JPS62276506A - Polarizing film - Google Patents

Abstract

PURPOSE:To obtain a polarizing film which has good polarization performance and is highly resistant to moisture and heat by using a conductive high polymer having unsatd. cyclic structure in the main chain exhibiting dichroism. CONSTITUTION:This film is formed of the conductive high polymer (conductive high polymer) having the unsatd. cyclic structure in the main chain which permits film formation and stretching and exhibits polarization performances by stretching. The conductive high polymer or conductive high polymer precursor which has dichroism and is dissolved in a solvent is adsorbed by an immersion method onto a base material high-polymer film which is swollen by the same solvent as said solvent or has solubility therewith and thereafter the film is uniaxially stretched, by which the polarizing film is obtd. The conductive high polymer is synthesized from the conductive high polymer precursor by subjecting the same to a suitable treatment such as heat treatment before, during or after the stretching.

Description

Detailed Description of the Invention 8. Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a polarizing film using a conductive polymer. polyvinyl alcohol
/L/ (hereinafter abbreviated as PVA) or its derivatives or polyvinyl chloride /L/ (hereinafter abbreviated as PvC) film was dehydrochlorinated, or PVA-based 74ym was dehydrated to produce a polyene and oriented. It is manufactured by adsorbing iodine or dichroic dye to a polyene film as a polarizing element.

Among these, -2. Polarizing films that use iodine as a polarizing element have excellent initial polarization performance, but are sensitive to water and heat, and when used for long periods of time in high temperature and high humidity conditions. There is a problem with durability.In order to improve the durability, methods are being considered such as strengthening the treatment with an aqueous solution containing formalin or boric acid, and using a polymer film with low moisture permeability as a protective film. However, it has insufficient durability under high temperature and high humidity conditions.

In addition, although polarizing films using dichroic dyes as polarizing elements have better water resistance and heat resistance than polarizing films using iodine, they are still not perfect when PVA is used as a base film. No, no.

An object of the present invention is to solve the above-mentioned problems of conventional polarizing films, and to provide a polarizing film that has good polarizing performance and is excellent in water resistance and heat resistance.

<Means for solving the problems> The present invention is a book completed as a result of repeated research in order to solve the above problems. Concerning a polarizing film that differs from conventional polarizing films that are uniaxially adsorbed and oriented in that it uses a conductive polymer that exhibits dichroism and has an unsaturated cyclic structure in its main chain instead of these dyes. (1) A conductive polymer (hereinafter referred to as a conductive polymer) having an unsaturated cyclic structure in its main chain that can be formed into a film and can be stretched, and exhibits polarizing performance as it is stretched. Examples include polyphenylene vinylene (ppv) and derivative polymers thereof.These conductive polymers are highly stretched and the light transmittance is adjusted to an appropriate value. A polarizing film with appropriate performance can be obtained by controlling the thickness so that

In addition, the conductive polymer Maroku, which exhibits dichroism and dissolves in solvents,
It is also possible to use a polymer precursor (hereinafter referred to as a conductive polymer precursor) that dissolves in a solvent and becomes a gastrically conductive polymer through appropriate post-treatment such as heat treatment. An example of the latter is water-soluble polyxylylene bis(diethyl II/7-N fonium bromide) which can be converted into cypolyphenylenepynylene by heat treatment. 74/I/mu is depleted by the manufacturing method of polarizing film A polarizing film can be obtained by swollen with the same solvent as the solvent or adsorbed to a base polymer film having solubility by a dipping method, and then stretched in the axial direction. For the conductive polymer precursor that can be obtained, a conductive polymer is synthesized by performing appropriate treatment before, during or after stretching.

