JPH09159819A - Molecular oriented optical parts and their production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to mold output parts of a large area as well and to enhance productivity by dissolving a cyano group-contg. compd. into a photosetting liquid monomer and arranging the cyano group-contg. compd. in a specified direction into the polymer at the time of curing the monomer by irradiating the monomer with light. SOLUTION: The cyano group-contg. compd. is oriented by molding the photosetting liquid monomer 2 dissolved with the cyano group-contg. compd. and irradiating the monomer with the light of the specified direction, by which the photosetting liquid monomer 2 is cured and the molecule oriented optical parts and the optical parts 1 are obtd. The optical parts 1 of this case signify all of optical parts including liquid crystal pannel members, such as optical filter, polarizing plate, phase difference plates, visual field angle control plates and liquid crystal oriented films, isolators for optical communication, electrically illuminated advertising boards, illumination covers and various kinds of window materials, with, through and by which light is irradiated, transmitted and reflected. The sheet shape body signifies all of mold out put parts having a flat front surface. These parts are not limited in the thickness. Then, the optical parts generally known as films, sheets and blocks are included as well.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a molecular weight oriented optical component made of plastic which is lightweight and has excellent heat resistance and weather resistance.
A polarizing plate, a viewing angle control plate, and a liquid crystal alignment film used for a liquid crystal panel or the like can be manufactured with high productivity.

[0002]

2. Description of the Related Art There have been proposed glass and plastics in which an inorganic compound or an organic compound is oriented in a certain direction to impart polarization performance. Infrared polarizing glass in which silver salts are deposited and oriented in the glass stretching direction is commercially available as a material in which molecules are oriented in glass, and the extinction ratio is 1: 1000 by controlling the size of silver salt particles.
It has a high-performance polarization performance of 10,000 to 10,000. However, it is difficult to make it heavy and thin and have a large area. There is a problem that the usable wavelength range is not in the visible light range.

On the other hand, as a polymer having oriented molecules in a plastic, a polarizing film in which a stretched film of polyvinyl alcohol or the like is doped with iodine or a dichroic dye and oriented is commercially available, and a degree of polarization of 90 in a visible light region. % Or more. However, although the above problems of glass can be solved, they are inferior in heat resistance and weather resistance. In addition, to achieve low prices, productivity is even better,
Development of a plastic molecular orientation optical component having excellent polarization performance is desired.

[0004]

The present invention solves the above-mentioned problems and is lightweight and can be molded even in a large area with a thickness of several μm to several cm, and can be used for light rays in the visible or infrared region. It is an object of the present invention to provide a molecular orientation optical component having a wide range of optical performance that can be selected, easy controllability, excellent heat resistance and weather resistance, and excellent productivity.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that when a cyano group-containing compound is dissolved in a photocurable liquid monomer and irradiated with light, the polymer is cured during curing. We found that cyano group-containing compounds were arranged in a certain direction in the development, and succeeded in producing molecularly oriented optical parts. That is, the present invention is a molecular orientation that shapes the photocurable liquid monomer in which the cyano group-containing compound is dissolved and irradiates light in a certain direction to orient the cyano group-containing compound and to cure the photocurable liquid monomer. The present invention relates to a method for manufacturing an optical component and an optical component obtained by the method.

In the present invention, the optical parts include liquid crystal panel members such as optical filters, polarizing plates, retardation plates, viewing angle control plates, liquid crystal alignment films, optical communication isolators, electronic advertising boards, lighting covers, and various windows. It means all materials such as materials that are irradiated with light and that are transmitted and reflected. The sheet-like material means all moldings having a flat front surface, and the thickness is not limited. Therefore, what is generally called a film, a sheet, or a block is included.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The photocurable liquid monomer used in the present invention is not particularly limited as long as it can be polymerized and cured by irradiation with light to form a transparent polymer, but it is generally (meth) Acrylate compounds are suitable.
Among them, triethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate,
2,2-bis [4- (meth) acryloyloxyphenyl] propane, 2,2-bis [4- (2- (meth) acryloyloxyethoxy) phenylpropane, bis (oxymethyl) tricyclo [5.2.1] .0 ^2,6 ] decane dimethacrylate, p-bis [β- (meth) acryloyloxyethylthio] xylylene, 4,4′-bis [β- (meth) acryloyloxyethylthio] diphenylsulfone, trimethylolpropane Polyfunctional (meth) acrylates such as tri (meth) acrylate, urethane acrylate and epoxy acrylate, and a mixture of these monomers with a monofunctional monomer copolymerizable therewith,
Further, a mixture of these polyfunctional (meth) acrylate compounds and addition-polymerizable polythiol can be mentioned. Examples of monofunctional monomers include methyl (meth) acrylate and benzyl (meth) acrylate, and examples of polythiols include pentaerythritol tetrakis (β-thiopropionate) and tris [2- (β-thiopropionyloxy) ethyl] tri. Examples include isocyanurate.

