufacturing method of the cholesteric reflective film)

(materials)

The base material used for the cholesteric reflective film of this invention is a base material normally used for a liquid crystal device, a display, an optical component, or an optical film, at the time of drying after application | coating of the polymeric liquid crystal composition of this invention, or at the time of manufacturing a liquid crystal device. There is no restriction | limiting in particular if it is a material which has the heat resistance which can endure the heating in the process. As such a base material, organic materials, such as a glass base material, a metal base material, a ceramic base material, and a plastic base material, are mentioned. In particular, when the substrate is an organic material, a cellulose derivative, polyolefin, polyester, polyolefin, polycarbonate, polyacrylate, polyarylate, polyethersulfone, polyimide, polyphenylene sulfide, polyphenylene ether, nylon, or polystyrene Etc. can be mentioned.

Especially, plastic base materials, such as polyester, a polystyrene, a polyolefin, a cellulose derivative, a polyarylate, and a polycarbonate, are preferable.

In order to improve the applicability | paintability and adhesiveness of the polymeric liquid crystal composition of this invention, you may surface-treat these base materials. Examples of the surface treatment include ozone treatment, plasma treatment, corona treatment, silane coupling treatment, and the like. In addition, in order to adjust the light transmittance and reflectance, 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 a method such as vapor deposition, or to add an optical value, the substrate is a pickup lens, a rod. A lens, an optical disc, a retardation film, a light diffusion film, a color filter, or the like may be used. Among them, a pickup lens, a retardation film, a light diffusing film, and a color filter having a higher added value are preferable.

Moreover, the said base material may orientate normally, or the orientation film may be provided so that a polymeric liquid crystal composition may orientate when apply | coating and drying the polymeric liquid crystal composition of this invention. Examples of the orientation treatment include stretching treatment, rubbing treatment, polarized ultraviolet visible light irradiation treatment, ion beam treatment, and the like. When using an oriented film, a well-known conventional thing can be used for an oriented film. As such an oriented film, polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin Compounds, such as a compound, a chalcone compound, a cinnamate compound, a pulled compound, an anthraquinone compound, an azo compound, an arylethene compound, are mentioned. It is preferable that crystallization of a material is accelerated by the compound which carries out the orientation process by rubbing by the heating process after an orientation process or an orientation process. It is preferable to use a photo-alignment material among the compounds which perform orientation processing other than rubbing.

(apply)

As a coating method for obtaining the cholesteric reflective film of the present invention, an applicator method, bar coating method, spin coating method, gravure printing method, flexographic printing method, ink jet method, die coating method, cap coating method, dipping Etc. A well-known conventional method can be performed. Usually, since the polymeric liquid crystal composition diluted with the solvent is apply | coated, it will dry after application | coating.

(Polymerization process)

About the polymerization operation of the polymeric liquid crystal composition of this invention, after removing the solvent in a polymeric liquid crystal composition by drying etc., it is generally performed by light irradiation, such as an ultraviolet-ray, or heating in the state which was planar aligned. When superposing | polymerizing is performed by light irradiation, it is preferable to irradiate ultraviolet light of 390 nm or less specifically, and it is most preferable to irradiate light of the wavelength of 250-370 nm. However, when the polymerizable liquid crystal composition causes decomposition or the like due to the ultraviolet light of 390 nm or less, it may be preferable to perform polymerization treatment 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, it is preferable to perform superposition | polymerization by heating at the temperature which a polymeric liquid crystal composition shows a liquid crystal phase, or lower than it, and especially when using the thermal-polymerization initiator which discharge | releases a radical by heating, the cleavage temperature is the said It is preferable to use what is in the temperature range of. Moreover, when using the said thermal polymerization initiator and a photoinitiator together, it is preferable to select superposition | polymerization temperature and each initiator so that the superposition | polymerization rate of both layers of a photoalignment film and a polymeric liquid crystal film may not differ so much with the said temperature range limitation. Although heating temperature is based also on the transition temperature from the liquid crystal phase to an isotropic phase of a polymeric liquid crystal composition, it is preferable to carry out at temperature lower than the temperature at which heterogeneous polymerization by heat becomes organic. However, when the glass transition point of the base material which consists of organic materials is exceeded, the thermal deformation of a base material will become remarkable, and the glass transition point of room temperature-a base material is preferable. For example, when a polymeric group is a methacryloyl group, it is preferable to carry out at temperature lower than 90 degreeC.

