WO2016047648A1 - 重合性化合物を含む重合性組成物、フィルム、および投映像表示用ハーフミラー - Google Patents
重合性化合物を含む重合性組成物、フィルム、および投映像表示用ハーフミラー Download PDFInfo
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- WO2016047648A1 WO2016047648A1 PCT/JP2015/076836 JP2015076836W WO2016047648A1 WO 2016047648 A1 WO2016047648 A1 WO 2016047648A1 JP 2015076836 W JP2015076836 W JP 2015076836W WO 2016047648 A1 WO2016047648 A1 WO 2016047648A1
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- 0 **(C=C)=C1CC*CC1 Chemical compound **(C=C)=C1CC*CC1 0.000 description 9
- RSFGMEMPFPHDKB-UHFFFAOYSA-N C=CC(OCCOC(C(CC1)CCC1C(O)=O)=O)=O Chemical compound C=CC(OCCOC(C(CC1)CCC1C(O)=O)=O)=O RSFGMEMPFPHDKB-UHFFFAOYSA-N 0.000 description 1
- DWCPINYOQGXVNS-UHFFFAOYSA-N Cc(cc1)ccc1OC(CC1)(CCC1C(Oc1ccc(C)cc1)=O)C=O Chemical compound Cc(cc1)ccc1OC(CC1)(CCC1C(Oc1ccc(C)cc1)=O)C=O DWCPINYOQGXVNS-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N OC(C(CC1)CCC1C(O)=O)=O Chemical compound OC(C(CC1)CCC1C(O)=O)=O PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- NZNMSOFKMUBTKW-UHFFFAOYSA-N OC(C1CCCCC1)=O Chemical compound OC(C1CCCCC1)=O NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 1
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Definitions
- the present invention relates to a polymerizable composition containing a polymerizable compound.
- the present invention also relates to a film produced using the above-mentioned polymerizable composition, and a half mirror for projection image display produced using the above-mentioned polymerizable composition.
- the birefringence of the polymerizable compound is one of the properties which are largely related to the optical properties of the obtained optical film.
- a film in which a cholesteric liquid crystal phase formed using a polymerizable compound having low birefringence is fixed, it is possible to obtain a reflective film having high selectivity in the reflection wavelength range.
- a low birefringence retardation film or a reflective film having high selectivity in a reflection wavelength range is obtained by using a non-liquid crystal (meth) acrylate compound having a specific structure together with a polymerizable liquid crystal compound. It is described.
- two or more polymerizable compounds may be used in combination in order to obtain necessary birefringence or reflection characteristics with a constant film thickness.
- the present inventors have found that a polymerizable compound containing a plurality of cyclic groups containing a trans-1,4-cyclohexylene group exhibits low birefringence, but a plurality of compounds including the compounds found by the present inventors It has not been investigated conventionally how to combine the polymerizable compounds of the above to control the liquid crystallinity to obtain a film having the required degree of birefringence or wavelength selectivity.
- the present inventors variously studied for the solution of the above-mentioned problems, and by controlling the ratio of trans-1, 4-cyclohexylene group and phenylene group of each compound to be combined, a polymerizable composition containing those compounds
- the inventors have found that the liquid crystallinity and birefringence of these compounds can be controlled, and further studies have been made based on this finding to complete the present invention. That is, the present invention provides the following ⁇ 1> to ⁇ 18>.
- A represents a phenylene group which may have a substituent or a trans-1,4-cyclohexylene group which may have a substituent;
- a nitrogen atom in which X 3 represents a single bond, -O-, -S-, or -N (Sp 4 -Q 4 )-or which forms a ring structure with Q 3 and Sp 3 is Sp 3 and Sp 4 are each independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, one or more linear or branched alkylene groups having 1 to 20 carbon atoms.
- ⁇ 11> A film comprising a layer obtained by curing the polymerizable composition according to any one of ⁇ 1> to ⁇ 10>.
- ⁇ 13> indicates selective reflection
- ⁇ 14> The film according to any one of ⁇ 11> to ⁇ 13>, which reflects visible light.
- a film comprising at least three layers formed from the polymerizable composition according to any one of ⁇ 1> to ⁇ 10>,
- the three layers are a layer in which a cholesteric liquid crystal phase having a central wavelength of selective reflection in the red light wavelength range is fixed, a layer in which a cholesteric liquid crystal phase having a central wavelength of selective reflection in the green light wavelength range is fixed, and a blue light wavelength range
- a film in which a cholesteric liquid crystal phase having a center wavelength of selective reflection is fixed to The half mirror for projection video display containing the film as described in ⁇ 16> ⁇ 15>.
- the half mirror for projection image display as described in ⁇ 16> containing the base material which is ⁇ 17> inorganic glass or an acrylic resin.
- the half mirror for projection image display as described in ⁇ 16> or ⁇ 17> which contains an anti-reflective layer in ⁇ 18> outermost surface.
- a polymerizable composition with low birefringence is provided as a polymerizable composition containing two or more kinds of polymerizable compounds having a trans-1,4-cyclohexylene group and a phenylene group.
- the polymerizable composition of the present invention can be used to provide a film such as a low birefringence retardation film or a reflective film having high selectivity in the reflection wavelength range.
- the term “retardation” refers to in-plane retardation, and when there is no mention of a wavelength, it refers to in-plane retardation at a wavelength of 550 nm.
- in-plane retardation is measured using a polarization retardation analyzer AxoScan manufactured by AXOMETRICS.
- the in-plane retardation at a wavelength of ⁇ nm can also be measured by causing light of wavelength ⁇ nm to be incident in the film normal direction with KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments).
- the polymerizable composition of the present invention contains two or more of the polymerizable compounds represented by the formula (I).
- the polymerizable composition may contain, in addition to the polymerizable compound represented by the formula (I), other components such as another liquid crystal compound, a chiral compound, a polymerization initiator, an alignment control agent, and the like. Each component will be described below.
- the polymerizable compound represented by the formula (I) has m cyclic divalent groups represented by A.
- the m A's may be different from each other, or some of the m A's may be identical to each other.
- the cyclic divalent group is a phenylene group which may have a substituent or a trans-1,4-cyclohexylene group which may have a substituent. That is, A represents a phenylene group which may have a substituent or a trans-1,4-cyclohexylene group which may have a substituent.
- a 1,4-phenylene group is preferable.
- the polymerizable composition of the present invention contains a phenylene group which may have at least one substituent and a trans-1,4-cyclohexylene group which may have at least one substituent. It may contain the polymerizable compound represented by (I).
- M represents an integer of 3 to 12, preferably 3 to 9, more preferably 3 to 7, and still more preferably 3 to 5.
- the substituent include a substituent selected from the group consisting of a group, an alkoxy group, an alkyl ether group, an amide group, an amino group, a halogen atom, and a group formed by combining two or more of the above-mentioned substituents.
- the phenylene group and the trans-1,4-cyclohexylene group may have 1 to 4 substituents. When two or more substituents are present, the two or more substituents may be the same as or different from each other.
- the alkyl group may be linear or branched.
- the carbon number of the alkyl group is preferably 1 to 30, more preferably 1 to 10, and particularly preferably 1 to 6.
- Examples of the alkyl group include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl Group, 1,1-dimethylpropyl group, n-hexyl group, isohexyl group, linear or branched heptyl group, octyl group, nonyl group, decyl group, undecyl group, or dodecyl group.
- alkyl group is the same as for the alkoxy group containing an alkyl group.
- specific examples of the alkylene group when it is referred to as an alkylene group include, in each of the examples of the alkyl group described above, divalent groups obtained by removing one arbitrary hydrogen atom, and the like.
- a halogen atom a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
- the carbon number of the cycloalkyl group is preferably 3 to 20, more preferably 5 or more, and preferably 10 or less, more preferably 8 or less, and still more preferably 6 or less.
- the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group.
- X 3 represents a single bond, -O-, -S-, or -N (Sp 4 -Q 4 )-or a nitrogen atom forming a ring structure with Q 3 and Sp 3 Show.
- the substitution position is not particularly limited. Among these, tetrahydrofuranyl is preferable, and 2-tetrahydrofuranyl is particularly preferable.
- the m L's may be the same or different.
- Q 1 and Q 2 each independently represent a hydrogen atom or the following formula (Q-1) ⁇ formula (Q-5) with a polymerizable group selected from the group consisting of groups represented, provided that Q 1 And one of Q 2 represents a polymerizable group.
- acryloyl group (formula (Q-1)) or methacryloyl group (formula (Q-2)) is preferable.
- polymerizable compound represented by the formula (I) include, in addition to the known compounds described in JP-A-2013-112631, JP-A-2010-70543, and JP-A-4725516, And a polymerizable compound represented by the formula (I-21), a polymerizable compound represented by the formula (I-21), and a polymerizable compound represented by the formula (I-31).
- R 11 represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or -Z 12 -Sp 12 -Q 12 ;
- R 12 represents a hydrogen atom or -Sp 12 -Q 12 ;
- Sp 11 and Sp 12 are each independently a single bond, a linear or branched alkylene group having from carbon atoms 1 be replaced by Q 11 12
- the polymerizable compound represented by formula (I-11) as R 11, Q 12 is selected from the group consisting of groups represented by the formula (Q-1) ⁇ formula (Q-5) Polymerization comprising at least one -Z 12 -Sp 12 -Q 12 is a sex group.
- the 1,4-cyclohexylene groups contained in the polymerizable compound represented by formula (I-11) are all trans-1,4-cyclohexene groups.
- the polymerizable compound represented by formula (I-11) particularly preferred are compounds, L 11 is a single bond, l 11 1 (di-cyclohexylene group), and Q 11 has the formula (Q-1) ⁇ Formula
- the compound which is a polymeric group selected from the group which consists of a group represented by (Q-5) is mentioned.
- m 11 is 2
- l 11 is 0, and both of R 11 are each —Z 12 -Sp 12 -Q
- R 12 represents a compound wherein Q 12 is a polymerizable group selected from the group consisting of groups represented by Formula (Q-1) to Formula (Q-5).
- each of Z 21 and Z 22 independently represents a trans-1, 4-cyclohexylene group which may have a substituent, or a phenylene group which may have a substituent
- the above substituents are each independently 1 to 4 substituents selected from the group consisting of -CO-X 21 -Sp 23 -Q 23 , an alkyl group, and an alkoxy group
- m21 represents an integer of 1 or 2
- n21 represents an integer of 0 or 1
- At least one of Z 21 and Z 22 is a phenylene group which may have a substituent
- Q 21 and Q 22 each independently represent any polymerizable group selected from the group consisting of groups represented by formulas (Q-1) to (Q-5)
- the polymerizable compound represented by the formula (I-21) is also preferably a structure in which a 1,4-phenylene group and a trans-1,4-cyclohexylene group are alternately present, and, for example, m21 is 2 , n21 is 0, and if Z 21 are each optionally substituted trans-1,4-cyclohexylene group, which may have a substituent arylene group from Q 21 side, Or a structure in which m21 is 1, n21 is 1, Z 21 is an arylene group which may have a substituent, and Z 22 is an arylene group which may have a substituent .
- a polymerizable compound represented by the formula (I-31) is a polymerizable compound represented by the formula (I-31);
- X 31 represents a single bond, -O-, -S-, or -N (Sp 34 -Q 34 )-or a nitrogen atom forming a ring structure with Q 33 and Sp 33 ,
- Z 31 represents a phenylene group which may have a substituent,
- Z 32 represents a trans-1,4-cyclohexylene group which may have a substituent, or a phenylene group which may have a substituent,
- the compound represented by the formula (I) also preferably has a partial structure represented by the following formula (II).
- the black circles indicate the bonding position with the other part of the formula (I).
- the partial structure represented by the formula (II) may be included as part of the partial structure represented by the following formula (III) in the formula (I).
- X 3 represents a single bond, -O-, -S-, or -N (Sp 4 -Q 4 )-or a nitrogen atom forming a ring structure with Q 3 and Sp 3 Show.
- X 3 is preferably a single bond or -O-.
- R 1 and R 2 are preferably identical to each other.
- the bonding position of each of R 1 and R 2 to the phenylene group is not particularly limited.
- a linear or branched alkylene group having 1 to 10 carbon atoms is preferable, a linear alkylene group having 1 to 5 carbon atoms is more preferable, and a straight chain having 1 to 3 carbon atoms is preferable More preferred is a chain alkylene group.
- the compound represented by the formula (I) preferably has, for example, a structure represented by the following formula (II-2).
- each of A 1 and A 2 independently represents a phenylene group which may have a substituent or a cyclohexylene group which may have a substituent.
- the polymerizable compound represented by the formula (I) can be produced by a known method, and can be produced, for example, by the following method.
- L 2 is —COO— in the formula (I-11-1)
- it can be produced by esterifying the carboxylic acid derivative A-1 with a phenol (or alcohol) derivative A-2.
- a phenol (or alcohol) derivative A-11 and a carboxylic acid It can be produced by esterification using derivatives A-21 and A-31.
- the polymerizable compound represented by the formula (I-31-1) it can be produced by esterification of the carboxylic acid C and the intermediate A.
- esterification a method in which an activated carboxylic acid and a phenol (or alcohol) derivative are caused to act in the presence of a base, or a carboxylic acid and a phenol (or alcohol) derivative are directly used using a condensing agent such as carbodiimide.
- the method of esterifying is mentioned.
- the method of activating the carboxylic acid is more preferable from the viewpoint of by-products. Examples of methods for activating the carboxylic acid include acid chlorination with thionyl chloride and oxalyl chloride, and methods of reacting with mesyl chloride to prepare a mixed acid anhydride.
- the polymerizable compound represented by the formula (I) generally exhibits liquid crystallinity and at the same time has a low birefringence, but utilizes a polymerizable composition containing the polymerizable compound represented by the formula (I) in the above combination.
- a polymerizable composition containing the polymerizable compound represented by the formula (I) in the above combination By preparing the retardation film, it is possible to adjust the birefringence of the retardation film to a desired range.
- a reflective film having a narrow wavelength band of selective reflection, ie, selectivity of the reflection wavelength band is obtained. A high reflective film can be obtained.
- the polymerizable compound represented by the formula (I) is colorless and transparent because the absorption in the visible light region is extremely small regardless of the kind of the substituent of the aromatic ring and the linking group, and the solvent has a wide liquid crystal phase range. Satisfy multiple characteristics such as easy dissolution and easy polymerization. From this, a cured film produced using a polymerizable composition containing a polymerizable compound represented by the formula (I) exhibits sufficient hardness, is colorless and transparent, and has excellent weather resistance and heat resistance. And so on, which can satisfy multiple characteristics.
- a cured film formed using the above-mentioned polymerizable composition includes, for example, a retardation plate which is a component of an optical element, a polarizing element, a selective reflection film, a color filter, an antireflective film, a viewing angle compensation film, It can be used for various applications such as holography and alignment film.
- the total amount of the polymerizable compound represented by the formula (I) may be 10% by mass or more, preferably 30 to 99.9% by mass, more preferably 50 to 50% by mass with respect to the solid content mass of the polymerizable composition. It may be 99.5% by mass, more preferably 70 to 99% by mass. However, it is not limited to this range.