Bifunctional or higher polyfunctional acrylates are particularly preferred. Known photopolymerization initiators may be used for curing these photocurable liquid monomers, and two or more of them may be used in combination. For example, 2,
4,6-trimethylbenzoyldiphenylphosphine oxide, trimethylbenzoylphenylphosphinic acid methyl ester, 1-hydroxycyclohexylphenyl ketone, benzophenone, diphenoxybenzophenone and the like. If necessary, an antioxidant, an ultraviolet absorber, a colorant, etc. may be added to the photocurable liquid monomer to cure it.

[0009] a cyano group-containing compound, can be widely used a compound having a cyano group, generally C ₆ -C ₁₀₀ carbon atoms are preferably C ₈ -C ₁₀₀ approximately hydrocarbons (O, A compound in which a cyano group is bonded to (may include other elements such as S and N) is used. In particular, a compound having a ring structure such as an aryl compound, an alicyclic compound or a condensed polycyclic compound is preferable. These compounds may contain hetero atoms such as N, O and S in the ring structure. The number of cyano groups is not particularly limited and may be one or more. When a plurality of cyano groups are bonded, the cyano groups may be on the same side or the target side with respect to the center of the compound.

Specifically, the following compounds can be used. Acrylonitrile, cyanoadamantane, cyanobenzaldehyde, cyanobenzoic acid, α-cyanocinnamic acid ethyl ester, cyanobenzene, cyanophenol, cyanotoluene, cyanonaphthalene, cyanothiophene, cyanopyridine, cyanoindole, 9-cyanophenanthrene, 9-cyanoanthracene , Chlorobenzonitrile, 4-cyanobiphenyl, 4-cyanobenzoic acid chloride, N- (2-cyanoethyl) piperidine,
2-cyano-6-methoxybenzotriazole, 4-cyanophenyl, 4-butylbenzoate, 4'-pentyl-4-biphenylcarbonitrile, 4'-amyloxybenzylidene-4-cyanoaniline, 4'-n-butoxybenzylidene -4-cyanoaniline, 4'-ethoxybenzylidene-4-cyanoaniline, 4'-cyanobenzylidene-4-n-butoxyaniline, 4- (4'-methoxybenzylidene) aminobenzonitrile, 4- (3
-Butenyloxy) benzoic acid, monofunctional cyano compounds such as 4'-cyanophenyl ester, dicyanohexane, dicyanobenzene, dicyanoaniline, 2,
6-dicyanotoluene, 1,2-dicyanonaphthalene,
2,3-dicyanonaphthalene, 9,10-dicyanoanthracene, 2,5-dicyano-p-xylene, α, α ′
-Dicyano-p-xylene, 4-n-propoxyphthalonitrile, 4-phenoxyphthalonitrile, α, β-dicyanobiphenyl, 1,2-dicyano-3,4,5,6
-Tetrafluorobenzene, 1,2-dicyano-4,5
-Dichlorobenzene, 2,3-dicyanohydroquinone,
4,5-dicyanoimidazole, 2,3-dicyanopyrazine, 1- (dicyanomethylene) -3-iminoisoindoline, D (-)-amigdalin, 1,1'-azobis (cyclohexane-1-carbonitrile), 9 -Dicyanomethylene-2,4,7-trinitrofluorene, 2,
3-dicyano-5,6-dichloro-p-benzoquinone,
2- (dicyanomethylene) indane-1,3-dione,
4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran, trans
orcis-1,2-dicyano-1,2-bis (2,
4,5-Trimethyl-3-thienyl) ethene, 1,2,
Examples include polyfunctional cyano compounds such as 4,5-tetracyanobenzene, 7,7,8,8-tetracyanodimethane, 11,11,12,12-tetracyanonaphtho-2,6-quinodimethane. Of these, polyfunctional cyano compounds are preferable, and among them, 2,3-dicyanonaphthalene, 2- (dicyanomethylene) indane-1,3-dione, 4- (dicyanomethylene) -2-methyl-6-
(4-Dimethylaminostyryl) -4H-pyran, 7,
Particularly preferred is 7,8,8-tetracyanoquinodimethane.

