WO2018070507A1 - 液晶配向剤、液晶配向膜及び液晶表示素子 - Google Patents
液晶配向剤、液晶配向膜及び液晶表示素子 Download PDFInfo
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- WO2018070507A1 WO2018070507A1 PCT/JP2017/037100 JP2017037100W WO2018070507A1 WO 2018070507 A1 WO2018070507 A1 WO 2018070507A1 JP 2017037100 W JP2017037100 W JP 2017037100W WO 2018070507 A1 WO2018070507 A1 WO 2018070507A1
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- 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
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/303—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one or more carboxylic moieties in the chain
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- 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
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
Definitions
- the present invention relates to a novel polymer composition, a liquid crystal alignment film using the same, and a method for producing a substrate having the alignment film. Further, the present invention relates to a novel method for manufacturing a liquid crystal display element having excellent tilt angle characteristics.
- the liquid crystal display element is known as a light, thin, and low power consumption display device and has been remarkably developed in recent years.
- the liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes.
- an organic film made of an organic material is used as the liquid crystal alignment film so that the liquid crystal is in a desired alignment state between the substrates.
- the liquid crystal alignment film is a component of the liquid crystal display element, and is formed on the surface of the substrate that holds the liquid crystal in contact with the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction between the substrates.
- the liquid crystal alignment film may be required to play a role of controlling the pretilt angle of the liquid crystal in addition to the role of aligning the liquid crystal in a certain direction such as a direction parallel to the substrate.
- alignment control ability is given by performing an alignment treatment on the organic film constituting the liquid crystal alignment film.
- the rubbing method is a method of rubbing (rubbing) the surface of an organic film such as polyvinyl alcohol, polyamide or polyimide on a substrate with a cloth such as cotton, nylon or polyester in the rubbing direction (rubbing direction).
- This is a method of aligning liquid crystals. Since this rubbing method can easily realize a relatively stable alignment state of liquid crystals, it has been used in the manufacturing process of conventional liquid crystal display elements.
- an organic film used for the liquid crystal alignment film a polyimide-based organic film excellent in reliability such as heat resistance and electrical characteristics has been mainly selected.
- Anisotropy is formed in the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is aligned according to the anisotropy.
- a decomposition type photo-alignment method is known as a main photo-alignment method.
- the polyimide film is irradiated with polarized ultraviolet rays, and anisotropic decomposition is caused by utilizing the polarization direction dependence of the ultraviolet absorption of the molecular structure. Then, the liquid crystal is aligned by the polyimide remaining without being decomposed (see Patent Document 1).
- a photo-alignment method using a photocrosslinking type is also known.
- polyvinyl cinnamate is used and irradiated with polarized ultraviolet rays to cause a dimerization reaction (crosslinking reaction) at the double bond portion of two side chains parallel to the polarized light.
- a pretilt angle appears by irradiating polarized ultraviolet rays in an oblique direction (see Non-Patent Document 1).
- Non-Patent Document 2 when a side chain polymer having coumarin in the side chain is used, polarized UV light is irradiated to cause a photocrosslinking reaction in the coumarin part of the side chain parallel to the polarized light, and the liquid crystal is aligned in a direction parallel to the polarization direction.
- the liquid crystal alignment film alignment treatment method by the photo alignment method eliminates the need for rubbing, and there is no fear of generation of dust or static electricity.
- An alignment process can be performed even on a substrate of a liquid crystal display element having an uneven surface, which is a method for aligning a liquid crystal alignment film suitable for an industrial production process.
- the alignment direction can be controlled by ultraviolet rays in the photo-alignment method, it is possible to form a plurality of regions having different alignment directions (alignment division) in a pixel to compensate for viewing angle dependency.
- the liquid crystal alignment film also plays a role of providing a certain tilt angle (pretilt angle) to the liquid crystal, and the provision of the pretilt angle has become an important issue in the development of liquid crystal alignment films (patents).
- pretilt angle a certain tilt angle
- the photo-alignment method eliminates the rubbing process itself as compared with the rubbing method that has been used industrially as an alignment treatment method for liquid crystal display elements, and thus has a great advantage. And compared with the rubbing method in which the alignment control ability becomes almost constant by rubbing, the photo alignment method can control the alignment control ability by changing the irradiation amount of polarized light.
- the photo-alignment method in order to achieve the same degree of alignment control ability as in the rubbing method, a large amount of polarized light irradiation may be required or stable liquid crystal alignment may not be realized. .
- the present invention provides a substrate having a liquid crystal alignment film for a liquid crystal display element having high efficiency and high alignment control ability and excellent tilt angle characteristics, and a twisted nematic liquid crystal display element and OCB type liquid crystal display element having the substrate.
- the purpose is to do.
- an object of the present invention is to provide a twisted nematic liquid crystal display element and an OCB liquid crystal display element having improved tilt angle characteristics, and a liquid crystal alignment film for the element.
- Monomer (A-1) a monomer having one cinnamoyl moiety, 2 to 4 benzene rings that do not constitute the cinnamoyl moiety, and a polymerizable group.
- Monomer (A-2) a monomer having one cinnamoyl moiety, one benzene ring that does not constitute the cinnamoyl moiety, and a polymerizable group. (The cinnamoyl moiety and the benzene ring may have a substituent.)
- the component (A) is polymerized into any one group selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2) A monomer to which a functional group is bonded is preferable.
- A, B and D each independently represent a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH— or —NH—CO—;
- S is an alkylene group having 1 to 12 carbon atoms, and each hydrogen atom bonded thereto may be independently replaced with a halogen group;
- T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
- B also represents a single bond;
- Y 1 is a divalent benzene ring;
- P 1 , Q 1 and Q 2 are each independently a group selected from the group consisting of a benzene ring and an alicyclic hydrocarbon ring having 5 to 8 carbon atoms;
- R 1 is a hydrogen atom, —CN, halogen group, alkyl group having 1 to 5 carbon atoms, (alkyl having 1 to 5 carbon
- each hydrogen atom bonded to the benzene ring is independently —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an (alkyl group having 1 to 5 carbon atoms) carbonyl group.
- X 1 and X 2 each independently represents a single bond, —O—, —COO— or —OCO—; n1 and n2 are each independently 0, 1 or 2, When the number of X 1 is 2, X 1 may be the same or different, and when the number of X 2 is 2, X 2 may be the same or different; When the number of Q 1 is 2, Q 1 may be the same or different, and when the number of Q 2 is 2, Q 2 may be the same or different; In the monomer (A-1), the total number of benzene rings other than Y 1 is 2 to 4; In the monomer (A-2), the total number of benzene rings other than Y 1 is 1; A broken line represents a bond with a polymerizable group.
- ⁇ 4> A step of applying the polymer composition according to any one of ⁇ 1> to ⁇ 3> above onto a substrate having an electrode for driving a liquid crystal to form a coating film; [II] A step of irradiating the coating film obtained in [I] with ultraviolet rays polarized from an oblique direction; and [III] a step of heating the coating film obtained in [II]; A method for producing a substrate having a liquid crystal alignment film, which obtains a twisted nematic liquid crystal display element and a liquid crystal alignment film for an OCB type liquid crystal display element to which an alignment control ability is imparted.
- ⁇ 5> A substrate having a twisted nematic liquid crystal display element and / or a liquid crystal alignment film for OCB type liquid crystal display element manufactured by the manufacturing method according to the above ⁇ 4>.
- ⁇ 6> A twisted nematic liquid crystal display element and an OCB type liquid crystal display element having the substrate of ⁇ 5> above.
- the present invention it is possible to provide a substrate having a liquid crystal alignment film which has high efficiency and orientation control ability and is excellent in tilt angle characteristics, and a twisted nematic liquid crystal display element and OCB type liquid crystal display element having the substrate.
- the twisted nematic liquid crystal display element and OCB type liquid crystal display element manufactured by the method of the present invention are imparted with an alignment control ability with high efficiency, so that display characteristics are not impaired even when driven continuously for a long time.
- the liquid crystal aligning agent used in the production method of the present invention has a photosensitive side chain polymer that can exhibit liquid crystallinity (hereinafter, also simply referred to as a side chain polymer).
- the coating film obtained by use is a film having a photosensitive side chain polymer that can exhibit liquid crystallinity. This coating film is subjected to orientation treatment by irradiation with polarized light without being rubbed. And after polarized light irradiation, it will become the coating film (henceforth a liquid crystal aligning film) to which the orientation control ability was provided through the process of heating the side chain type polymer film.
- Component (A) is a copolymer (hereinafter also referred to as a side chain polymer) obtained from a monomer mixture containing the following monomer (A-1) and monomer (A-2).
- Monomer (A-1) a monomer having one cinnamoyl moiety, 2 to 4 benzene rings that do not constitute the cinnamoyl moiety, and a polymerizable group.
- a methyl group, a methoxy group, a tertiary butyl group, an acetyl group, a fluorine group, a cyano group etc. are mentioned, for example.
- a side chain having photosensitivity is bonded to the main chain, and can react with light to cause a crosslinking reaction and an isomerization reaction.
- the structure of the side chain having photosensitivity is not particularly limited, but a structure that causes a crosslinking reaction in response to light is desirable. In this case, even if exposed to external stress such as heat, the achieved orientation control ability can be stably maintained for a long period of time.
- More specific examples of the structure of the side chain polymer of component (A) include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, and norbornene.