Another method is (8) uniaxial stretching of a dichroic conductive polymer or conductive polymer precursor that is swollen or soluble in the same solvent as the solvent. A polarizing film can be obtained by highly oriented adsorption onto a base polymer film using a dipping method.For conductive polymer precursors, a suitable treatment is performed after dipping. Synthesize conductive polymers. As yet another method, (4) a dichroic conductive polymer or its precursor that can be dissolved in a solvent is mixed with a base polymer that can be dissolved in the same solvent as the solvent in a proportion appropriate to the solvent. Dissolve and mix and form a film by solution casting method.Then, by uniaxially stretching the film, the conductive polymer is highly oriented.K) 4J4 Optical film can be obtained. In some cases, a conductive polymer is synthesized by performing appropriate treatment such as heat treatment before, during or after stretching. As yet another method, (6) a conductive polymer exhibiting dichroism or its precursor;
Compatible base polymers are melt-mixed in appropriate proportions and formed into a film using an extruder, etc. After that, the film is uniaxially stretched to highly orient the conductive polymer. A polarizing film can be obtained. In the case of a precursor, appropriate treatment may be carried out during or after melting, during or after film formation, or during or after stretching.
Synthesize more conductive polymers.

Further, the conductive polymer used here is not limited to one type, but a plurality of types can be used simultaneously as required.

In that case, after a conductive polymer and a base polymer composite film are produced by a solution casting method or melt-mixed using an extruder or the like, the base polymer film is dissolved in a solvent that can swell or dissolve it. A polarizing film is obtained by adsorbing a conductive polymer containing a substance, and then stretching it to obtain a polarizing film. The above (1) is mixed, formed into a film by a solution casting method, and then stretched in the -axis direction to obtain a polarizing film.
By appropriately combining the methods of (5) to (5), a polarizing film using a plurality of conductive polymers can be obtained.

Furthermore, the polarizing film produced by the above method,
The polarization properties can be further improved by dipping the dichroic dye solution into a solution containing one or more conductive polymers and a base polymer. Conventional methods for producing dye-based polarizing films can be used in methods (1) to (5) above, such as mixing one or more types of polarizing dyes in appropriate proportions as necessary, forming a film by a solution casting method, and then stretching. By combining these methods, a polarizing film using conductive polymers can be obtained. The dye to be used may be a conductive polymer or its precursor, and K may be any dye as long as it has good compatibility with the base film used and has a high dichroic ratio. Dyes, other quinophthalone dyes, perylene dyes, naphthoquinone yarn dyes, tetofuzine dyes, etc. can be used.In addition, it is possible to highly orient a conductive polymer that exhibits dichroism. When using a polarizing dye, the method for producing a polarizing film of the present invention is not necessarily limited to the above range, as long as both the conductive polymer and the dichroic dye can be highly oriented. The present invention may be a single conductive polymer film, or a film in which the conductive polymer is adsorbed, blended, or laminated and oriented with another base polymer; however, in the latter case, the base material used Examples of polymers include PVA or its derivatives, acetic acid superlose or its derivatives, and those capable of forming FfAP, such as polyetherimide, poly/L/*n, polyether-sulfone, and polycarbonate. If so, any polymer may be used without being limited to these polymers. Among them, it is preferable to use a heat-resistant film such as polyether sulfone in terms of improving the durability of the polarizing film. In the present invention, the conductive polymer film method or conductivity%! Dry method is a method for stretching a molecular precursor film or a composite film consisting of a electrocardiographic polymer and a base polymer.
The method most suitable for the film to be stretched may be used, such as axial stretching, wet-axial stretching, or low rho rolling.

A polarizing film using a conductive polymer can be obtained by the above method, but in order to further strengthen the light-emitting property and heat resistance, VC
It is also possible to add additives such as ultraviolet absorbers and stabilizers as necessary, and when the conductive polymer is a hydrophilic polymer, it is also possible to perform a post-treatment to make it hydrophobic.

In addition, when using these polarizing films as a circularly polarizing plate by laminating a protective film, a quarter-wave plate, etc., these additives should be added to the protective film or quarter-wave plate. Alternatively, it can be added to the polarizing film and the adhesive M for bonding them together, or to the pressure-sensitive adhesive layer for bonding them to a liquid crystal panel.

<Examples> The present invention will be described in more detail with reference to Examples below, but these are merely illustrative and are not intended to be limiting.