- the polymerizable composition of the present invention has a number of trans-1,4-cyclohexylene groups which may have a substituent represented by A divided by m, as mc is 0.5 At least one polymerizable compound satisfying ⁇ mc ⁇ 0.7 (hereinafter sometimes referred to as “compound of Gr. 1”), and a polymerizable compound satisfying 0.1 ⁇ mc ⁇ 0.3 (hereinafter And at least one of the compounds of Gr.
- mc is a number represented by the following formula.
- the polymerizable composition of the present invention contains the polymerizable compound represented by the formula (I) in the combination as described above, thereby achieving low birefringence (for example, a liquid crystal layer in a uniaxially oriented state shown in the examples at 50 ° C.
- the birefringence determined from the retardation of the polymerized layer and the film thickness thereof is 0.040 to 0.110), and exhibits good liquid crystallinity. That is, birefringence can be adjusted in a relatively low value range as long as good liquid crystallinity is exhibited.
- a polymeric compound does not precipitate easily.
- repelling tends not to occur, and the surface state also tends to be less likely to be disturbed.
- the polymerizable composition of the present invention has, for example, at least one kind of a compound having m and a cyclohexane number shown in Gr. 1 and a m and a cyclohexane number shown in Gr. 2 in Table 1 above. And at least one compound may be included.
- preferred combinations include: a combination of a compound in which m is 3 and the number of cyclohexane is 2 and a compound in which m is 4 and the number of cyclohexane is 1; a combination of a compound in which m is 5 and the number of cyclohexane is 3 with a compound in which m is 4 and the number of cyclohexane is 1; a combination of a compound in which m is 3 and the number of cyclohexane is 2 and a compound in which m is 5 and the number of cyclohexane is 1; A combination of a compound in which m is 5 and the number of cyclohexane is 3 with a compound in which m is 5 and the number of cyclohexane is 1. More preferred combinations include the following: A combination of a compound in which m is 5 and the number of cyclohexane is 3 with a compound in which m is 5 and the number of cyclohexan
- the polymerizable composition of the present invention preferably contains, for example, at least one compound represented by the formula (V) and at least one compound represented by the formula (VI).
- Preferred combinations of polymerizable compounds in the polymerizable composition of the present invention include any one or more compounds selected from the compounds 1-1 to 1-25 exemplified above and the compounds 2-1 to 1 exemplified above. A combination with any one or more compounds selected from -31 may be mentioned.
- the content ratio of the compound of Gr. 1 to the compound of Gr. 2 in the polymerizable composition of the present invention is not particularly limited, but the weight ratio of (compound of Gr. 1): (compound of Gr. 2) is 90
- the ratio is preferably from 10 to 10:90, more preferably from 85:15 to 20:80, still more preferably from 80:20 to 50:50.
- the polymerizable composition may contain one or more other liquid crystal compounds, in addition to the polymerizable compound represented by the formula (I). Since the polymerizable compound represented by the formula (I) has high compatibility with other liquid crystal compounds, it is possible to form a highly transparent film without causing opacity and the like even when the other liquid crystal compounds are mixed. is there. Since other liquid crystal compounds can be used in combination, compositions of various compositions suitable for various applications can be provided. Examples of other liquid crystal compounds that can be used in combination include rod-like nematic liquid crystal compounds.
- rod-like nematic liquid crystal compounds examples include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano substituted phenyl pyrimidines, alkoxy substituted phenyl Pyrimines, phenyldioxanes, tolanes and alkenylcyclohexyl benzonitriles can be mentioned. Not only low molecular weight liquid crystal compounds but also high molecular weight liquid crystal compounds can be used.
- liquid crystal compounds may be polymerizable or non-polymerizable.
- Rod-like liquid crystal compounds having no polymerizable group are described in various documents (for example, Y. Goto et. Al., Mol. Cryst. Liq. Cryst. 1995, Vol. 260, pp. 23-28).
- the polymerizable rod-like liquid crystal compound can be obtained by introducing a polymerizable group into the rod-like liquid crystal compound.
- the polymerizable group include unsaturated polymerizable groups, epoxy groups, and aziridinyl groups, with unsaturated polymerizable groups being preferred, and ethylenically unsaturated polymerizable groups being particularly preferred.
- the polymerizable group can be introduced into the molecule of the rod-like liquid crystal compound by various methods.
- the number of polymerizable groups contained in the polymerizable rod-like liquid crystal compound is preferably 1 to 6, and more preferably 1 to 3. Examples of polymerizable rod-like liquid crystal compounds are described in Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), U.S. Pat. No. 4,683,327, U.S. Pat. No. 5,622,648, U.S. Pat. No. 5,570,107, WO 95/22586. No. 95/24455, No. 97/00600, No. 98/23580, No.
- Two or more kinds of polymerizable rod-like liquid crystal compounds may be used in combination.
- the alignment temperature can be lowered.
- the addition amount of the other liquid crystal compound is not particularly limited, and is preferably 0 to 70% by mass, more preferably 0 to 50% by mass, and still more preferably 0 to 30% by mass with respect to the solid content mass of the polymerizable composition. It should be%. However, it is not limited to this range.
- the mass ratio of the polymerizable compound represented by the formula (I) to the other liquid crystal compound is 100 / It may be from 0 to 30/70, preferably from 100/0 to 50/50, and more preferably from 100/0 to 70/30. This ratio can be adjusted to a preferred range depending on the application.
- the polymerizable composition may contain a chiral compound.
- a chiral compound By using a chiral compound, it can be prepared as a composition exhibiting a cholesteric liquid crystal phase.
- the chiral compound may be liquid crystalline or non-liquid crystalline.
- the chiral compound is selected from various known chiral agents (for example, described in Liquid Crystal Device Handbook, Chapter 3 4-3, TN, chiral agents for STN, page 199, edited by 142th Committee of Japan Society for the Promotion of Science, 1989). It can be selected.
- the chiral compound generally contains an asymmetric carbon atom, but an axial asymmetric compound or a planar asymmetric compound not containing an asymmetric carbon atom can also be used.
- Examples of axial asymmetric compounds or planar asymmetric compounds include binaphthyl, helicene, paracyclophane and derivatives thereof.
- the chiral compound (chiral agent) may have a polymerizable group.
- the rod-like liquid crystal compound used in combination also has a polymerizable group, a repeating unit derived from the rod-like liquid crystal compound by the polymerization reaction of the polymerizable chiral compound and the polymerizable rod-like liquid crystal compound And polymers having repeating units derived from chiral compounds.
- the polymerizable group contained in the polymerizable chiral compound is preferably the same type as the polymerizable group contained in the polymerizable rod-like liquid crystal compound, in particular, the polymerizable compound represented by the formula (I). Accordingly, the polymerizable group of the chiral compound is also preferably an unsaturated polymerizable group, an epoxy group or an aziridinyl group, more preferably an unsaturated polymerizable group, and an ethylenically unsaturated polymerizable group Particularly preferred.
- the chiral compound is preferably 0.5 to 30% by mass with respect to the liquid crystal compound including the polymerizable compound represented by the formula (I).
- the amount of chiral compound used is preferred because less will tend to not affect the liquid crystallinity. Therefore, as the chiral compound, a compound having a strong twisting power is preferable so that the desired helical pitch twist orientation can be achieved even in a small amount.
- a chiral agent exhibiting strong twisting power for example, the chiral agent described in JP-A No. 2003-287623 can be mentioned.
- chiral agents described in Japanese Patent Application Laid-Open Nos. 2002-302487, 2002-80478, 2002-80851, and 2014-034581 and LC-756 manufactured by BASF are listed.
- a film formed by fixing the polymerizable composition of the embodiment containing the chiral compound into a cholesteric liquid crystal phase and then fixing it has a selective reflection property to light of a predetermined wavelength according to the helical pitch. It is useful as a reflective film (for example, a visible light reflective film or an infrared reflective film).
- a reflective film for example, a visible light reflective film or an infrared reflective film.
- the polymerizable composition preferably contains a polymerization initiator.
- a polymerization initiator for example, in the aspect which advances a curing reaction by ultraviolet irradiation and forms a cured film, it is preferable that the polymerization initiator to be used is a photoinitiator which can start a polymerization reaction by ultraviolet irradiation.
- the photopolymerization initiator include an ⁇ -carbonyl compound (described in each specification of US Pat. Nos. 2,367,661 and 2367670), an acyloin ether (described in US Pat. No. 2,448,828), an ⁇ -hydrocarbon substituted aroma Acyloin compounds (as described in US Pat. No.
- the photopolymerization initiator is preferably contained in the polymerizable composition in an amount of 0.1 to 20% by mass, and preferably 1 to 8% by mass, based on the solid content mass of the polymerizable composition. More preferable.
- alignment control agent In the polymerizable composition, an alignment control agent that contributes to the formation of a stable or rapid liquid crystal phase (for example, a cholesteric liquid crystal phase) may be added.
- alignment control agents include fluorine-containing (meth) acrylate polymers, compounds represented by general formulas (X1) to (X3) described in WO2011 / 162291, and paragraph [0020] to JP-A-2013-47204. Included are compounds described in [0031]. You may contain 2 or more types selected from these. These compounds can reduce the tilt angles or substantially horizontally align the molecules of the liquid crystal compound at the air interface of the layer.
- horizontal alignment means that the major axis of the liquid crystal molecule is parallel to the film surface, but does not require that the major axis be exactly parallel to each other.
- the angle of inclination to make shall mean orientation less than 20 degrees.
- the liquid crystal compound is horizontally aligned near the air interface, alignment defects are less likely to occur, and therefore, the transparency in the visible light region is increased.
- the molecules of the liquid crystal compound are oriented at a large tilt angle, for example, in the case of a cholesteric liquid crystal phase, the helical axis deviates from the film surface normal, resulting in a decrease in reflectance or generation of a fingerprint pattern.
- fluorine-containing (meth) acrylate polymers that can be used as an orientation control agent are described in [0018] to [0043] and the like of JP-A-2007-272185.
- orientation control agent one type of compound may be used alone, or two or more types of compounds may be used in combination.
- the content of the orientation control agent in the polymerizable composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and more preferably 0.02 to 1% of the mass of the compound of the formula (I). % By weight is particularly preferred.
- the polymerizable composition may optionally contain a crosslinking agent in order to improve film strength after curing and improve durability.
- a crosslinking agent one which is cured by ultraviolet light, heat, moisture or the like can be suitably used.
- polyfunctional acrylate compounds such as trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetraacrylate; Epoxy compounds such as glycidyl (meth) acrylate and ethylene glycol diglycidyl ether; 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], 4,4-bis (ethyleneiminocarbonylamino) diphenylmethane and the like
- a known catalyst can be used according to the reactivity of the crosslinking agent, and in addition to the improvement of the film strength and the durability, the productivity can be improved. These may be used alone or in combination of two or more.
- the content of the crosslinking agent is preferably 3% by mass to 20% by mass, and more preferably 5% by mass to 15% by mass, with respect to the solid content mass of the polymerizable composition. When the content of the crosslinking agent is 3% by mass or more, the effect of improving the crosslinking density is higher, and when the content is 20% by mass or less, the stability of the cholesteric liquid crystal layer is higher.
- the polymerizable composition comprises one or more of an antioxidant, an ultraviolet light absorber, a sensitizer, a stabilizer, a plasticizer, a chain transfer agent, a polymerization inhibitor, an antifoaming agent, a leveling agent, Other additives such as a tackifier, a flame retardant, a surfactant, a dispersant, a dye, and a coloring material such as a pigment may be contained.
- the polymerizable composition of the present invention is useful as a material of various optical films such as a retardation film and a reflective film, and various polymeric films can be formed using the polymerizable composition of the present invention.
- Method of producing film One example of a method of producing an optical film is (i) applying a polymerizable composition to the surface of a substrate or the like to form a liquid crystal phase (cholesteric liquid crystal phase etc.); (ii) advancing the curing reaction of the polymerizable composition to fix the liquid crystal phase to form a cured film, A manufacturing method including at least The process of (i) and (ii) can be repeated several times, and the film in which the said several cured film was laminated
- the polymerizable composition is applied to the surface of the substrate or the alignment film formed thereon.
- the polymerizable composition is preferably prepared as a coating solution in which the material is dissolved and / or dispersed in a solvent.
- a solvent used for preparation of a coating liquid an organic solvent is used preferably.
- amide eg, N, N-dimethylformamide
- sulfoxide eg, dimethyl sulfoxide
- heterocyclic compound eg, pyridine
- hydrocarbon eg, benzene, hexane
- alkyl halide eg, chloroform, dichloromethane
- ester Eg methyl acetate, butyl acetate, propylene glycol monoethyl ether acetate
- ketones eg acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone
- ethers eg tetrahydrofuran, 1,2-dimethoxyethane
- alkyl halides, esters and ketones are particularly preferred.
- Two or more organic solvents may be used in combination.
- the coating solution can be performed by various methods such as wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating and the like.
- the composition can be discharged from the nozzle using an inkjet device to form a coating film.
- the polymerizable composition which has been applied to the surface to form a coating film is brought into the state of a liquid crystal phase such as a cholesteric liquid crystal phase.
- a liquid crystal phase such as a cholesteric liquid crystal phase.
- the coating film may be dried to remove the solvent, whereby the liquid crystal phase may be obtained.
- the coating film may be heated, if desired, to achieve a transition temperature to the liquid crystal phase.
- the liquid crystal phase can be stably brought into a state by temporarily heating to a temperature of an isotropic phase and then cooling to a liquid crystal phase transition temperature.
- the liquid crystal phase transition temperature of the polymerizable composition is preferably in the range of 10 to 250 ° C., and more preferably in the range of 10 to 150 ° C., from the viewpoint of production suitability and the like. If the temperature is less than 10 ° C., a cooling step or the like may be required to lower the temperature to a temperature range exhibiting a liquid crystal phase. If the temperature exceeds 200 ° C., the liquid phase needs to be at a high temperature to obtain an isotropic liquid state having a temperature higher than that of the liquid crystal phase, which is disadvantageous from the waste of heat energy, the deformation of the substrate and the like. There is.
- the coating film in the liquid crystal phase is cured.
- Curing may be advanced according to any polymerization method such as radical polymerization method, anion polymerization method, cation polymerization method, coordination polymerization method and the like.
- a suitable polymerization method may be selected.
- ultraviolet radiation is applied to drive the curing reaction.
- a light source such as a UV lamp is used for UV irradiation.
- the curing reaction of the composition proceeds by irradiating ultraviolet light, and the liquid crystal phase (cholesteric liquid crystal phase etc.) is fixed to form a cured film.
- the amount of irradiation energy of ultraviolet rays in general, 0.1J / cm 2 ⁇ 0.8J / cm 2 is preferably about.
- UV irradiation may be performed under heating conditions to accelerate the curing reaction. Further, the temperature at the time of ultraviolet irradiation is preferably maintained in a temperature range in which the liquid crystal phase is exhibited so that the liquid crystal phase is not disturbed. Further, since the oxygen concentration in the atmosphere is related to the polymerization degree, the desired polymerization degree can not be reached in air, and if the film strength is insufficient, the oxygen concentration in the atmosphere is reduced by a method such as nitrogen substitution. Is preferred.
- the liquid crystal phase is fixed to form a cured film.
- the state in which the liquid crystal phase is “fixed” is the most typical and preferable aspect in which the alignment of the compound in the liquid crystal phase is maintained.