- A, B and D each independently represent a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH— or —NH—CO—;
- S is an alkylene group having 1 to 12 carbon atoms, and each hydrogen atom bonded thereto may be independently replaced with a halogen group;
- T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
- B also represents a single bond;
- Y 1 is a divalent benzene ring;
- P 1 , Q 1 and Q 2 are each independently a group selected from the group consisting of a benzene ring and an alicyclic hydrocarbon ring having 5 to 8 carbon atoms;
- R 1 is a hydrogen atom, —CN, halogen group, alkyl group having 1 to 5 carbon atoms, (alkyl having 1 to 5 carbon
- each hydrogen atom bonded to the benzene ring is independently —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an (alkyl group having 1 to 5 carbon atoms) carbonyl group.
- X 1 and X 2 each independently represents a single bond, —O—, —COO— or —OCO—; n1 and n2 are each independently 0, 1 or 2, When the number of X 1 is 2, X 1 may be the same or different, and when the number of X 2 is 2, X 2 may be the same or different; When the number of Q 1 is 2, Q 1 may be the same or different, and when the number of Q 2 is 2, Q 2 may be the same or different; In the monomer (A-1), the total number of benzene rings other than Y 1 is 2 to 4; In the monomer (A-2), the total number of benzene rings other than Y 1 is 1; A broken line represents a bond with a polymerizable group.
- the content of the side chain derived from (A-1) in the total of the content of the side chain derived from (A-1) and the content of the side chain derived from (A-2) in the side chain type polymer of the present invention Is preferably from 10 mol% to 90 mol%, more preferably from 20 mol% to 80 mol%, and even more preferably from 30 mol% to 70 mol%, from the viewpoints of liquid crystal alignment and solubility of the side chain polymer.
- the side chain polymer of the present invention contains side chains derived from (A-1) and other side chains other than the side chain derived from (A-2) as long as the effects of the present invention are not impaired. Also good.
- the content is the remaining portion when the total content of the photoreactive side chain and the liquid crystalline side chain is less than 100%.
- the photosensitive side chain polymer capable of exhibiting the above liquid crystallinity can be obtained by polymerizing a monomer mixture containing at least the monomer (A-1) and the monomer (A-2).
- the photoreactive side chain monomer is a monomer capable of forming a polymer having a photosensitive side chain at the side chain portion of the polymer when the polymer is formed.
- the photoreactive group possessed by the side chain the following structures and derivatives thereof are preferred.
- the monomer (A-1) and the monomer (A-2) include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, Photosensitivity selected from a polymerizable group composed of at least one selected from the group consisting of radically polymerizable groups such as norbornene and trialkoxysilyl groups, and structures represented by the above formulas (1) and (2) A structure having a side chain is preferred.
- the polymerizable group is preferably selected from groups represented by the following formulas PG1 to PG8. Among these, an acrylic group or a methacryl group represented by PG1 is preferable from the viewpoint of easy control of the polymerization reaction and the stability of the polymer.
- the broken line represents a bond with the photosensitive side chain represented by the formula (1) or (2).
- M1 is a hydrogen atom or a methyl group.
- Examples of the monomer (A-1) include monomers selected from the following formulas A1-1 to A1-7.
- PG represents a polymerizable group selected from the groups represented by the above formulas PG1 to PG8, s1 and s2 each independently represents the number of methylene groups, It is a natural number.
- Examples of the monomer (A-2) include monomers selected from the following formulas A2-1 to A2-14.
- PG represents a polymerizable group selected from the groups represented by the above formulas PG1 to PG8, s1 and s2 each independently represents the number of methylene groups, It is a natural number.
- the side chain polymer can be obtained by the copolymerization reaction of the monomer (A-1) and the monomer (A-2) described above. Furthermore, it can be copolymerized with other monomers as long as the liquid crystallinity is not impaired.
- examples of the other monomers include industrially available monomers capable of radical polymerization reaction.
- Specific examples of the other monomer include unsaturated carboxylic acid, acrylic ester compound, methacrylic ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound and vinyl compound.
- unsaturated carboxylic acid examples include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
- acrylic ester compound examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl.
- methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl.
- vinyl compound examples include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
- styrene compound examples include styrene, methyl styrene, chlorostyrene, bromostyrene, and the like.
- maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
- the content of the photoreactive side chain represented by (A-1) and (A-2) in the side chain polymer of the present invention is preferably 10 mol% to 100 mol% from the viewpoint of liquid crystal alignment. 20 mol% to 100 mol% is more preferable, and 30 mol% to 100 mol% is still more preferable.
- the production method of the side chain polymer of the present embodiment is not particularly limited, and a general-purpose method that is handled industrially can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using the vinyl group of the monomer (A-1) or (A-2). Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control.
- reaction temperature reaction temperature
- solvent and the like of radical polymerization known conditions described in International Patent Application Publication No. WO2014 / 074785 can be used.
- the method for obtaining the polysiloxane is not particularly limited.
- the monomer (A-1) and the monomer (A-2) described above are obtained by condensing an alkoxysilane mixture containing a monomer whose polymerizable group is a trialkoxysilyl group as an essential component in an organic solvent. It is done.
- polysiloxane is obtained as a solution obtained by polycondensation of such alkoxysilanes and uniformly dissolved in an organic solvent.
- an alkoxysilane represented by the following formula (3) can also be used. Since the alkoxysilane represented by the formula (3) can impart various characteristics to the polysiloxane, one or more kinds can be selected and used according to the required characteristics.
- R 5 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group
- R 6 represents an alkyl group having 1 to 5, preferably 1 to 3 carbon atoms, and n represents an integer of 0 to 3, preferably 0 to 2.
- R 5 of the alkoxysilane represented by the formula (3) is a hydrogen atom or an organic group having 1 to 6 carbon atoms (hereinafter also referred to as a third organic group).
- the third organic group include aliphatic hydrocarbons; ring structures such as aliphatic rings, aromatic rings and heterocycles; unsaturated bonds; and heteroatoms such as oxygen atoms, nitrogen atoms and sulfur atoms. It is an organic group having 1 to 6 carbon atoms, which may be included and may have a branched structure.
- the organic group may be substituted with a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group, a ureido group, or the like.
- a halogen atom an amino group, a glycidoxy group, a mercapto group, an isocyanate group, a ureido group, or the like.
- R 5 is a hydrogen atom
- specific examples of the alkoxysilane when R 5 is a hydrogen atom include trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane and the like.
- alkoxysilane of the formula (3) specific examples of the alkoxysilane when R 5 is a third organic group include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane.
- the polysiloxane used in the present invention is a kind of the alkoxysilane represented by the above formula (3) as long as the effect of the present invention is not impaired for the purpose of improving the adhesion with the substrate and the affinity with the liquid crystal molecules. Or you may have multiple types.
- the alkoxysilane in which n is 0 is tetraalkoxysilane.
- Tetraalkoxysilane is preferable for obtaining the polysiloxane of the present invention because it easily condenses with the alkoxysilane represented by the formulas (1) and (2).
- tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is more preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable.
- the polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating.
- impurities in the polymer can be reduced.
- the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
- the molecular weight of the (A) side chain polymer of the present invention is measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, workability at the time of forming the coating film, and uniformity of the coating film.
- the weight average molecular weight is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000.
- the organic solvent used for the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. Specific examples are given below. N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone,
- liquid crystal aligning agent is applied to the side of the substrate on which the electrodes are formed.
- the liquid crystal aligning agent of the present invention uses the polymer composition according to the present invention, and contains (A) a copolymer obtained from the monomer mixture containing the monomer (A-1) and the monomer (A-2). To do.
- the liquid crystal aligning agent used for this invention is prepared as a coating liquid so that it may become suitable for formation of a liquid crystal aligning film. That is, the liquid crystal aligning agent used in the present invention is preferably prepared as a solution in which a resin component for forming a resin film is dissolved in an organic solvent.
- the resin component is a resin component containing the side chain polymer that is the component (A) already described.
- the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.
- the above-mentioned resin component may be a side chain type polymer that is all the component (A), but other polymers may be used as long as the liquid crystal aligning ability is not impaired. It may be mixed. In that case, the content of the other polymer in the resin component is 0.5 to 80% by mass, preferably 1 to 50% by mass.
- Such other polymers are composed of, for example, poly (meth) acrylate, polyamic acid, polyimide, and the like, and examples thereof include polymers other than the side chain type polymer as the component (A).
- the polymer composition used in the present invention may contain components other than the side chain polymer and organic solvent as the component (A).
- components other than the side chain polymer and organic solvent examples thereof include solvents and compounds that improve film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, compounds that improve the adhesion between the liquid crystal alignment film and the substrate, and the like. It is not limited to this.
- solvent poor solvent which improves the uniformity of film thickness and surface smoothness.
- solvents may be used alone or in combination.
- it is preferably 5% by mass to 80% by mass of the total solvent, more preferably so as not to significantly reduce the solubility of the entire solvent contained in the polymer composition. Is 20% by mass to 60% by mass.
- Examples of the compound that improves film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), MegaFac (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (Manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Company), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.) It is done.
- the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the polymer
- the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds.
- phenoplasts and epoxy group-containing compounds for the purpose of preventing the deterioration of electrical characteristics due to the backlight when the liquid crystal display element is constructed
- An agent may be contained in the liquid crystal aligning agent. Specific phenoplast additives are shown below, but are not limited to this structure.
- Specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N ′,-tetraglycidyl- , 4'-diaminodip
- the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent. More preferably, it is 1 to 20 parts by mass. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
- a photosensitizer can also be used as an additive. Colorless and triplet sensitizers are preferred.
- photosensitizers aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarins, carbonyl biscoumarins, aromatic 2-hydroxyketones, and amino-substituted Aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl- ⁇ -naphthothiazoline, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazoline, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-b
- Aromatic 2-hydroxy ketone (benzophenone), coumarin, ketocoumarin, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal are preferred.
- the method for producing a substrate having the liquid crystal alignment film of the present invention is as follows. [I] (A) A step of applying a liquid crystal aligning agent containing a side chain polymer and an organic solvent on a substrate having a transparent electrode to form a coating film; [II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II]; Have Through the above steps, a liquid crystal alignment film for a liquid crystal display element to which alignment control ability is imparted can be obtained, and a substrate having the liquid crystal alignment film can be obtained.
- a liquid crystal display element can be obtained by preparing a 2nd board
- the second substrate can be obtained by using the above steps [I] to [III] on the second substrate having a transparent electrode to obtain a second substrate having a liquid crystal alignment film imparted with alignment control ability. it can.
- the manufacturing method of the twist nematic type liquid crystal display element and the OCB type liquid crystal display element is as follows: [IV] A step of obtaining a liquid crystal display element by arranging the first and second substrates obtained above so that the liquid crystal alignment films of the first and second substrates face each other with liquid crystal interposed therebetween; Have Thereby, a twisted nematic liquid crystal display element can be obtained.
- step [I] a liquid crystal aligning agent containing (A) a side chain polymer and an organic solvent is applied to a substrate having a liquid crystal driving electrode to form a coating film.
- ⁇ Board> Although it does not specifically limit about a board
- the method for applying the liquid crystal aligning agent described above on a substrate having an electrode for driving liquid crystal is not particularly limited.
- the application method is generally performed by screen printing, offset printing, flexographic printing, an inkjet method, or the like.
- Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method (rotary coating method), or a spray method, and these may be used depending on the purpose.
- the temperature is set to 50 to 230 ° C., preferably 50 to 200 ° C. by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven.
- the coating film can be obtained by evaporating the solvent for 0.4 minutes to 60 minutes, preferably 0.5 minutes to 10 minutes.
- the drying temperature at this time is preferably lower than the temperature range of the temperature at which the side chain polymer of the side chain polymer as component (A) exhibits liquid crystallinity (hereinafter referred to as liquid crystal expression temperature).
- the thickness of the coating film is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. It is.
- step [II] the coating film obtained in step [I] is irradiated with ultraviolet rays polarized from an oblique direction.
- the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a certain direction.
- ultraviolet rays to be used ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used.
- the optimum wavelength is selected through a filter or the like depending on the type of coating film to be used.
- ultraviolet light having a wavelength in the range of 290 nm to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced.
- the ultraviolet light for example, light emitted from a high-pressure mercury lamp can be used.
- the irradiation amount of polarized ultraviolet rays depends on the coating film used.
- the amount of irradiation is polarized ultraviolet light that realizes the maximum value of ⁇ A (hereinafter also referred to as ⁇ Amax), which is the difference between the ultraviolet light absorbance in a direction parallel to the polarization direction of polarized ultraviolet light and the ultraviolet light absorbance in a direction perpendicular to the polarization direction of the polarized ultraviolet light.
- the amount is preferably in the range of 1% to 70%, more preferably in the range of 1% to 50%.
- the direction of irradiation of polarized ultraviolet rays is usually 1 ° to 89 ° with respect to the substrate, preferably 10 ° to 80 °, particularly preferably 20 ° to 70 °.
- this angle is too small, there is a problem that the pretilt angle becomes small, and when it is too large, there is a problem that the pretilt angle becomes high.
- the method of adjusting the irradiation direction to the above angle includes a method of tilting the substrate itself and a method of tilting the light source, but tilting the light source itself is more preferable from the viewpoint of throughput.
- the pretilt angle obtained is preferably 1 ° to 20 °, more preferably 2 ° to 15 ° as a pretilt angle suitable for the twisted nematic mode.
- step [III] the ultraviolet-irradiated coating film polarized in step [II] is heated.
- An orientation control ability can be imparted to the coating film by heating.
- a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven can be used.
- the heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the coating film used is developed.
- the heating temperature is preferably within the temperature range of the temperature at which the side chain polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal expression temperature).
- the liquid crystal expression temperature on the coating film surface is expected to be lower than the liquid crystal expression temperature when the side chain polymer as the component (A) is observed in bulk. Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal expression temperature on the coating film surface. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is 10 ° C. lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain polymer used, and 10 ° C. lower than the upper limit of the liquid crystal temperature range.
- the temperature of the range which makes an upper limit it is the temperature of the range which makes an upper limit. If the heating temperature is lower than the above temperature range, the anisotropic amplification effect due to heat in the coating film tends to be insufficient, and if the heating temperature is too higher than the above temperature range, the state of the coating film Tends to be close to an isotropic liquid state (isotropic phase), and in this case, self-organization may make it difficult to reorient in one direction.
- the liquid crystal expression temperature is not less than the glass transition temperature (Tg) at which the side chain polymer or coating film surface undergoes a phase transition from the solid phase to the liquid crystal phase, and from the liquid crystal phase to the isotropic phase (isotropic phase). It means a temperature below the isotropic phase transition temperature (Tiso) that causes a phase transition.
- the thickness of the coating film formed after heating is preferably 5 nm to 300 nm, more preferably 50 nm to 150 nm, for the same reason described in the step [I].
- the production method of the present invention can realize highly efficient introduction of anisotropy into the coating film. And a board
- the process includes two substrates obtained in [III] arranged so that the side on which the liquid crystal alignment film is formed faces each other, a liquid crystal layer provided between the substrates, a substrate and a liquid crystal layer And a liquid crystal cell having the liquid crystal alignment film formed with the liquid crystal aligning agent of the present invention.
- a liquid crystal display element of the present invention a twisted nematic (TN) method, a vertical alignment (VA) method, a horizontal alignment (IPS) method, an OCB alignment (OCB: OCB).
- TN twisted nematic
- VA vertical alignment
- IPS horizontal alignment
- OCB alignment OCB: OCB
- There are various types such as Optically Compensated Bend).
- the first and second substrates described above are prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside.
- the other substrate is bonded so that the ultraviolet light exposure directions are orthogonal to each other, and the liquid crystal is injected under reduced pressure to seal it, or after the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed,
- the method of sticking together and performing sealing etc. can be illustrated.
- the diameter of the spacer at this time is preferably 1 ⁇ m to 30 ⁇ m, more preferably 2 ⁇ m to 10 ⁇ m. This spacer diameter determines the distance between the pair of substrates that sandwich the liquid crystal layer, that is, the thickness of the liquid crystal layer.
- the obtained liquid crystal display element is preferably annealed for further alignment stability.
- the heating temperature is the phase transition temperature of the liquid crystal, preferably 10 to 160 ° C., more preferably 50 to 140 ° C.
- substrate with a coating film of this invention irradiates the polarized ultraviolet-ray, after apply
- high-efficiency anisotropy is introduced into the side chain polymer film, and a substrate with a liquid crystal alignment film having a liquid crystal alignment control ability is manufactured.
- the coating film used in the present invention realizes the introduction of highly efficient anisotropy into the coating film by utilizing the principle of molecular reorientation induced by the side chain photoreaction and liquid crystallinity. .
- the coating film used in the method of the present invention is a liquid crystal alignment film having anisotropy introduced with high efficiency and excellent alignment control ability by sequentially performing irradiation of polarized ultraviolet rays on the coating film and heat treatment. can do.
- the irradiation amount of polarized ultraviolet rays to the coating film and the heating temperature in the heat treatment are optimized. Thereby, introduction of anisotropy into the coating film with high efficiency can be realized.
- the optimum irradiation amount of polarized ultraviolet rays for introducing highly efficient anisotropy into the coating film used in the present invention is polarized light that optimizes the amount of photocrosslinking reaction or photoisomerization reaction of the photosensitive group in the coating film. Corresponds to the amount of UV irradiation.
- the photoreaction amount is not sufficient. In that case, sufficient self-organization does not proceed even after heating.
- the crosslinking reaction between the side chains is caused when the photosensitive group of the side chain undergoing the crosslinking reaction becomes excessive. Too much progress. In that case, the resulting film may become rigid and hinder the progress of self-assembly by subsequent heating.
- the optimum amount of the photopolymerization reaction or photoisomerization reaction of the side chain photosensitive group by irradiation with polarized ultraviolet rays is the amount of the photosensitive group possessed by the side chain polymer film.
- the amount is preferably 0.1 mol% to 60 mol%, more preferably 0.1 mol% to 40 mol%.
- the coating film used in the method of the present invention by optimizing the irradiation amount of polarized ultraviolet rays, photocrosslinking reaction or photoisomerization reaction of photosensitive groups or photofleece rearrangement reaction in the side chain of the side chain polymer film Optimize the amount of. Then, in combination with the subsequent heat treatment, highly efficient introduction of anisotropy into the coating film used in the present invention is realized. In that case, a suitable amount of polarized ultraviolet rays can be determined based on the evaluation of ultraviolet absorption of the coating film used in the present invention.
- the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorption in the vertical direction after the irradiation with the polarized ultraviolet ray are measured.
- ⁇ A which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays.