In order to stabilize the solvent characteristic and heat resistance of the obtained cholesteric reflective film, you can heat-process a cholesteric reflective film. In this case, it is preferable to heat above the glass transition point of the said polymeric liquid crystal film. Usually, heating in the range which does not exceed the glass transition point of the base material which consists of organic materials is preferable. It may also be subjected to light irradiation for the above purpose. In this case, it is preferable that the liquid crystal compound component in a cholesteric reflective film does not photodecompose by light irradiation.

(Reflective polarizer)

The reflective polarizing plate of the present invention is a reflective polarizing plate in which a base material, a cholesteric reflective film, and a retardation film are sequentially stacked, and a reflective polarizing plate in which a base material, a cholesteric reflective film, a retardation film, and a linear polarizing film are sequentially stacked. The cholesteric reflective film uses the cholesteric reflective film of the present invention.

Moreover, the aspect which has two or more retardation films in a reflection type polarizing plate, and the said retardation film used the retardation film from which retardation differs is also preferable.

Lamination | stacking of a base material and a cholesteric reflective film is as having described with the manufacturing method of the said cholesteric reflective film. The lamination | stacking of retardation film is a method shown below.

(When laminated directly to cholesteric reflective film)

It can obtain by forming an oriented film on the cholesteric reflective film of this invention, apply | coating and drying the solution containing the said liquid crystal compound on it, and superposing | polymerizing in the state which the said liquid crystal compound uniaxially oriented. When the liquid crystal compound is uniaxially aligned even without forming the alignment film, the solution containing the liquid crystal compound is applied and dried and polymerized directly on the cholesteric film of the present invention. In the case of using the alignment film, as the alignment film described in the section of the above description, a known conventional one can be used.

(When bonding to cholesteric reflective film)

Application drying is performed on the said base material by the method of the said application | coating, and a retardation film is obtained by the method similar to the said polymerization process. After bonding an adhesive agent or an adhesive film to the obtained retardation film, it can obtain by bonding together the cholesteric reflective film of this invention and the said retardation film via an adhesive agent or an adhesive film. When using an adhesive agent or an adhesive film, the adhesive and adhesive film can use the well-known conventional thing of optical film uses.

Moreover, the said retardation film can also provide two other retardation films. As a combination of two other retardation films, the orientation of a liquid crystal compound is homogeneous (positive A plate), homogeneous (positive A plate), homogeneous (positive A plate), homeotropic (positive C plate), and homogeneous ( Positive A plate) and hybrid (O plate).

Moreover, when providing a linear polarizing film on the said retardation film, it laminates normally by a bonding method.

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

By performing X-ray irradiation treatment or electron beam irradiation treatment on the cholesteric reflective film of the present invention, the adhesion between the substrate and the polymer of the polymerizable liquid crystal composition of the present invention is improved. X-rays are electromagnetic waves having a wavelength of 0.1 to 100 kW (angstrom) and energy of about 0.1 to 100 keV, and a commercially available X-ray irradiation apparatus can be used. The energy of X-rays should just be a grade which the cholesteric reflective film of this invention does not decompose | disassemble by X-ray irradiation process, Specifically, 1-100 kGy (gray) is preferable. On the other hand, the electron beam EB is a flow of accelerated electrons which is given a large energy by an accelerator, and a commercially available electron beam irradiation apparatus can be used normally. The output of an electron beam should just be a grade which the cholesteric reflective film of this invention does not decompose by an electron beam irradiation process, and 10-200 kGy is preferable specifically ,.

