WO2016143884A1 - Composition polymérisable, film, et demi-miroir pour l'affichage d'images projetées - Google Patents

Composition polymérisable, film, et demi-miroir pour l'affichage d'images projetées Download PDF

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Publication number
WO2016143884A1
WO2016143884A1 PCT/JP2016/057697 JP2016057697W WO2016143884A1 WO 2016143884 A1 WO2016143884 A1 WO 2016143884A1 JP 2016057697 W JP2016057697 W JP 2016057697W WO 2016143884 A1 WO2016143884 A1 WO 2016143884A1
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group
liquid crystal
polymerizable
polymerizable composition
film
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PCT/JP2016/057697
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English (en)
Japanese (ja)
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峻也 加藤
昭裕 安西
裕樹 斉木
吉川　将
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富士フイルム株式会社
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • G02B5/0816—Multilayer mirrors, i.e. having two or more reflecting layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters

Definitions

  • the present invention relates to a polymerizable composition.
  • the present invention particularly relates to a polymerizable composition containing a polymerizable liquid crystal compound having a partial structure in which a cyclohexylene group and a phenylene group are ester-bonded.
  • the present invention also relates to a film produced using the polymerizable composition and a half mirror for displaying projected images produced using the polymerizable composition.
  • Various optical films such as a retardation film and a reflective film can be prepared using a polymerizable composition containing a polymerizable liquid crystal compound having liquid crystallinity.
  • a retardation film produced using a polymerizable liquid crystal compound having a partial structure in which a cyclohexylene group and a phenylene group having a hydrazone structure substituent are ester-bonded is ideal for exhibiting broadband properties. It is described that it showed wavelength dispersion.
  • a polymerizable liquid crystal compound having a partial structure in which a cyclohexylene group and a phenylene group are ester-bonded is useful for producing a retardation film as described in Patent Document 1.
  • some polymerizable liquid crystal compounds having a cyclohexylene group and a phenylene group are found to have low birefringence, and a narrow-band reflective film is provided by forming a cholesteric liquid crystal phase. I know I can do it.
  • a cured film was produced using a polymerizable composition containing the polymerizable liquid crystal compound in the course of the study by the present inventors, a problem of yellowing occurred in a humidity resistance test.
  • an object of the present invention is to provide a polymerizable composition containing a polymerizable liquid crystal compound having a partial structure in which a cyclohexylene group and a phenylene group are ester-bonded and hardly yellowing after curing. It is to be.
  • Another object of the present invention is to provide a film that hardly causes yellowing and a half mirror for displaying projected images.
  • the inventors of the present invention have made various studies to solve the above problems, and using an acylphosphine oxide compound as a polymerization initiator used in combination with a polymerizable liquid crystal compound, and adding an amine, the yellowing can be prevented. I found it difficult to occur. And based on this knowledge, further examination was repeated and the present invention was completed. That is, the present invention provides the following ⁇ 1> to ⁇ 17>.
  • a polymerizable composition comprising a polymerizable liquid crystal compound represented by formula (I), an acylphosphine oxide compound, and an amine;
  • a 1 and A 2 each independently represent a phenylene group which may have a substituent or a trans-1,4-cyclohexylene group which may have a substituent
  • L 1 and L 2 are each independently a single bond, —CH 2 O—, —OCH 2 —, — (CH 2 ) 2 OC ( ⁇ O) —, —C ( ⁇ O) O (CH 2 ) 2 — , —C ( ⁇ O) O—, —OC ( ⁇ O) —, —OC ( ⁇ O) O—, —CH ⁇ CH—C ( ⁇ O) O—, and —OC ( ⁇ O) —CH ⁇
  • a linking group selected from the group consisting of CH-, Sp 1 and Sp 2 are each independently one or more of a single bond, a linear or branched alkylene group having 1
  • —CH 2 — is —O—, —S—, —NH—, —N (CH 3 ) —, —C ( ⁇ O) —, —OC ( ⁇ O) —, or —C ( ⁇ O) O—.
  • a linking group selected from the group consisting of groups substituted with Q 1 and Q 2 are each independently a hydrogen atom or Formulas Q-1 to Q-5:
  • X 3 represents a linking group selected from the group consisting of a single bond, —O—, —C ( ⁇ O) and —C ( ⁇ O) O—
  • Sp 3 is a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, or one or two or more —CH 2 — in the linear or branched alkylene group having 1 to 20 carbon atoms is —O—.
  • ⁇ 2> The polymerizable composition according to ⁇ 1>, wherein the amine is a secondary amine or a tertiary amine.
  • ⁇ 3> Polymerizability in which X represents a group represented by —X 3 —Sp 3 —Q 3 in formula (I), X 3 is —C ( ⁇ O) O—, and 1 is 1.
  • the polymerizable composition as described in ⁇ 1> or ⁇ 2> containing a liquid crystal compound.
  • a 1 and A 2 each independently represent a 1,4-phenylene group which may have a substituent, m is 1 or 2, and n is 0 or 1
  • ⁇ 5> Polymerizability in which in formula (I), A 1 and A 2 are both unsubstituted trans-1,4-cyclohexylene groups, m is 0 or 1, and n is 1 or 2
  • a 21 represents an optionally substituted 1,4-phenylene group
  • a 22 represents an unsubstituted trans-1,4-cyclohexylene group
  • m 1 is an integer of 0 to 1
  • N 1 represents an integer of 0 to 1.
  • L 11 and L 12 are each independently selected from the group consisting of a single bond, —C ( ⁇ O) O—, —OC ( ⁇ O) —, and —OC ( ⁇ O) O—.
  • a linking group is shown.
  • L 21 and L 22 are each independently selected from the group consisting of a single bond, —C ( ⁇ O) O—, —OC ( ⁇ O) —, and —OC ( ⁇ O) O—.
  • a linking group is shown.
  • ⁇ 10> The polymerizable composition according to any one of ⁇ 1> to ⁇ 9>, containing a chiral compound.
  • ⁇ 11> The polymerizable composition according to any one of ⁇ 1> to ⁇ 10>, containing a crosslinking agent.
  • ⁇ 12> A film comprising a layer obtained by curing the polymerizable composition as described in any one of ⁇ 1> to ⁇ 11>.
  • ⁇ 13> A film comprising two or more layers obtained by curing the polymerizable composition as described in any one of ⁇ 1> to ⁇ 11>.
  • ⁇ 14> The film according to ⁇ 12> or ⁇ 13>, which reflects visible light.
  • a film comprising at least three layers formed from the polymerizable composition according to any one of ⁇ 1> to ⁇ 11>,
  • the three layers are a layer in which a cholesteric liquid crystal phase having a central wavelength of selective reflection is fixed in a red light wavelength region, a layer in which a cholesteric liquid crystal phase having a central wavelength of selective reflection is fixed in a green light wavelength region, and a blue light wavelength region
  • a half mirror for displaying projected images including the film according to ⁇ 15>.