- the maximum value of ⁇ A ( ⁇ Amax) realized in the coating film used in the present invention and the irradiation amount of polarized ultraviolet light that realizes it are obtained.
- a preferable amount of polarized ultraviolet rays to be irradiated in the production of the liquid crystal alignment film can be determined on the basis of the amount of polarized ultraviolet rays to realize this ⁇ Amax.
- the amount of irradiation of polarized ultraviolet rays onto the coating film used in the present invention is preferably in the range of 1% to 70% of the amount of polarized ultraviolet rays that realizes ⁇ Amax. More preferably, it is within the range of 50%.
- the irradiation amount of polarized ultraviolet light within the range of 1% to 50% of the amount of polarized ultraviolet light that realizes ⁇ Amax is 0. 0% of the entire photosensitive group of the side chain polymer film. 1 mol% to 20 mol% corresponds to the amount of polarized ultraviolet light that undergoes a photocrosslinking reaction.
- a suitable heating temperature as described above is set based on the liquid crystal temperature range of the side chain polymer. It is good to decide. Therefore, for example, when the liquid crystal temperature range of the side chain polymer used in the present invention is 100 ° C. to 200 ° C., the heating temperature after irradiation with polarized ultraviolet light is desirably 90 ° C. to 190 ° C. By doing so, greater anisotropy is imparted to the coating film used in the present invention.
- the liquid crystal display element provided by the present invention exhibits high reliability against external stresses such as light and heat.
- the twisted nematic type liquid crystal display element substrate manufactured by the method of the present invention, the liquid crystal display element having the substrate, the OCB type liquid crystal display element substrate, or the liquid crystal display element having the substrate is reliable. It can be suitably used for a large-screen and high-definition liquid crystal television. Moreover, it is useful also for a liquid crystal antenna, a light control element, etc.
- MA-1 was synthesized by a synthesis method described in non-patent literature (Macromolecules 2002, 35, 706-713).
- MA-2 was synthesized by the synthesis method described in British Patent GB2306470B.
- MA-3 was synthesized by a synthesis method described in non-patent literature (Macromolecules 2007, 40, 6355-6360).
- MA-4 was synthesized by the synthesis method described in the pamphlet of International Patent Application Publication No. WO2014 / 054785.
- MA-5 was synthesized by the synthesis method described in the patent document (Japanese Patent Laid-Open No. 9-118717).
- MA-6 was purchased from Tokyo Chemical Industry Co., Ltd. and used.
- MA-7 was purchased from Tokyo Chemical Industry Co., Ltd. and used.
- MA-8 was purchased from Tokyo Chemical Industry Co., Ltd. and used.
- MA-9 was purchased from Sigma-Aldrich Japan and used.
- methacrylate polymer powders P2 and P3 were produced using the same method as in synthesis example 1.
- methacrylate polymer powder P9 was produced using the same method as in Synthesis Example 8.
- methacrylate polymer powder P11 was produced using the same method as in Synthesis Example 10.
- methacrylate polymer powders P13 and P14 were prepared using the same method except that MA-7 in Synthesis Example 12 was replaced with MA-8 and MA-9. did.
- methacrylate polymer powder P17 was produced using the same method as in Synthesis Example 16.
- methacrylate polymer powder P21 was prepared in the same manner except that MA-2 in Synthesis Example 19 was replaced with MA-3.
- liquid crystal aligning agent A2 With respect to the liquid crystal aligning agents A2, A3, A5, A11, A12, A16 to A20, and the like under the conditions shown in Table 1, a liquid crystal aligning agent was produced using the same method as the liquid crystal aligning agent A1.
- liquid crystal aligning agent B2 B4, and B5 under the conditions shown in Table 1, a liquid crystal aligning agent was prepared using the same method as the liquid crystal aligning agent B1.
- liquid crystal aligning agent A6 With respect to the liquid crystal aligning agents A6, A7, and A13 under the conditions shown in Table 1, a liquid crystal aligning agent was produced using the same method as the liquid crystal aligning agent A4.
- liquid crystal aligning agent A9 under the conditions shown in Table 1, a liquid crystal aligning agent was prepared using the same method except that PGMEA of the liquid crystal aligning agent A8 was replaced with PGMEA.
- liquid crystal aligning agent A15 and A21 under the conditions shown in Table 1, a liquid crystal aligning agent was prepared using the same method as the liquid crystal aligning agent A10.
- liquid crystal aligning agent B3 under the conditions shown in Table 1, a liquid crystal aligning agent was prepared using the same method except that the BCA of the liquid crystal aligning agent A14 was replaced with BCS.
- a substrate for photoreaction rate measurement was prepared in the following procedure.
- a quartz substrate having a size of 40 mm ⁇ 40 mm and a thickness of 1.0 mm was used as the substrate.
- the liquid crystal aligning agent A1 was filtered through a filter having a filter pore size of 1.0 ⁇ m, spin-coated on a quartz substrate, and dried on a hot plate at 70 ° C. for 90 seconds to form a liquid crystal aligning film having a thickness of 100 nm.
- Example 1 After irradiating the surface of the coating film with ultraviolet rays of 313 nm at 80 mJ / cm 2 via a polarizing plate, it was heated on a hot plate at 120 ° C. for 20 minutes to obtain a substrate with a liquid crystal alignment film that had undergone photoreaction.
- a para represents the absorbance in the direction parallel to the irradiated polarized UV direction
- a per represents the absorbance in the direction perpendicular to the irradiated polarized UV direction.
- a large represents the absorbance having a larger value by comparing the absorbance in the parallel direction and the vertical direction
- a small represents the absorbance having a smaller value by comparing the absorbance in the parallel direction and the vertical direction.
- the absolute value of the in-plane orientation degree is closer to 1, indicating that the orientation is more uniform.
- the liquid crystal alignment agent (A1) was filtered through a 0.45 ⁇ m filter, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C. for 90 seconds to form a liquid crystal alignment film having a thickness of 100 nm. .
- Example 15 The coated surface was tilted by 40 °, and ultraviolet rays of 313 nm were irradiated through a polarizing plate at 80 mJ / cm 2 and then heated on a hot plate at 140 ° C. for 20 minutes to obtain a substrate with a liquid crystal alignment film. Two substrates with such a liquid crystal alignment film are prepared, a spacer of 4 ⁇ m is set on the liquid crystal alignment film surface of one of the substrates, and then combined so that the rubbing directions of the two substrates are parallel to each other. The periphery was sealed, and an empty cell with a cell gap of 4 ⁇ m was produced.
- Liquid crystal MLC-2003 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an anti-parallel liquid crystal cell. After heating at a temperature of 120 ° C. for 30 minutes, the pretilt angle of this liquid crystal cell was measured.
- liquid crystal cells were prepared using the same method as in Example 1, and the pretilt angle was measured.
- an in-plane orientation degree measurement substrate was prepared using the same method as in Example 1 under the conditions described in Table 4. Then, when the degree of orientation and the pretilt angle were measured according to the above examples, it was found that the pretilt angle can be adjusted according to the polarized UV irradiation dose and the main baking conditions as shown in Table 4.
