JPH0414738A - Laminated substance - 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 (Industrial Application Field) The present invention relates to a laminate having an antistatic layer on its surface containing a dye that absorbs a specific wavelength, and more specifically, a laminate that is suitable as a material for the surface of a cathode ray tube. This relates to a laminate.

(Conventional technology) Conventionally, to prevent static electricity on the surface of cathode ray tubes in televisions, etc.
Treatment with silicon-based compounds and nonionic surfactants is known.

However, when a surfactant is used, there are problems such as poor sustainability of the effect and excessive influence of humidity in the air.

Furthermore, after applying and baking an alcoholic solution of tetraalkoxysilane on a glass substrate, a top coat layer containing silanol groups is provided (Japanese Unexamined Patent Publication No. 61-118
No. 948), however, there are problems such as the antistatic effect is greatly affected by the humidity in the air, and the adhesion between glass and silica as a substrate is poor.

Recently, a technique for solving the above-mentioned problems has been proposed, for example, in Japanese Patent Laid-Open No. 124331/1983.

That is, this invention contains water and an acid as a hydrolysis catalyst in a solvent such as an alcohol such as a tetraalkoxysilicate or a mixture of an alcohol and a ketone, and imparts conductivity to a silica sol liquid obtained by hydrolyzing and condensing the water. This method is characterized by adding a substance to the substrate, applying it to the substrate, and then baking it.

The laminate thus formed has the advantage that in addition to having an anti-glare effect on the surface of the cathode ray tube, it is stable against humidity in the air and has high adhesion to the substrate.

However, the cathode ray tube obtained in this manner is also required to have various better performances in terms of contrast and the like.

(Problems to be Solved by the Invention) The present invention provides that, on the surface of a cathode ray tube such as a television,
Based on the knowledge that eliminating the reflection of light in a specific wavelength band increases the contrast of the image reflected on the cathode ray tube surface, the above-mentioned antistatic coating on the cathode ray tube surface is replaced with a colored film containing a pigment that absorbs light in that wavelength band. By,
The object of the present invention is to provide a laminate for use on the surface of a cathode ray tube, which has the effects of antiglare and antistatic properties on the surface of the cathode ray tube, as well as improving the contrast of images.

In addition to its absorption spectrum, the dye must also have excellent solubility in the antistatic film coating solution.

2. Good color development in the antistatic film.

3. Excellent stability in antistatic film.

4. Excellent heat resistance.

The following characteristics are required.

(Means for Solving the Problem) That is, the gist of the present invention is to provide a laminate in which an antistatic film is provided on a transparent support.
The present invention relates to a laminate characterized by containing a dye having a maximum absorption wavelength in the mm region.

Hereinafter, the present invention will be explained in detail.

In the present invention, the dye to be contained in the antistatic film is as follows:
Any dye may be used as long as its maximum absorption wavelength is from 560 to 610 mm, but in the present invention, cationic dyes are preferred, and rhodamine dyes are particularly preferred. Examples of rhodamine dyes include those having a structure represented by the following formula [I].

[In the formula, R1, R2, R3, and R4 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms; It represents a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and R6 is cooe, so, e, -C
R6 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted alkyl group having 2 to 20 carbon atoms; Unsubstituted alkenyl group; Substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; Substituted or unsubstituted aryl group having 6 to 20 carbon atoms; -COOA, or -803A group (A represents a hydrogen atom or a cation); ) is shown.R7, R8, R9
and RIO are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.
represents an alkoxy group or an alkylthio group. Also R1 and R
9. R2 and R7, R3 and RIG, and R4 and R8 may be bonded to each other to form a ring.