  • the half mirror for displaying projected images according to ⁇ 16> including a base material made of inorganic glass or acrylic resin.
  • a polymerizable composition containing a polymerizable liquid crystal compound having a partial structure in which a cyclohexylene group and a phenylene group are ester-bonded
  • a polymerizable composition that hardly causes yellowing after curing is provided.
  • the polymerizable composition of the present invention it is possible to provide a film that hardly causes yellowing.
  • the term “retardation” means in-plane retardation, and if there is no mention of wavelength, it means in-plane retardation at a wavelength of 550 nm.
  • in-plane retardation is measured using a polarization phase difference analyzer AxoScan manufactured by AXOMETRIC.
  • In-plane retardation at a wavelength of ⁇ nm can also be measured by making light at a wavelength of ⁇ nm incident in the normal direction of the film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments).
  • the polymerizable composition of the present invention contains a polymerizable liquid crystal compound represented by formula (I), an acylphosphine oxide compound, and an amine.
  • the polymerizable composition may contain other components such as the above-described polymerizable liquid crystal compound, acylphosphine oxide compound, amine, other liquid crystal compounds, other polymerization initiators, chiral compounds, and alignment control agents. . Each component will be described below.
  • the polymerizable liquid crystal compound contained in the polymerizable composition of the present invention has a trans-1,4-cyclohexylene group and a 1,4-phenylene group having a substituent, and is represented by the following formula (I). It is a liquid crystal compound.
  • a 1 and A 2 each independently represents a phenylene group which may have a substituent or a trans-1,4-cyclohexylene group which may have a substituent.
  • the phenylene group which may have a substituent represented by A 1 or A 2 is preferably a 1,4-phenylene group which may have a substituent.
  • a 1 or A 2 is preferably a 1,4-phenylene group which may have a substituent or an unsubstituted trans-1,4-cyclohexylene group.
  • the substituent when “may have a substituent” is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an amide group, an amino group, And a halogen atom and a substituent selected from the group consisting of a group constituted by combining two or more of the above-mentioned substituents.
  • the substituent include a substituent represented by X described later.
  • the phenylene group and trans-1,4-cyclohexylene group may have 1 to 4 substituents. When it has two or more substituents, the two or more substituents may be the same or different from each other.
  • substituent that the phenylene group and the trans-1,4-cyclohexylene group may have, a substituent selected from the group consisting of an alkyl group, an alkoxy group, and X is particularly preferable.
  • the number of substituents is preferably 1 or 2, and more preferably 1.
  • an alkyl group means either a linear or branched alkyl group.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
  • 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.
  • alkylene 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 for the alkoxy group containing an alkyl group.
  • specific examples of the alkylene group referred to as an alkylene group include a divalent group obtained by removing one arbitrary hydrogen atom in each of the above examples of the alkyl group.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 5 or more, more preferably 10 or less, still more preferably 8 or less, and still more preferably 6 or less.
  • Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • L 1 and L 2 are each independently a single bond, —CH 2 O—, —OCH 2 —, — (CH 2 ) 2 OC ( ⁇ O) —, —C ( ⁇ O) O.
  • L 1 and L 2 are preferably each independently a single bond, —C ( ⁇ O) O— or —OC ( ⁇ O) —.
  • the m L 1 s may be the same or different.
  • n L 2 s may be the same or different.
  • the element on the left side (“O” if “—OC ( ⁇ O) —”) is bonded to the element on the Q 1 side of the general formula (1). It shall be.
  • Sp 1 and Sp 2 are each independently one or more of a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, and a linear or branched alkylene group having 1 to 20 carbon atoms.
  • CH 2 — is —O—, —S—, —NH—, —N (CH 3 ) —, —C ( ⁇ O) —, —OC ( ⁇ O) —, or —C ( ⁇ O) O—.
  • a linking group selected from the group consisting of substituted groups is shown.
  • Sp 1 and Sp 2 are each independently a group consisting of a single bond, —O—, —OC ( ⁇ O) —, —C ( ⁇ O) O— and —OC ( ⁇ O) O— at both ends, respectively.
  • Q 1 and Q 2 are each independently a hydrogen atom or Formulas Q-1 to Q-5:
  • the polymerizable group an acryloyl group (formula Q-1) or a methacryloyl group (formula Q-2) is preferable.
  • n represents an integer of 0 to 2, and is preferably an integer of 1 to 2.
  • n represents an integer of 0 to 2, and is preferably 1.
  • n is 2, two A 2 may be the same or different, and two L 2 may be the same or different.
  • m + n is preferably 2 or more, and more preferably 3 or more.
  • X represents a group represented by —X 3 —Sp 3 —Q 3 , or two X are bonded to form a condensed ring together with a phenylene group to which two X are bonded.
  • X 3 represents a single bond, a linking group selected from the group consisting of —O—, —C ( ⁇ O) or —C ( ⁇ O) —O—.
  • X 3 is preferably —C ( ⁇ O) —O—.
  • Sp 3 has the same meaning as Sp 1 , and the preferred range is also the same as Sp 1 .
  • the polymerizable group here is preferably an acryloyl group (formula Q-1) or a methacryloyl group (formula Q-2).
  • —CH 2 — is —O—, —S—, —NH—, —N (CH 3 ) —, —C ( ⁇ O) —, —OC ( ⁇ O).
  • Specific examples of the group substituted with — or —C ( ⁇ O) 2 O— include a tetrahydrofuranyl group, a pyrrolidinyl group, an imidazolidinyl group, a pyrazolidinyl group, a piperidyl group, a piperazinyl group, and a morpholinyl group.
  • the substitution position is not particularly limited.
  • tetrahydrofuranyl group is preferable, and 2-tetrahydrofuranyl group is particularly preferable.
  • l represents an integer of 1 to 4, and when 1 is 2 to 4, 1 X may be the same or different. l is preferably 1 or 2, and more preferably 1.
  • X is preferably a group selected from the group consisting of an alkyl group, an alkoxy group, an alkoxycarbonyl group optionally substituted with an alkoxy group, an acyl group optionally substituted with an alkoxy group, and a formyl group.
  • Examples of the condensed ring formed by combining two Xs together with the benzene ring of the phenylene group to which the two Xs are bonded include naphthalene, chroman, isochroman, indoline, isoindoline, chromene, xanthene, phenoxathiin, thianthrene, Examples include quinoline, isoquinoline, phthalazine, quinoxaline, 1,3-benzodithiol-2-ylidene, 1,3-benzothiazol-2-yl and the like. Any of the above examples of the condensed ring may have a substituent.
  • Preferable examples of the polymerizable liquid crystal compound represented by the formula (I) include a 1,4-phenylene group in which A 1 and A 2 each independently have a substituent in the formula (I).
  • a polymerizable liquid crystal compound in which m is 0 or 1, and n is 1 or 2 and a polymerizable liquid crystal compound represented by the following formula (I-21).
  • Q 1 , Q 2 , Sp 1 , Sp 2 , L 1 , L 2 , X, 1 and m have the same definitions as in formula (I), respectively.