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Abstract
Description
のなかに配向方向の異なる領域を複数形成(配向分割)し,視野角依存性を補償することが可能である。
一方、液晶配向膜は液晶に対し、ある一定の傾斜角(プレチルト角)を付与する役割も担っており、プレチルト角の付与が液晶配向膜の開発において重要な課題となって来ている(特許文献1~4参照)。
また、本発明の目的は、上記目的に加えて、向上したチルト角特性を有するツイストネマチック型液晶表示素子及びOCB型液晶表示素子及び該素子のための液晶配向膜を提供することにある。
モノマー(A-1):シンナモイル部位を1つと、シンナモイル部位を構成しないベンゼン環を2~4つと、重合性基とを有するモノマー。
モノマー(A-2):シンナモイル部位を1つと、シンナモイル部位を構成しないベンゼン環を1つと、重合性基とを有するモノマー。
(上記シンナモイル部位とベンゼン環は、置換基を有していてもよい。)
Sは、炭素数1~12のアルキレン基であり、それに結合する水素原子はそれぞれ独立にハロゲン基に置き換えられていてもよい;
Tは、単結合または炭素数1~12のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい;
Tが単結合であるときはBも単結合を表す;
Y1は、2価のベンゼン環である;
P1、Q1及びQ2は、それぞれ独立にベンゼン環及び炭素数5~8の脂環式炭化水素環からなる群から選ばれる基である;
R1は、水素原子、-CN、ハロゲン基、炭素数1~5のアルキル基、(炭素数1~5のアルキル)カルボニル基、炭素数3~7のシクロアルキル基又は炭素数1~5のアルキルオキシ基である。
Y1、P1、Q1及びQ2において、ベンゼン環に結合する水素原子はそれぞれ独立に-CN、ハロゲン基、炭素数1~5のアルキル基、(炭素数1~5のアルキル)カルボニル基、又は炭素数1~5のアルキルオキシ基で置換されてもよい;
X1及びX2は、それぞれ独立に単結合、-O-、-COO-又は-OCO-を表す;
n1及びn2はそれぞれ独立に0、1または2である、
X1の数が2となるときは、X1同士は同一でも異なっていてもよく、X2の数が2となるときは、X2同士は同一でも異なっていてもよい;
Q1の数が2となるときは、Q1同士は同一でも異なっていてもよく、Q2の数が2となるときは、Q2同士は同一でも異なっていてもよい;
モノマー(A-1)においては、Y1以外のベンゼン環の数の合計は2~4である;
モノマー(A-2)においては、Y1以外のベンゼン環の数の合計は1である;
破線は重合性基との結合手を表す。
[II] [I]で得られた塗膜に斜め方向から偏光した紫外線を照射する工程;及び
[III] [II]で得られた塗膜を加熱する工程;
を有することによって配向制御能が付与されたツイストネマチック型液晶表示素子及びOCB型液晶表示素子用液晶配向膜を得る、前記液晶配向膜を有する基板の製造方法。
<6> 上記<5>の基板を有するツイストネマチック型液晶表示素子及びOCB型液晶表示素子。
[I’] 第2の基板上に、上記<1>~<4>のいずれに記載の重合体組成物を、塗布して塗膜を形成する工程;
[II’] [I’]で得られた塗膜に偏光した紫外線を照射する工程;及び
[III’] [II’]で得られた塗膜を加熱する工程;
を有することによって配向制御能が付与された液晶配向膜を得る、該液晶配向膜を有する第2の基板を得る工程;及び
[IV] 液晶を介して第1及び第2の基板の液晶配向膜が相対するように、露光方向が互いに直交するように第1及び第2の基板を対向配置して液晶表示素子を得る工程;
を有することにより、ツイストネマチック型液晶表示素子及びOCB型液晶表示素子を得る、該液晶表示素子の製造方法。
<8> 上記<7>により製造されたツイストネマチック型液晶表示素子及びOCB型液晶表示素子。
本発明の方法によって製造されたツイストネマチック型液晶表示素子及びOCB型液晶表示素子は、高効率に配向制御能が付与されているため長時間連続駆動しても表示特性が損なわれることがない。
<液晶配向膜を有する基板の製造方法>及び<液晶表示素子の製造方法>
(A)成分は、下記モノマー(A-1)及びモノマー(A-2)を含むモノマー混合物から得られる共重合体(以下、側鎖型高分子とも言う)である。
モノマー(A-1):シンナモイル部位を1つと、シンナモイル部位を構成しないベンゼン環を2~4つと、重合性基とを有するモノマー。
モノマー(A-2):シンナモイル部位を1つと、シンナモイル部位を構成しないベンゼン環を1つと、重合性基とを有するモノマー。
(上記シンナモイル部位とベンゼン環は、置換基を有していてもよい。)
Sは、炭素数1~12のアルキレン基であり、それに結合する水素原子はそれぞれ独立にハロゲン基に置き換えられていてもよい;
Tは、単結合または炭素数1~12のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい;
Tが単結合であるときはBも単結合を表す;
Y1は、2価のベンゼン環である;
P1、Q1及びQ2は、それぞれ独立にベンゼン環及び炭素数5~8の脂環式炭化水素環からなる群から選ばれる基である;
R1は、水素原子、-CN、ハロゲン基、炭素数1~5のアルキル基、(炭素数1~5のアルキル)カルボニル基、炭素数3~7のシクロアルキル基又は炭素数1~5のアルキルオキシ基である。
Y1、P1、Q1及びQ2において、ベンゼン環に結合する水素原子はそれぞれ独立に-CN、ハロゲン基、炭素数1~5のアルキル基、(炭素数1~5のアルキル)カルボニル基、又は炭素数1~5のアルキルオキシ基で置換されてもよい;
X1及びX2は、それぞれ独立に単結合、-O-、-COO-又は-OCO-を表す;
n1及びn2はそれぞれ独立に0、1または2である、
X1の数が2となるときは、X1同士は同一でも異なっていてもよく、X2の数が2となるときは、X2同士は同一でも異なっていてもよい;
Q1の数が2となるときは、Q1同士は同一でも異なっていてもよく、Q2の数が2となるときは、Q2同士は同一でも異なっていてもよい;
モノマー(A-1)においては、Y1以外のベンゼン環の数の合計は2~4である;
モノマー(A-2)においては、Y1以外のベンゼン環の数の合計は1である;
破線は重合性基との結合手を表す。
上記の液晶性を発現し得る感光性の側鎖型高分子は、上記のモノマー(A-1)およびモノマー(A-2)を少なくとも含むモノマー混合物を重合することによって得ることができる。
光反応性側鎖モノマーとは、高分子を形成した場合に、高分子の側鎖部位に感光性側鎖を有する高分子を形成することができるモノマーのことである。
側鎖の有する光反応性基としては下記の構造およびその誘導体が好ましい。
その他のモノマーの具体例としては、不飽和カルボン酸、アクリル酸エステル化合物、メタクリル酸エステル化合物、マレイミド化合物、アクリロニトリル、マレイン酸無水物、スチレン化合物及びビニル化合物等が挙げられる。
本発明に用いる(A)成分である重合体がポリシロキサンである場合、当該ポリシロキサンを得る方法は特に限定されない。本発明においては、上記したモノマー(A-1)及びモノマー(A-2)において、重合性基がトリアルコキシシリル基であるモノマーを必須成分とするアルコキシシラン混合物を有機溶媒中で縮合させて得られる。通常、ポリシロキサンは、このようなアルコキシシランを重縮合して、有機溶媒に均一に溶解した溶液として得られる。
このような式(3)で表されるアルコキシシランの具体例を挙げるが、これに限定されるものではない。
式(3)のアルコキシシランにおいて、R5が水素原子である場合のアルコキシシランの具体例としては、トリメトキシシラン、トリエトキシシラン、トリプロポキシシラン、トリブトキシシラン等が挙げられる。
このような式(3)においてnが0であるアルコキシシランとしては、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン又はテトラブトキシシランがより好ましく、特に、テトラメトキシシラン又はテトラエトキシシランが好ましい。
上述の反応により得られた、液晶性を発現し得る感光性の側鎖型高分子の反応溶液から、生成した高分子を回収する場合には、反応溶液を貧溶媒に投入して、それら重合体を沈殿させれば良い。沈殿に用いる貧溶媒としては、メタノール、アセトン、ヘキサン、ヘプタン、ブチルセルソルブ、ヘプタン、メチルエチルケトン、メチルイソブチルケトン、エタノール、トルエン、ベンゼン、ジエチルエーテル、メチルエチルエーテル、水等を挙げることができる。貧溶媒に投入して沈殿させた重合体は、濾過して回収した後、常圧あるいは減圧下で、常温あるいは加熱して乾燥することができる。また、沈殿回収した重合体を、有機溶媒に再溶解させ、再沈殿回収する操作を2回~10回繰り返すと、重合体中の不純物を少なくすることができる。この際の貧溶媒として、例えば、アルコール類、ケトン類、炭化水素等が挙げられ、これらの中から選ばれる3種類以上の貧溶媒を用いると、より一層精製の効率が上がるので好ましい。
本発明に用いられる重合体組成物に用いる有機溶媒は、樹脂成分を溶解させる有機溶媒であれば特に限定されない。その具体例を以下に挙げる。
N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン、N-メチルカプロラクタム、2-ピロリドン、N-エチルピロリドン、N-ビニルピロリドン、ジメチルスルホキシド、テトラメチル尿素、ピリジン、ジメチルスルホン、ヘキサメチルスルホキシド、γ-ブチロラクトン、3-メトキシ-N,N-ジメチルプロパンアミド、3-エトキシ-N,N-ジメチルプロパンアミド、3-ブトキシ-N,N-ジメチルプロパンアミド、1,3-ジメチル-イミダゾリジノン、エチルアミルケトン、メチルノニルケトン、メチルエチルケトン、メチルイソアミルケトン、メチルイソプロピルケトン、シクロヘキサノン、エチレンカーボネート、プロピレンカーボネート、ジグライム、4-ヒドロキシ-4-メチル-2-ペンタノン、プロピレングリコールモノアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコール-tert-ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコール、ジエチレングリコールモノアセテート、ジエチレングリコールジメチルエーテル、ジプロピレングリコールモノアセテートモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノアセテートモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノアセテートモノプロピルエーテル、3-メチル-3-メトキシブチルアセテート、トリプロピレングリコールメチルエーテル等が挙げられる。これらは単独で使用しても、混合して使用してもよい。
上記基板の電極が形成された側に、液晶配向剤を塗布する。
本発明の液晶配向剤は、本発明による重合体組成物を用いるものであり、(A)上記モノマー(A-1)及びモノマー(A-2)を含むモノマー混合物から得られる共重合体を含有する。
本発明に用いられる液晶配向剤は、液晶配向膜の形成に好適となるように塗布液として調製されることが好ましい。すなわち、本発明に用いられる液晶配向剤は、樹脂被膜を形成するための樹脂成分が有機溶媒に溶解した溶液として調製されることが好ましい。ここで、その樹脂成分とは、既に説明した(A)成分である側鎖型高分子を含む樹脂成分である。その際、樹脂成分の含有量は、1質量%~20質量%が好ましく、より好ましくは3質量%~15質量%、特に好ましくは3質量%~10質量%である。