X represents an anion. However, when No and R5 in the formula form an inner salt, Xo does not exist. ] In general formula [I], R1x R4, R6, R7~R
Examples of the alkyl group having 1 to 20 carbon atoms in IO and R11 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group. , n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n
-dodecyl group, n-)lysocyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group,
Examples of the alkenyl group having 2 to 2 carbon atoms in R1-R4 and R6 include n-eicosyl group, vinyl group, 1-propenyl group, allyl group, 3-butenyl group, 4
-pentenyl group, 5-hexenyl group, 6-heptenyl group, 7-octenyl group, 8-nonenyl group, 9-decenyl group, 12-tridecenyl group, 14-pentadecenyl group, 1
Examples include 7-octadecenyl group, 19-eicosyl group, etc., and examples of the cycloalkyl group having 3 to 20 carbon atoms in R1-R4 and R6 include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclo Examples include octyl group, cyclodecyl group, cyclododecyl group, cyclopentadecyl group, cycloheptadecyl group, cycloeicosyl group, etc. R1x)j
Examples of the aryl group having 6 to 20 carbon atoms in 4 and R6 include phenyl group, naphthyl group, anthryl group, 1-pyrenyl group, phenanthryl group, and R7 to RIG
Examples of the halogen atom in R7 to RIG include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and examples of the alkoxy group having 1 to 20 carbon atoms in R7 to RIG include a methoxy group, an ethoxy group, an n-propoxy group, an i- Propoxy group, n-butoxy group, t-butoxy group, n-pentoxy group, n-hexyloxy group, n-hebutyloxy group, n
-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-) lysosyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n- Examples include hexadecyloxy group, n-hebutadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, and n-eicosyloxy group. Moreover, as a C1-C20 alkylthio group, the group corresponding to said alkoxy group is mentioned.

Furthermore, in general formula [I], R1, R2, R3, R4
Examples of substituents for the alkyl group, aryl group, alkenyl group, or cycloalkyl group of R6 include an alkoxy group, an alkoxyalkoxy group, an alkoxyalkoxyalkoxy group, an allyloxy group, an aryl group, an aryloxy group, a cyano group, a nitro group, Examples include a hydroxy group, a tetrahydrofuryl group, an alkylsulfonylamino group, a halogen atom, and in addition, an alkyl group or a vinyl group as a substituent for an aryl group or a cycloalkyl group.

Furthermore, in general formula [I], R7, R8, R9, RIG
When R7 is R2, R8 is R4, R9 is R1, and RIO is R3, these groups may be bonded to form a six-membered ring.

X is a halogen atom such as a chlorine atom, a bromine atom, an iodine atom, an anion such as Ni, Co, Cu, Mn, Pd.
, quencher anions such as anions of transition metal chelate compounds such as Pt and the like.

Examples of quencher anions include the following transition metal complex compounds.

Cations in A include alkaline earth metals such as Li, Na, and K, as well as Ni, Co, Cu, Mn, and P.
d, cations of transition metal chelate compounds such as Pt, and the like.

Examples of the cationic transition metal chelate compound in A include the following.

In the present invention, specific examples of rhodamine type dyes include the following.

In addition, R1 and R9, R2 and R7, R3 and RIO1R4 and R
Specific structural examples of rhodamine type dyes in which 8 are bonded to each other and cyclized include the following.

O3H For these dyes, if the substituent is an alkyl group, alkenyl group, etc., or if these groups have various substituents, it is preferable to have a straight chain or a carbon number of about 1 (or 2) to 8, rather than a long chain. A branched alkyl group is better.

The laminate of the present invention basically comprises a transparent support and an antistatic film containing the above-mentioned cationic dye.

For details on antistatic films, see, for example, Japanese Patent Application Laid-open No. 63+1243.
It is formed by a method similar to that described in No. 31.

That is, a conductivity-imparting substance is added to a silica sol liquid which is made of silicon halide, silane alkoxide, silyl isocyanate, etc. as a solvent, water, and an acid as a catalyst for hydrolysis, and subjected to hydrolysis and dehydration condensation. The laminate of the present invention can be obtained by applying a liquid containing a dye having a maximum absorption wavelength in the region of ~610 nm onto a transparent support and then baking the liquid.

More specifically, examples of the silane compound used in the antistatic film include silicon halides such as silicon tetrachloride, tetraalkoxysilanes such as tetraethoxysilane, tetraalkylsilanes, and silyl isocyanates.

Examples of the solvent include alcohols such as methanol and ethanol alone, two or more types of alcohols, and mixed solvents of alcohols and carboxylic acid esters or ketones.

The acid of the hydrolysis catalyst may be either an inorganic acid or an organic acid.

Further, examples of substances imparting conductivity include various metal compounds, particularly metal compounds having an atomic number of 13 to 50, such as Fe and Co.

Ni, Cu, Ag, Zn, Zr, In, 8
Examples include halides, oxides, nitrates, and sulfates of n.

An example of this is FeCl3. FeCl2. FeB
r2. NiC16°Ni (NO3)2. Co (
NO3)2. CoCl2. Fe (NO3)21
Cu (NO3)2゜CuCl2. Zn (NO3)
2. ZnCl2. AlCl3. AI (NO3)
2. ZrO2゜5n02. InCl3. Zn (
804)2. ZnSO4・(NH3)2804. C
oSO4°FeSO4 etc. can be used, and these may contain water of crystallization, but are not limited to these as long as they are soluble in the silica sol solution.