- the layer is not particularly limited, and specifically, the layer has no fluidity in a temperature range of 0 ° C. to 50 ° C., usually -30 ° C. to 70 ° C. under more severe conditions, and the orientation form by external field or external force It means that the fixed orientation form can be kept stable without any change in the above.
- the composition in the cured film does not have to exhibit liquid crystallinity any longer.
- the composition may be polymerized by the curing reaction to lose the liquid crystallinity.
- the preferred film thickness may be determined according to the application or according to the desired optical properties. Generally, the thickness is preferably 0.05 to 50 ⁇ m, and more preferably 1 to 35 ⁇ m.
- the film may have a substrate.
- the substrate is self-supporting, and there is no limitation on the material and the optical properties as long as it supports the cured film. It can be selected from a glass plate, a quartz plate, a polymer film and the like. Depending on the application, one having high transparency to ultraviolet light may be used. Examples of the polymer film having high transparency to visible light include polymer films for various optical films used as members of display devices such as liquid crystal display devices.
- polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate and polyethylene naphthalate (PEN); polycarbonate (PC) film, polymethyl methacrylate film; polyolefin films such as polyethylene and polypropylene; polyimide film, triacetyl A cellulose (TAC) film etc. are mentioned.
- PET polyethylene terephthalate
- PEN polybutylene terephthalate
- PEN polyethylene naphthalate
- PC polycarbonate
- polyolefin films such as polyethylene and polypropylene
- polyimide film triacetyl A cellulose (TAC) film etc.
- TAC triacetyl A cellulose
- the film may have an orientation layer between the substrate and the cured film.
- the alignment layer has a function of more precisely defining the alignment direction of the liquid crystal compound.
- the orientation layer can be provided by means such as rubbing treatment of an organic compound (preferably a polymer), oblique deposition of an inorganic compound, formation of a layer having a microgroove, or the like.
- an alignment layer in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known.
- the alignment layer is preferably formed on the surface of the polymer film by rubbing.
- a polymer of an organic compound is preferable, and a polymer which is itself crosslinkable or a polymer which is crosslinked by a crosslinking agent is often used. Of course, polymers having both functions are also used.
- polymers examples include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleinimide copolymer, polyvinyl alcohol and modified polyvinyl alcohol, poly (N-methylol acrylamide), styrene / vinyl toluene copolymer Combined, chlorosulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, carboxymethyl cellulose, gelatin, polyethylene, polypropylene, polycarbonate etc. And polymers such as silane coupling agents.
- polymers examples include water-soluble polymers such as poly (N-methylol acrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol and modified polyvinyl alcohol, of which gelatin, polyvinyl alcohol and modified polyvinyl alcohol are preferred. In particular, polyvinyl alcohol and modified polyvinyl alcohol are preferred.
- Adhesive layer When a plurality of cured films are bonded with an adhesive, an adhesive layer is provided between the cured films.
- the adhesive layer may be formed of an adhesive.
- Adhesives include hot melt type, thermosetting type, light curing type, reaction curing type, and pressure sensitive adhesive type that does not require curing from the viewpoint of curing method, and as materials, acrylate type, urethane type, urethane acrylate type, epoxy respectively Use compounds such as epoxy acrylate type, polyolefin type, modified olefin type, polypropylene type, ethylene vinyl alcohol type, vinyl chloride type, chloroprene rubber type, cyanoacrylate type, polyamide type, polyimide type, polystyrene type, polyvinyl butyral type etc.
- a photo-curing type is preferable as the curing method, and from the viewpoint of optical transparency and heat resistance, it is preferable to use an acrylate type, urethane acrylate type, epoxy acrylate type or the like as the material.
- the thickness of the adhesive layer may be 0.5 to 10 ⁇ m, preferably 1 to 5 ⁇ m. When used as a half mirror for projection image display, it is preferable that the film thickness be uniform in order to reduce color unevenness and the like.
- Examples of the film formed using the polymerizable composition include a film in which the alignment (for example, horizontal alignment, vertical alignment, hybrid alignment, etc.) of the liquid crystal phase of the polymerizable composition is fixed. Such a film usually exhibits optical anisotropy and is used as an optical compensation film for liquid crystal display devices and the like.
- Another example is a film including a layer in which the cholesteric liquid crystal phase of the polymerizable composition is fixed, and showing a selective reflection property to light of a predetermined wavelength range. In the cholesteric liquid crystal phase, liquid crystal molecules are arranged helically.
- the layer in which the cholesteric liquid crystal phase is fixed selectively reflects either right circularly polarized light or left circularly polarized light in the selective reflection wavelength range, It functions as a circularly polarized light selective reflection layer that transmits the circularly polarized light of the other sense.
- Films comprising one or more cholesteric liquid crystal layers can be used in various applications.
- the sense of the circularly polarized light reflected by each cholesteric liquid crystal layer may be the same or the reverse depending on the application.
- the central wavelength of the selective reflection described later of each cholesteric liquid crystal layer may be the same or different depending on the application.
- the term "sense” for circularly polarized light means that it is right circularly polarized light or left circularly polarized light.
- the sense of circularly polarized light is right circularly polarized when the tip of the electric field vector rotates clockwise with time increase when the light is viewed as it travels to the front, and left when counterclockwise. Defined as circularly polarized.
- the term “sense” may be used with respect to the twist direction of the helix of the cholesteric liquid crystal.
- the selective reflection by the cholesteric liquid crystal reflects right circularly polarized light when the twisting direction (sense) of the cholesteric liquid crystal spiral is right, transmits left circularly polarized light, and reflects left circularly polarized light when the sense is left, and right Transmits circularly polarized light.
- a film including a cholesteric liquid crystal layer exhibiting selective reflection characteristics in the visible light wavelength range can be used as a screen or a half mirror for projection image display.
- it can be used as a filter (see, for example, JP-A-2003-294948) for improving the color purity of display light of a color filter or a display.
- the optical film can be used for various applications such as a polarizing element, a reflective film, an antireflective film, a viewing angle compensation film, holography, an alignment film, and the like which are components of an optical element.
- projection display member According to the above-described function of the cholesteric liquid crystal layer, it is possible to reflect the circularly polarized light of either one of the sense lights at the wavelength showing selective reflection among the projection light to form a projection image.
- the projection video may be displayed on the surface of the projection display member surface and may be viewed as such, or may be a virtual image that appears to be floated on the tip of the projection display member as viewed from the observer.
- the central wavelength ⁇ of selective reflection of the cholesteric liquid crystal layer means a wavelength located at the center of gravity of the reflection peak of the circularly polarized light reflection spectrum measured from the normal direction of the cholesteric liquid crystal layer.
- the central wavelength of selective reflection can be adjusted by adjusting the pitch of the helical structure.
- the central wavelength ⁇ is adjusted and apparent selection is made.
- the central wavelength of reflection can be in the wavelength range of 450 nm to 495 nm.
- the apparent central wavelength of selective reflection is the wavelength at the center of gravity of the reflection peak of the circularly polarized light reflection spectrum of the cholesteric liquid crystal layer measured from the observation direction in practical use (when used as a projection image display member). means.
- the pitch of the cholesteric liquid crystal phase depends on the type of chiral agent to be used together with the polymerizable liquid crystal compound, or the addition concentration thereof, and by adjusting these, the desired pitch can be obtained.
- ⁇ / ⁇ which is the ratio of the half width ⁇ of the selective reflection wavelength region to the central wavelength ⁇ of selective reflection.
- the film of the present invention particularly a film used as a projection image display member, preferably has ⁇ / ⁇ of 0.09 or less, more preferably 0.07 or less. More specifically, in the cholesteric liquid crystal layer in the film, ⁇ / ⁇ preferably satisfies the above, and in a film including two or more cholesteric liquid crystal layers, ⁇ / ⁇ in each of the two or more cholesteric liquid crystal layers is It is preferable to satisfy the above. In each layer, ⁇ and ⁇ may be the same or different.
- a cured film having a central wavelength of apparent selective reflection in each of a red light wavelength range, a green light wavelength range and a blue light wavelength range is produced, and a full color is obtained by laminating them. It is possible to produce a projection video display member capable of displaying a projection video. Specifically, laminating a cured film having half mirrors in the respective ranges of 750 to 620 nm, 630 to 500 nm, and 530 to 420 nm and having different central wavelengths of selective reflection (for example, different by 50 nm or more) Is preferred.
- a clear projected light image can be displayed with efficient use of light by adjusting the central wavelength of the selective reflection of each cured film according to the light emission wavelength range of the light source used for projection and the usage mode of the projected image display member it can.
- the central wavelength of the selective reflection of the cured film in accordance with the emission wavelength range of the light source used for projection, it is possible to display a clear color projection image with good light utilization efficiency.
- the incident angle of the projection light to the projection mirror display half mirror surface, the projection video observation direction of the projection video display member surface, and the like can be particularly mentioned.
- a half mirror usable as a combiner for a head-up display can be provided.
- the projection-image display half mirror can visibly display an image projected from a projector or the like, and when the projection-image display half mirror is observed from the same side on which the image is displayed, the opposite is true.
- the information or landscape on the side can be viewed simultaneously.
- the substrate is preferably transparent in the visible light region and low in birefringence.
- the retardation of the substrate at a wavelength of 550 nm is preferably 50 nm or less, and more preferably 20 nm or less.
- the substrate examples include inorganic glass and polymer resin (acrylic resin (acrylic acid esters such as polymethyl (meth) acrylate), polycarbonate, cyclic polyolefin such as cyclopentadiene-based polyolefin and norbornene-based polyolefin, and polyolefin such as polypropylene And aromatic vinyl polymers such as polystyrene, polyarylates, cellulose acylates and the like).
- acrylic resin acrylic acid esters such as polymethyl (meth) acrylate
- polycarbonate cyclic polyolefin such as cyclopentadiene-based polyolefin and norbornene-based polyolefin
- polyolefin such as polypropylene And aromatic vinyl polymers such as polystyrene, polyarylates, cellulose acylates and the like.
- the projection image display half mirror may include an antireflective layer.
- the antireflective layer is preferably contained in the outermost surface. It may be provided on the outermost surface on the observation side when using the half mirror for projection image display, or on the outermost surface on the opposite side, but provided on the outermost surface on the observation side Is preferred.
- an antireflective layer may be provided on both the substrate surface and the cured film side to be the observation side. Such a configuration makes it difficult to form a double image which may occur particularly when the substrate has high birefringence.
- the antireflective layer for example, in addition to a film having a fine surface asperity, a two-layered film combining a high refractive index layer and a low refractive index layer, a middle refractive index layer, a high refractive index layer, and a low refractive index layer
- stacked the refractive index layer one by one are mentioned.
- two layers of high refractive index layer / low refractive index layer, and three layers having different refractive indices, middle refractive index layer (refractive index is higher than that of lower layer, high refractive index Layers having a refractive index lower than that of the layer) / high refractive index layer / low refractive index layer are laminated in this order, and those in which more antireflection layers are laminated have also been proposed.
- JP-A-8-110401, JP-A-10-300902, JP-A-2002-243906, JP-A-2000-111706, etc. may be mentioned.
- an antireflection film having a three-layer structure excellent in robustness to film thickness fluctuation is described in Japanese Patent Application Laid-Open No. 2008-262187.
- the three-layer antireflective film When installed on the surface of an image display device, the three-layer antireflective film can have an average reflectance value of 0.5% or less, and can significantly reduce reflection, resulting in a three-dimensional effect. An excellent image can be obtained.
- other functions may be imparted to each layer, for example, a low refractive index layer with antifouling property, a high refractive index layer with antistatic property, a hard coat layer with antistatic property, and a hard coat layer with antiglare property And the like (eg, JP-A-10-206603, JP-A-2002-243906, JP-A-2007-264113, etc.) and the like.
- SiO 2, SiO, ZrO 2 , TiO 2, TiO, Ti 2 O 3, Ti 2 O 5, Al 2 O 3, Ta 2 O 5, CeO 2, MgO, Y 2 O 3 , SnO 2 , MgF 2 , WO 3 and the like can be mentioned, and these can be used alone or in combination of two or more.
- SiO 2 , ZrO 2 , TiO 2 and Ta 2 O 5 are preferable because they can be vacuum deposited at low temperatures and can form a film on the surface of a plastic substrate.
- the total optical film thickness of the ZrO 2 layer and the SiO 2 layer is ⁇ / 4 from the substrate side, the optical film thickness of the ZrO 2 layer is ⁇ / 4, and the outermost SiO 2 layer
- ⁇ is a design wavelength, and usually 520 nm is used.
- the outermost layer is preferably SiO 2 because it has a low refractive index and can impart mechanical strength to the antireflective layer.
- the antireflective layer with an inorganic material
- a vacuum deposition method for example, a vacuum deposition method, an ion plating method, a sputtering method, a CVD method, a method of depositing by a chemical reaction in a saturated solution, or the like can be employed.
- Examples of the organic material used for the low refractive index layer include FFP (tetrafluoroethylene-hexafluoropropylene copolymer), PTFE (polytetrafluoroethylene), ETFE (ethylene-tetrafluoroethylene copolymer), etc.
- JP-A-2002-317152, JP-A-2003-202406, and JP-A-2003-292831 disclose compositions containing a fluorine-containing curable resin and inorganic fine particles described in JP-A-2007-298974.
- the hollow silica fine particle-containing low refractive index coating composition described in Japanese Patent Laid-Open Publication No. H9-118118 can be suitably used.
- the film can be formed by a coating method excellent in mass productivity, such as a spin coating method, a dip coating method, and a gravure coating method in addition to the vacuum deposition method.
- the low refractive index layer preferably has a refractive index of 1.30 to 1.51. It is preferably from 1.30 to 1.46, more preferably from 1.32 to 1.38.
- an ionizing radiation curable compound containing an aromatic ring examples thereof include binders obtained by crosslinking or polymerization reaction such as ionizing radiation curable compounds containing atoms such as S, N and P, and inorganic particles mainly composed of TiO 2 added thereto.
- binders obtained by crosslinking or polymerization reaction such as ionizing radiation curable compounds containing atoms such as S, N and P, and inorganic particles mainly composed of TiO 2 added thereto.
- the refractive index of the high refractive index layer is preferably 1.65 to 2.20, and more preferably 1.70 to 1.80.
- the refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer.
- the refractive index of the middle refractive index layer is preferably 1.55 to 1.65, and more preferably 1.58 to 1.63.
- the film thickness of the antireflective layer is not particularly limited, but may be about 0.1 to 10 ⁇ m, 1 to 5 ⁇ m, or 2 to 4 ⁇ m.
- 4- (4-acryloyloxybutyloxy) benzoic acid was synthesized with reference to the method described on pages 18 [0085] to [0087] of Patent No. 4397550.
- BHT 60 mg
- methanesulfonyl chloride 1.62 mL
- tetrahydrofuran 10 mL
- the internal temperature was cooled to -5.degree.
- a separately prepared solution of 4- (4-acryloyloxybutyloxy) benzoic acid (5.5 g) and diisopropylethylamine (3.7 mL) in tetrahydrofuran (8 mL) was added dropwise so that the internal temperature did not rise above 0 ° C.