[Example]

Although this invention is demonstrated by the synthesis example, the Example, and a comparative example below, this invention is not limited to these originally. In addition, "part" and "%" are mass references | standards unless there is particular notice.

(Preparation of Polymerizable Liquid Crystal Composition (1))

Liquid crystal compound represented by Formula (A-1), Liquid crystal compound represented by Formula (B-1), Liquid crystal compound represented by Formula (C-1), Liquid crystal compound represented by Formula (C-2), Formula ( Chiral compound represented by D-1), a polymerization initiator represented by formula (E-1), a polymerization initiator represented by formula (E-2), and 0.5 parts of liquid paraffin (G-1) by mixing Liquid crystal composition (1) was obtained. 0.07 part of 4-methoxy-1-naphthol (H-1) and 60 parts of siloxanehexanone (F-1) were added to the obtained polymerizable liquid crystal composition, and it melt | dissolves at 60 degreeC, and the polymerizable liquid crystal composition of this invention (2 )

(Preparation of polymerizable liquid crystal compositions (3) to (25))

The polymerizable liquid crystal compositions (3) to (21) and the polymerizable liquid crystal compositions (22) to (25) of the comparative example were obtained in the same manner as the preparation of the polymerizable liquid crystal composition (2) of the present invention. In Table 1-Table 6, the specific composition of the polymeric liquid crystal composition (1)-(21) of this invention and the polymeric liquid crystal composition (22)-(25) of a comparative example is shown.

TABLE 1

TABLE 2

[Table 3]

[Table 4]

TABLE 5

TABLE 6

The compound shown in Table 1-Table 6 is as showing below.

Cyclopentanone (F-2)

Toluene (F-3)

Polypropylene (G-2) with mass average molecular weight 2200

4-methoxyphenol (H-2)

(Example 1)

The coating film was obtained by apply | coating the polyimide solution for oriented films to the glass base material of thickness 0.7mm using spin coating method, drying at 100 degreeC for 10 minutes, and baking at 200 degreeC for 60 minutes. The obtained coating film was rubbed and used as the base material for cholesteric reflective films of this invention. The rubbing treatment was performed using a commercially available rubbing device.

The polymeric liquid crystal composition (2) of this invention was apply | coated to the rubbed base material by spin coating, and it dried at 80 degreeC for 2 minutes. The obtained coating film was placed on a hot plate at 60 ° C, and UV light was applied for 10 seconds at an intensity of 15 mW / cm 2 by using a high-pressure mercury lamp adjusted to obtain ultraviolet light (UV light) of only 365 nm around with a band pass filter. Investigated. Next, the bandpass filter was removed, and the cholesteric reflective film of the present invention was obtained by irradiating UV light for 20 seconds at an intensity of 70 mW / cm 2.

When the selective reflection wavelength of the obtained cholesteric reflection film was measured using the spectrophotometer (U-4100 "made by Hitachi Chemical Co., Ltd. U-4100"), the polarization reflection band was about 350 nm as shown in FIG.

(Examples 2 to 16)

In the same manner as in Example 1, the cholesteric reflective films of Examples 2 to 16 were obtained. As shown in Table 7, the polarization reflection bands of the obtained cholesteric reflection film were all 300 nm or more. 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. Moreover, it can be said that application | coating, drying, and irradiation at the time of manufacturing a cholesteric reflective film can all be performed in shorter time than before, and it is excellent also in productivity.

TABLE 7

(Comparative Examples 1 to 3)

A cholesteric reflective film of Comparative Examples 1 to 3 was 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 polarization reflection band of the obtained reflective film was 150 nm or less in all.

[Table 8]

(Comparative Examples 4 to 5)

In the same manner as in Example 1, attempts were made to obtain the cholesteric reflective films of Comparative Examples 4 and 5 using the polymerizable liquid crystal compositions (24) and (25). A steric reflective film could not be obtained.

