JPS6110443A - Conductive laminate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION 1. Industrial Application Field The present invention relates to a conductive laminate, and more specifically, an electroluminescent display device (hereinafter referred to as RLD).
The present invention relates to an improved conductive laminate suitable for display devices such as liquid crystal display devices (hereinafter referred to as LCD) and electrochromic display devices (hereinafter referred to as ECD).

2. Prior Art Examples of conductive laminates that can be used in display devices such as ELDs, LCDs, and ECDs include substrates. 2. xn! A conductive laminate (Japanese Unexamined Patent Publication No. 52-49489) has been proposed in which a transparent conductive film made of O3 and a transparent conductive film made of Snow are sequentially provided to improve abrasion resistance and chemical resistance.

Among ELDs, those having a display material layer consisting of luminescent material or phosphor particles (ZnS: Cu is widely used) dispersed in an organic polymer binder resin, F. In the manufacturing process of LD, the transparent conductive film of the transparent conductive laminate (Indium Tin 0x
ide) is widely used. ) side may be brought into contact with the display material layer and thermocompression bonded. However, it has been found that in this case, uneven brightness or light emission of the ELD may occur.

In addition to ELD, the above-mentioned ELD problems also exist in conductive laminates used in LCDs that use polyvinyl alcohol, polyimide resin, etc. as alignment film materials, and ECDs that use organic dyes as light emitters. .

3. Purpose of the Invention The present invention solves the problems of conventional conductive laminates as described above, and provides a conductive laminate that does not cause uneven brightness or light emission in display devices. It has been discovered that this problem occurs due to poor adhesion between the transparent conductive film and the display material layer, and the present invention has been completed.

4. Structure of the Invention The present invention provides a conductive laminate in which a transparent conductive film is provided on a substrate, and a layer made of a substance that has good adhesion to an organic polymer substance is provided on the transparent conductive film. It depends.

In the present invention, as the material of the substrate, non-airy glasses such as quartz glass, soda glass, potash glass, etc. can be used. Regarding polymeric organic materials,
For example, polyethylene terephthalate, polyethylene naphthalate, poly-3-caproamide, polyetherimide, polyhexamethylene diamide, polymethaxylene diamine terephthalamide, aromatic polyesters or aromatics whose main components are bisphenol A and its halides and acid dichlorides. Polyamides, polycarbonates, polypropylene, polyimides, polyamides, imidopolybenzimidazole, polyethersulfones, polyetheretherketones, polysulfones, polyetherimides, such as polyester carbonates, copolymers of metaphenylenediamine and isophthalic acid and terephthalic acid, etc. Triacetylcellulose can be used.

The thickness of the substrate is preferably 0.5 mm to 15 mm for glass substrates, and about 1100 mm for polymeric organic substrates.

Materials for the transparent conductive film include Au, metal thin films such as PdXCr, SnOz, Int03, ZnO1TiO
*, CdO, CdOSnow, and the above-mentioned ITO are suitable.

The thickness is preferably 200 to 9000 people.

The thickness of the layer made of a material that has good adhesion to the organic polymer material is preferably 20 to 500 layers.

As the substance having good adhesion to organic polymer substances, silane coupling agents and titanium coupling agents are preferable.

The above-mentioned silane coupling agent refers to a compound in which at least one reactive group and one or more atoms are bonded to a tetravalent silicon atom directly or via a linking group. Examples of the reactive group include an amitribut group, an alkoxy group, an alkyl group, an acyloxy group,
Examples include isocyanato groups and ammonium compound residues. Examples of alkoxy groups include those having 1 to 4 carbon atoms, such as methoxy and ethoxy groups. Examples of the alkyl group include those having 1 to 4 carbon atoms, such as a methyl group and an ethyl group. Examples of the acyloxy group include alkylcarbonyloxy groups having 2 to 4 carbon atoms such as acedeloxy group and butyryloxy group. Examples of ammonium compound residues include quaternary ammonium compound residues such as octadecyldimethylammonium chloride residues.

These groups may have a substituent, and examples of groups having IflA groups include α-methylvinyl group, β-methoxyethoxy group, anilino group, bis(β-hydroxyethyl)amino group, etc. .

Examples of atoms bonded to the silicon atom directly or via a linking group include halogen atoms such as chlorine atoms.