  • a 21 represents an optionally substituted 1,4-phenylene group
  • a 22 represents an unsubstituted trans-1,4-cyclohexylene group
  • m 1 represents an integer of 0 to 1
  • n 1 represents an integer of 0 to 1.
  • the formula (I- And the compound represented by 12 the formula (I- And the compound represented by 12).
  • Q 1 , Q 2 , Q 3 , Sp 1 , Sp 2 , Sp 3 are the same as defined in formula (I), L 11 is independently a single bond, A linking group selected from the group consisting of C ( ⁇ O) O—, —OC ( ⁇ O) —, and —OC ( ⁇ O) O— is shown.
  • a particularly preferred example of the polymerizable liquid crystal compound represented by the formula (I-21) includes a compound represented by the formula (I-22).
  • Q 1 , Q 2 , Q 3 , Sp 1 , Sp 2 , Sp 3 have the same definitions as in formula (I), respectively.
  • L 22 each independently represents a single bond, a linking group selected from the group consisting of —C ( ⁇ O) O—, —OC ( ⁇ O) —, and —OC ( ⁇ O) O—.
  • Examples of the polymerizable liquid crystal compound represented by the formula (I) are shown below, but are not limited to these examples.
  • the polymerizable liquid crystal compound represented by the formula (I) may be used alone or in combination of two or more.
  • the polymerizable composition of the present invention includes, for example, at least one compound represented by the above formula (I-12) and the above formula (I-22) as the polymerizable liquid crystal compound represented by the formula (I). It is also preferable to contain at least one compound to be prepared.
  • the content ratio of the polymerizable liquid crystal compound represented by formula (I-12) and the compound represented by formula (I-22) at this time is not particularly limited, but the polymerizable liquid crystal represented by formula (I-12) is not limited.
  • the mass ratio of the compound: the polymerizable liquid crystal compound represented by formula (I-22) is preferably 90:10 to 10:90, more preferably 80:20 to 15:85, and 50:50 More preferably, it is ⁇ 20: 80.
  • the polymerizable liquid crystal compound represented by the formula (I) can be produced by a known method.
  • phenol (or alcohol) derivative A-11 and carboxylic acid derivatives A-21 and A-31 are used. It can be produced by an esterification reaction.
  • esterification method an activated carboxylic acid and a phenol (or alcohol) derivative are allowed to act in the presence of a base, and a carboxylic acid and a phenol (or alcohol) derivative are directly used with a condensing agent such as carbodiimide.
  • the method of esterifying is mentioned.
  • a method of activating carboxylic acid from the viewpoint of by-products is more preferable.
  • Examples of the carboxylic acid activation method include acid chloride conversion using thionyl chloride, oxalyl chloride, and the like, and a method of preparing a mixed acid anhydride by reacting with mesyl chloride.
  • the polymerizable liquid crystal compound represented by the formula (I) exhibits liquid crystallinity and simultaneously has low birefringence
  • a retardation film using the polymerizable liquid crystal compound represented by the formula (I) The birefringence of the retardation film can be adjusted to a desired range.
  • a reflective film having a narrow selective reflection wavelength range, that is, selectivity of the reflection wavelength range is obtained. Highly reflective film can be obtained.
  • the polymerizable liquid crystal compound represented by the formula (I) is colorless and transparent because of its extremely small absorption in the visible light region, regardless of the type of aromatic ring substituent and the linking group, and has a wide liquid crystal phase range. It satisfies a plurality of characteristics such as being easily dissolved in a solvent and being easily polymerized. Derived from this, the cured film produced using the polymerizable composition containing the polymerizable liquid crystal compound represented by formula (I) exhibits sufficient hardness, is colorless and transparent, and has weather resistance and heat resistance. A plurality of characteristics can be satisfied such as being good.
  • the cured film formed using the polymerizable composition is, for example, a retardation plate, a polarizing element, a selective reflection film, a color filter, an antireflection film, a viewing angle compensation film, which is a component of the optical element, It can be used for various applications such as holography and alignment films.
  • the total amount of the polymerizable liquid crystal compound represented by the formula (I) may be 10% by mass or more, preferably 30 to 99.9 based on the solid content mass (mass excluding the solvent) of the polymerizable composition. % By mass, more preferably 50 to 99.5% by mass, still more preferably 70 to 99% by mass. However, it is not limited to this range.
  • the polymerizable composition of the present invention contains an acylphosphine oxide compound as a polymerization initiator.
  • examples of the acylphosphine oxide compounds include compounds described in JP-B-63-40799, JP-B-5-29234, JP-A-10-95788, JP-A-10-29997, and JP-A-4225898. Can be mentioned.
  • [2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide] is available under the trade name Darocur TPO (BASF) and [bis (2,4,6-trimethylbenzoyl) -phenylphosphine Oxide] is available under the trade name Irgacure 819 (BASF).
  • BASF Darocur TPO
  • Irgacure 819 Irgacure 819
  • acyl phosphine oxide type compound as described in WO201404026, a compound having a polymerizable group may be used.
  • the acylphosphine oxide compounds may be used alone or in combination of two or more.
  • the total amount of the acylphosphine oxide compound is preferably 0.01% by mass to 30% by mass, and 0.1% by mass to 20% by mass with respect to the solid content mass (mass excluding the solvent) of the polymerizable composition. More preferred is 1% by mass to 10% by mass. However, it is not limited to this range.
  • the present inventors have found that the polymerizable composition containing the polymerizable liquid crystal compound represented by formula (I) contains an amine together with an acylphosphine oxide compound, so that yellowing after curing is less likely to occur. It was. In particular, it has been found that yellowing that tends to occur in a humidity resistance test of a film formed by curing a polymerizable composition containing a polymerizable liquid crystal compound represented by formula (I) is reduced. This is presumably because the partial structure in which the cyclohexylene group and the phenylene group in the polymerizable liquid crystal compound represented by the formula (I) are ester-bonded is not easily decomposed by the amine.
  • the boiling point of the amine contained in the polymerizable composition of the present invention may be 150 ° C. or higher, preferably 180 ° C. or higher, more preferably 200 ° C. or higher.
  • the amine include benzylamine derivatives and piperidine derivatives.
  • a basic light stabilizer generally referred to as HALS (hindered amine light stabilizer) can be used.
  • HALS a structure in which the nitrogen atom of the piperidine structure is substituted with hydrogen or a methyl group is preferable, and it has a 2,2,6,6-tetramethylpiperidyl group or a 1,2,2,6,6-pentamethylpiperidyl group.
  • a structure is further preferred.
  • Specific examples of HALS include ADEKA's ADK STAB LA series (LA52, LA57, LA-63P, LA68, LA-72, LA-77, LA-82, LA-87) and BASF's Tinuvin series (Tinuvin 111). , Tinuvin 123, Tinuvin 144, Tinuvin 292, Tinuvin 765) Clariant's hostabin series (Hostavin N20, Hostavin N24).