(Example 17)

The polymeric liquid crystal composition (4) of this invention was apply | coated to the rubbing process PET film by the bar coater, and it dried at 90 degreeC for 2 minutes. The obtained coating film was hold | maintained at 60 degreeC, and UV light was irradiated for 10 second by the intensity | strength of 15 mW / cm <2> using the high pressure mercury lamp adjusted so that UV band light of only 365 nm vicinity might be obtained by a bandpass filter. Next, the bandpass 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. When the selective reflection wavelength of the obtained cholesteric reflective film was measured, as in Example 2, the polarization reflection band was about 360 nm as shown in FIG.

(Examples 18 to 32)

In the same manner as in Example 17, the cholesteric reflective films of Examples 18 to 32 were obtained. As shown in Table 9, the polarization reflection bands of the obtained cholesteric reflection film were all 300 nm or more.

TABLE 9

(Example 33)

Two parts of polyvinyl butyral (product name "Esrek BM-2" Sekisui Chemical Co., Ltd. product) were dissolved in 49 parts of ethanol and 49 parts of 2-butoxyethanol. The obtained polyvinyl butyral solution was apply | coated to the cholesteric reflective film obtained in Example 1 by spin coating, and it dried at 80 degreeC for 2 minutes. The obtained coating film was rubbed. The rubbing treatment was performed using a commercially available rubbing device.

Next, the toluene solution (solid content ratio: 20%) of the polymeric liquid crystal composition (product name: UV curable liquid crystal "UCL-017" DIC Corporation make) for retardation film was apply | coated to the said rubbing process base material by the spin coating method. And it dried at 80 degreeC for 2 minutes. The obtained coating film was irradiated with UV light for 15 second by the intensity | strength of 30 mW / cm <2> using the high pressure mercury lamp, and the reflective polarizing plate of Example 33 was obtained.

The spectral characteristics of the obtained reflective polarizing plate were measured using the spectrophotometer (U-4100 "made by Hitachi Seisakusho"). The measurement was made perpendicular to the case where the polarization directions of the reflective polarizer of Example 33 and the commercially available linear polarizer of Example 33 were parallel to each other (parallel nicole) with a commercially available linear polarizer between the detector and the detector. In this case (cross nicol), the transmittance was measured. In the case of parallel nicol, the transmittance was 90% or more in the visible region. In the case of cross nicol, the transmittance was almost 0% in the visible region.

(Example 34)

The toluene solution of UCL-017 used in Example 33 was apply | coated to the polyacetyl cellulose film which carried out the surface rubbing process, and it dried at 60 degreeC for 3 minutes. UV light was irradiated to the obtained coating film for 15 second by the intensity | strength of 30 mW / cm <2> using the high pressure mercury lamp, and the retardation film which consists of a polymeric liquid crystal composition was obtained. After peeling one peeling layer of a commercially available transparent double-sided adhesive tape, it stuck on the obtained retardation film, peeled off the other peeling layer, and bonded together on the cholesteric reflective film of Example 17, and Example 34 The reflective polarizing plate of was obtained. When the spectral characteristics of the obtained reflective polarizing plate were performed in the same manner as in Example 33, good polarization characteristics could be obtained as in Example 33.

(Example 35)

The polyvinyl butyral solution of Example 33 was applied on the reflective polarizing plate of Example 33 by spin coating, and dried at 80 ° C for 2 minutes.

Next, the xylene solution (solid content ratio: 25%) of the polymeric liquid crystal composition (product name: UV curable liquid crystal "UCL-018" DIC Corporation make) for retardation film was apply | coated to the said reflective polarizing plate by spin coating method, and It dried at 80 degreeC for 2 minutes. UV light was irradiated to the obtained coating film for 20 second with the intensity | strength of 30 mW / cm <2> using the high pressure mercury lamp, and the reflective polarizing plate of Example 35 was obtained.