そのような他の重合体は、例えば、ポリ(メタ)アクリレートやポリアミック酸やポリイミド等からなり、(A)成分である側鎖型高分子以外の重合体等が挙げられる。
例えば、イソプロピルアルコール、メトキシメチルペンタノール、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルカルビトール、エチルカルビトール、エチルカルビトールアセテート、エチレングリコール、エチレングリコールモノアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコール、プロピレングリコールモノアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコール-tert-ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコール、ジエチレングリコールモノアセテート、ジエチレングリコールジメチルエーテル、ジプロピレングリコールモノアセテートモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノアセテートモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノアセテートモノプロピルエーテル、3-メチル-3-メトキシブチルアセテート、トリプロピレングリコールメチルエーテル、3-メチル-3-メトキシブタノール、ジイソプロピルエーテル、エチルイソブチルエーテル、ジイソブチレン、アミルアセテート、ブチルブチレート、ブチルエーテル、ジイソブチルケトン、メチルシクロへキセン、プロピルエーテル、ジヘキシルエーテル、1-ヘキサノール、n-へキサン、n-ペンタン、n-オクタン、ジエチルエーテル、乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸n-ブチル、酢酸プロピレングリコールモノエチルエーテル、ピルビン酸メチル、ピルビン酸エチル、3-メトキシプロピオン酸メチル、3-エトキシプロピオン酸メチルエチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸、3-メトキシプロピオン酸、3-メトキシプロピオン酸プロピル、3-メトキシプロピオン酸ブチル、1-メトキシ-2-プロパノール、1-エトキシ-2-プロパノール、1-ブトキシ-2-プロパノール、1-フェノキシ-2-プロパノール、プロピレングリコールモノアセテート、プロピレングリコールジアセテート、プロピレングリコール-1-モノメチルエーテル-2-アセテート、プロピレングリコール-1-モノエチルエーテル-2-アセテート、ジプロピレングリコール、2-(2-エトキシプロポキシ)プロパノール、乳酸メチルエステル、乳酸エチルエステル、乳酸n-プロピルエステル、乳酸n-ブチルエステル、乳酸イソアミルエステル等の低表面張力を有する溶媒等が挙げられる。
より具体的には、例えば、エフトップ(登録商標)301、EF303、EF352(トーケムプロダクツ社製)、メガファック(登録商標)F171、F173、R-30(DIC社製)、フロラードFC430、FC431(住友スリーエム社製)、アサヒガード(登録商標)AG710(旭硝子社製)、サーフロン(登録商標)S-382、SC101、SC102、SC103、SC104、SC105、SC106(AGCセイミケミカル社製)等が挙げられる。これらの界面活性剤の使用割合は、重合体組成物に含有される樹脂成分の100質量部に対して、好ましくは0.01質量部~2質量部、より好ましくは0.01質量部~1質量部である。
例えば、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、2-アミノプロピルトリメトキシシラン、2-アミノプロピルトリエトキシシラン、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、N-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシラン、3-ウレイドプロピルトリメトキシシラン、3-ウレイドプロピルトリエトキシシラン、N-エトキシカルボニル-3-アミノプロピルトリメトキシシラン、N-エトキシカルボニル-3-アミノプロピルトリエトキシシラン、N-トリエトキシシリルプロピルトリエチレントリアミン、N-トリメトキシシリルプロピルトリエチレントリアミン、10-トリメトキシシリル-1,4,7-トリアザデカン、10-トリエトキシシリル-1,4,7-トリアザデカン、9-トリメトキシシリル-3,6-ジアザノニルアセテート、9-トリエトキシシリル-3,6-ジアザノニルアセテート、N-ベンジル-3-アミノプロピルトリメトキシシラン、N-ベンジル-3-アミノプロピルトリエトキシシラン、N-フェニル-3-アミノプロピルトリメトキシシラン、N-フェニル-3-アミノプロピルトリエトキシシラン、N-ビス(オキシエチレン)-3-アミノプロピルトリメトキシシラン、N-ビス(オキシエチレン)-3-アミノプロピルトリエトキシシラン等が挙げられる。
光増感剤としては、芳香族ニトロ化合物、クマリン(7-ジエチルアミノ-4-メチルクマリン、7-ヒドロキシ4-メチルクマリン)、ケトクマリン、カルボニルビスクマリン、芳香族2-ヒドロキシケトン、およびアミノ置換された、芳香族2-ヒドロキシケトン(2-ヒドロキシベンゾフェノン、モノ-もしくはジ-p-(ジメチルアミノ)-2-ヒドロキシベンゾフェノン)、アセトフェノン、アントラキノン、キサントン、チオキサントン、ベンズアントロン、チアゾリン(2-ベンゾイルメチレン-3-メチル-β-ナフトチアゾリン、2-(β-ナフトイルメチレン)-3-メチルベンゾチアゾリン、2-(α-ナフトイルメチレン)-3-メチルベンゾチアゾリン、2-(4-ビフェノイルメチレン)-3-メチルベンゾチアゾリン、2-(β-ナフトイルメチレン)-3-メチル-β-ナフトチアゾリン、2-(4-ビフェノイルメチレン)-3-メチル-β-ナフトチアゾリン、2-(p-フルオロベンゾイルメチレン)-3-メチル-β-ナフトチアゾリン)、オキサゾリン(2-ベンゾイルメチレン-3-メチル-β-ナフトオキサゾリン、2-(β-ナフトイルメチレン)-3-メチルベンゾオキサゾリン、2-(α-ナフトイルメチレン)-3-メチルベンゾオキサゾリン、2-(4-ビフェノイルメチレン)-3-メチルベンゾオキサゾリン、2-(β-ナフトイルメチレン)-3-メチル-β-ナフトオキサゾリン、2-(4-ビフェノイルメチレン)-3-メチル-β-ナフトオキサゾリン、2-(p-フルオロベンゾイルメチレン)-3-メチル-β-ナフトオキサゾリン)、ベンゾチアゾール、ニトロアニリン(m-もしくはp-ニトロアニリン、2,4,6-トリニトロアニリン)またはニトロアセナフテン(5-ニトロアセナフテン)、(2-[(m-ヒドロキシ-p-メトキシ)スチリル]ベンゾチアゾール、ベンゾインアルキルエーテル、N-アルキル化フタロン、アセトフェノンケタール(2,2-ジメトキシフェニルエタノン)、ナフタレン、アントラセン(2-ナフタレンメタノール、2-ナフタレンカルボン酸、9-アントラセンメタノール、および9-アントラセンカルボン酸)、ベンゾピラン、アゾインドリジン、メロクマリン等がある。
好ましくは、芳香族2-ヒドロキシケトン(ベンゾフェノン)、クマリン、ケトクマリン、カルボニルビスクマリン、アセトフェノン、アントラキノン、キサントン、チオキサントン、およびアセトフェノンケタールである。
[I] (A)側鎖型高分子、及び有機溶媒を含有する液晶配向剤を、透明電極を有する基板上に塗布して塗膜を形成する工程;
[II] [I]で得られた塗膜に偏光した紫外線を照射する工程;及び
[III] [II]で得られた塗膜を加熱する工程;
を有する。
上記工程により、配向制御能が付与された液晶表示素子用液晶配向膜を得ることができ、該液晶配向膜を有する基板を得ることができる。
第2の基板は、透明電極を有する第二の基板に、上記工程[I]~[III]を用いることにより、配向制御能が付与された液晶配向膜を有する第2の基板を得ることができる。
[IV] 上記で得られた第1及び第2の基板を、液晶を介して第1及び第2の基板の液晶配向膜が相対するように、対向配置して液晶表示素子を得る工程;
を有する。これによりツイストネマチック型液晶表示素子を得ることができる。
<工程[I]>
工程[I]では、液晶駆動用の電極を有する基板上に、(A)側鎖型高分子、及び有機溶媒を含有する液晶配向剤を塗布して塗膜を形成する。
基板については、特に限定はされないが、製造される液晶表示素子が透過型である場合、透明性の高い基板が用いられることが好ましい。その場合、特に限定はされず、ガラス基板、またはアクリル基板やポリカーボネート基板等のプラスチック基板等を用いることができる。
液晶駆動のための電極としてはITO(Indium Tin Oxide:酸化インジウムスズ)、IZO(Indium Zinc Oxide:酸化インジウム亜鉛)などが好ましい。また、反射型の液晶表示素子では片側の基板のみにならばシリコンウエハー等の不透明な物でも使用でき、この場合の電極はアルミ等の光を反射する材料も使用できる。
基板に電極を形成する方法は、従来公知の手法を用いることができる。
塗布方法は、工業的には、スクリーン印刷、オフセット印刷、フレキソ印刷またはインクジェット法などで行う方法が一般的である。その他の塗布方法としては、ディップ法、ロールコータ法、スリットコータ法、スピンナ法(回転塗布法)またはスプレー法などがあり、目的に応じてこれらを用いてもよい。
塗膜の厚みは、厚すぎると液晶表示素子の消費電力の面で不利となり、薄すぎると液晶表示素子の信頼性が低下する場合があるので、好ましくは5nm~300nm、より好ましくは10nm~150nmである。
尚、[I]工程の後、続く[II]工程の前に塗膜の形成された基板を室温にまで冷却する工程を設けることも可能である。
工程[II]では、工程[I]で得られた塗膜に、斜め方向から偏光した紫外線を照射する。塗膜の膜面に偏光した紫外線を照射する場合、基板に対して一定の方向から偏光板を介して偏光された紫外線を照射する。使用する紫外線としては、波長100nm~400nmの範囲の紫外線を使用することができる。好ましくは、使用する塗膜の種類によりフィルター等を介して最適な波長を選択する。そして、例えば、選択的に光架橋反応を誘起できるように、波長290nm~400nmの範囲の紫外線を選択して使用することができる。紫外線としては、例えば、高圧水銀灯から放射される光を用いることができる。
工程[III]では、工程[II]で偏光した紫外線の照射された塗膜を加熱する。加熱により、塗膜に配向制御能を付与することができる。
加熱は、ホットプレート、熱循環型オーブンまたはIR(赤外線)型オーブンなどの加熱手段を用いることができる。加熱温度は、使用する塗膜の液晶性を発現させる温度を考慮して決めることができる。
[IV]工程は、基板の液晶配向膜が形成された側が対向するように配置された2枚の[III]で得られた基板と、基板間に設けられた液晶層と、基板と液晶層との間に設けられ本発明の液晶配向剤により形成された上記液晶配向膜とを有する液晶セルを具備する液晶表示素子である。このような本発明の液晶表示素子としては、ツイストネマティック(TN:Twisted Nematic)方式、垂直配向(VA:Vertical Alignment)方式や、水平配向(IPS:In-Plane Switching)方式、OCB配向(OCB:Optically Compensated Bend)等、種々のものが挙げられる。