- Carboxylic acid A (1.0 g), BHT (. 0.05 g) and thionyl chloride (0.27 mL) were stirred in toluene (2.0 mL) at room temperature for 1 hour. After distilling off the solvent under reduced pressure, ethyl acetate (3 mL) and methylhydroquinone (0.18 g) are added, and N, N-dimethylaminopyridine (0.03 g) and triethylamine (0.7 mL) are added dropwise to obtain a room temperature. The mixture was stirred for 3 hours.
- Phenol derivative 1 (11.9 g) was stirred in 70 mL of tetrahydrofuran, and dimethylaminopyridine (0.3 g) and carboxylic acid chloride derivative 1 (12.7 g) were added. The reaction solution was cooled to an internal temperature of 0 ° C., triethylamine (7.6 mL) was added dropwise, the mixture was stirred at 25 ° C. for 2 hours, methanol (20 mL) was added, and the mixture was further stirred for 30 minutes.
- Phenol derivative 2 (13.1 g) was stirred in 70 mL of tetrahydrofuran, and dimethylaminopyridine (0.3 g) and carboxylic acid chloride derivative 1 (12.7 g) were added.
- the reaction solution was cooled to an internal temperature of 0 ° C., triethylamine (7.6 mL) was added dropwise, the mixture was stirred at 25 ° C. for 2 hours, methanol (20 mL) was added, and the mixture was further stirred for 30 minutes.
- the above-mentioned phenol derivative was synthesized in the same manner as for the phenol derivative B. Furthermore, purification was performed by column chromatography using a synthesis method similar to that of compound 1-3, to obtain compound 1-26.
- Dicarboxylic acid chloride I-6 (960 mg) and 2- (methoxycarbonyl) hydroquinone (1.5 g) were stirred in THF (5.7 mL). Triethylamine (1.5 mL) and N, N-dimethylaminopyridine (56 mg) were added at an internal temperature of 2 ° C., and the mixture was stirred at room temperature for 2 hours. Water and ethyl acetate were added to remove the aqueous layer, and the organic layer was washed successively with water and brine. After drying the organic layer with magnesium sulfate and filtering the desiccant, the solvent was evaporated under reduced pressure. Methanol (15 mL) was added, and the mixture was stirred at an internal temperature of 0 ° C. for 30 minutes, and the generated crystals were filtered to obtain 1.85 g of a phenol derivative C.
- the above carboxylic acid was synthesized in the same manner as in Compound 1-29. Furthermore, purification was performed by column chromatography using a synthesis method similar to that of compound 1-3, to obtain a mixture of compounds 1-33, 1-34, and 1-35.
- a polyimide alignment film SE-130 manufactured by Nissan Chemical Industries, Ltd. was applied by spin coating, dried, and fired at 250 ° C. for 1 hour. This was rubbed to prepare a substrate with an alignment film.
- the above-mentioned polymerizable composition coating solution is applied at room temperature by spin coating on the rubbing-treated surface of the alignment film of this substrate, heated at 80 ° C. for 1 minute, and allowed to stand at room temperature for 10 minutes.
- a coated sample was prepared.
- Examples 2 to 7 and Comparative Example were the same as Example 1 except that the polymerizable compounds (compounds 1-3 and compounds 2-3) of the above-mentioned polymerizable composition coating liquid were changed as shown in the following table.
- the coated samples of Examples 1 to 5 were prepared.
- the liquid crystalline composition coating liquid (1) having the following composition was prepared using the exemplary compounds synthesized in the above examples.
- Compound 1-3 80 parts by mass Compound 2-3 20 parts by mass Air interface alignment agent (1) 0.1 parts by mass Polymerization initiator IRGACURE 819 (manufactured by BASF Corp.) 2 parts by mass Solvent chloroform 900 parts by mass
- a polyimide alignment film SE-130 manufactured by Nissan Chemical Industries, Ltd. was applied by spin coating on the cleaned glass substrate, dried, and fired at 250 ° C. for 1 hour. This was rubbed to prepare a substrate with an alignment film.
- the liquid crystal composition coating solution (1) is applied at room temperature by spin coating on the rubbed surface of the produced substrate with alignment film, and after orientation ripening at 80 ° C. for 1 minute, it is at 50 ° C. under nitrogen gas atmosphere.
- the alignment was fixed by irradiating light for 30 seconds using a high pressure mercury lamp, and the retardation film 1 was formed. During the time after polymerization and before polymerization, precipitation of crystals was not observed in the coated film.
- the average tilt angle of the liquid crystal calculated by this device is 2.8 degrees, and the retardation film of the A-plate type is It confirmed that it could form.
- the phase difference (Re) measured using this apparatus was 135 nm.
- the film thickness (d) measured using a non-contact three-dimensional surface shape measurement system (BW-A501 manufactured by Nikon Corporation) is 2.2 nm, which is calculated from the ratio of retardation (Re) to film thickness (d) (Re / d) at a wavelength of 550 nm was 0.061.
- Examples 2 to 9 and Comparative Examples are carried out in the same manner as Example 1, except that the polymerizable compounds (Compounds 1-3 and Compound 2-3) of the above-mentioned polymerizable composition coating liquid are changed as shown in the following table.
- the retardation films of 1 to 5 were prepared, and the retardation and the film thickness were calculated.
- crystallization was seen by the comparative example 1, 2, 3, 5 until it superposes
- the cured film of Comparative Example 4 was an isotropic film having no phase difference.
- the liquid crystalline composition coating liquid (8) having the following composition was prepared using the exemplary compounds synthesized in the above examples. Mixture of compounds 1-33, 1-34, 1-35 80 parts by mass Compound 2-3 20 parts by mass Air interface alignment agent (1) 0.1 parts by mass Polymerization initiator IRGACURE 819 (manufactured by BASF Corp.) 2 parts by mass Solvent chloroform 900 parts by mass
- a polyimide alignment film SE-130 manufactured by Nissan Chemical Industries, Ltd. was applied by spin coating on the cleaned glass substrate, dried, and fired at 250 ° C. for 1 hour. This was rubbed to prepare a substrate with an alignment film.
- the liquid crystal composition coating solution (1) is applied at room temperature by spin coating on the rubbed surface of the substrate with alignment film prepared, and after orientation ripening at 140 ° C. for 1 minute, it is at 50 ° C. under nitrogen gas atmosphere.
- the alignment was fixed by light irradiation using a high pressure mercury lamp for 30 seconds to form a retardation film of Example 10. Between the coating and heating, no deposition of crystals was observed in the coated film.
- the average tilt angle of the liquid crystal calculated by this device is 2.1 degrees, and the retardation film of the A-plate type is It confirmed that it could form.
- the phase difference measured using this apparatus was 143 nm.
- the film thickness measured using a noncontact three-dimensional surface shape measurement system (BW-A501 manufactured by Nikon Corporation) is 2.0 nm, and ⁇ n at a wavelength of 550 nm calculated from the ratio of retardation and film thickness is 0.071. Met.
- the polymerizable composition coating liquid (1) having the following composition was prepared using the exemplary compounds synthesized above.
- Polymerizable Composition Coating Liquid (1) Compound 1-3 80 parts by mass Compound 2-3 20 parts by mass Chiral agent LC-756 (manufactured by BASF) 4.6 parts by mass Air interface alignment agent (1) 0.07 parts by mass Polymerization initiator IRGACURE 819 (manufactured by BASF) 3 parts by mass solvent methyl ethyl ketone 250 parts by mass solvent cyclohexanone 50 parts by mass
- the thickness of the dry film after drying the polymerizable composition coating solution (1) is 5.2 ⁇ m on the rubbing-treated surface of PET by Fujifilm Corp. subjected to the rubbing treatment It applied.
- the coated layer is dried at room temperature for 10 seconds, heated for 2 minutes in an atmosphere of 75 ° C., and then irradiated with UV light at 80% for 8 seconds at 50 ° C. with a Fusion D bulb (lamp 90 mW / cm) for selective reflection Film 1 was obtained. Between the coating and heating, no deposition of crystals was observed in the coated film.
- the transmission spectrum of this film was measured by a spectrophotometer UV-3100PC manufactured by Shimadzu Corporation.
- the polymerizable composition coating solution (2) having the following composition was prepared in the same manner as the polymerizable composition coating solution (1).
- Polymerizable composition coating liquid (2) Compound 1-3 80 parts by mass Compound 2-3 20 parts by mass Chiral agent LC-756 (manufactured by BASF) 5.3 parts by mass Air interface alignment agent (1) 0.07 parts by mass Polymerization initiator IRGACURE 819 (manufactured by BASF) 3 parts by mass solvent methyl ethyl ketone 250 parts by mass solvent cyclohexanone 50 parts by mass
- the polymerizable composition coating solution (3) having the following composition was prepared in the same manner as the polymerizable composition coating solution (1).
- Polymerizable composition coating liquid (3) Compound 1-3 80 parts by mass Compound 2-3 20 parts by mass Chiral agent LC-756 (manufactured by BASF) 4.0 parts by mass Air interface alignment agent (1) 0.07 parts by mass Polymerization initiator IRGACURE 819 (manufactured by BASF) 3 parts by mass solvent methyl ethyl ketone 250 parts by mass solvent cyclohexanone 50 parts by mass
- the polymerizable composition coating liquid (7) having the following composition was prepared using the exemplary compounds synthesized above.
- Polymerizable composition coating liquid (7) Compound 1-26 55 parts by mass Compound 2-8 30 parts by mass Compound (M-1) 13 parts by mass Compound (M-2) 2 parts by mass Polymerization initiator IRGACURE 819 (manufactured by BASF Corp.) 3 parts by mass Chiral agent LC756 (BASF Corporation) Made of) 4.4 parts by mass Alignment agent (2) 0.01 parts by mass Alignment agent (3) 0.02 parts by mass Methyl acetate 260 parts by mass Cyclohexanone 65 parts by mass
- a wire bar was applied to the rubbing-treated surface of Toyobo PET (A-4100) which had been subjected to rubbing treatment at room temperature so that the thickness of the dry film after drying the polymerizable composition coating solution (7) was 4.5 ⁇ m. It applied using.
- the coated layer is dried at room temperature for 30 seconds, heated for 1 minute in an atmosphere of 85 ° C., and irradiated with UV light at 60 ° C. under a nitrogen gas atmosphere using a high pressure mercury lamp so that the irradiation amount is 300 mJ / cm 2 .
- the selective reflection film 4 was obtained. Between the coating and heating, no deposition of crystals was observed in the coated film. Per this film.
- the transmission spectrum was measured by a spectrophotometer UV-3100PC manufactured by Shimadzu Corporation. As a result, there was a selective reflection peak centered at 544 nm, and the half width was 33 nm. The ratio ( ⁇ / ⁇ ) of the half width of the selective reflection wavelength range to the central wavelength of the selective reflection was 0.062.
- the polymerizable composition coating liquid (8) having the following composition was prepared using the exemplary compounds synthesized above.
- Polymerizable composition coating solution (8) Compound 1-28 55 parts by mass Compound 2-34 30 parts by mass Compound (M-1) 13 parts by mass Compound (M-2) 2 parts by mass Polymerization initiator IRGACURE 819 (manufactured by BASF Corp.) 3 parts by mass Chiral agent LC756 (BASF Corporation) Made of) 4.4 parts by mass Alignment agent (2) 0.01 parts by mass Alignment agent (3) 0.02 parts by mass Methyl acetate 260 parts by mass Cyclohexanone 65 parts by mass
- a wire bar is applied at room temperature so that the thickness of the dry film after drying the polymerizable composition coating solution (8) is 4.5 ⁇ m. It applied using.
- the coated layer is dried at room temperature for 30 seconds, heated for 1 minute in an atmosphere of 85 ° C., and irradiated with UV light at 60 ° C. under a nitrogen gas atmosphere using a high pressure mercury lamp so that the irradiation amount is 300 mJ / cm 2 .
- the selective reflection film 5 was obtained. Between the coating and heating, no deposition of crystals was observed in the coated film.
- the transmission spectrum of this film was measured by a spectrophotometer UV-3100PC manufactured by Shimadzu Corporation. As a result, there was a selective reflection peak centered on 570 nm, and the half width was 35 nm. The ratio ( ⁇ / ⁇ ) of the half width of the selective reflection wavelength range to the central wavelength of the selective reflection was 0.061.
- the polymerizable composition coating liquid (9) having the following composition was prepared using the exemplary compounds synthesized above.
- Polymerizable composition coating liquid (9) Compound 1-36 55 parts by mass Compound 2-35 30 parts by mass Compound (M-1) 13 parts by mass Compound (M-2) 2 parts by mass Polymerization initiator IRGACURE 819 (manufactured by BASF Corp.) 3 parts by mass Chiral agent LC756 (BASF Corporation) Made of) 4.4 parts by mass Alignment agent (2) 0.01 parts by mass Alignment agent (3) 0.02 parts by mass Methyl acetate 260 parts by mass Cyclohexanone 65 parts by mass
- a wire bar is applied at room temperature so that the thickness of the dry film after drying the polymerizable composition coating solution (9) is 4.5 ⁇ m. It applied using.
- the coated layer is dried at room temperature for 30 seconds, heated for 1 minute in an atmosphere of 85 ° C., and irradiated with UV light at 60 ° C. under a nitrogen gas atmosphere using a high pressure mercury lamp so that the irradiation amount is 300 mJ / cm 2 .
- the selective reflection film 6 was obtained. Between the coating and heating, no deposition of crystals was observed in the coated film.
- the transmission spectrum of this film was measured with a spectrophotometer UV-3100PC manufactured by Shimadzu Corporation. As a result, there was a selective reflection peak centered on 588 nm, and the half width was 40 nm. The ratio ( ⁇ / ⁇ ) of the half width of the selective reflection wavelength range to the central wavelength of the selective reflection was 0.068.
- ⁇ Production 1 of laminated film (including two or more liquid crystal layers)>
- the liquid crystal layer of the polymerizable composition coating liquid (1) is formed on the liquid crystal layer of the selective reflection film 2 under the same conditions as forming the liquid crystal layer with the selective reflection film 1 to obtain a laminated film 1
- the liquid crystal layer of the polymerizable composition coating liquid (3) is formed on the liquid crystal layer of the laminated film 1 under the same conditions as forming the liquid crystal layer in the selective reflection film 3, and the laminated film 2 is obtained. Obtained.
- the surfaces of the laminated films 1 and 2 were uniform without repelling defects.
- the transmission spectrum of the laminated film 2 was measured using a spectrophotometer UV-3100PC manufactured by Shimadzu Corporation. It had selective reflection peaks centered at 464 nm, 563 nm and 640 nm, respectively, and had high visible light transmittance of 70% or more all right. The transmission spectrum obtained is shown in FIG.
- the polymerizable composition coating liquid (4) having the following composition was prepared using the exemplary compounds synthesized above.
- Polymerizable composition coating liquid (4) Compound 1-3 55 parts by mass Compound 2-3 30 parts by mass Compound (M-1) 13 parts by mass Compound (M-2) 2 parts by mass Polymerization initiator IRGACURE 819 (manufactured by BASF Corp.) 3 parts by mass Chiral agent LC756 (BASF Corporation) Made in) 3.7 parts by mass Alignment agent (2) 0.01 parts by mass Alignment agent (3) 0.02 parts by mass Methyl acetate 260 parts by mass Cyclohexanone 65 parts by mass
- a wire bar is applied at room temperature so that the thickness of the dry film after drying the polymerizable composition coating liquid (4) becomes 5.0 ⁇ m. It applied using.