The amount of the cyano compound added is 0.001 to 50 parts by weight, preferably 0.01 to 10 parts by weight, and particularly preferably 0.1 to 100 parts by weight of the photocurable liquid monomer.
１1 part by weight. A polymerization monomer composition obtained by mixing a cyano group-containing compound and a photopolymerization initiator with a photocurable liquid monomer is molded on a transparent casting mold such as glass or plastic or a flat plate, and then polymerized by light.

Referring to FIG. 1 in more detail, FIG.
Shows an example of manufacturing a sheet-shaped optical component 1, in which a liquid monomer composition 2 in which the respective components are mixed is cast into a frame-shaped spacer 4 on a glass plate 3 and shaped into a sheet. To be done. Liquid monomer composition shaped into a sheet 2
A linear light source 5 is provided above (in parallel to) the upper surface of the liquid monomer (horizontal), and irradiates light in a fixed direction to cure the liquid monomer 2.

A diffused light source is used as a light source, and light having a distribution of irradiation light quantity is irradiated so that the illuminance of the liquid monomer surface is inclined. In the present invention, irradiating with light in a certain direction means that the irradiation angle of light with respect to the surface of the shaped liquid monomer composition does not change with time. Usually, irradiation is performed with the shaped liquid monomer and the light source fixed and stationary. The liquid monomer composition 2 that has been irradiated with light is photo-cured, and the coexisting cyano group-containing compound is oriented in the direction of the line of the linear light source 5. When a plurality of line light sources are used, when the line light sources are placed in parallel with each other (not shown), the compound having a cyano group is oriented in one direction as shown in FIG.

When the linear light sources 5a and 5b orthogonal to each other as shown in FIG. 2 are used as the linear light source, the compound containing a cyano group has two kinds of orientations in the directions orthogonal to each other. When the point light source 5c is used as the light source, the compound containing a cyano group is concentrically oriented as shown in FIG. In the case of partially producing a molecular alignment state, after selectively irradiating the alignment portion with a mask or the like, the whole is rotated to uniformly irradiate the light so that curing is performed stepwise. .

The intensity of the irradiation light is determined in consideration of the degree of molecular orientation and the cured area, but is several mw / cm ² to several hundred mw.
Light in the illuminance range of / cm ² is used. The irradiation time is set considering the monomer to be cured and the film thickness, but the total irradiation light amount is 1 m even in the lowest illuminance part of the light intensity distribution.
J / cm ² or more, that is, curing is completed. The light source for light irradiation can be appropriately selected according to the characteristic wavelength of the photocurable liquid monomer or the photopolymerization initiator. Generally, an ultraviolet light source such as a high pressure mercury lamp, a metal halide lamp or a short arc lamp is used as a point light source or a line light source, but a visible or infrared light source such as a laser can also be used in combination with a photosensitizer.

Although the principle of arrangement of the cyano group-containing compound has not been clarified, it seems that the orientation direction is determined by the following two factors. Molecular structure of a cyano group-containing compound. In particular, the position and bonding direction of the cyano group in the molecule. Intensity distribution of irradiation light during curing and direction of curing shrinkage. For example, when a relatively straight-chain cyano group-containing compound is used, the light intensity is uniformly arranged in the plane of the sheet (FIG. 1). On the other hand, in the case of a compound containing a cyano group in the side chain, the arrangement direction having the orientation component also in the sheet thickness direction is considerably influenced by the position and bonding direction of the cyano group in the molecule. , And interacts with irradiation light, that is, electromagnetic waves, and determines the orientation direction of the molecule as a whole. In particular, in the case of a compound having two or more cyano groups in the molecule, the action of further fixing the molecular orientation in one direction is strong.