The degree of polarization in the present invention refers to the degree of polarization measured by preparing two polarizing films or plates and measuring the light transmittance with the two sheets overlapped using a measuring device (Model 2 Hitachi UV-880) as follows. Here, H7 is the value measured when the two samples ρ are stacked so that the polarizing films are aligned in the same direction (this is called the parallel transmittance). 9, H, is set so that the orientation directions of the polarizing films are perpendicular to each other when the two samples are superimposed [1
This is a value measured in a state where they are aligned (called orthogonal transmittance).

Example 1 Polyphenylene vinylene precursor (polyxylylene bis-
(Diethylsulfonium bromide)) It was cast onto a water gr&woholieste film (made of Mylar film bundle) to obtain a film with a thickness of about 15μ. After this film was uniaxially stretched 10 times, it was heat-treated at 120° C. for 1 hour to obtain a −axially stretched l-phenylene vinylene film. The obtained film exhibited a yellow color and 420
The light transmittance measured at °Cm was 81 g6, and the degree of polarization was 99 g6. PVA of
Aqueous solution and polyphenylene vinylene for PVA
The mixture was mixed in such a manner as to give a ZX ratio and cast onto a polyester film to obtain a film with a thickness of about 50μ.90 This film was uniaxially stretched 4 times, and then heat treated at 120°C for 1 hour to form a polarizing film. QThe obtained polarizing film showed a yellow color, and the light transmittance measured at 420°C was 81%.
Example 8 Polyphenylene vinylene precursor used in Example 2 and PV
C.I. Direct Red 2 (C, I.

Dir@ot R@d21) and C.I. Direct Blue 202 (C,l, D1r@et Blu
e 202) (both are color index generic names) at 0.8% by weight relative to PVAIC,
After adding 2.4% by weight, the film was cast onto a polyester film to obtain a film with a thickness of about 50 μm. After this film was uniaxially stretched to 4 times, it was heat-treated at 120°C for 1rFP to form a polarized light film. 7 I/I/mu obtained 90 The obtained polarizing film showed a gray color, and the average light transmittance in the visible light wavelength range (400 to 700 nm) was 87.
4, and the degree of polarization was 92% (Example 4) The polarizing film obtained in Example 1 was ripened at 100°C for 500 hours. There was no change in performance before and after the test. The results are shown in Table 1. ◇ Example 5 The polarizing film obtained in %!Example was subjected to a 500-hour moisture resistance aging test at 86°C and 90 RH. There was no change in performance before and after the test. -1.

Table 1 Day A ((transformation): Single light transmittance B (@: Degree of polarization <Effects of the invention>) The present invention provides polarized light that has excellent durability at high temperatures and high humidity, and also has good durability against chemicals. ◎The polarizing film of the present invention has a luxurious and wide range of applicable FA environmental conditions, and is suitable for applications where durability in a wide range of temperature and humidity is not required, such as 'J4L Zaikawa's liquid use. It can be used for display elements, anti-glare filters, etc.

Furthermore, conductive polymer single film or #thermal,
Polarizing films that use heat-and-moisture resistant films as the base film do not require protective films or support films, and contribute to simplifying the manufacturing process of polarizing films and reducing costs. useful.

Written amendment 1, Indication of the case 1986 Patent application No. 779252 2, Name of the invention Polarizing film 3, Relationship with the person making the amendment Address of the applicant for the applicant Address: 5-15 Kitahama, Higashi-ku, Osaka +0612
20-3404'-Σ-6, 16 of Detailed Description of the Invention of Specification d Subject to Amendment, Contents of Amendment (1) Change "Water Resistance" in Line 2 and Line 7 of Page 411ia of Specification to "Material Layer"``sexuality''.

(2) Ming-JF 41i lines 16-17 and 1st
"Polyxylylene bis(diethylsulfonium bromide)" nylene-alf t-diethylsulfonicum ethylene bromide" on page 1, lines 14 to 16.