- the coated layer is dried at room temperature for 30 seconds, heated for 1 minute in an atmosphere of 85 ° C., and irradiated with UV light at 60 ° C. under a nitrogen gas atmosphere using a high pressure mercury lamp so that the irradiation amount is 300 mJ / cm 2 .
- the selective reflection film 4 was obtained. Between the coating and heating, no deposition of crystals was observed in the coated film.
- the transmission spectrum of this film was measured with a spectrophotometer UV-3100PC manufactured by Shimadzu Corporation. As a result, there was a selective reflection peak centered on 672 nm, and the half width was 40 nm. The ratio ( ⁇ / ⁇ ) of the half width of the selective reflection wavelength range to the central wavelength of the selective reflection was 0.059.
- the polymerizable composition coating liquids (5) and (6) having the following compositions were prepared in the same manner as the polymerizable composition coating liquid (4).
- Polymerizable composition coating solution (5) Compound 1-3 55 parts by mass Compound 2-3 30 parts by mass Compound (M-1) 13 parts by mass Compound (M-2) 2 parts by mass Polymerization initiator IRGACURE 819 (manufactured by BASF Corp.) 3 parts by mass Chiral agent LC756 (BASF Corporation) Made of) 4.7 parts by mass Alignment agent (2) 0.005 parts by mass Alignment agent (3) 0.01 parts by mass Methyl acetate 260 parts by mass Cyclohexanone 65 parts by mass
- Polymerizable composition coating liquid (6) Compound 1-3 55 parts by mass Compound 2-3 30 parts by mass Compound (M-1) 13 parts by mass Compound (M-2) 2 parts by mass Polymerization initiator IRGACURE 819 (manufactured by BASF Corp.) 3 parts by mass Chiral agent LC756 (BASF Corporation) Made in) 5.4 parts by mass Alignment agent (2) 0.005 parts by mass Alignment agent (3) 0.01 parts by mass Methyl acetate 260 parts by mass Cyclohexanone 65 parts by mass
- the thickness of the dry film after drying the polymerizable composition coating solution (5) on the surface of the liquid crystal layer of the selective reflection film 4 is 4.1 ⁇ m (the total film thickness with the lower layer is 9.2 ⁇ m) at room temperature It applied using a wire bar.
- the coated layer is dried at room temperature for 30 seconds, then heated for 1 minute in an atmosphere of 85 ° C., irradiated with UV light at a temperature of 60 ° C. under nitrogen gas using a high pressure mercury lamp so that the irradiation amount is 300 mJ / cm 2.
- Film 3 was obtained.
- the thickness of the dry film after drying the polymerizable composition coating solution (6) on the surface of the liquid crystal layer of the laminated film 3 is 3.9 ⁇ m (the total film thickness with the lower layer is 13.1 ⁇ m) at room temperature It applied using a wire bar.
- the coated layer is dried at room temperature for 30 seconds, then heated for 1 minute in an atmosphere of 85 ° C., irradiated with UV light at a temperature of 60 ° C. under nitrogen gas using a high pressure mercury lamp so that the irradiation amount is 300 mJ / cm 2.
- Film 4 was obtained.
- the transmission spectrum of this laminated film 4 was measured with a spectrophotometer UV-3100PC manufactured by Shimadzu Corporation, and reflection peaks were found at 680 nm, 538 nm, and 466 nm, and it was found that the visible light transmittance was 75% or more.
- the transmission spectrum obtained is shown in FIG.
- UV curable adhesive Exp. U12034-6 was applied using a wire bar at room temperature such that the dry film thickness after drying was 5 ⁇ m.
- a transparent substrate made of meta acrylic Mitsubishi Rayon Co., Ltd. “Mitsubishi Rayon Co.” "Acrylite L”
- the adhesive coated surface of the laminated film 2 are bonded and irradiated with UV, and the PET film of the laminated film 2 is peeled off to produce the half mirror 1 for projection image display having an acrylic substrate. did.
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Abstract
Description
本発明は、特に、トランス-1,4-シクロヘキシレン基およびフェニレン基を有する重合性化合物を2種以上含む重合性組成物として、複屈折性の低い重合性組成物を提供することを課題とする。本発明はまた、上記重合性組成物を用いて低複屈折性位相差膜、または反射波長域の選択性の高い反射膜等のフィルムを提供することを課題とする。
すなわち、本発明は以下の<1>~<18>を提供するものである。
Aは、置換基を有していてもよいフェニレン基または置換基を有していてもよいトランス-1,4-シクロヘキシレン基を示し、
Lは単結合、-CH2O-、-OCH2-、-(CH2)2OC(=O)-、-C(=O)O(CH2)2-、-C(=O)O-、-OC(=O)-、-OC(=O)O-、-CH=CH-C(=O)O-、および-OC(=O)-CH=CH-からなる群から選択される連結基を示し、
mは3~12の整数を示し、
Sp1およびSp2はそれぞれ独立に、単結合、炭素数1から20の直鎖もしくは分岐のアルキレン基、および炭素数1から20の直鎖もしくは分岐のアルキレン基において1つまたは2つ以上の-CH2-が-O-、-S-、-NH-、-N(CH3)-、-C(=O)-、-OC(=O)-、または-C(=O)O-で置換された基からなる群から選択される連結基を示し、
Q1およびQ2はそれぞれ独立に、水素原子または以下の式(Q-1)~式(Q-5)で表される基からなる群から選択される重合性基を示し、ただしQ1およびQ2のいずれか一方は重合性基を示す;
Aで表される置換基を有していてもよいトランス-1,4-シクロヘキシレン基の数をmで割った数をmcとしたとき、上記重合性化合物の少なくとも1種が0.5<mc<0.7を満たし、かつ、上記重合性化合物の他の少なくとも1種が0.1<mc<0.3を満たす重合性組成物。
<2>式(I)において、フェニレン基およびトランス-1,4-シクロヘキシレン基が有していてもよい上記置換基が、アルキル基、アルコキシ基、および-C(=O)-X3-Sp3-Q3で表される基からなる群から選択され、ここで、X3が単結合、-O-、-S-、もしくは-N(Sp4-Q4)-を示すか、または、Q3およびSp3と共に環構造を形成している窒素原子を示し、Sp3およびSp4はそれぞれ独立に、単結合、炭素数1から20の直鎖もしくは分岐のアルキレン基、および炭素数1から20の直鎖もしくは分岐のアルキレン基において1つまたは2つ以上の-CH2-が-O-、-S-、-NH-、-N(CH3)-、-C(=O)-、-OC(=O)-、または-C(=O)O-で置換された基からなる群から選択される連結基を示し、Q3およびQ4はそれぞれ独立に、水素原子、シクロアルキル基、シクロアルキル基において1つもしくは2つ以上の-CH2-が-O-、-S-、-NH-、-N(CH3)-、-C(=O)-、-OC(=O)-、もしくは-C(=O)O-で置換された基、または式(Q-1)~式(Q-5)で表される基からなる群から選択されるいずれかの重合性基を示す<1>に記載の重合性組成物。
<4>式(I)で表される化合物が、以下の式(II)で表される部分構造を有する<1>~<3>のいずれか一項に記載の重合性組成物;
<5>R1およびR2がそれぞれ独立に、-C(=O)-X3-Sp3-Q3であり、X3が-O-である<4>に記載の重合性組成物。
<6>R1およびR2が同一である<4>または<5>に記載の重合性組成物。
<7>式(V)で表される化合物を少なくとも1種類および式(VI)で表される化合物を少なくとも1種類含む<4>~<6>のいずれか一項に記載の重合性組成物;
<8>架橋剤を含有する<1>~<7>のいずれか一項に記載の重合性組成物。
<9>重合開始剤を含有する<1>~<8>のいずれか一項に記載の重合性組成物。
<10>キラル化合物を含有する<1>~<9>のいずれか一項に記載の重合性組成物。
<11><1>~<10>のいずれか1項に記載の重合性組成物の硬化により得られる層を含むフィルム。
<12><1>~<10>のいずれか1項に記載の重合性組成物の硬化により得られる層を2層以上含むフィルム。
<13>選択反射を示し、
上記選択反射の波長域の半値幅Δλと上記選択反射の中心波長λとの比であるΔλ/λが0.09以下である<11>または<12>に記載のフィルム。
<14>可視光を反射する<11>~<13>のいずれか一項に記載のフィルム。
上記3層が、赤色光波長域に選択反射の中心波長を有するコレステリック液晶相を固定した層、緑色光波長域に選択反射の中心波長を有するコレステリック液晶相を固定した層、および青色光波長域に選択反射の中心波長を有するコレステリック液晶相を固定した層であるフィルム。
<16><15>に記載のフィルムを含む投映像表示用ハーフミラー。
<17>無機ガラスまたはアクリル樹脂である基材を含む<16>に記載の投映像表示用ハーフミラー。
<18>最表面に反射防止層を含む、<16>または<17>に記載の投映像表示用ハーフミラー。
本明細書において、「(メタ)アクリレート」との記載は、「アクリレートおよびメタクリレートのいずれか一方または双方」の意味を表す。「(メタ)アクリル基」等も同様であり、「(メタ)アクリロイル基」は、「アクリロイル基およびメタクリロイル基のいずれか一方または双方」の意味を表す。
本発明の重合性組成物は、式(I)で示される重合性化合物を2種以上含む。
重合性組成物は、式(I)で示される重合性化合物のほか、他の液晶化合物、キラル化合物、重合開始剤、配向制御剤などの他の成分を含んでいてもよい。以下各成分について説明する。
式(I)で示される重合性化合物は、Aで表される環状の2価の基をm個有する。m個のAは互いに異なっていてもよく、m個のAのうちの一部のAが互いに同一であってもよい。環状の2価の基は置換基を有していてもよいフェニレン基または置換基を有していてもよいトランス-1,4-シクロヘキシレン基である。すなわち、Aは置換基を有していてもよいフェニレン基または置換基を有していてもよいトランス-1,4-シクロヘキシレン基を示す。本明細書において、フェニレン基というとき、1,4-フェニレン基であることが好ましい。
本発明の重合性組成物は、少なくとも1つの置換基を有していてもよいフェニレン基を含みかつ少なくとも1つの置換基を有していてもよいトランス-1,4-シクロヘキシレン基を含む式(I)で示される重合性化合物を含んでいればよい。
Q3およびQ4はそれぞれ独立に、水素原子、シクロアルキル基、シクロアルキル基において1つもしくは2つ以上の-CH2-が-O-、-S-、-NH-、-N(CH3)-、-C(=O)-、-OC(=O)-、もしくは-C(=O)O-で置換された基、または式(Q-1)~式(Q-5)で表される基からなる群から選択されるいずれかの重合性基を示す。
L11は単結合、-C(=O)O-、または-O(C=O)-を示し、
L12は-C(=O)O-、-OC(=O)-または-CONR2-を示し、
Z11およびZ12はそれぞれ独立に、単結合、-O-、-NH-、-N(CH3)-、-S-、-C(=O)O-、-OC(=O)-、-OC(=O)O-、または-C(=O)NR12-を示し、
R12は水素原子もしくは-Sp12-Q12を示し、
Sp11およびSp12はそれぞれ独立に、単結合、Q11で置換されていてもよい炭素数1から12の直鎖もしくは分岐のアルキレン基、または、Q11で置換されていてもよい炭素数1から12の直鎖もしくは分岐のアルキレン基において、いずれか1つ以上の-CH2-を、-O-、-S-、-NH-、-N(Q11)-、または、-C(=O)-に置き換えて得られる連結基を示し、