Examples of the above-mentioned linking group include ethylene group, propylene group,
1 carbon atom, such as trimethylene group and tetramethylene group
an alkylene group having 2 to 8 carbon atoms, such as an I-limethyleneoxymethylene group, an ethyleneoxyethylene group, an alkylene amino group having 2 to 8 carbon atoms, such as a trimethyleneaminoethylene group; Alkynone group, ethyleneoxycarbonyl group,
Alkyleneoxycarbonyl group having 2 to 5 carbon atoms, such as trimethyleneoxycarbonyl group (however, the alkylene group is directly bonded to the silicon atom), and 9 to 15 carbon atoms, such as trimethyleneaminoethyleneaminomethylenephenylene group. alkyleneaminoalkyleneaminoalkylenephenylene groups (however, the alkylene group is directly bonded to the silicon atom), and the like. Also,
The aforementioned epoxyethylene group is bonded to a linking group to form, for example, β
-(3゜4-epoxycyclohexylethyl group,
Bonded to the silicon atom as an epoxycycloalkylalkyl group.

The silane coupling agent further includes disilazane compounds such as hexaalkyldisilazane.

Among the above-mentioned silane coupling agents, those that generate a silanol group are preferred, such as those having at least one alkoxy group or acyloxy group directly bonded to a silicon atom. Particularly preferred are those that generate silanol groups,
Furthermore, it is a silane coupling agent having 1 to 2 epoxyethyl groups, mercapto groups, isocyanato groups, amino groups, or vinyl groups.

Moreover, one type of silane coupling agent may be used,
Two or more types may be used in combination.

Next, specific examples of silane coupling agents that can be used in the present invention will be shown.

Exemplary compound (1) NH, (CHi)zN)f(CH,)ssi(O
C■,)a(2) N Hz(CHx>tNH(CH
g)+5i(OC)Is)z■CR3 (3)NHbaCHz)isi(QCssummer■,).

l O\ (4)NHiCI-1zs+(OCzHs)s(5)N
Ht(CHz)zsi(OCgHs)s(6)NHg(
CHJiSi(OCHz)s(9)CHi=CHSi(
OCH3)+(10)CHt=CH-3t(OCHiC
HtOCHi)i(11)CHg”CH31(OCOC
Hs)+(12)CHz-CCOO(CHz)ssi(
OCHs)sCR3-3i(OCHz)s) ・HCl(15) C
Ht-CH5I C#.

(20) CH3Si (OCH co).

(21) (CHz)ssic p (22)CH,5iC1゜(23)(CHs)tsic 1x (24) CP(CHthSi(OCHs)s(27
)R3(CHt)sSi(OCHs)s. ) (29)(CHs)ssiNH3i(CHshIn addition to the above silane coupling agent, the following general formula (1), (TI
), [■], or (TV) can also be used.

General formula [I]: (R1-Oh-q′″i・(P (oR”)z 011
) ff1 (However, R1 and R1 are substituted or unsubstituted hydrocarbon groups.) General formula [■]: (However, R1 and R2 are the same as above, n = o ~ 3
is an integer. ) General formula [■]: (However, R1, R1 and n are the same as described above.

) General formula [■]: (However, R1 is the same as the above-mentioned one, and R3 is a divalent organic group.) Specific examples of the titanium coupling agent include those shown below.

(5) (CaH+v 0h-Ti・CI”((
) CIzHzJzOII)z Below, the effects of the bipedal cambling agent will be explained.

F. 1. In , D, a display material such as a light emitter or a phosphor is usually dispersed in an organic polymeric substance, and a binder resin such as a cellulose resin, a phenolic resin, or a vinyl resin is used as the polymeric substance. has been done.

For example, the organosilicon compound having the functional group has good adhesion or affinity with the binder resin. In addition, this organosilicon compound has good bonding properties with the surface of the metal or metal compound that is the material of the transparent conductive film, and therefore has good adhesion to both the binder resin and the metal or metal compound. According to the invention, the substances include organosilicon compounds having the above-mentioned functional groups.

It is thought that the bond between the organosilicon compound and the transparent conductive film material (for example, metal oxide) occurs through the following mechanism.

YBa-3i (OR)s+ 3 HzO→YmesoSi
(OH)3+ 3 ROH-(1) (organosilicon compound:
(Y is a functional group, R is an alkyl group)
(OH) 3 reacts with the metal oxide according to the following formula (2) at the part in contact with the transparent conductive film that has absorbed moisture on the surface,
The two are strongly connected.