  • Irgacure 907 and Irgacure 369 can also be preferably used.
  • Preferred examples of the amine contained in the polymerizable composition of the present invention are shown below. However, it is not limited to these.
  • Amine may be used alone or in combination of two or more.
  • the total amount of amine is 0.01 to 10% by mass, preferably 0.1 to 7% by mass, based on the solid content mass (the mass excluding the solvent) of the polymerizable composition. %, More preferably 0.3-5% by mass, still more preferably 0.5-4% by mass. However, it is not limited to this range.
  • the polymerizable composition of the present invention may contain other polymerization initiator.
  • examples of other polymerization initiators include ⁇ -carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), ⁇ -hydrocarbon substitution Aromatic acyloin compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. Nos. 3,046,127 and 2,951,758), combinations of triarylimidazole dimers and p-aminophenyl ketone (US) Patent No.
  • the other polymerization initiator may be an amine.
  • examples of such a polymerization initiator include Irgacure 907 and Irgacure 369 (manufactured by BASF).
  • the other polymerization initiator is preferably contained in the polymerizable composition in an amount of 0.01 to 20% by mass with respect to the solid content mass (the mass excluding the solvent) of the polymerizable composition. More preferably, it is contained in an amount of ⁇ 8% by mass.
  • the polymerizable composition may contain one or more other liquid crystal compounds together with the polymerizable liquid crystal compound represented by the formula (I).
  • the polymerizable liquid crystal compound represented by the formula (I) is highly compatible with other liquid crystal compounds, so that even when mixed with other liquid crystal compounds, no opacification occurs and a highly transparent film can be formed. It is. Since other liquid crystal compounds can be used in combination, compositions having various compositions suitable for various applications can be provided. Examples of other liquid crystal compounds that can be used in combination include rod-shaped 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 phenylpyrimidines, alkoxy-substituted phenyl Pyrimidines, phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles. Not only low-molecular liquid crystal compounds but also high-molecular liquid crystal compounds can be used.
  • liquid crystal compounds may be polymerizable or non-polymerizable.
  • the rod-like liquid crystal compound having no polymerizable group is 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 an unsaturated polymerizable group, an epoxy group, and an aziridinyl group, preferably an unsaturated polymerizable group, and particularly preferably an ethylenically unsaturated polymerizable group.
  • the polymerizable group can be introduced into the molecule of the rod-like liquid crystal compound by various methods.
  • the number of polymerizable groups possessed by the polymerizable rod-like liquid crystal compound is preferably 1 to 6, more preferably 1 to 3.
  • Examples of the polymerizable rod-like liquid crystal compound are described in Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. No. 4,683,327, US Pat. No. 5,622,648, US Pat. No. 5,770,107, International Publication WO95 / 22586. No. 95/24455, No. 97/00600, No. 98/23580, No.
  • 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 further preferably 0 to 30% by mass based on the solid content mass of the polymerizable composition. %. However, it is not limited to this range.
  • the mass ratio of the polymerizable liquid crystal compound represented by the formula (I) and the other liquid crystal compound is: It may be 100/0 to 30/70, preferably 100/0 to 50/50, and more preferably 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 showing a cholesteric liquid crystal phase.
  • the chiral compound may be liquid crystalline or non-liquid crystalline.
  • the chiral compound is derived from various known chiral agents (for example, described in Liquid Crystal Device Handbook, Chapter 3-4-3, TN, chiral agent for STN, 199 pages, edited by Japan Society for the Promotion of Science, 142nd Committee, 1989). You can choose.
  • a chiral compound generally contains an asymmetric carbon atom, but an axial asymmetric compound or a planar asymmetric compound containing no asymmetric carbon atom can also be used.
  • Examples of the axial asymmetric compound or the planar asymmetric compound include binaphthyl, helicene, paracyclophane, and derivatives thereof.
  • the chiral compound (chiral agent) may have a polymerizable group.
  • the rod-shaped liquid crystal compound used in combination also has a polymerizable group, a repeating unit derived from the rod-shaped liquid crystal compound by a polymerization reaction between the polymerizable chiral compound and the polymerizable rod-shaped liquid crystal compound And polymers having repeating units derived from chiral compounds.
  • the polymerizable group possessed by the polymerizable chiral compound is preferably the same type of group as the polymerizable rod-shaped liquid crystal compound, particularly the polymerizable group possessed by the polymerizable liquid crystal compound represented by formula (I). Therefore, 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 liquid crystal compound represented by the formula (I).
  • a smaller amount of chiral compound is preferred because it tends not to affect liquid crystallinity. Therefore, as the chiral compound, a compound having a strong twisting power is preferable so that a twisted orientation with a desired helical pitch can be achieved even with a small amount. Examples of such a chiral agent exhibiting a strong twisting force include a chiral agent described in JP-A-2003-287623. Further, chiral agents described in JP-A Nos. 2002-302487, 2002-80478, 2002-80851, and 2014-034581, LC-756 manufactured by BASF, and the like can be mentioned. It is done.
  • a film formed by fixing a polymerizable composition containing a chiral compound into a cholesteric liquid crystal phase and then fixing the cholesteric liquid crystal phase exhibits selective reflection characteristics with respect 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).
  • the polymerizable liquid crystal compound represented by the formula (I) showing low birefringence the reflection wavelength range is narrowed compared with a film having the same thickness using a higher birefringence liquid crystal compound. There is an advantage that the selectivity becomes high.
  • orientation control agent An alignment controller that contributes to the formation of a stable or rapid liquid crystal phase (for example, a cholesteric liquid crystal phase) may be added to the polymerizable composition.
  • orientation control agents include fluorine-containing (meth) acrylate polymers, compounds represented by general formulas (X1) to (X3) described in WO2011 / 162291, and paragraphs [0020] to JP2013-47204A.
  • the compounds described in [0031] are included. You may contain 2 or more types selected from these. These compounds can reduce the tilt angle of the molecules of the liquid crystal compound or can be substantially horizontally aligned 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 it is not required to be strictly parallel.
  • An orientation with an inclination angle of less than 20 degrees is meant.
  • the liquid crystal compound is horizontally aligned in the vicinity of the air interface, alignment defects are less likely to occur, and thus transparency in the visible light region is increased.
  • the molecules of the liquid crystal compound are aligned at a large tilt angle, for example, in the case of a cholesteric liquid crystal phase, the spiral axis is deviated from the film surface normal, so that the reflectance decreases or a fingerprint pattern occurs, This is not preferable because it increases haze and shows diffractive properties.
  • fluorine-containing (meth) acrylate-based polymers that can be used as orientation control agents are described in JP-A-2007-272185, [0018] to [0043].
  • the alignment controller one kind of compound may be used alone, or two or more kinds 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% by mass of the compound of the formula (I). Mass% is particularly preferred.
  • the polymerizable composition may optionally contain a crosslinking agent in order to improve the film strength after hardening and the durability.
  • a crosslinking agent one that can be cured by ultraviolet rays, heat, moisture, or the like can be suitably used.