(8) 8th line of the 5th bar on the detail stand, 17th line Z and 6th box 1
Let the 13th line ``4-dou na α-ri'' be rkA8-ri etc. 0) Ja tof 节报り''.

(4) Details tlA (3rd ward, 3rd line to 4th line, 18th line to L
In the fourth line, 1゛to stretch 1ζ up'' is changed to ``to stretch.''

(5) Akira m1'j$ 5 [Line 15 11-16 B
The r4Wl property term molecule drive' 2 'tetraelectric polymer precursor'.

(6) The "circle A light plate" in the 8th line of the 10th line of the specification 4 shall be referred to as the "enbatsu light plate, etc."

(7) Details! 414 r in K- & -1 (400-
700nm average value)” to r (measured at 420nm)
”.

(8) Specification (l, line 2g, line 11, filO [line 18, Condolences IL page, line 6 and line 8, ``Film of Light'' is defined as ``polarizing film.''

(9) Add the following example and amend Table 1 and <Effects of the invention> on page 14 of the specification.

"Example 6 The polyphenylene vinylene@body aqueous solution used in Example 11ζ
of PVA aqueous solution and the polyphenylene vinylene precursor to PV A +c was 1.8 tli i%1.
Mix this and cast onto a polyester film to a thickness of about 1.
149 for 100u film. This film is 4 times more expensive
- After axial stretching for 1 time, heat treatment was carried out at 100° C. for 1 time with 1 trowel to obtain a t@optical film having a thickness of 62Q μm. The developed polarizing film exhibited a yellow color, the transmittance measured at 450 nm was 42%, and the degree of polarization was 89%.

Example 7 The polyphenylene vinylene precursor aqueous solution used in Example 1 had an average degree of modification of 1,700. Denification rl 99. sX
PV Al5a and PV A B: Polyphenylene vinylene + 'rT1 Mix 1 part so that the donated body is 2.6%, and add 1 part Sumilite Spura Blue 8
GS (Order Kagaku Kogyo Niji Re) BK (Order Kagaku Kogyo Niji Re) (Order Kagaku Kogyo Niji I Direct L/-) Do 2 (C, 1, Direct Re
d 2 )) 2.14% each to wo f'VA
, 0.24t Wk % and 0.7 , ξ pupil % were added, and one polyester film J was cast to form a film with a thickness of about 70 μm. This film was stretched 6 times with a single knife, and heat treated at 100C for 1 hour to obtain a sunlight film with a thickness of 22μn1. Area (400~
The average light transmittance at 700 nm) is 85 circles, m
The light intensity was 99%.

Example 8 The polyphenylene vinylene precursor aqueous solution used in Example 1 was poured onto a 100 μm thick polycarbonate film in a thickness of 100 μml, and poly7-phenylene vinylene+i
A n8A coated film was obtained. This film is 18
By stretching the film 2.6 times along the ζ-axis at 0° C. and performing an anecdote once, a capping film in which polycarbonate I and polyphenylene vinylene were laminated was obtained.

The obtained scrap optical film showed positive color, the transmittance measured at 450 nm was 27%, and the luminous intensity was 99%.

Example 9 The polarizing film obtained in Example 8 was soaked in 1100C hot water for 1 hour to measure its durability, but almost no change was observed. The results are shown below.

Comparative Example 1 The same durability test as in Example 9 was conducted on a commercially available PVP-dye polarizing film with an acrylic protective film (Nitto Electric Works@dliQ-12), but XXX
xxxxxxxxxxxxxxxxxxxxx The results are shown in Table-2 Table-2 Above

Claims (4)

[Claims] (1) A polarizing film characterized by using a conductive polymer having dichroism and having an unsaturated cyclic structure in its main chain. (2) The polarizing film according to claim 1, comprising a conductive polymer film having an unsaturated cyclic structure in its main chain that exhibits visible dichroism when oriented in one direction. (3) The polarizing film according to claim 1, wherein the polarizing film is adsorbed, blended, or laminated onto another base polymer film and oriented. (4) The polarizing film according to claim 1, characterized in that a dichroic dye is used in combination.