Q11は水素原子、シクロアルキル基、シクロアルキル基において1つまたは2つ以上の-CH2-が-O-、-S-、-NH-、-N(CH3)-、-C(=O)-、-OC(=O)-、もしくは-C(=O)O-で置換された基、または式(Q-1)~式(Q-5)で表される基からなる群から選択される重合性基を示し、
Q12は水素原子または式(Q-1)~式(Q-5)で表される基からなる群から選択される重合性基を示し、
l11は0~2の整数を示し、
m11は1または2の整数を示し、
n11は1~3の整数を示し、
複数のR11、複数のL11、複数のL12、複数のl11、複数のZ11、複数のSp11、複数のQ11はそれぞれ互いに同じでも異なっていてもよい。また、式(I-11)で表される重合性化合物は、R11として、Q12が式(Q-1)~式(Q-5)で表される基からなる群から選択される重合性基である―Z12-Sp12-Q12を少なくとも1つ含む。Z11が-C(=O)O-もしくは-C(=O)NR12-であって、かつQ11が式(Q-1)~式(Q-5)で表される基からなる群から選択される重合性基である―Z11-Sp11-Q11、およびZ12が-C(=O)O-もしくは-C(=O)NR12-であって、かつQ12が式(Q-1)~式(Q-5)で表される基からなる群から選択される重合性基である―Z12-Sp12-Q12からなる群から選択される基を少なくとも1つ含むことも好ましい。
式(I-11)で表される重合性化合物として、特に好ましい化合物としては、L11が単結合、l11が1(ジシクロヘキシレン基)、かつQ11が式(Q-1)~式(Q-5)で表される基からなる群から選択される重合性基である化合物が挙げられる。
式(I-11)で表される重合性化合物として、もうひとつの特に好ましい化合物としては、m11が2、l11が0、かつ2つのR11がいずれも-Z12-Sp12-Q12を表し、Q12が式(Q-1)~式(Q-5)で表される基からなる群から選択される重合性基である化合物が挙げられる。
上記置換基はいずれもそれぞれ独立に、-CO-X21-Sp23-Q23、アルキル基、およびアルコキシ基からなる群から選択される1から4個の置換基であり、
m21は1または2の整数を示し、n21は0または1の整数を示し、
m21が2を示すときn21は0を示し、
m21が2を示すとき2つのZ21は同一であっても異なっていてもよく、
Z21およびZ22の少なくともいずれか一つは置換基を有していてもよいフェニレン基であり、
L21、L22、L23、L24はそれぞれ独立に、単結合、-CH2O-、-OCH2-、-(CH2)2OC(=O)-、-C(=O)O(CH2)2-、-C(=O)O-、-OC(=O)-、-OC(=O)O-、-CH=CH-C(=O)O-、および-OC(=O)-CH=CH-、からなる群から選択される連結基を示し、
X21は-O-、-S-、もしくは-N(Sp25-Q25)-を示すか、または、Q23およびSp23と共に環構造を形成する窒素原子を示し、
r21は1から4の整数を示し、
Sp21、Sp22、Sp23、Sp24、Sp25はそれぞれ独立に、単結合、炭素数1から20の直鎖もしくは分岐のアルキレン基、および炭素数1から20の直鎖もしくは分岐のアルキレン基において1つまたは2つ以上の-CH2-が-O-、-S-、-NH-、-N(CH3)-、-C(=O)-、-OC(=O)-、または-C(=O)O-で置換された基からなる群から選択される連結基を示し、
Q21およびQ22はそれぞれ独立に、式(Q-1)~式(Q-5)で表される基からなる群から選択されるいずれかの重合性基を示し、
Q23は水素原子、シクロアルキル基、シクロアルキル基において1つもしくは2つ以上の-CH2-が-O-、-S-、-NH-、-N(CH3)-、-C(=O)-、-OC(=O)-、もしくは-C(=O)O-で置換された基、または式(Q-1)~式(Q-5)で表される基からなる群から選択されるいずれかの重合性基、または、X21がQ23およびSp23と共に環構造を形成する窒素原子である場合において単結合を示し、
Q25は、水素原子、シクロアルキル基、シクロアルキル基において1つもしくは2つ以上の-CH2-が-O-、-S-、-NH-、-N(CH3)-、-C(=O)-、-OC(=O)-、もしくは-C(=O)O-で置換された基、または式(Q-1)~式(Q-5)で表される基からなる群から選択されるいずれかの重合性基を示し、Sp25が単結合のとき、Q25は水素原子ではない。
n31、n32はそれぞれ独立して0~4の整数を示し、
X31は単結合、-O-、-S-、もしくは-N(Sp34-Q34)-を示すか、または、Q33およびSp33と共に環構造を形成している窒素原子を示し、
Z31は、置換基を有していてもよいフェニレン基を示し、
Z32は、置換基を有していてもよいトランス-1,4-シクロヘキシレン基、または置換基を有していてもよいフェニレン基を示し、
上記置換基はいずれもそれぞれ独立に、アルキル基、およびアルコキシ基、-C(=O)-X31-Sp33-Q33からなる群から選択される1から4個の置換基であり、
m31は1または2の整数を示し、m32は0~2の整数を示し、
m31,m32が2を示すとき2つのZ31、Z32は同一であっても異なっていてもよく、
L31、L32はそれぞれ独立に、単結合、-CH2O-、-OCH2-、-(CH2)2OC(=O)-、-C(=O)O(CH2)2-、-C(=O)O-、-OC(=O)-、-OC(=O)O-、-CH=CH-C(=O)O-、および-OC(=O)-CH=CH-、からなる群から選択される連結基を示し、
Sp31、Sp32、Sp33、Sp34、はそれぞれ独立に、単結合、炭素数1から20の直鎖もしくは分岐のアルキレン基、および炭素数1から20の直鎖もしくは分岐のアルキレン基において1つまたは2つ以上の-CH2-が-O-、-S-、-NH-、-N(CH3)-、-C(=O)-、-OC(=O)-、または-C(=O)O-で置換された基からなる群から選択される連結基を示し、
Q31およびQ32はそれぞれ独立に、式(Q-1)~式(Q-5)で表される基からなる群から選択されるいずれかの重合性基を示し、
Q33、Q34はそれぞれ独立に、水素原子、シクロアルキル基、シクロアルキル基において1つもしくは2つ以上の-CH2-が-O-、-S-、-NH-、-N(CH3)-、-C(=O)-、-OC(=O)-、もしくは-C(=O)O-で置換された基、または式(Q-1)~式(Q-5)で表される基からなる群から選択されるいずれかの重合性基を示し、Q33はX31およびSp33と共に環構造を形成している場合において、単結合を示してもよく、Sp34が単結合のとき、Q34は水素原子ではない。
式(I-31)で表される重合性化合物として、特に好ましい化合物としては、Z32がフェニレン基である化合物およびm32が0である化合物が挙げられる。
Q3およびQ4はそれぞれ独立に、水素原子、シクロアルキル基、シクロアルキル基において1つもしくは2つ以上の-CH2-が-O-、-S-、-NH-、-N(CH3)-、-C(=O)-、-OC(=O)-、もしくは-C(=O)O-で置換された基、または式(Q-1)~式(Q-5)で表される基からなる群から選択されるいずれかの重合性基を示す。
L1、およびL2およびL3は単結合、-CH2O-、-OCH2-、-(CH2)2OC(=O)-、-C(=O)O(CH2)2-、-C(=O)O-、-OC(=O)-、-OC(=O)O-、-CH=CH-C(=O)O-、-OC(=O)-CH=CH-、からなる群から選択される連結基を示し、
n1、n2はそれぞれ独立して0から9の整数を示し、かつn1+n2は9以下である。
エステル化の方法としては、活性化したカルボン酸とフェノール(もしくはアルコール)誘導体とを塩基の存在下で作用させる方法や、カルボン酸とフェノール(もしくはアルコール)誘導体をカルボジイミドなどの縮合剤を用いて直接エステル化する方法が挙げられる。副生成物の観点からカルボン酸を活性化する方法がより好ましい。
カルボン酸の活性化方法としては、塩化チオニルやオキザリルクロリドなどによる酸クロリド化や、メシルクロリドと作用させ混合酸無水物を調整する方法が挙げられる。
本発明の重合性組成物は、Aで表される置換基を有していてもよいトランス-1,4-シクロヘキシレン基の数をmで割った数をmcとしたときに、0.5<mc<0.7を満たす重合性化合物(以下、「Gr.1の化合物」ということがある。)を少なくとも一種、および0.1<mc<0.3を満たす重合性化合物(以下、「Gr.2の化合物」ということがある。)を少なくとも一種含む。mcは、すなわち、以下の計算式で表される数である。
mc=(Aで表される置換基を有していてもよいトランス-1,4-シクロヘキシレン基の数)÷ m
Gr.2の化合物としては、mが4でありかつシクロヘキサン数が1である化合物、mが5でありかつシクロヘキサン数が1である化合物、mが6でありかつシクロヘキサン数が1である化合物、mが7でありかつシクロヘキサン数が2または1である化合物が好ましく、mが4でありかつシクロヘキサン数が1である化合物、mが5でありかつシクロヘキサン数が1である化合物がより好ましい。
mが3でありかつシクロヘキサン数が2である化合物とmが4でありかつシクロヘキサン数が1である化合物との組み合わせ;
mが5でありかつシクロヘキサン数が3である化合物とmが4でありかつシクロヘキサン数が1である化合物との組み合わせ;
mが3でありかつシクロヘキサン数が2である化合物とmが5でありかつシクロヘキサン数が1である化合物との組み合わせ;
mが5でありかつシクロヘキサン数が3である化合物とmが5でありかつシクロヘキサン数が1である化合物との組み合わせ。
より好ましい組み合わせとしては、以下が挙げられる:
mが5でありかつシクロヘキサン数が3である化合物とmが5でありかつシクロヘキサン数が1である化合物との組み合わせ。
重合性組成物は、式(I)で示される重合性化合物とともに、他の1種以上の液晶化合物を含有していてもよい。式(I)で示される重合性化合物は、他の液晶化合物との相溶性が高いので、他の液晶化合物を混合しても、不透明化等が生じず、透明性の高い膜を形成可能である。他の液晶化合物を併用可能であることから、種々の用途に適する種々の組成の組成物を提供できる。併用可能な他の液晶化合物の例には、棒状ネマチック液晶化合物が挙げられる。棒状ネマチック液晶化合物の例には、アゾメチン類、アゾキシ類、シアノビフェニル類、シアノフェニルエステル類、安息香酸エステル類、シクロヘキサンカルボン酸フェニルエステル類、シアノフェニルシクロヘキサン類、シアノ置換フェニルピリミジン類、アルコキシ置換フェニルピリミジン類、フェニルジオキサン類、トラン類およびアルケニルシクロヘキシルベンゾニトリル類が挙げられる。低分子液晶化合物だけではなく、高分子液晶化合物も用いることができる。
重合性棒状液晶化合物は、重合性基を棒状液晶化合物に導入することで得られる。重合性基の例には、不飽和重合性基、エポキシ基、およびアジリジニル基が含まれ、不飽和重合性基が好ましく、エチレン性不飽和重合性基が特に好ましい。重合性基は種々の方法で、棒状液晶化合物の分子中に導入できる。重合性棒状液晶化合物が有する重合性基の個数は、好ましくは1~6個、より好ましくは1~3個である。重合性棒状液晶化合物の例は、Makromol.Chem.,190巻、2255頁(1989年)、Advanced Materials 5巻、107頁(1993年)、米国特許第4683327号明細書、同5622648号明細書、同5770107号明細書、国際公開WO95/22586号公報、同95/24455号公報、同97/00600号公報、同98/23580号公報、同98/52905号公報、特開平1-272551号公報、同6-16616号公報、同7-110469号公報、同11-80081号公報、および特開2001-328973号公報などに記載の化合物が含まれる。2種類以上の重合性棒状液晶化合物を併用してもよい。2種類以上の重合性棒状液晶化合物を併用すると、配向温度を低下させることができる。
重合性組成物はキラル化合物を含んでいてもよい。キラル化合物を利用することにより、コレステリック液晶相を示す組成物として調製することができる。キラル化合物は液晶性であっても、非液晶性であってもよい。キラル化合物は、公知の種々のキラル剤(例えば、液晶デバイスハンドブック、第3章4-3項、TN、STN用カイラル剤、199頁、日本学術振興会第142委員会編、1989に記載)から選択することができる。キラル化合物は、一般に不斉炭素原子を含むが、不斉炭素原子を含まない軸性不斉化合物あるいは面性不斉化合物も用いることができる。軸性不斉化合物または面性不斉化合物の例には、ビナフチル、ヘリセン、パラシクロファンおよびこれらの誘導体が含まれる。キラル化合物(キラル剤)は、重合性基を有していてもよい。キラル化合物が重合性基を有するとともに、併用する棒状液晶化合物も重合性基を有する場合は、重合性キラル化合物と重合性棒状液晶化合物との重合反応により、棒状液晶化合物から誘導される繰り返し単位と、キラル化合物から誘導される繰り返し単位とを有するポリマーを形成することができる。したがって、重合性キラル化合物が有する重合性基は、重合性棒状液晶化合物、特に式(I)で示される重合性化合物が有する重合性基と、同種の基であることが好ましい。従って、キラル化合物の重合性基も、不飽和重合性基、エポキシ基またはアジリジニル基であることが好ましく、不飽和重合性基であることがさらに好ましく、エチレン性不飽和重合性基であることが特に好ましい。
重合性組成物は、重合開始剤を含有していることが好ましい。例えば、紫外線照射により硬化反応を進行させて硬化膜を形成する態様では、使用する重合開始剤は、紫外線照射によって重合反応を開始可能な光重合開始剤であることが好ましい。光重合開始剤の例には、α-カルボニル化合物(米国特許第2367661号、同2367670号の各明細書記載)、アシロインエーテル(米国特許第2448828号明細書記載)、α-炭化水素置換芳香族アシロイン化合物(米国特許第2722512号明細書記載)、多核キノン化合物(米国特許第3046127号、同2951758号の各明細書記載)、トリアリールイミダゾールダイマーとp-アミノフェニルケトンとの組み合わせ(米国特許第3549367号明細書記載)、アクリジンおよびフェナジン化合物(特開昭60-105667号公報、米国特許第4239850号明細書記載)およびオキサジアゾール化合物(米国特許第4212970号明細書記載)等が挙げられる。
重合性組成物中に、安定的または迅速な液晶相(例えば、コレステリック液晶相)の形成に寄与する配向制御剤を添加してもよい。配向制御剤の例には、含フッ素(メタ)アクリレート系ポリマー、WO2011/162291に記載の一般式(X1)~(X3)で表される化合物、および特開2013-47204の段落[0020]~[0031]に記載の化合物が含まれる。これらから選択される2種以上を含有していてもよい。これらの化合物は、層の空気界面において、液晶化合物の分子のチルト角を低減若しくは実質的に水平配向させることができる。尚、本明細書で「水平配向」とは、液晶分子長軸と膜面が平行であることをいうが、厳密に平行であることを要求するものではなく、本明細書では、水平面とのなす傾斜角が20度未満の配向を意味するものとする。液晶化合物が空気界面付近で水平配向する場合、配向欠陥が生じ難いため、可視光領域での透明性が高くなる。一方、液晶化合物の分子が大きなチルト角で配向すると、例えば、コレステリック液晶相とする場合は、その螺旋軸が膜面法線からずれるため、反射率が低下したり、フィンガープリントパターンが発生し、ヘイズの増大や回折性を示したりするため好ましくない。
配向制御剤として利用可能な含フッ素(メタ)アクリレート系ポリマーの例は、特開2007-272185号公報の[0018]~[0043]等に記載がある。
重合性組成物中における、配向制御剤の含有量は、式(I)の化合物の質量の0.01~10質量%が好ましく、0.01~5質量%がより好ましく、0.02~1質量%が特に好ましい。
重合性組成物は、硬化後の膜強度向上、耐久性向上のため、任意に架橋剤を含有していてもよい。架橋剤としては、紫外線、熱、湿気等で硬化するものが好適に使用できる。