  • polyfunctional acrylate compounds such as a trimethylol propane tri (meth) acrylate, a pentaerythritol tri (meth) acrylate, a 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, etc.
  • Aziridine compounds such as hexamethylene diisocyanate and biuret type isocyanate; polyoxazoline compounds having an oxazoline group in the side chain; vinyltrimethoxysilane, N- Such as 2-aminoethyl) 3-aminopropyl alkoxysilane compounds such as trimethoxysilane.
  • a well-known catalyst can be used according to the reactivity of a crosslinking agent, and productivity can be improved in addition to membrane strength and durability improvement. These may be used individually by 1 type and may use 2 or more types together.
  • 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.
  • the content of the crosslinking agent is 3% by mass or more, the effect of improving the crosslinking density is higher, and when it is 20% by mass or less, the stability of the cholesteric liquid crystal layer is higher.
  • the polymerizable composition may be one or more kinds of antioxidants, ultraviolet absorbers, sensitizers, stabilizers, plasticizers, chain transfer agents, polymerization inhibitors, antifoaming agents, leveling agents, enhancers. It may contain other additives such as a sticking agent, a flame retardant, a surfactant, a dispersant, a coloring material such as a dye and a pigment.
  • the polymerizable composition of the present invention is useful as a material for various optical films such as a retardation film and a reflective film, and various optical films can be formed using the polymerizable composition of the present invention.
  • An example of a method for producing an optical film is: (i) Applying a polymerizable composition to the surface of a substrate or the like to bring it into a liquid crystal phase (cholesteric liquid crystal phase, etc.) (ii) proceeding the curing reaction of the polymerizable composition, fixing the liquid crystal phase to form a cured film; Is a production method comprising at least The steps (i) and (ii) can be repeated a plurality of times to produce a film in which a plurality of the cured films are laminated. Moreover, the some laminated
  • a 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 a material is dissolved and / or dispersed in a solvent.
  • a solvent used for preparing the coating solution an organic solvent is preferably used.
  • Organic solvents include amides (eg N, N-dimethylformamide); sulfoxides (eg dimethyl sulfoxide); heterocyclic compounds (eg pyridine); hydrocarbons (eg benzene, hexane); alkyl halides (eg chloroform, dichloromethane); esters (Eg methyl acetate, butyl acetate, propylene glycol monoethyl ether acetate); ketones (eg acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone); ethers (eg tetrahydrofuran, 1,2-dimethoxyethane); 1,4-butanediol di Acetate and the like are included. Of these, alkyl halides, esters and ketones are particularly preferred. Two or more organic solvents may be used in combination.
  • the coating solution can be applied by various methods such as a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method.
  • a coating film can be formed by discharging the composition from a nozzle using an ink jet apparatus.
  • the polymerizable composition applied to the surface to become a coating film is brought into a liquid crystal phase state such as a cholesteric liquid crystal phase.
  • the liquid crystal phase may be obtained by drying the coating film and removing the solvent.
  • the liquid crystal phase can be stably formed by heating to the temperature of the isotropic phase and then cooling to the 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., more preferably in the range of 10 to 150 ° C.
  • a cooling step or the like may be required to lower the temperature to a temperature range exhibiting a liquid crystal phase. Also, if it exceeds 200 ° C, a high temperature is required to make the isotropic liquid state higher than the temperature range once exhibiting the liquid crystal phase, which is disadvantageous from waste of thermal energy, deformation of the substrate, and alteration. There is.
  • the coating film in a liquid crystal phase is cured.
  • Curing may proceed according to any polymerization method such as a radical polymerization method, an anionic polymerization method, a cationic polymerization method, or a coordination polymerization method.
  • a suitable polymerization method may be selected according to the polymerizable liquid crystal compound represented by the formula (I).
  • a polymer having a unit derived from the polymerizable liquid crystal compound represented by the formula (I) in the structural unit is obtained.
  • ultraviolet light is irradiated to advance the curing reaction.
  • a light source such as an ultraviolet lamp is used.
  • the curing reaction of the composition proceeds by irradiating ultraviolet rays, the liquid crystal phase (cholesteric liquid crystal phase or the like) is fixed, and a cured film is formed.
  • the amount of irradiation energy of ultraviolet rays in general, 0.1J / cm 2 ⁇ 0.8J / cm 2 is preferably about.
  • limiting in particular about the time which irradiates a coating film with an ultraviolet-ray is just to determine from the viewpoint of both sufficient intensity
  • ultraviolet irradiation may be performed under heating conditions. Moreover, it is preferable to maintain the temperature at the time of ultraviolet irradiation in the temperature range which exhibits a liquid crystal phase so that a liquid crystal phase may not be disturbed. Also, since the oxygen concentration in the atmosphere is related to the degree of polymerization, if the desired degree of polymerization is not reached in the air and the film strength is insufficient, the oxygen concentration in the atmosphere is reduced by a method such as nitrogen substitution. It is preferable.
  • the liquid crystal phase is fixed and a cured film is formed.
  • the state in which the liquid crystal phase is “fixed” is the most typical and preferred state in which the orientation of the compound that is the liquid crystal phase is maintained. However, it is not limited to this. Specifically, in the temperature range of 0 ° C. to 50 ° C., and in the temperature range of ⁇ 30 ° C. to 70 ° C. under harsher conditions, the layer has no fluidity, and the orientation form by external field or external force This means a state in which the fixed orientation form can be kept stable without causing a change in the above.
  • the alignment state of the liquid crystal phase is preferably fixed by a curing reaction that proceeds by ultraviolet irradiation.
  • the composition in the cured film no longer needs to exhibit liquid crystal properties.
  • the composition may be no longer liquid crystalline due to a high molecular weight due to the curing reaction.
  • the thickness of the cured film is not particularly limited. What is necessary is just to determine a preferable film thickness according to an application or according to the optical characteristic made desired. In general, the thickness is preferably 0.05 to 50 ⁇ m, more preferably 1 to 35 ⁇ m.
  • the film may have a substrate.
  • the substrate is self-supporting and supports the cured film, there is no limitation on the material and optical characteristics. It can be selected from a glass plate, a quartz plate, a polymer film, and the like. Depending on the application, those 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.
  • substrates examples include polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate (PEN); polycarbonate (PC) films and polymethyl methacrylate films; polyolefin films such as polyethylene and polypropylene; polyimide films and 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 films and triacetyl A cellulose (TAC) film etc. are mentioned.
  • a polyethylene terephthalate film and a triacetyl cellulose film are preferred.
  • the film may have an alignment 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 alignment layer can be provided by means such as a rubbing treatment of an organic compound (preferably a polymer), oblique vapor deposition of an inorganic compound, or formation of a layer having a microgroove.
  • 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 treatment.