本発明に用いる塗膜では、側鎖の光反応と液晶性に基づく自己組織化によって誘起される分子再配向の原理を利用して、塗膜への高効率な異方性の導入を実現する。本発明の製造方法では、側鎖型高分子に光反応性基として光架橋性基を有する構造の場合、側鎖型高分子を用いて基板上に塗膜を形成した後、偏光した紫外線を照射し、次いで、加熱を行った後、液晶表示素子を作成する。
<メタクリルモノマー>
MA-2は英国特許GB2306470Bに記載の合成法にて合成した。
MA-3は非特許文献(Macromolecules 2007, 40, 6355-6360)に記載の合成法にて合成した。
MA-4は国際特許出願公開WO2014/054785号パンフレットに記載の合成法にて合成した。
MA-5は特許文献(特開平9-118717)に記載の合成法にて合成した。
MA-6は東京化成工業株式会社より購入して使用した。
MA-7は東京化成工業株式会社より購入して使用した。
MA-8は東京化成工業株式会社より購入して使用した。
MA-9はシグマアルドリッチジャパンより購入して使用した。
THF:テトラヒドロフラン
NMP:N-メチル-2-ピロリドン
BCS:ブチルセロソルブ
BCA:ブチルセロソルブアセテート
CHN:シクロヘキサノン
GBL:γ-ブチルラクトン
PGME:プロピレングリコールモノメチルエーテル
PGMEA:プロピレングリコールモノメチルエーテルアセテート
<重合開始剤>
AIBN:2,2’-アゾビスイソブチロニトリル
MA-1(21g:40mmol)、MA-2(26g:60mmol)をTHF(270g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.5g:3mmol)を加え再び脱気を行った。この後、60℃で6時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をメタノール(2000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をメタノールで洗浄し、減圧乾燥しメタクリレートポリマー粉末P1を得た。
MA-3(23g:40mmol)、MA-2(26g:60mmol)をTHF(282g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.5g:3mmol)を加え再び脱気を行った。この後、60℃で6時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をメタノール(2000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をメタノールで洗浄し、減圧乾燥しメタクリレートポリマー粉末P4を得た。
MA-3(23g:40mmol)、MA-4(31g:60mmol)をTHF(310g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.5g:3mmol)を加え再び脱気を行った。この後、60℃で6時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をメタノール(2000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をメタノールで洗浄し、減圧乾燥しメタクリレートポリマー粉末P6を得た。
MA-1(21g:40mmol)、MA-2(13g:30mmol)、MA-4(9g:30mmol)をTHF(246g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.5g:3mmol)を加え再び脱気を行った。この後、60℃で6時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をメタノール(2000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をメタノールで洗浄し、減圧乾燥しメタクリレートポリマー粉末P8を得た。
MA-1(21g:40mmol)、MA-2(26g:60mmol)、MA-5(2g:20mmol)をTHF(280g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.5g:3mmol)を加え再び脱気を行った。この後、60℃で6時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をメタノール(2000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をメタノールで洗浄し、減圧乾燥しメタクリレートポリマー粉末P10を得た。
MA-1(21g:40mmol)、MA-2(26g:60mmol)、MA-7(3g:10mmol)をTHF(283g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.5g:3mmol)を加え再び脱気を行った。この後、60℃で6時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をメタノール(2000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をメタノールで洗浄し、減圧乾燥しメタクリレートポリマー粉末P12を得た。
MA-3(34g:60mmol)、MA-2(9g:20mmol)、MA-5(6g:20mmol)をTHF(282g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.5g:3mmol)を加え再び脱気を行った。この後、60℃で6時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をメタノール(2000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をメタノールで洗浄し、減圧乾燥しメタクリレートポリマー粉末P15を得た。
MA-1(21g:40mmol)、MA-5(6g:60mmol)をTHF(154g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.5g:3mmol)を加え再び脱気を行った。この後、60℃で6時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をメタノール(2000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をメタノールで洗浄し、減圧乾燥しメタクリレートポリマー粉末P16を得た。
MA-3(46g:80mmol)、MA-5(6g:20mmol)をTHF(297g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.5g:3mmol)を加え再び脱気を行った。この後、60℃で6時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をメタノール(2000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をメタノールで洗浄し、減圧乾燥しメタクリレートポリマー粉末P18を得た。
MA-2(44g:100mmol)をTHF(251g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.5g:3mmol)を加え再び脱気を行った。この後、60℃で6時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をメタノール(2000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をメタノールで洗浄し、減圧乾燥しメタクリレートポリマー粉末P19を得た。
上記合成例1にて得られたメタクリレートポリマー粉末P1(0.6g)にNMP(11.4g)を加え、室温で1時間攪拌して溶解させた。この溶液に、BCS(3.0g)を加え、固形分濃度が4.0wt%、のポリマー溶液(A1)を得た。このポリマー溶液は、そのまま液晶配向膜を形成するための液晶配向剤となる。
上記合成例1にて得られたメタクリレートポリマー粉末P16(0.6g)にNMP(11.4g)を加え、室温で1時間攪拌して溶解させた。この溶液に、BCS(3.0g)を加え、固形分濃度が4.0wt%、のポリマー溶液(B1)を得た。このポリマー溶液は、そのまま液晶配向膜を形成するための液晶配向剤となる。
上記合成例1にて得られたメタクリレートポリマー粉末P3(0.6g)にNMP(9.9g)を加え、室温で1時間攪拌して溶解させた。この溶液に、BCA(4.5g)を加え、固形分濃度が4.0wt%、のポリマー溶液(A4)を得た。このポリマー溶液は、そのまま液晶配向膜を形成するための液晶配向剤となる。
上記合成例1にて得られたメタクリレートポリマー粉末P5(0.6g)にCHN(11.4g)を加え、温度50℃で加温しながら1時間攪拌して溶解させた。この溶液に、PGME(3.0g)を加え、固形分濃度が4.0wt%、のポリマー溶液(A8)を得た。このポリマー溶液は、そのまま液晶配向膜を形成するための液晶配向剤となる。
上記合成例1にて得られたメタクリレートポリマー粉末P5(0.6g)にCHN(15.0g)を加え、温度50℃で加温しながら1時間攪拌して溶解させ、固形分濃度が4.0wt%、のポリマー溶液(A10)を得た。このポリマー溶液は、そのまま液晶配向膜を形成するための液晶配向剤となる。
上記合成例1にて得られたメタクリレートポリマー粉末P9(0.6g)にNMP(5.4g)を加え、室温で1時間攪拌して溶解させた。この溶液に、GBL(4.5g)、BCA(4.5g)を加え、固形分濃度が4.0wt%、のポリマー溶液(A14)を得た。このポリマー溶液は、そのまま液晶配向膜を形成するための液晶配向剤となる。
上記で得られた液晶配向剤を用いて下記に示すような手順で光反応率測定用基板の作製を行った。基板は、40mm×40mmの大きさで、厚さが1.0mmの石英基板を用いた。液晶配向剤A1をフィルター孔径1.0μmのフィルターで濾過した後、石英基板上にスピンコートし、70℃のホットプレート上で90秒間乾燥後、膜厚100nmの液晶配向膜を形成した
塗膜面に偏光板を介して313nmの紫外線を80mJ/cm2照射した後に、120℃のホットプレートで20分間加熱し、光反応済みの液晶配向膜付き基板を得た。
上記で作製した液晶配向膜付き基板を用い、液晶配向膜の光学的異方性を測定するために、偏光の吸光度から面内配向度であるSを下式より算出した。算出値は照射量範囲内で最も高い値を用いた。
なお、吸光度の測定には、島津製作所製の紫外線可視近赤外分析光度計U-3100PCを使用した。
液晶配向剤(A1)を0.45μmのフィルターで濾過した後、透明電極付きガラス基板上にスピンコートし、70℃のホットプレート上で90秒間乾燥後、膜厚100nmの液晶配向膜を形成した。