However, Y represents the aforementioned functional group (for example, an epoxy group), and M represents a metal atom in the transparent conductive film, which is indicated by diagonal lines.

The bond between this organosilicon compound and the binder resin is
For example, a functional group-containing organosilicon compound reacts with the oxygen-containing heterocycle of cellulose during the thermocompression bonding described above, for example, according to the following formula (3), and the two are firmly bonded.

In addition to the above-described binding mechanism, other coupling effects are also considered. That is, the coupling agent used in the present invention only needs to have a lipophilic group that has good affinity with the hydrophilic surface of the transparent conductive film side on the one hand and has good affinity with the binder resin on the other hand. Adhesion to the binder resin may be improved when this lipophilic group exhibits sufficient affinity with the binder resin. It is also conceivable that the above-mentioned functional groups and the functional groups of the binder resin are bonded to each other by a type of bonding force such as a hydrogen bond.

The present invention has been made based on the above findings.

In addition, because the bipedal coupling agent makes the surface of the transparent conductive film hydrophobic (that is, a state that is compatible with hydrophobic substances), for example, before thermocompression bonding with ELD, the conductive laminate can be pressure bonded. The surface is already hydrophobic and can prevent atmospheric moisture from adhering to it. Therefore, during thermocompression bonding with ELD, the influence of moisture can be prevented, and thermocompression bonding can be performed satisfactorily.

5. Example large width
A TTOIIQ with a thickness of 500 mm was formed on a 3 inch, 75 μm thick polyethylene tereft film,
Next, an organic silicon compound containing an epoxyethyl group (XG-11 manufactured by Chisso Corporation) was coated on the ITO film to a thickness of 150 cm, and dried by blowing hot air at 150°C for 5 minutes. rTOi3 on the base film 2 as shown in
A conductive laminate 1 was prepared in which a bright conductive Ps3 and an organic silicon compound layer 4 were sequentially deposited.

A specific method for forming each of the above films will be described later.

Silicone 5H- manufactured by Toshi Co., Ltd. with a functional group-containing organosilicon compound layer
6075 (CHI-CH3I(OCOCHI)3) to form an organic silicon compound layer having an acetoxy group,
A conductive laminate was otherwise prepared in the same manner as in Example 1 above.

As shown in FIG. 2, these conductive laminates 1 and AI
l ZnS powder and C are placed in cellulose resin on the electrode plate 6.
A laminate on which a light-emitting layer 7 in which an equal amount of mixed powder with U powder is dispersed is bonded by thermocompression (150° C. , 0.2 minutes) and set as ELD5.

As shown in FIG. 3, the conductive laminate 1 is pulled in the 1806 direction and peeled between the functional group organosilicon compound layer 4 and the light emitting layer 7, and the load at the start of peeling and the maximum load are A 180" beer test was carried out to measure.

The results are shown in Table 1. For comparison, the same table also shows the results of conducting the same tests on conductive laminates produced under the same conditions as in the examples without providing the functional group-containing organosilicon compound layer.

As can be seen from the table, the conductive laminate according to the present invention has a peeling initiation load approximately twice that of the comparative conductive laminate, and a maximum load approximately 3 to 3.5 times, The adhesion between the respective layers is significantly improved. Further, when this ELD was driven to emit light, uneven brightness and uneven light emission were extremely small even during long-time driving.

Next, the method and apparatus for manufacturing a conductive laminate according to the present invention will be illustrated with reference to FIGS. 4 to 6.

In FIG. 4, the apparatus is divided into chambers 30, 31, and 33, and a take-up roll 34 and a supply roll 35 for the sheet substrate 2 are arranged in the chambers 30, 33 on both sides, and the substrate 2 is held between the two rolls. The following processing is performed while being sent sequentially. first,
The adsorbed moisture of the substrate 2 is removed by preheating (100° C.) in the chamber 33, and then the substrate 2, which enters the chamber 31 as a vapor deposition tank, is conveyed by a conveyance roller 36 (conveyance speed is 10 cs /
In-Sn alloy or ITO is heated with the halogen heater lamp 41.
An evaporation source 42 consisting of In and Sn, or two evaporation sources 42 of In and Sn is heated and evaporated, and oxygen gas is transferred to a discharge device 43.
An ITO transparent conductive film (3 above) is deposited on the surface of the substrate 2 by ionizing or activating the ITO and introducing the ITO into the substrate. The conditions for each vapor deposition are as follows.