  • a polymer of an organic compound is preferable, and a polymer that can be crosslinked by itself or a polymer that 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 / maleimide copolymer, polyvinyl alcohol and modified polyvinyl alcohol, poly (N-methylolacrylamide), styrene / vinyltoluene copolymer Polymer, chlorosulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, carboxymethyl cellulose, gelatin, polyethylene, polypropylene and polycarbonate And polymers such as silane coupling agents and the like.
  • preferred polymers include water-soluble polymers such as poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol and modified polyvinyl alcohol, among which gelatin, polyvinyl alcohol and modified polyvinyl alcohol are preferred, Polyvinyl alcohol and modified polyvinyl alcohol are preferred.
  • water-soluble polymers such as poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol and modified polyvinyl alcohol, among which gelatin, polyvinyl alcohol and modified polyvinyl alcohol are preferred, Polyvinyl alcohol and modified polyvinyl alcohol are preferred.
  • Adhesive layer When bonding a plurality of cured films with an adhesive, an adhesive layer is provided between the cured films.
  • the adhesive layer may be formed from an adhesive.
  • Adhesives include hot melt type, thermosetting type, photocuring type, reactive curing type, and pressure-sensitive adhesive type that does not require curing, from the viewpoint of curing method, and the materials are acrylate, urethane, urethane acrylate, epoxy , Epoxy acrylate, polyolefin, modified olefin, polypropylene, ethylene vinyl alcohol, vinyl chloride, chloroprene rubber, cyanoacrylate, polyamide, polyimide, polystyrene, polyvinyl butyral, etc. can do.
  • the photocuring type is preferable as the curing method, and from the viewpoint of optical transparency and heat resistance, it is preferable to use an acrylate, urethane acrylate, epoxy acrylate, or the like material.
  • the thickness of the adhesive layer may be 0.5 to 10 ⁇ m, preferably 1 to 5 ⁇ m. When used as a projected image display half mirror, it is preferably provided with a uniform film thickness to reduce color unevenness and the like.
  • Examples of the film formed using the polymerizable composition include a film in which the alignment of the liquid crystal phase (for example, horizontal alignment, vertical alignment, hybrid alignment, etc.) of the polymerizable composition is fixed. Such a film usually exhibits optical anisotropy and is used as an optical compensation film for a liquid crystal display device or the like.
  • Another example is a film that includes a layer in which a cholesteric liquid crystal phase of a polymerizable composition is fixed, and that exhibits selective reflection characteristics with respect to light in a predetermined wavelength range. In the cholesteric liquid crystal phase, the liquid crystal molecules are arranged in a spiral.
  • a layer in which a cholesteric liquid crystal phase is fixed selectively reflects either right circularly polarized light or left circularly polarized light in a selective reflection wavelength region, It functions as a circularly polarized light selective reflection layer that transmits the circularly polarized light of the other sense.
  • a film containing one or more cholesteric liquid crystal layers can be used for various applications.
  • the sense of circularly polarized light reflected by each cholesteric liquid crystal layer may be the same or opposite depending on the application.
  • the center wavelength of 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 whether it is right circularly polarized light or left circularly polarized light.
  • the sense of circularly polarized light is right-handed circularly polarized light when the electric field vector tip turns clockwise as time increases when viewed as the light travels toward you, and left when it turns counterclockwise. Defined as being circularly polarized.
  • the term “sense” may be used for the twist direction of the spiral of the cholesteric liquid crystal.
  • the twist direction (sense) of the cholesteric liquid crystal When the twist direction (sense) of the cholesteric liquid crystal is right, it reflects right circularly polarized light and transmits left circularly polarized light, and when sense is left, it reflects left circularly polarized light and transmits right circularly polarized light. .
  • a film including a cholesteric liquid crystal layer exhibiting selective reflection characteristics in the visible light wavelength region can be used as a screen for projecting image display and a half mirror. Further, by controlling the reflection band, it can be used as a color filter or a filter that improves the color purity of display light of a display (see, for example, JP-A-2003-294948).
  • the optical film can be used for various applications such as a polarizing element, a reflection film, an antireflection film, a viewing angle compensation film, a holography, and an alignment film, which are constituent elements of the optical element.
  • the use as a projection image display member will be described.
  • the above function of the cholesteric liquid crystal layer it is possible to form a projected image by reflecting the circularly polarized light of one of the senses at a wavelength showing selective reflection in the projection light.
  • the projected image may be displayed on the surface of the projected image display member and viewed as such, or may be a virtual image that appears above the projected image display member when viewed from the observer.
  • the selective reflection center wavelength ⁇ of the cholesteric liquid crystal layer means the wavelength at the center of gravity of the reflection peak of the circularly polarized reflection spectrum measured from the normal direction of the cholesteric liquid crystal layer.
  • the center wavelength of selective reflection can be adjusted by adjusting the pitch of the helical structure.
  • the center wavelength ⁇ is adjusted, and an apparent selection is made.
  • the central wavelength of reflection can be in the wavelength range of 450 nm to 495 nm.
  • the apparent selective reflection center wavelength is the wavelength at the center of gravity of the reflection peak of the circularly polarized 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 length of the cholesteric liquid crystal phase depends on the kind of chiral agent used together with the polymerizable liquid crystal compound or the concentration of the chiral agent, the desired pitch length can be obtained by adjusting these.
  • ⁇ / ⁇ which is a ratio of the half-value width ⁇ of the selective reflection wavelength region and the central wavelength ⁇ of selective reflection
  • ⁇ / ⁇ is preferably 0.09 or less, and 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.
  • Each layer may have the same or different ⁇ and ⁇ .
  • a cured film having an apparent selective reflection center wavelength in each of the red light wavelength region, the green light wavelength region, and the blue light wavelength region is prepared, and a full color is obtained by laminating them.
  • a projection image display member capable of displaying the projection image can be produced.
  • the half mirror is laminated with cured films having respective selective reflection center wavelengths in the respective ranges of 750 to 620 nm, 630 to 500 nm, and 530 to 420 nm (different from each other, for example, 50 nm or more). Is preferred.
  • the center wavelength of selective reflection of each cured film By adjusting the center wavelength of selective reflection of each cured film according to the emission wavelength range of the light source used for projection and the usage mode of the projection image display member, it is possible to display a clear projection image with high light utilization efficiency. it can.
  • a clear color projection image can be displayed with high light utilization efficiency.
  • usage of the projection image display member include an incident angle of projection light on the surface of the projection image display half mirror, a projection image observation direction on the surface of the projection image display member, and the like.
  • a half mirror that can be used as a combiner for a head-up display can be obtained by configuring the projection image display member to be transparent to light in the visible light region.
  • the projected image display half mirror can display an image projected from a projector or the like so that the projected image can be viewed.
  • the projected image displayed half mirror is observed from the same side where the image is displayed, It is possible to observe information or scenery on the surface side at the same time.
  • the substrate is preferably transparent in the visible light region and low 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.
  • base materials include inorganic glass and polymer resins (acrylic resins (acrylic esters such as polymethyl (meth) acrylate)), polycarbonate, cyclic polyolefins such as cyclopentadiene polyolefin and norbornene polyolefin, and polyolefins such as polypropylene. And aromatic vinyl polymers such as polystyrene, polyarylate, cellulose acylate, etc.).