In addition, as for the amount of these compounds used, for example, the silane compound should be used in an amount of 0.000 m/100 me of solvent in terms of 5i02.
01 mol or more and 0.13 mol or less, and the conductivity imparting substance is 0.0 mol or more based on the 5i02 solid content in the silica sol solution.
03 wt% or more and 50.0 wt% or less is preferable.

The amount of dye used is 0 based on the total amount of conductive liquid to be added.
．． 01-0.3 wt%, preferably 0.03-0.15
Examples include wt%.

Furthermore, glass is suitable as the transparent support in the present invention in various respects.

Various methods can be applied to the coating on the support, but a coating method such as a spinner method or a spraying method is preferable.

At this time, it is preferable that the surface of the support has been treated for coating, but if the surface is preheated to a surface temperature in the range of 35°C to IOO'C after cleaning, the antistatic film can be applied. Sometimes a fine uneven surface can be formed, which provides an excellent anti-glare effect.

After applying in this way, the temperature is 100°C to 350°C.
The laminate of the present invention is obtained by firing at a temperature of preferably 150°C to 250°C, particularly preferably 160°C to 180°C, for about 30 minutes.

The thickness of the antistatic film in this laminate is 0.01 to 51
m is preferable, more preferably 0.05 to 0
．． It is 5 μm.

Further, the laminate of the present invention may further include an undercoat layer between the transparent support and the antistatic film or a protective layer on the antistatic film, if necessary.

In addition, to improve the stability and light resistance of the antistatic film, transition metal chelate compounds (e.g., acetylacetonate chelate, bisphenyldithiol, salicylaldehyde oxime, bisdithio-α-diketone, etc.) are used as -heavyt oxygen quenchers. ) may also be included. Furthermore, other dyes can be used in combination as necessary. The other dyes may be other types of compounds of the same type, or dyes of other types such as triarylmethane dyes, azo dyes, cyanine dyes, squarylium dyes, metal complexes of azo compounds, Ni indoaniline dyes, etc. But that's fine.

(Examples) The present invention will be specifically explained below with reference to Examples, but these Examples are not intended to limit the present invention.

Example 1 (Film Formation) 5 mg of a dye having the following structural formula Ia was dissolved in Niresancoat As + 04A (trade name, manufactured by Asahi Glass ■) 10me as a conductive liquid, and coated on a glass substrate with a spin coater (4
00 rpm, 605 ec). This was heat treated in an oven at 160°C for 130 minutes.

a (Evaluation) Figure 1 shows the transmission spectrum of the laminate having the colored antistatic film manufactured above, and since it has absorption at λmax 575 nm, it absorbs external light at 575 nm,
Improved display contrast.

(Comparative Example) A sample was prepared in the same manner as in Example 1 except that the dye 1a shown in Example 1 was not used.

(Evaluation) Since there is no absorption in the wavelength range of 560 to 610 nm, external light having the same wavelength is reflected, resulting in insufficient contrast.

Example 2 A sample was prepared in the same manner as in Example 1 except that a dye having the following structural formula IIa was used instead of the dye used in Example 1.

(Evaluation) 1a As shown in the transmission spectrum of the laminate in Figure 2, λmax
Since it has absorption at 589 nm, it absorbs this 589 nm external light, improving display contrast.

Example 3 Samples were prepared in the same manner as in Example 1 using each of the compounds shown in Table 1 instead of the dyes used in Example 1, and their transmission spectra were measured. Contrast was also good.

Table 1 Table 1 Table 1 Table 1 4゜ (Effect of the invention) According to the laminate of the present invention, since the dye contained in the antistatic layer absorbs wavelengths of 560 to 610 nm,
By using such a laminate in a cathode ray tube such as a television, the contrast of an image can be improved.

[Brief explanation of drawings]

FIG. 1 is a drawing showing the transmission spectrum of the sample prepared in Example 1. FIG. 2 is a diagram showing the transmission spectrum of the sample prepared in Example 2. In the figure, the vertical axis represents transmittance (%), and the horizontal axis represents wavelength (nm
).

Claims (1)

[Claims] (1) A laminate comprising an antistatic film provided on a transparent support, characterized in that the antistatic film contains a dye having a maximum absorption wavelength in a region of 560 to 610 nm.