架橋剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えばトリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラアクリレート等の多官能アクリレート化合物;グリシジル(メタ)アクリレート、エチレングリコールジグリシジルエーテル等のエポキシ化合物;2,2-ビスヒドロキシメチルブタノール-トリス[3-(1-アジリジニル)プロピオネート]、4,4-ビス(エチレンイミノカルボニルアミノ)ジフェニルメタン等のアジリジン化合物;ヘキサメチレンジイソシアネート、ビウレット型イソシアネート等のイソシアネート化合物;オキサゾリン基を側鎖に有するポリオキサゾリン化合物;ビニルトリメトキシシラン、N-(2-アミノエチル)3-アミノプロピルトリメトキシシラン等のアルコキシシラン化合物などが挙げられる。また、架橋剤の反応性に応じて公知の触媒を用いることができ、膜強度および耐久性向上に加えて生産性を向上させることができる。これらは、1種単独で使用してもよいし、2種以上を併用してもよい。
架橋剤の含有量は、重合性組成物の固形分質量に対して、3質量%~20質量%が好ましく、5質量%~15質量%がより好ましい。架橋剤の含有量が、3質量%以上であると、架橋密度向上の効果がより高く、20質量%以下であると、コレステリック液晶層の安定性がより高い。
重合性組成物は、1種または2種類以上の、酸化防止剤、紫外線吸収剤、増感剤、安定剤、可塑剤、連鎖移動剤、重合禁止剤、消泡剤、レべリング剤、増粘剤、難燃剤、界面活性物質、分散剤、染料、顔料等の色材、等の他の添加剤を含有していてもよい。
本発明の重合性組成物は、位相差膜、反射フィルム等の種々の光学フィルムの材料として有用であり、本発明の重合性組成物を用いて種々の光学フィルムを形成することができる。
[フィルムの製造方法]
光学フィルムの製造方法の一例は、
(i)基板等の表面に、重合性組成物を塗布して、液晶相(コレステリック液晶相等)の状態にすること、
(ii)重合性組成物の硬化反応を進行させ、液晶相を固定して硬化膜を形成すること、
を少なくとも含む製造方法である。
(i)および(ii)の工程を、複数回繰り返して、複数の上記硬化膜が積層されたフィルムを作製することもできる。また、複数の硬化膜同士を接着剤により貼合して、複数の硬化膜が積層されたフィルムを作製することもできる。
一例では、紫外線を照射して、硬化反応を進行させる。紫外線照射には、紫外線ランプ等の光源が利用される。この工程では、紫外線を照射することによって、組成物の硬化反応が進行し、液晶相(コレステリック液晶相等)が固定されて、硬化膜が形成される。
紫外線の照射エネルギー量については特に制限はないが、一般的には、0.1J/cm2~0.8J/cm2程度が好ましい。また、塗膜に紫外線を照射する時間については特に制限はないが、硬化膜の充分な強度および生産性の双方の観点から決定すればよい。
なお、フィルムにおいては、液晶相の光学的性質が層中において保持されていれば十分であり、最終的に硬化膜中の組成物がもはや液晶性を示す必要はない。例えば、組成物が、硬化反応により高分子量化して、もはや液晶性を失っていてもよい。
フィルムは、基板を有していてもよい。当該基板は自己支持性があり、上記硬化膜を支持するものであれば、材料および光学的特性についてなんら限定はない。ガラス板、石英板、およびポリマーフィルム等から選択することができる。用途によっては、紫外光に対する高い透明性を有するものを用いてもよい。可視光に対する透過性が高いポリマーフィルムとしては、液晶表示装置等の表示装置の部材として用いられる種々の光学フィルム用のポリマーフィルムが挙げられる。基板としては、例えばポリエチレンテレフタレート(PET)、ポリブチレンテレフタレート、ポリエチレンナフタレート(PEN)等のポリエステルフィルム;ポリカーボネート(PC)フィルム、ポリメチルメタクリレートフィルム;ポリエチレン、ポリプロピレン等のポリオレフィンフィルム;ポリイミドフィルム、トリアセチルセルロース(TAC)フィルム、などが挙げられる。ポリエチレンテレフタレートフィルム、トリアセチルセルロースフィルムが好ましい。
フィルムは、基板と硬化膜との間に、配向層を有していてもよい。配向層は、液晶化合物の配向方向をより精密に規定する機能を有する。配向層は、有機化合物(好ましくはポリマー)のラビング処理、無機化合物の斜方蒸着、マイクログルーブを有する層の形成等の手段で設けることができる。さらには、電場の付与、磁場の付与、或いは光照射により配向機能が生じる配向層も知られている。配向層は、ポリマーの膜の表面に、ラビング処理により形成することが好ましい。
複数の硬化膜同士を接着剤により貼合する場合、硬化膜の間には接着層が設けられる。接着層は接着剤から形成されるものであればよい。
接着剤としては硬化方式の観点からホットメルトタイプ、熱硬化タイプ、光硬化タイプ、反応硬化タイプ、硬化の不要な感圧接着タイプがあり、それぞれ素材としてアクリレート系、ウレタン系、ウレタンアクリレート系、エポキシ系、エポキシアクリレート系、ポリオレフィン系、変性オレフィン系、ポリプロピレン系、エチレンビニルアルコール系、塩化ビニル系、クロロプレンゴム系、シアノアクリレート系、ポリアミド系、ポリイミド系、ポリスチレン系、ポリビニルブチラール系などの化合物を使用することができる。作業性、生産性の観点から、硬化方式として光硬化タイプが好ましく、光学的な透明性、耐熱性の観点から、素材はアクリレート系、ウレタンアクリレート系、エポキシアクリレート系などを使用することが好ましい。
接着層の膜厚は0.5~10μm、好ましくは1~5μmであればよい。投映像表示用ハーフミラーとして用いられる場合、色ムラ等を軽減するため均一な膜厚で設けられることが好ましい。
重合性組成物を用いて形成されるフィルムの例としては、重合性組成物の、液晶相の配向(例えば、水平配向、垂直配向、ハイブリッド配向等)を固定したフィルムが挙げられる。このようなフィルムは通常、光学異方性を示し、液晶表示装置等の光学補償フィルム等として利用される。
別の例としては、重合性組成物のコレステリック液晶相を固定した層を含むフィルムであって、所定の波長域の光に対して選択反射特性を示すフィルムがあげられる。
コレステリック液晶相では、液晶分子は螺旋状に配列している。コレステリック液晶相を固定した層(以下「コレステリック液晶層」または「液晶層」ということがある。)は選択反射波長域において、右円偏光または左円偏光のいずれか一方を選択的に反射させ、他方のセンスの円偏光を透過させる円偏光選択反射層として機能する。コレステリック液晶層を1層または2層以上含むフィルムは、様々な用途に用いることができる。コレステリック液晶層を2層以上含むフィルムにおいて、各コレステリック液晶層が反射する円偏光のセンスは用途に応じて同じでも逆であってもよい。また、各コレステリック液晶層の後述の選択反射の中心波長も用途に応じて同じでも異なっていてもよい。
また、光学フィルムは、光学素子の構成要素である、偏光素子、反射膜、反射防止膜、視野角補償膜、ホログラフィー、配向膜等、種々の用途に利用することができる。
以下特に好ましい用途である投映像表示用部材としての用途について説明する。
コレステリック液晶層の上記の機能により、投射光のうち選択反射を示す波長において、いずれか一方のセンスの円偏光を反射させて、投映像を形成することができる。投映像は投映像表示用部材表面で表示され、そのように視認されるものであってもよく、観察者から見て投映像表示用部材の先に浮かび上がって見える虚像であってもよい。
基材の例としては、無機ガラスや高分子樹脂(アクリル樹脂(ポリメチル(メタ)アクリレートなどのアクリル酸エステル類など)、ポリカーボネート、シクロペンタジエン系ポリオレフィンやノルボルネン系ポリオレフィンなどの環状ポリオレフィン、ポリプロピレンなどのポリオレフィン類、ポリスチレンなどの芳香族ビニルポリマー類、ポリアリレート、セルロースアシレート等)が挙げられる。
構成例としては、下側から順に、高屈折率層/低屈折率層の2層のものや、屈折率の異なる3層を、中屈折率層(下層よりも屈折率が高く、高屈折率層よりも屈折率の低い層)/高屈折率層/低屈折率層の順に積層されているもの等があり、更に多くの反射防止層を積層するものも提案されている。中でも、耐久性、光学特性、コストや生産性等から、ハードコート層上に、中屈折率層/高屈折率層/低屈折率層の順に有することが好ましく、例えば、特開平8-122504号公報、特開平8-110401号公報、特開平10-300902号公報、特開2002-243906号公報、特開2000-111706号公報等に記載の構成が挙げられる。また、膜厚変動に対するロバスト性に優れる3層構成の反射防止フィルムは特開2008-262187号公報に記載されている。上記3層構成の反射防止フィルムは、画像表示装置の表面に設置した場合、反射率の平均値を0.5%以下とすることができ、映り込みを著しく低減することができ、立体感に優れる画像を得ることができる。また、各層に他の機能を付与させてもよく、例えば、防汚性の低屈折率層、帯電防止性の高屈折率層、帯電防止性のハードコート層、防眩性のハードコート層としたもの(例、特開平10-206603号公報、特開2002-243906号公報、特開2007-264113号公報等)等が挙げられる。
無機材料で形成される多層膜としては、基板側からZrO2層とSiO2層の合計光学的膜厚がλ/4、ZrO2層の光学的膜厚がλ/4、最表層のSiO2層の光学的膜厚がλ/4の、高屈折率材料層と低屈折率材料層とを交互に成膜する積層構造が例示される。ここで、λは設計波長であり、通常520nmが用いられる。最表層は、屈折率が低く、かつ反射防止層に機械的強度を付与できることからSiO2とすることが好ましい。
無機材料で反射防止層を形成する場合、成膜方法は例えば真空蒸着法、イオンプレーティング法、スパッタリング法、CVD法、飽和溶液中での化学反応により析出させる方法等を採用することができる。
低屈折率層は、屈折率が1.30~1.51であることが好ましい。1.30~1.46であることが好ましく、1.32~1.38が更に好ましい。
高屈折率層の屈折率は、1.65~2.20であることが好ましく、1.70~1.80であることがより好ましい。中屈折率層の屈折率は、低屈折率層の屈折率と高屈折率層の屈折率との間の値となるように調整される。中屈折率層の屈折率は、1.55~1.65であることが好ましく、1.58~1.63であることが更に好ましい。
反射防止層の膜厚は、特に限定されるものではないが、0.1~10μm、1~5μm、2~4μm程度であればよい。
1.25(t,6H),1.6-1.7(m,4H),2.2-2.4(m,4H),2.5-2.6(m,2H),3.55-3.65(m,4H),3.8-3.85(m,4H),4.45-4.5(m,4H),7.0(d,2H),7.2(dd,2H),7.6(d,2H)
1.2(t,6H),1.4-1.8(m,18H),2.1-2.2(m,4H),2.2-2.4(m,12H),2.5-2.7(m,4H),3.5(q,4H),3.7-3.8(m,4H),4.1-4.3(m,8H),4.4-4.5(m,4H),5.8(dd,2H),6.1(dd,2H),6.4(dd,2H),7.1(d,2H),7.3(dd,2H),7.7(d,2H)
メタンスルホニルクロリド(1.62mL)のテトラヒドロフラン(10mL)溶液に、BHT(60mg)を加え、内温を-5℃まで冷却した。別途調製した4-(4-アクリロイルオキシブチルオキシ)安息香酸(5.5g)とジイソプロピルエチルアミン(3.7mL)のテトラヒドロフラン(8mL)溶液を、内部温度が0℃以上に上昇しないように滴下した。-5℃で1時間撹拌した後、N-メチルイミダゾールを少量加え、フェノール誘導体B(5.2g)を加え、テトラヒドロフランを15mL追加したのち、トリエチルアミン(3.1mL)を滴下し、その後、室温で3時間攪拌した。水(13mL)を加えて反応を停止し、酢酸エチルを加えて水層を除去し、希塩酸、食塩水の順に洗浄した。乾燥剤を加えてろ別したのち、水、メタノールを加えて生じた結晶をろ過することで、化合物2-3を8.4g得た。
1H-NMR(溶媒:CDCl3)δ(ppm):
1.2(t,6H),1.65-1.8(m,4H),1.85-1.95(m,8H),2.3-2.4(m,4H),2.6-2.7(m,2H),3.4(q,4H),3.5-3.6(m,4H),4.1(m,4H),4.15-4.25(m,8H),5.85(dd,2H),6.1(dd,2H),6.4(dd,2H),7.0(d,4H),7.25(d,2H),7.35(dd,2H),7.8(d,2H),8.15(d,4H)
1.5-1.8(m,8H),2.1-2.4(s+m,3H+10H),2.5-2.7(m,2H),4.1-4.3(m,8H),5.8(dd,2H),6.1(dd,2H),6.4(dd,2H),6.85-7.0(m,3H)
0.8-1.3(m,14H),1.5-1.6(m,2H),1.7-1.9(m,10H),2.1-2.2(m,2H),2.4-2.5(m,1H),4.2(t,2H),4.4(t,2H),5.8(dd,1H),6.1(dd,1H),6.4(dd,1H),7.1(d,2H),8.1(d,2H)
0.8-1.3(m,14H),1.5-1.6(m,2H),1.7-1.9(m,10H),2.1-2.2(m,2H),2.5-2.6(m,1H),3.9(s,3H),4.2(t,2H),4.4(t,2H),5.8(dd,1H),6.1(dd,1H),6.4(dd,1H),7.0(d,1H),7.6-7.7(m,2H)
1.45-1.8(m,18H),2.1-2.2(m,4H),2.25-2.4(m,12H),2.5-2.7(m,4H),4.1-4.35(m,8H),4.4-4.55(m,8H),5.8(dd,4H),6.1(dd,4H),6.4(dd,4H),7.1(d,2H),7.3(dd,2H),7.7(d,2H)
1.3-1.6(m,4H),2.0-2.2(m,4H),2.2-2.4(m,2H),4.3-4.4(m,4H),5.9(dd,1H),6.1(dd,1H),6.4(dd,1H)
1H-NMR(溶媒:CDCl3)δ(ppm):
1.2(t,6H),1.5-1.7(m,12H),2.1-2.2(m,4H),2.2-2.5(m,10H),2.5-2.7(m,4H),3.5(q,4H),3.7-3.8(m,4H),4.3-4.4(m,12H),5.9(dd,2H),6.1(dd,2H),6.4(dd,2H),7.1(d,2H),7.3(dd,2H),7.7(d,2H)
1.6-1.7(m,4H),2.2-2.4(m,4H),2.5-2.6(m,2H),3.9(s,6H),7.0(d,2H),7.2(dd,2H),7.6(d,2H)
1.2-1.3(m,6H),1.5-1.7(m,12H),2.1-2.2(m,4H),2.2-2.4(m,10H),2.6-2.7(m,4H),3.9(s,6H),4.1-4.3(m,4H),5.2-5.3(m,2H),5.8-5.9(m,2H),6.1-6.2(m,2H),6.4-6.5(m,2H),7.1(d,2H),7.3(dd,2H),7.7(d,2H)
1H-NMR(溶媒:CDCl3)δ(ppm):
1.45-1.8(m,18H),1.95(s,6H),2.1-2.2(m,4H),2.25-2.4(m,12H),2.5-2.7(m,4H),4.1-4.35(m,8H),4.4-4.55(m,8H),5.6(s,2H),5.8(dd,2H),6.1-6.2(m,4H),6.4(dd,2H),7.1(d,2H),7.3(dd,2H),7.7(d,2H)
1H-NMR(溶媒:CDCl3)δ(ppm):
1.45-1.8(m,18H),2.1-2.2(m,4H),2.25-2.4(m,12H),2.5-2.7(m,4H),4.1-4.35(m,4H),4.4-4.55(m,4H),4.6-4.7(m,4H),5.2-5.45(m,4H),5.8-6.0(m,4H),6.1(dd,2H),6.4(d,2H),7.1(d,2H),7.3(dd,2H),7.7(d,2H)
1H-NMR(溶媒:CDCl3)δ(ppm):
1.65-1.8(m,4H),1.9-1.95(m,8H),2.3-2.4(m,4H),2.6-2.7(m,2H),4.05-4.15(m,4H),4.2-4.3(m,8H),4.4-4.45(m,4H),5.85(dd,4H),6.0-6.2(m,4H),6.4(dd,4H),6.95(d,4H),7.25(d,2H),7.35(dd,2H),7.8(d,2H),8.15(d,4H)
1H-NMR(溶媒:CDCl3)δ(ppm):
1.65-1.8(m,4H),1.9-2.0(m,14H),2.3-2.4(m,4H),2.6-2.7(m,2H),4.05-4.15(m,4H),4.2-4.35(m,8H),4.4-4.45(m,4H),5.6(s,2H),5.85(dd,2H),6.1-6.2(m,4H),6.4(d,2H),6.95(d,4H),7.25(d,2H),7.35(dd,2H),7.8(d,2H),8.15(d,4H)