Evaporation source 42: In-Sn alloy (resistance heating) or I
TO (electron gun heating), deposition rate 200 people/min to 1o00 people/1n.

Discharge device 43: 50 to 100cc/ll1i of oxygen gas
Introduced at n (degree of vacuum 5 x lO-'Torr ~ 9 x
lo-'Torr, 200-700W direct current or high frequency discharge).

Further, instead of the above-mentioned reactive vapor deposition method or vapor deposition method, the above-mentioned transparent conductive film can also be formed by a known sputtering method, ion blating method, or electron beam evaporation method.

Next, a functional group-containing organosilicon compound layer is deposited on the transparent conductive film of the sheet substrate on which the transparent conductive film is deposited as described above. As described above, the deposition method is a method of applying an organic silicon compound having the above-mentioned functional group.

Application methods include air knife coat, blade coat, air knife coat, squeeze coat, impregnation coat, reverse roll coat, transfer roll coat, gravure coat, kiss coat, cast coat, spray coat, direct roll coat, roll coater,
Wire barcodes, extrusion coatings, etc. can be used, and other methods are also possible.

For example, as shown in FIG. 5, first, the sheet substrate 2 fed out from the supply roll 11 is coated with an organosilicon compound coating material 4a having the functional group, such as the XG-11, by a known reverse roll coater 11-2. Or silicone S
After applying H-6075, it is introduced into a dryer 12, where hot air 14 is introduced from nozzles 13 arranged above and below to dry it, and it is wound onto a roll 24.

In this process, the coating material 4a is coated using a method in which the entire amount of the coating liquid sent to the coater is applied immediately, rather than using a reverse roll coater or a gravure coater, such as an extrusion method (or a reverse roll knife) as shown in FIG. method) can be used. It is desirable that the discharge portion of the coating liquid 4a be formed using a fountain beam. This fountain beam 38 supplies the paint 4a from the treatment tank to the introduction pipe 3.
After being received from 0, it is immediately discharged through the slit 31 onto the roll 11-3, and therefore,
Almost no paint remains before being discharged. The discharged paint is sequentially applied onto the sheet substrate 2 from the roll 11-3.

In this way, the conductive laminate 1 shown in FIG. 1 is manufactured.

Note that the formation of the transparent conductive film and the formation of the functional group-containing organosilicon compound may be performed in the reverse order.

FIG. 7 shows an example of an ELD manufactured using the transparent conductive laminate 1 described above. According to this EI-D 5-2, a high dielectric insulating plate 6-2 made of barium titanate for stable operation is disposed on the AI electrode plate 6 provided on the support plate 10. A blue-green luminescent layer 7 made of a mixed powder of ZnS and Cu using a cellulose resin as a binder is arranged on top, and a conductive laminate l is placed on top of the blue-green luminescent layer 7.
The functional group organosilicon compound layer 4 side is attached to the light emitter N7 side and is bonded with a hot roll, and a water trapping (or water retaining) layer 20 made of polyvinyl alcohol with high water absorption is placed on top of the layer 4 to absorb moisture from the atmosphere. This prevents it from penetrating into the interior. The entire structure is covered with a transparent fluororesin package film 21 fixed to the peripheral portion 10a of the support plate 10.

As the binder resin for the light emitting layer 7, in addition to cellulose resin, urethane resin, epoxy resin, melamine resin, phenol resin, polyethylene resin, polyamide resin, etc. are used, and the light emitting layer 7 made of the above resin and a conductive laminate are used. In order to improve the adhesion of the body 1, it is desirable that the organic silicon compound layer 4 has a specific functional group.

For example, epoxy groups, acetoxy groups, urethane resins are suitable for cellulose resins, epoxy groups, mercapto groups, melamine resins are suitable for epoxy resins, epoxy groups are suitable for phenol resins, and amino groups are suitable for polyethylene resins and polyamide resins. There is.

Note that ZnS:Cu, which is the light emitting material of ELD, liquid crystal of LCD, and organic dye, which is the light emitting material of ECD, are all degraded by ultraviolet rays, and there is a limit to the lifespan of the display device. FIG. 8 shows an example in which an ultraviolet absorbing filter film is provided on the conductive laminate to prevent deterioration of the light emitting layer due to ultraviolet rays.