  • acrylic resins acrylic esters such as polymethyl (meth) acrylate
  • polycarbonate cyclic polyolefins such as cyclopentadiene polyolefin and norbornene polyolefin
  • polyolefins such as polypropylene.
  • aromatic vinyl polymers such as polystyrene, polyarylate, cellulose acylate, etc.
  • the half mirror for displaying projected images may include an antireflection layer.
  • the antireflection layer is preferably contained on the outermost surface. It may be provided on the outermost surface on the observation side when using the half mirror for projected image display, or may be provided on the outermost surface on the opposite side, but provided on the outermost surface on the observation side Is preferred.
  • an antireflection layer may be provided on both the substrate side surface and the cured film side on the observation side. This is because such a configuration makes it difficult to generate a double image that may occur particularly when the base material has high birefringence.
  • the antireflection layer for example, in addition to a film having fine surface irregularities, a two-layer film structure in which a high refractive index layer and a low refractive index layer are combined, a middle refractive index layer, a high refractive index layer, and a low refractive index layer are used.
  • examples thereof include a layer having a three-layer film structure in which refractive index layers are sequentially stacked.
  • two layers of a high refractive index layer / low refractive index layer or three layers having different refractive indexes are arranged in order from the bottom, and a medium refractive index layer (having a higher refractive index than the lower layer and a high refractive index).
  • a layer having a lower refractive index than a layer) / a layer having a higher refractive index / a layer having a lower refractive index are stacked in this order.
  • a medium refractive index layer / high refractive index layer / low refractive index layer in this order on the hard coat layer.
  • JP-A-8-122504 Examples include the configurations described in JP-A-8-110401, JP-A-10-300902, JP-A-2002-243906, JP-A-2000-11706, and the like.
  • each layer may be provided with other functions, for example, an antifouling low refractive index layer, an antistatic high refractive index layer, an antistatic hard coat layer, an antiglare hard coat layer, and the like. (For example, JP-A-10-206603, JP-A-2002-243906, JP-A-2007-264113, etc.).
  • 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 a low temperature 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 from the substrate side is ⁇ / 4
  • the optical film thickness of the ZrO 2 layer is ⁇ / 4
  • the outermost SiO 2 layer is SiO 2.
  • a laminated structure in which a high refractive index material layer and a low refractive index material layer having an optical film thickness of ⁇ / 4 are alternately formed is exemplified.
  • ⁇ is a design wavelength, and usually 520 nm is used.
  • the outermost layer is preferably made of SiO 2 because it has a low refractive index and can impart mechanical strength to the antireflection layer.
  • the antireflection layer is formed of an inorganic material
  • a vacuum deposition method for example, 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), and the like. And a composition containing a fluorine-containing curable resin and inorganic fine particles described in JP-A-2007-298974, JP-A-2002-317152, JP-A-2003-202406, and JP-A-2003-292831.
  • the low-refractive-index coating composition containing hollow silica fine particles described in the Japanese Patent Publication No. 1 can be suitably used.
  • the film can be formed by a coating method having excellent mass productivity such as a spin coating method, a dip coating method, and a gravure coating method in addition to the vacuum vapor deposition method.
  • the low refractive index layer preferably has a refractive index of 1.30 to 1.51. It is preferably 1.30 to 1.46, more preferably 1.32 to 1.38.
  • Examples of organic materials used for the medium refractive index layer and the high refractive index layer include ionizing radiation curable compounds containing aromatic rings, ionizing radiation curable compounds containing halogenated elements other than fluorine (eg, Br, I, Cl, etc.), 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. Specifically, those described in paragraph numbers [0074] to [0094] of JP-A-2008-262187 can be exemplified.
  • the refractive index of the high refractive index layer is preferably 1.65 to 2.20, 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 thickness of the antireflection 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 by referring to the method described on page 18 [0085] to [0087] of Japanese Patent No. 4379550.
  • BHT 60 mg
  • the internal temperature was cooled to ⁇ 5 ° C.
  • 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.
  • the thickness of the dry film after drying the polymerizable composition coating liquid (1) is 4.6 ⁇ m on the rubbing treated surface of PET manufactured by Fuji Film Co., Ltd. that has been rubbed. Applied.
  • the coating layer is dried at room temperature for 10 seconds, heated in an atmosphere of 85 ° C. for 1 minute, and then selectively irradiated by UV irradiation at 80 ° C. for 8 seconds at a fusion D bulb (lamp 90 mW / cm) at 60 ° C. Film 1 was obtained. During the period after application and before heating, no crystal deposition was observed in the coating film.
  • the superiority or inferiority of the liquid crystal alignment was determined according to the following criteria depending on the presence or absence of alignment defects when the film was observed with a polarizing microscope.
  • the evaluation is preferably any one of evaluation criteria A to C. If it is evaluation standard A or B, it is excellent in production efficiency and can be used suitably, and it is more preferable that it is evaluation standard A.
  • Toyobo PET (A-4100) that has undergone rubbing treatment
  • a wire bar is placed at room temperature so that the dry film thickness after drying the polymerizable composition coating liquid (4) becomes 5.0 ⁇ m.
  • the coating layer was dried at room temperature for 30 seconds, then heated in an atmosphere of 85 ° C. for 1 minute, and irradiated with UV at 60 ° C. in a nitrogen gas atmosphere using a high-pressure mercury lamp so that the irradiation amount was 300 mJ / cm 2 .
  • a selective reflection film 11 was obtained. During the period after application and before heating, no crystal deposition was observed in the coating film.
  • Polymeric composition coating solution (12) Rod-like liquid crystal compound 101 55 parts by weight Rod-like liquid crystal compound 102 30 parts by weight Rod-like liquid crystal compound 201 13 parts by weight Rod-like liquid crystal compound 202 2 parts by weight Polymerization initiator Irgacure819 (manufactured by BASF) 2 parts by weight amine compound Adekastab LA-72 (manufactured by ADEKA) ) 0.5 parts by mass Chiral agent LC756 (manufactured by BASF) 4.7 parts by mass Orientation agent (2) 0.005 parts by mass Orientation agent (3) 0.01 parts by mass Methyl acetate 260 parts by mass Cyclohexanone 65 parts by mass
  • Polymerizable composition coating solution (13) Rod-like liquid crystal compound 101 55 parts by weight Rod-like liquid crystal compound 102 30 parts by weight Rod-like liquid crystal compound 201 13 parts by weight Rod-like liquid crystal compound 202 2 parts by weight Polymerization initiator Irgacure819 (manufactured by BASF) 2 parts by weight amine compound Adekastab LA-72 (manufactured by ADEKA) 0.5 parts by mass Chiral agent LC756 (manufactured by BASF) 5.5 parts by mass Orientation agent (2) 0.005 parts by mass Orientation agent (3) 0.01 parts by mass Methyl acetate 260 parts by mass Cyclohexanone 65 parts by mass
  • the dry film thickness after drying the polymerizable composition coating liquid (12) on the surface of the liquid crystal layer of the selective reflection film 11 is 4.1 ⁇ m (the total film thickness with the lower layer is 9.2 ⁇ m). It apply
  • the coating layer was dried at room temperature for 30 seconds, then heated in an atmosphere of 85 ° C. for 1 minute, and irradiated with UV at 60 ° C. in a nitrogen gas atmosphere using a high-pressure mercury lamp so that the irradiation amount was 300 mJ / cm 2 .