The orientation direction and degree can be controlled by changing the type and addition amount of the cyano group-containing compound, and by changing the intensity distribution and direction of the irradiation light during curing. Furthermore, by selectively irradiating light, it is possible to prepare a molecularly oriented site at a desired position on the film or sheet. Utilizing this molecular orientation, for example, if it is two-dimensionally oriented in the plane of the sheet-like body, it is possible to prepare a polarizing plate that transmits or absorbs only polarized light in the orientation direction.
A liquid crystal alignment film can be produced without rubbing by utilizing the orientation of the surface of the sheet. Further, by orienting in the thickness direction of the sheet-shaped body, it is possible to manufacture a viewing angle control plate which transmits a light ray incident at a specific incident angle with respect to the surface of the sheet-shaped body and scatters at other angles and is opaque.

[0018]

EXAMPLES The following examples serve to explain the present invention more specifically. In addition, the part in an example shows a weight part. The degree of polarization of the molecular orientation sheet described in the examples was calculated according to the following formula.

[0019]

[Equation 1]

Example 1 100 parts of p-bis (β-methacryloyloxyethylthio) xylylene was mixed with 0.1 part of 2,3-dicyanonaphthalene.
And 0.1 part of 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photopolymerization initiator were uniformly mixed with stirring. This composition has a thickness of 1
Liquid was poured into a glass mold using a mm silicon plate, and ultraviolet rays were irradiated for 3 minutes with a metal halide lamp above the glass surface at a distance of 40 cm. The intensity distribution of irradiation light was as shown in FIG. After irradiation, the mold was released to obtain a cured product. The light transmittance of the cured product was 50% in the range of 400 to 900 nm, and the polarization degree was 90%. This cured product is 100 at 100 ℃
No decrease in light transmittance or degree of polarization was observed after heating in an oven for a period of time.

Example 2 A cured product was obtained in the same manner as in Example 1 except that 0.1 part of 2- (dicyanomethylene) indane-1,3-dione was used instead of 2,3-dicyanonaphthalene. 5 of cured product
Light transmittance at 00 nm is the incident angle of light (0 °)
In the vicinity, the light transmittance is about 20%, but when the incident angle is changed in parallel to the alignment direction, the transmittance increases from around ± 10 °, and the maximum transmittance is around 50% around ± 30 °. . The viewing angle control performance after heating this cured product in an oven at 100 ° for 100 hours was not different from that before heating.

[Brief description of the drawings]

FIG. 1 is a schematic perspective view for explaining a production example of the present invention,

FIG. 2 is a schematic perspective view for explaining another production example of the present invention,

FIG. 3 is a schematic perspective view for explaining an example of a manufacturing method using a point light source,

FIG. 4 is a graph showing the intensity distribution of irradiation light used in Example 1.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Optical component 2 Liquid monomer composition 3 Glass plate 4 Frame spacer 5a, 5b, 5c Light source

Claims (9)

[Claims] 1. A photocurable liquid monomer having a cyano group-containing compound dissolved therein is shaped and irradiated with light in a predetermined direction to orient the cyano group-containing compound and to cure the photocurable liquid monomer. Molecularly oriented optical components. 2. The molecular alignment optical component according to claim 1, which has a selective scattering power for a specific light incident angle and a viewing angle control function. 3. The molecular alignment optical component according to claim 1, which is a sheet-like body. 4. A photocurable liquid monomer having a cyano group-containing compound dissolved therein is shaped and irradiated with light in a certain direction to orient the cyano group-containing compound and to cure the photocurable liquid monomer. A method for producing a molecular orientation optical component, characterized by: 5. The method for producing a molecular alignment optical component according to claim 4, wherein the photocurable liquid monomer is a monomer containing a polyfunctional (meth) acrylate having two or more unsaturated bonds in the molecule as an essential component. . 6. The method for producing a molecular alignment optical component according to claim 4, wherein the light irradiation is cured by a linear light source provided parallel to the surface of the shaped photocurable liquid monomer. 7. The method for producing a molecular alignment optical component according to claim 6, wherein the linear light sources are a plurality of linear light sources parallel to each other. 8. The method for producing a molecular alignment optical component according to claim 6, wherein the linear light sources are linear light sources provided in directions orthogonal to each other. 9. The method for producing a molecular alignment optical component according to claim 4, wherein the irradiation of light is a point light source.