1H-NMR(溶媒:CDCl3)δ(ppm):
1.65-1.8(m,4H),1.9-1.95(m,8H),2.3-2.4(m,4H),2.6-2.7(m,2H),4.05-4.15(m,4H),4.2-4.3(m,4H),4.6-4.7(m,4H),5.2-5.45(m,4H),5.8--6.2(m,6H),6.4(d,2H),6.95(d,4H),7.25(d,2H),7.35(dd,2H),7.8(d,2H),8.15(d,4H)
1.15(t,3H),1.2-1.25(m,6H),1.6-1.75(m,6H),1.9-2.0(m,4H),2.3-2.35(m,4H),2.6-2.7(m,2H),2.75-2.85(m,2H),2.95-3.05(m,2H),3.4(q,2H),3.5-3.6(m,4H),3.75(q,2H),4.1-4.35(m,8H),4.4-4.45(m,2H),5.2-5.3(m,1H),5.85(dd,2H),6.1-6.2(m,2H),6.4(dd,2H),6.95(d,2H),7.1(d,1H),7.2-7.35(m,3H),7.75(d,2H),8.15(d,2H)
[重合性組成物の調製]
下記組成の重合性組成物塗布液を調製した。
化合物1-3 80質量部
化合物2-3 20質量部
クロロホルム 900質量部
洗浄したガラス基板上に日産化学社製ポリイミド配向膜SE-130をスピンコート法により塗布し、乾燥後に250℃で1時間焼成した。これをラビング処理して配向膜付き基板を作製した。この基板の配向膜のラビング処理面上に、上記重合性組成物塗布液をスピンコート法により室温で塗布し、80℃で1分加熱したのち、室温で10分静置し、実施例1の塗布サンプルを作製した。
上記重合性組成物塗布液の重合性化合物(化合物1-3および化合物2-3)につき、下記表に示すように、変更した以外は実施例1と同様にして、実施例2~7および比較例1~5の塗布サンプルを作製した。
実施例1~7および比較例1~5の塗布サンプルにつき、ヘイズメーター(日本電飾工業製、NDH2000)により、静置後の塗布サンプルのヘイズを測定した。実施例1の塗布サンプルのヘイズは0.35であった。各サンプルの評価結果をヘイズが1以上でC、1未満でAとして表2に示す。
<位相差膜の作製>
上記実施例で合成した例示化合物を用いて、下記の組成の液晶性組成物塗布液(1)を調製した。
化合物1-3 80質量部
化合物2-3 20質量部
空気界面配向剤(1) 0.1質量部
重合開始剤IRGACURE819(BASF社製) 2質量部
溶媒 クロロホルム 900質量部
作製した位相差膜をAXOMETRIX社製のAxoScanを用いてTip-Tiltモードで測定した結果、この装置が算出した液晶の平均傾斜角度は2.8度であり、A-plate型の位相差膜が形成できていることを確認した。また、この装置を用いて測定した位相差(Re)は135nmであった。
また、非接触三次元表面形状計測システム(ニコン社製BW-A501)を用いて測定した膜厚(d)は2.2nmであり、位相差(Re)と膜厚(d)の比から算出した波長550nmにおけるΔn(Re/d)は0.061であった。
上記実施例で合成した例示化合物を用いて、下記の組成の液晶性組成物塗布液(8)を調製した。
化合物1-33、1-34、1-35の混合物 80質量部
化合物2-3 20質量部
空気界面配向剤(1) 0.1質量部
重合開始剤IRGACURE819(BASF社製) 2質量部
溶媒 クロロホルム 900質量部
また、非接触三次元表面形状計測システム(ニコン社製BW-A501)を用いて測定した膜厚は2.0nmであり、位相差と膜厚の比から算出した波長550nmにおけるΔnは0.071であった。
[選択反射フィルム1]
上記で合成した例示化合物を用いて、下記の組成の重合性組成物塗布液(1)を調製した。
重合性組成物塗布液(1)
化合物1-3 80質量部
化合物2-3 20質量部
キラル剤 LC-756(BASF社製) 4.6質量部
空気界面配向剤(1) 0.07質量部
重合開始剤IRGACURE819(BASF社製) 3質量部
溶媒 メチルエチルケトン 250質量部
溶媒 シクロヘキサノン 50質量部
得られた透過スペクトルを図1に示す。
重合性組成物塗布液(1)と同様に下記の組成の重合性組成物塗布液(2)を調製した。
重合性組成物塗布液(2)
化合物1-3 80質量部
化合物2-3 20質量部
キラル剤 LC-756(BASF社製) 5.3質量部
空気界面配向剤(1) 0.07質量部
重合開始剤IRGACURE819(BASF社製) 3質量部
溶媒 メチルエチルケトン 250質量部
溶媒 シクロヘキサノン 50質量部
重合性組成物塗布液(1)と同様に下記の組成の重合性組成物塗布液(3)を調製した。
重合性組成物塗布液(3)
化合物1-3 80質量部
化合物2-3 20質量部
キラル剤 LC-756(BASF社製) 4.0質量部
空気界面配向剤(1) 0.07質量部
重合開始剤IRGACURE819(BASF社製) 3質量部
溶媒 メチルエチルケトン 250質量部
溶媒 シクロヘキサノン 50質量部
上記で合成した例示化合物を用いて、下記の組成の重合性組成物塗布液(7)を調製した。
重合性組成物塗布液(7)
化合物1-26 55質量部
化合物2-8 30質量部
化合物(M―1) 13質量部
化合物(M-2) 2質量部
重合開始剤IRGACURE819(BASF社製) 3質量部
キラル剤LC756(BASF社製) 4.4質量部
配向剤(2) 0.01質量部
配向剤(3) 0.02質量部
酢酸メチル 260質量部
シクロヘキサノン 65質量部
このフィルムにつき。島津社製の分光光度計UV-3100PCで透過スペクトルを測定したところ544nmに中心を持つ選択反射ピークがあり、その半値幅が33nmであった。選択反射波長域の半値幅と選択反射の中心波長の比(Δλ/λ)は0.062であった。
上記で合成した例示化合物を用いて、下記の組成の重合性組成物塗布液(8)を調製した。
重合性組成物塗布液(8)
化合物1-28 55質量部
化合物2-34 30質量部
化合物(M―1) 13質量部
化合物(M-2) 2質量部
重合開始剤IRGACURE819(BASF社製) 3質量部
キラル剤LC756(BASF社製) 4.4質量部
配向剤(2) 0.01質量部
配向剤(3) 0.02質量部
酢酸メチル 260質量部
シクロヘキサノン 65質量部
このフィルムにつき、島津社製の分光光度計UV-3100PCで透過スペクトルを測定したところ570nmに中心を持つ選択反射ピークがあり、その半値幅が35nmであった。選択反射波長域の半値幅と選択反射の中心波長の比(Δλ/λ)は0.061であった。
上記で合成した例示化合物を用いて、下記の組成の重合性組成物塗布液(9)を調製した。
重合性組成物塗布液(9)
化合物1-36 55質量部
化合物2-35 30質量部
化合物(M―1) 13質量部
化合物(M-2) 2質量部
重合開始剤IRGACURE819(BASF社製) 3質量部
キラル剤LC756(BASF社製) 4.4質量部
配向剤(2) 0.01質量部
配向剤(3) 0.02質量部
酢酸メチル 260質量部
シクロヘキサノン 65質量部
このフィルムにつき、島津社製の分光光度計UV-3100PCで透過スペクトルを測定したところ588nmに中心を持つ選択反射ピークがあり、その半値幅が40nmであった。選択反射波長域の半値幅と選択反射の中心波長の比(Δλ/λ)は0.068であった。
選択反射フィルム1にて液晶層を形成した条件と同じ条件を用いて、重合性組成物塗布液(1)の液晶層を選択反射フィルム2の液晶層の上に形成し、積層フィルム1を得た。次に、選択反射フィルム3において液晶層を形成した条件と同じ条件を用いて、重合性組成物塗布液(3)の液晶層を積層フィルム1の液晶層の上に形成し、積層フィルム2を得た。積層フィルム1,2の表面はハジキ欠陥がなく、均一であった。積層フィルム2を島津社製の分光光度計UV-3100PCで透過スペクトルを測定したところ464nm、563nm、640nmにそれぞれ中心を持つ選択反射ピークがあり、70%以上の高い可視光透過率を有することがわかった。得られた透過スペクトルを図2に示す。
上記で合成した例示化合物を用いて、下記の組成の重合性組成物塗布液(4)を調製した。
重合性組成物塗布液(4)
化合物1-3 55質量部
化合物2-3 30質量部
化合物(M-1) 13質量部
化合物(M-2) 2質量部
重合開始剤IRGACURE819(BASF社製) 3質量部
キラル剤LC756(BASF社製) 3.7質量部
配向剤(2) 0.01質量部
配向剤(3) 0.02質量部
酢酸メチル 260質量部
シクロヘキサノン 65質量部
このフィルムを島津社製の分光光度計UV-3100PCで透過スペクトルを測定したところ672nmに中心を持つ選択反射ピークがあり、その半値幅が40nmであった。選択反射波長域の半値幅と選択反射の中心波長の比(Δλ/λ)は0.059であった。
重合性組成物塗布液(5)
化合物1-3 55質量部
化合物2-3 30質量部
化合物(M-1) 13質量部
化合物(M-2) 2質量部
重合開始剤IRGACURE819(BASF社製) 3質量部
キラル剤LC756(BASF社製) 4.7質量部
配向剤(2) 0.005質量部
配向剤(3) 0.01質量部
酢酸メチル 260質量部
シクロヘキサノン 65質量部
化合物1-3 55質量部
化合物2-3 30質量部
化合物(M-1) 13質量部
化合物(M-2) 2質量部
重合開始剤IRGACURE819(BASF社製) 3質量部
キラル剤LC756(BASF社製) 5.4質量部
配向剤(2) 0.005質量部
配向剤(3) 0.01質量部
酢酸メチル 260質量部
シクロヘキサノン 65質量部
さらに、積層フィルム3の液晶層の表面に重合性組成物塗布液(6) を乾燥後の乾膜の厚みが3.9μm(下層との合計膜厚が13.1μm)となるように室温にてワイヤーバーを用いて塗布した。塗布層を室温にて30秒間乾燥させた後、85℃の雰囲気で1分間加熱し、窒素ガス雰囲気下60℃で高圧水銀ランプを用いて照射量が300mJ/cm2となるようUV照射し積層フィルム4を得た。
島津社製の分光光度計UV-3100PCにてこの積層フィルム4の透過スペクトルを測定したところ680nmと538nmと466nmに反射ピークがあり、75%以上の高い可視光透過率を有することがわかった。得られた透過スペクトルを図3に示す。
積層フィルム2の液晶層側に、DIC株式会社製UV硬化型接着剤Exp.U12034-6を、乾燥後の乾膜の厚みが5μmになるように室温にてワイヤーバーを用いて塗布した。偏光板を直交させてその間に設置した状態で、面内に色ムラが視認できない10cm角の面内で最大5nmの位相差の厚さ5mmのメタアクリル製の透明基材(三菱レイヨン社製「アクリライトL」)表面と、積層フィルム2の接着剤塗布面を貼りあわせてUV照射し、積層フィルム2のPETフィルムを剥離することで、アクリル基材を有する投映像表示用ハーフミラー1を作製した。
Claims (18)
- 式(I):
Aは、置換基を有していてもよいフェニレン基または置換基を有していてもよいトランス-1,4-シクロヘキシレン基を示し、
Lは単結合、-CH2O-、-OCH2-、-(CH2)2OC(=O)-、-C(=O)O(CH2)2-、-C(=O)O-、-OC(=O)-、-OC(=O)O-、-CH=CH-C(=O)O-、および-OC(=O)-CH=CH-からなる群から選択される連結基を示し、
mは3~12の整数を示し、
Sp1およびSp2はそれぞれ独立に、単結合、炭素数1から20の直鎖もしくは分岐のアルキレン基、および炭素数1から20の直鎖もしくは分岐のアルキレン基において1つまたは2つ以上の-CH2-が-O-、-S-、-NH-、-N(CH3)-、-C(=O)-、-OC(=O)-、または-C(=O)O-で置換された基からなる群から選択される連結基を示し、
Q1およびQ2はそれぞれ独立に、水素原子または以下の式(Q-1)~式(Q-5)で表される基からなる群から選択される重合性基を示し、ただしQ1およびQ2のいずれか一方は重合性基を示す;
Aで表される置換基を有していてもよいトランス-1,4-シクロヘキシレン基の数をmで割った数をmcとしたとき、前記重合性化合物の少なくとも1種が0.5<mc<0.7を満たし、かつ、前記重合性化合物の他の少なくとも1種が0.1<mc<0.3を満たす重合性組成物。 - 式(I)において、フェニレン基およびトランス-1,4-シクロヘキシレン基が有していてもよい前記置換基が、アルキル基、アルコキシ基、および-C(=O)-X3-Sp3-Q3で表される基からなる群から選択され、ここで、X3が単結合、-O-、-S-、もしくは-N(Sp4-Q4)-を示すか、または、Q3およびSp3と共に環構造を形成している窒素原子を示し、Sp3およびSp4はそれぞれ独立に、単結合、炭素数1から20の直鎖もしくは分岐のアルキレン基、および炭素数1から20の直鎖もしくは分岐のアルキレン基において1つまたは2つ以上の-CH2-が-O-、-S-、-NH-、-N(CH3)-、-C(=O)-、-OC(=O)-、または-C(=O)O-で置換された基からなる群から選択される連結基を示し、Q3およびQ4はそれぞれ独立に、水素原子、シクロアルキル基、シクロアルキル基において1つもしくは2つ以上の-CH2-が-O-、-S-、-NH-、-N(CH3)-、-C(=O)-、-OC(=O)-、もしくは-C(=O)O-で置換された基、または式(Q-1)~式(Q-5)で表される基からなる群から選択されるいずれかの重合性基を示す請求項1に記載の重合性組成物。
- 式(I)において、mが3~5の整数である請求項1または2に記載の重合性組成物。
- 式(I)で表される化合物が、以下の式(II)で表される部分構造を有する請求項1~3のいずれか一項に記載の重合性組成物;
- R1およびR2がそれぞれ独立に、-C(=O)-X3-Sp3-Q3であり、X3が-O-である請求項4に記載の重合性組成物。
- R1およびR2が同一である請求項4または5に記載の重合性組成物。
- 架橋剤を含有する請求項1~7のいずれか一項に記載の重合性組成物。
- 重合開始剤を含有する請求項1~8のいずれか一項に記載の重合性組成物。
- キラル化合物を含有する請求項1~9のいずれか一項に記載の重合性組成物。
- 請求項1~10のいずれか1項に記載の重合性組成物の硬化により得られる層を含むフィルム。
- 請求項1~10のいずれか1項に記載の重合性組成物の硬化により得られる層を2層以上含むフィルム。
- 選択反射を示し、
前記選択反射の波長域の半値幅Δλと前記選択反射の中心波長λとの比であるΔλ/λが0.09以下である請求項11または12に記載のフィルム。 - 可視光を反射する請求項11~13のいずれか一項に記載のフィルム。
- 請求項1~10のいずれか一項に記載の重合性組成物から形成される層を少なくとも3層含むフィルムであって、
前記3層が、赤色光波長域に選択反射の中心波長を有するコレステリック液晶相を固定した層、緑色光波長域に選択反射の中心波長を有するコレステリック液晶相を固定した層、および青色光波長域に選択反射の中心波長を有するコレステリック液晶相を固定した層であるフィルム。 - 請求項15に記載のフィルムを含む投映像表示用ハーフミラー。
- 無機ガラスまたはアクリル樹脂である基材を含む請求項16に記載の投映像表示用ハーフミラー。
- 最表面に反射防止層を含む、請求項16または17に記載の投映像表示用ハーフミラー。
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CN107075034A (zh) | 2017-08-18 |
US10323120B2 (en) | 2019-06-18 |
JPWO2016047648A1 (ja) | 2017-06-22 |
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US20170190821A1 (en) | 2017-07-06 |
EP3199561A4 (en) | 2017-08-30 |
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CN107075034B (zh) | 2019-07-12 |
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