(Example 36)

The xylene solution of UCL-018 used in Example 35 was apply | coated to the polyacetyl cellulose film surface-treated, and it dried at 60 degreeC for 3 minutes. UV light was irradiated to the obtained coating film for 20 second by the intensity | strength of 30 mW / cm <2> using the high pressure mercury lamp, and the retardation film which consists of a polymeric liquid crystal composition was obtained. After peeling one peeling layer of a commercially available transparent double-sided adhesive tape, it stuck on the obtained retardation film, and after peeling off the other peeling layer, it bonded on the reflective polarizing plate of Example 34, and obtained the reflective polarizing plate of Example 36. .

(Example 37)

After peeling one peeling layer of the commercially available transparent double-sided adhesive tape on the cholesteric reflective film of Example 17, peeling off another peeling layer, the cholesteric reflective film of Example 17 was bonded together, and an Example 37 cholesteric reflective films were obtained.

When the selective reflection wavelength of the cholesteric reflective film of Example 37 was measured, the polarization reflection band was about 400 nm like Example 2. In addition, the transmittance was almost 50% or less over the entire visible light.

(Example 38)

The cholesteric reflective film of Example 17 was irradiated with X-ray of 5 kGy at room temperature using the commercially available X-ray irradiation apparatus, and the cholesteric reflective film of Example 38 was obtained.

Evaluation of the adhesiveness of the obtained cholesteric reflective film was performed by the cross cut test of JIS-K5400. The cross cut test cut | disconnected longitudinally and horizontally at 2 mm intervals using the cutter, and made 25 grids. A cello tape was affixed on this grid, and when the grid was removed, 24 grids were left.

(Example 39)

The cholesteric reflective film of Example 17 was irradiated to 10 kGy of electron beams at room temperature using the commercially available electron beam irradiation apparatus in Example 17.

When the adhesiveness was evaluated in the same manner as in Example 38, 20 grids were left.

Claims (19)

a) general formula (1)

(In formula, R <_1> and R <_2> respectively independently represents a fluorine atom, a chlorine atom, a cyano group, a C1-C12 alkyl group, or a C2-C12 alkenyl group, and one of the hydrogen atoms contained in these groups Or more 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-, Z ₂ is a single bond, -O-, -S-, -COO-, -OCO-, -CH ₂ O-, -CH = CH-, -CH = CH- COO- or -OCO-CH = CH-, A represents -C≡C-, -C = N-, -N = N- or -C = NN = C- or any of the following ring structures

R <_3> represents a fluorine atom, a chlorine atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a cyano group, B is the following ring structure