  • a selective reflection film 12 was obtained.
  • the dry film thickness after drying the polymerizable composition coating liquid (13) on the surface of the liquid crystal layer of the selective reflection film 12 is 3.9 ⁇ m (the total film thickness with the lower layer is 13.1 ⁇ m) at room temperature. And using a wire bar.
  • the coating layer was dried at room temperature for 30 seconds, then heated in an atmosphere of 85 ° C. for 1 minute, and irradiated with UV at 60 ° C. in a nitrogen gas atmosphere using a high-pressure mercury lamp so that the irradiation amount was 300 mJ / cm 2 .
  • a selective reflection film 13 was obtained.
  • this selective reflection film 13 When the transmission spectrum of this selective reflection film 13 was measured with a spectrophotometer UV-3100PC manufactured by Shimadzu Corporation, it had reflection peaks at 680 nm, 540 nm and 459 nm, and had a high visible light transmittance of 75% or more. all right.
  • UV curing adhesive Exp. U12034-6 was applied using a wire bar at room temperature so that the dry film thickness after drying was 5 ⁇ m.
  • the surface and the adhesive-coated surface of the laminated film 13 of the visible light reflecting layer are bonded together and irradiated with UV, and the PET film of the film 13 is peeled off.
  • a half mirror 1 for projecting image display was produced. Using a commercially available LCD imager, a color image was projected on a half mirror, and when the image was observed through the half mirror, a virtual image image with no color unevenness could be confirmed.
  • Polymeric composition coating solution (14) Photocurable acrylic polymer (Vanaresin GH1202, manufactured by Shin-Nakamura Chemical Co., Ltd.) 50 parts by mass Biscoat 360 (manufactured by Osaka Organic Chemical) 50 parts by mass polymerization initiator Irgacure819 (manufactured by BASF) 2 parts by mass amine compound ADK STAB LA-72 (ADEKA 0.5 parts by mass orientation agent (2) 0.01 parts by mass Methyl ethyl ketone 230 parts by mass
  • the polymerizable composition coating liquid (14) was applied on the liquid crystal layer side of the selective reflection film 13 using a wire bar at room temperature so that the dry film thickness after drying was 5 ⁇ m.
  • the coating layer is dried at room temperature for 30 seconds, then heated in an atmosphere of 85 ° C. for 1 minute, and UV irradiation is performed using a high-pressure mercury lamp at 30 ° C. in a nitrogen gas atmosphere so that the irradiation dose is 300 mJ / cm 2.
  • a reflective film 14 was obtained.
  • UVX-5457 UV curable adhesive manufactured by Toagosei Co., Ltd. is used on the liquid crystal layer side of the selective reflection film 14, and a wire bar is used at room temperature so that the dry film thickness after drying becomes 5 ⁇ m. And applied.
  • a 2 mm thick glass plate surface and an adhesive-coated surface of the selective reflection film 14 are bonded together and irradiated with UV, and the PET film of the selective reflection film 14 is peeled off, so that a visible light transmissive projection image is formed on the glass substrate.
  • a display half mirror 2 was produced. Using a commercially available LCD imager, a color image was projected on a half mirror, and when the image was observed through the half mirror, a virtual image image with no color unevenness could be confirmed.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polarising Elements (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

La présente invention concerne une composition polymérisable comprenant une amine et un composé polymérisable de type cristaux liquides à base d'un acyle-oxyde de phosphine représenté par la formule (I). (Dans la formule : A1 et A2 représentent des groupes phénylène, des groupes trans-1,4-cyclohexylène, ou autres; L1 et L2 représentent des liaisons simples, -C(=O)O-, -OC(=O)-, ou autres; Q1 et Q2 représentent des groupes polymérisables ou autres; m et n représentent des entiers de 0 à 2; X représente –X3-Sp3-Q3 ou deux X peuvent être liés pour former un cycle condensé; X3 représente –C(=O)O- ou autre; Sp1, Sp2, et Sp3 représentent des liaisons simples, des groupes alkylène, ou autres; Q3 représente un atome d'hydrogène, un groupe cycloalkyle, un groupe polymérisable, ou autre; et l représente un entier de 0 à 4). Cette composition polymérisable n'est pas sujette à jaunissement après durcissement et est utile pour fabriquer un film et un demi-miroir pour l'affichage d'images projetées.
PCT/JP2016/057697 2015-03-12 2016-03-11 Composition polymérisable, film, et demi-miroir pour l'affichage d'images projetées WO2016143884A1 (fr)

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Cited By (1)

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TWI712678B (zh) * 2018-03-30 2020-12-11 南韓商Ｌｇ化學股份有限公司 液晶配向劑組成物、製備液晶配向膜的方法與液晶配向膜、以及使用上述的液晶顯示器

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JP2010270108A (ja) * 2009-04-21 2010-12-02 Sumitomo Chemical Co Ltd 化合物
WO2015115390A1 (fr) * 2014-01-28 2015-08-06 富士フイルム株式会社 Composé polymérisable, composition polymérisable, film et demi-miroir pour afficher une image projetée
WO2015147243A1 (fr) * 2014-03-28 2015-10-01 富士フイルム株式会社 Composé polymérisable, polymère, composition polymérisable, film, et demi-miroir pour affichage d'images par projection
WO2016047648A1 (fr) * 2014-09-25 2016-03-31 富士フイルム株式会社 Composition polymérisable comprenant des composés polymérisables, film, et demi-miroir pour l'affichage d'images projetées

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JP2009244433A (ja) * 2008-03-29 2009-10-22 Fujifilm Corp 液晶組成物および液晶表示装置
JP2010024438A (ja) * 2008-05-20 2010-02-04 Sumitomo Chemical Co Ltd 光学フィルム、偏光板、表示装置及び光学フィルムの製造方法
JP2010270108A (ja) * 2009-04-21 2010-12-02 Sumitomo Chemical Co Ltd 化合物
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Publication number Priority date Publication date Assignee Title
TWI712678B (zh) * 2018-03-30 2020-12-11 南韓商Ｌｇ化學股份有限公司 液晶配向劑組成物、製備液晶配向膜的方法與液晶配向膜、以及使用上述的液晶顯示器
US11307462B2 (en) 2018-03-30 2022-04-19 Lg Chem, Ltd. Liquid crystal aligning agent composition, method for preparing liquid crystal alignment film using same, and liquid crystal alignment film and liquid crystal display using same

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