The conductive laminate 1-2 is constructed by sequentially depositing a transparent conductive film 3 and a functional silicon compound layer 4 on a substrate 2, and a UV absorbing filter film 8 deposited on the opposite side. A light emitting layer 7 is provided on the functional group-containing organosilicon compound layer 4, and an Al electrode plate 6 is provided on the outside thereof to constitute an ELD 5-3.

In this way, as in Example 1.2, the transparent conductive film 3 and the light emitting layer 7 are formed by the functional group-containing organosilicon compound layer 4.
In addition, the light emitting body does not deteriorate due to ultraviolet rays, and the life of the ELD is significantly extended.

The material for the filter membrane is 2-(2-hydroxyphenyl)benzotriazole represented by the following general formula = (where R1 and R1 are a hydrogen atom or an alkyl group, and R3 is a hydrogen atom or a halogen atom.) is suitable.

Furthermore, in FIGS. 1 and 2, the same effect as above can be achieved by forming layer 4 into a layer containing a mixture of the ultraviolet absorption filter film material and the functional group-containing organosilicon compound. .

FIG. 9 shows an example in which the conductive laminate 1 shown in FIG. 1 is used in a CD.

Transparent conductive film 3 and organosilicon compound N4 of conductive laminate 1
The unnecessary portions are etched and removed by conventional photo-etching so that they are arranged in a predetermined pattern, for example, in a sun-shaped pattern, and the two conductive laminates 1 are formed as shown in FIG. The functional group organosilicon compound layers 4 were made to face each other, and the liquid crystal 16 was sandwiched from both sides with an alignment film 17 interposed therebetween, thereby obtaining an LCD 9. Note that a deflection film 18 is formed on the outside of the base film 2.

In this way, since the functional group organosilicon compound layer 4 is interposed between the transparent conductive film 3 and the alignment film 16 (for example, a polyvinyl alcohol film), each layer is Adhesion is extremely good.

6. As described in detail of the invention, the conductive laminate of the present invention has a transparent conductive film provided on the base, and this transparent conductive film is made of a material that has good adhesiveness to an organic polymer substance. Because it has a structure with layers, it has extremely good adhesion with organic polymer materials, such as the light emitting layer of display devices, and prevents uneven brightness and light emission of display devices due to film peeling over a long period of time. It never happens again.

[Brief explanation of drawings]

FIG. 1 is a sectional view showing an example of a conductive laminate according to the present invention, FIG. 2 is a sectional view showing an example of an electroluminescent display device using the conductive laminate according to the present invention, and FIG. 4, 5, and 6 are schematic sectional views showing an apparatus for manufacturing a conductive laminate, and FIG. 7 is a cross-sectional view of a main part for explaining the method. FIG. 8 is a sectional view showing another example of an electroluminescent device using the conductive laminate according to the present invention, and FIG. 9 is a sectional view of the main part of the electroluminescent display device. It is a sectional view showing an example of the liquid crystal display device used. In addition, in the reference numerals shown in the drawings, 1.1-2... Conductive laminate 2... Substrate 3... Transparent conductive film 4... Functional group-containing organosilicon compound layer 4a...Functional group-containing organosilicon compound liquid 5.5-3...Electroluminescence display device 6...Electrode plate 7...Light emitter layer 8...Ultraviolet absorption filter film 9... . . . Liquid crystal display device 16 . . . Liquid crystal 17 . . . Alignment film 18 . . . Deflection film.

Claims (1)

[Scope of Claims] 1. A conductive laminate, in which a transparent conductive film is provided on a substrate, and a layer made of a substance that has good adhesion to an organic polymer substance is provided on the transparent conductive film. 2. Substances that have good adhesion to organic polymeric substances include epoxyethyl groups, epoxyethylene groups, acetoxy groups, vinyl groups, mercapto groups, alkyl groups, alkoxy groups, acyloxy groups, isocyanato groups, ammonium compound residues, and amino The conductive laminate according to claim 1, which is a substance made of an organosilicon compound having one or more types of groups. 3. A layer consisting of an organic polymer material and a material with good adhesive properties,
The conductive laminate according to claim 1 or 2, which is pressure-bonded with a display material layer containing a display material and an organic polymer substance.