塗膜面を40°傾けて、偏光板を介し313nmの紫外線を基板80mJ/cm2照射した後に140℃のホットプレートで20分間加熱し、液晶配向膜付き基板を得た。このような液晶配向膜付き基板を2枚用意し、一方の基板の液晶配向膜面に4μmのスペーサを設置した後、2枚の基板のラビング方向が平行になるようにして組み合わせ、液晶注入口を残して周囲をシールし、セルギャップが4μmの空セルを作製した。この空セルに減圧注入法によって、液晶MLC-2003(メルク株式会社製)を注入し、注入口を封止して、アンチパラレル液晶セルを得た。 温度120℃で30分間加熱した後、この液晶セルについてプレチルト角を測定した。
上記合成例15にて得られたメタクリレートポリマー粉末P15(0.6g)にNMP(8.4g)を加え、室温で1時間攪拌して溶解させた。この溶液に、BCS(6.0g)を加え、固形分濃度が4.0wt%、のポリマー溶液(A22)を得た。このポリマー溶液は、そのまま液晶配向膜を形成するための液晶配向剤となる。
Claims (8)
- (A)下記モノマー(A-1)及びモノマー(A-2)を含むモノマー混合物から得られる共重合体を含有する、重合体組成物。
モノマー(A-1):シンナモイル部位を1つと、シンナモイル部位を構成しないベンゼン環を2~4つと、重合性基とを有するモノマー。
モノマー(A-2):シンナモイル部位を1つと、シンナモイル部位を構成しないベンゼン環を1つと、重合性基とを有するモノマー。
(上記シンナモイル部位とベンゼン環は、置換基を有していてもよい。) - 上記モノマー(A-1)及びモノマー(A-2)の重合性基が、アクリル基またはメタクリル基である、請求項1に記載の重合体組成物。
- 上記モノマー(A-1)及びモノマー(A-2)が、下記式(1)で表される基及び下記式(2)で表される基からなる群から選ばれるいずれか1種の基に重合性基が結合したモノマーである、請求項1に記載の重合体組成物。
式中、A、B、Dはそれぞれ独立に、単結合、-O-、-CH2-、-COO-、-OCO-、-CONH-又は-NH-CO-を表す;
Sは、炭素数1~12のアルキレン基であり、それに結合する水素原子はそれぞれ独立にハロゲン基に置き換えられていてもよい;
Tは、単結合または炭素数1~12のアルキレン基であり、それらに結合する水素原子はハロゲン基に置き換えられていてもよい;
Tが単結合であるときはBも単結合を表す;
Y1は、2価のベンゼン環である;
P1、Q1及びQ2は、それぞれ独立にベンゼン環及び炭素数5~8の脂環式炭化水素環からなる群から選ばれる基である;
R1は、水素原子、-CN、ハロゲン基、炭素数1~5のアルキル基、(炭素数1~5のアルキル)カルボニル基、炭素数3~7のシクロアルキル基又は炭素数1~5のアルキルオキシ基である。
Y1、P1、Q1及びQ2において、ベンゼン環に結合する水素原子はそれぞれ独立に-CN、ハロゲン基、炭素数1~5のアルキル基、(炭素数1~5のアルキル)カルボニル基、又は炭素数1~5のアルキルオキシ基で置換されてもよい;
X1及びX2は、それぞれ独立に単結合、-O-、-COO-又は-OCO-を表す;
n1及びn2はそれぞれ独立に0、1または2である、
X1の数が2となるときは、X1同士は同一でも異なっていてもよく、X2の数が2となるときは、X2同士は同一でも異なっていてもよい;
Q1の数が2となるときは、Q1同士は同一でも異なっていてもよく、Q2の数が2となるときは、Q2同士は同一でも異なっていてもよい;
モノマー(A-1)においては、Y1以外のベンゼン環の数の合計は2~4である;
モノマー(A-2)においては、Y1以外のベンゼン環の数の合計は1である;
破線は重合性基との結合手を表す。 - [I] 請求項1~3のいずれか一項に記載の重合体組成物を、液晶駆動用の電極を有する基板上に塗布して塗膜を形成する工程;
[II] [I]で得られた塗膜に斜め方向から偏光した紫外線を照射する工程;及び
[III] [II]で得られた塗膜を加熱する工程;
を有することによって配向制御能が付与された液晶配向膜を得る、前記液晶配向膜を有する基板の製造方法。 - 請求項4記載の方法により製造された液晶配向膜を有する基板。
- 請求項5記載の基板を有する、ツイストネマチック型液晶表示素子。
- 請求項5に記載の基板(第1の基板)を準備する工程;
[I’] 第2の基板上に請求項1~4のいずれか一項に記載の重合体組成物を、塗布して塗膜を形成する工程;
[II’] [I’]で得られた塗膜に偏光した紫外線を照射する工程;及び
[III’] [II’]で得られた塗膜を加熱する工程;
を有することによって配向制御能が付与された液晶配向膜を得る、前記液晶配向膜を有する第2の基板を得る工程;及び
[IV] 液晶を介して前記第1及び第2の基板の液晶配向膜が相対するように、紫外線露光方向が互いに直交するように前記第1及び第2の基板を対向配置して液晶表示素子を得る工程;
を有することにより、ツイストネマチック型液晶表示素子を得る、該液晶表示素子の製造方法。 - 請求項7記載の方法により製造された、ツイストネマチック型液晶表示素子。
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Cited By (2)
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WO2020203632A1 (ja) * | 2019-03-29 | 2020-10-08 | 日産化学株式会社 | 重合体組成物及び単層位相差材 |
WO2021106979A1 (ja) * | 2019-11-26 | 2021-06-03 | 日産化学株式会社 | 液晶配向剤、液晶配向膜及び液晶表示素子 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002317013A (ja) * | 2000-08-30 | 2002-10-31 | Dainippon Ink & Chem Inc | 光配向膜用材料、光配向膜及びその製造方法 |
JP2014034631A (ja) * | 2012-08-08 | 2014-02-24 | Jnc Corp | 光配向性位相差剤、並びにこれから得られる位相差フィルム、光学フィルム、表示素子 |
JP2014097938A (ja) * | 2012-11-13 | 2014-05-29 | Jnc Corp | 重合性化合物、重合性組成物および液晶表示素子 |
JP2015129210A (ja) * | 2014-01-06 | 2015-07-16 | 大阪有機化学工業株式会社 | ブロックカルボン酸型光配向材料 |
WO2017065080A1 (ja) * | 2015-10-16 | 2017-04-20 | Dic株式会社 | 光配向膜用ポリマー、ポリマー溶液、光配向膜、光学異方体、及び液晶表示素子 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2780183B2 (ja) | 1989-02-27 | 1998-07-30 | セイコーエプソン株式会社 | 配向膜および液晶装置 |
JP2893671B2 (ja) | 1991-03-11 | 1999-05-24 | ジェイエスアール株式会社 | 液晶配向剤 |
JP3097702B2 (ja) | 1991-08-13 | 2000-10-10 | 日産化学工業株式会社 | 新規な液晶配向処理剤 |
DE4232394A1 (de) * | 1992-09-26 | 1994-03-31 | Basf Ag | Copolymerisate mit nichtlinear optischen Eigenschaften und deren Verwendung |
EP0900239B1 (de) * | 1996-05-22 | 2002-03-27 | Bayer Ag | Schnell fotoadressierbare substrate sowie fotoadressierbare seitengruppenpolymere mit hoher induzierbarer doppelbrechung |
JP3840743B2 (ja) | 1997-06-03 | 2006-11-01 | Jsr株式会社 | 液晶配向剤 |
JP2000212310A (ja) | 1999-01-19 | 2000-08-02 | Hayashi Telempu Co Ltd | 配向膜およびその製造方法、液晶表示装置 |
KR100720454B1 (ko) * | 2005-06-14 | 2007-05-22 | 엘지.필립스 엘시디 주식회사 | 액정표시소자 및 그 제조방법 |
WO2014061778A1 (ja) * | 2012-10-18 | 2014-04-24 | 日産化学工業株式会社 | 組成物、液晶配向処理剤、液晶配向膜および液晶表示素子 |
JP2014206715A (ja) * | 2013-03-19 | 2014-10-30 | 日産化学工業株式会社 | 横電界駆動型液晶表示素子用液晶配向膜を有する基板の製造方法 |
KR102254609B1 (ko) * | 2013-05-13 | 2021-05-20 | 닛산 가가쿠 가부시키가이샤 | 횡전계 구동형 액정 표시 소자용 액정 배향막을 갖는 기판의 제조 방법 |
WO2014196590A1 (ja) * | 2013-06-05 | 2014-12-11 | 日産化学工業株式会社 | 横電界駆動型液晶表示素子用液晶配向膜を有する基板の製造方法 |
-
2017
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002317013A (ja) * | 2000-08-30 | 2002-10-31 | Dainippon Ink & Chem Inc | 光配向膜用材料、光配向膜及びその製造方法 |
JP2014034631A (ja) * | 2012-08-08 | 2014-02-24 | Jnc Corp | 光配向性位相差剤、並びにこれから得られる位相差フィルム、光学フィルム、表示素子 |
JP2014097938A (ja) * | 2012-11-13 | 2014-05-29 | Jnc Corp | 重合性化合物、重合性組成物および液晶表示素子 |
JP2015129210A (ja) * | 2014-01-06 | 2015-07-16 | 大阪有機化学工業株式会社 | ブロックカルボン酸型光配向材料 |
WO2017065080A1 (ja) * | 2015-10-16 | 2017-04-20 | Dic株式会社 | 光配向膜用ポリマー、ポリマー溶液、光配向膜、光学異方体、及び液晶表示素子 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020203632A1 (ja) * | 2019-03-29 | 2020-10-08 | 日産化学株式会社 | 重合体組成物及び単層位相差材 |
JP7517328B2 (ja) | 2019-03-29 | 2024-07-17 | 日産化学株式会社 | 重合体組成物及び単層位相差材 |
WO2021106979A1 (ja) * | 2019-11-26 | 2021-06-03 | 日産化学株式会社 | 液晶配向剤、液晶配向膜及び液晶表示素子 |
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