Represents a, R ₄ is 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 represents a cyano group), a liquid crystal compound of two or more kinds represented by and, b) One or two or more liquid crystal compounds having only one polymerizable functional group, c) one or two or more liquid crystal compounds having two or more polymerizable functional groups, and d) one or more polymerizable functional groups. 1 type (s) or 2 or more types of chiral compounds which have, and e) 1 type (s) or 2 or more types of polymerization initiators, The polymerizable liquid crystal composition characterized by the above-mentioned. The method of claim 1,
The polymeric liquid crystal composition whose content rate of the compound represented by General formula (1) is 0.1-20 mass%. The method according to claim 1 or 2,
a) Polymerizable liquid crystal composition containing two or more types of liquid crystal compounds which have only one polymerizable functional group. The method according to claim 1, 2 or 3,
Polymeric liquid crystal composition containing two or more types of liquid crystal compounds which have two polymerizable functional groups. The method according to any one of claims 1 to 4,
Liquid crystal compounds having only one polymerizable functional group are represented by 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- denotes a, G ₁ represents a single bond, 1,4-phenylene group, naphthalene-2,6-diyl or 1 Although a 4-cyclohexylene group is shown, 1 or 2 or more hydrogen atoms which exist in these groups are substituted by a fluorine atom, a chlorine atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a cyano group M may be a single bond, -O-, -S-, -COO-, -OCO-, -OCH _2- , -CH = CH-, -CH = CH-COO- or -OCO-CH = CH-, but 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 , -O-, -S-, -COO-, -OCO-, -OCH _2- , -CH = CH-, -CH = CH-COO- or -OCO-CH = CH-, G ₂ is Hydrogen atom, phenyl group, cycle Hexyl group, naphthyl group, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, carboxyl group, carbamoyl group, cyano group, nitro group or halogen atom, but hydrogen in the phenyl group, cyclohexyl group or naphthyl group The atom may be unsubstituted, or may be 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 carboxy group or carbamoyl group is unsubstituted. The substituent may be substituted with an alkyl group having 1 to 10 carbon atoms, and 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. Polymerizable liquid crystal composition represented by). The method according to any one of claims 1 to 5,
The polymeric liquid crystal composition whose content rate of the compound represented by General formula (2) is 5-80 mass%. The method according to any one of claims 1 to 6,
Liquid crystal compounds having only one polymerizable functional group are represented by 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 are each independently a single bond, -O-, -S-,- COO-, -OCO-, -OCH _2- , -CH = CH-, -CH = CH-COO- or -OCO-CH = CH-, and Y ₃ , Y ₄ , Y ₅ and Y ₆ are each independently And 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, but the hydrogen atom in the alkyl group or alkoxy group is one or two 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. The method according to any one of claims 1 to 7,
The polymeric liquid crystal composition whose content rate of a polymerization initiator is 1-10 mass%. The method according to any one of claims 1 to 8,
A polymerizable liquid crystal composition containing one or two or more surfactants or polymers for promoting planar orientation. 10. The method of claim 9,
Polymeric liquid crystal composition whose surfactant and planar content which promote planar orientation or polymer content are 0.01-3 mass%. The composition containing 1 type (s) or 2 or more types of the polymeric liquid crystal composition and solvent as described in any one of Claims 1-10. As a cholesteric reflective film comprised by the hardened | cured material of the planar oriented polymeric liquid crystal composition, the said polymeric liquid crystal composition is
a) general formula (1)

(In formula, R <_1> and R <_2> respectively independently represents a fluorine atom, a chlorine atom, a cyano group, a C1-C12 alkyl group, or a C2-C12 alkenyl group, and one of the hydrogen atoms contained in these groups Or more 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-, Z ₂ is a single bond, -O-, -S-, -COO-, -OCO-, -CH ₂ O-, -CH = CH-, -CH = CH- COO- or -OCO-CH = CH-, A represents -C≡C-, -C = N-, -N = N-, or -C = NN = C- or any of the following

R <_3> represents a fluorine atom, a chlorine atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a cyano group, B is the following ring structure

Represents a, R ₄ is 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 represents a cyano group), a liquid crystal compound of two or more kinds represented by and, b) One or two or more liquid crystal compounds having only one polymerizable functional group, c) one or two or more liquid crystal compounds having two or more polymerizable functional groups, and d) one or more polymerizable functional groups. 1 type (s) or 2 or more types of chiral compound which has, and e) 1 type (s) or 2 or more types of polymerization initiators, The cholesteric reflective film characterized by the above-mentioned. The method of claim 12,
The cholesteric reflective film whose polarization reflection band is 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 polarizing plate in which a substrate, a cholesteric reflective film and a retardation film are sequentially laminated, wherein the cholesteric reflective film is a cholesteric reflective film according to any one of claims 12 to 14. Type polarizer. A reflective polarizing plate in which a substrate, a cholesteric reflective film, a retardation film, and a linear polarizing film are sequentially stacked, wherein the cholesteric reflective film is the cholesteric reflective film according to any one of claims 12 to 14. Reflective polarizing plate. The method according to claim 15 or 16,
The reflection type polarizing plate which has two or more phase difference films in a reflection type polarizing plate, and the said phase difference film has a phase difference film from which phase difference differs. The method according to any one of claims 12 to 14,
X-ray irradiation treatment or electron beam irradiation treatment, The cholesteric reflective film characterized by the above-mentioned. The method according to any one of claims 15 to 17,
The base material is a light-diffusion film, The reflection type polarizing plate characterized by the above-mentioned.

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