JPH06130202A - Heat resistant optical resin plate - Google Patents

Abstract

PURPOSE:To provide a heat resistance optical resin plate having such heat resistance that function imparting treatment such as antireflection treatment can be satisfactorily carried out and capable of controlling the quantity of light without varying the color tone of transmitted light. CONSTITUTION:This heat resistant optical resin plate has >=150 deg.C glass transition temp. and satisfies 0.30<=x<=0.32, 0.31<=y<=0.32 and 30<=Y<=60 in a color coordinate system stipulated by CIE (Commission Inter nationale de I'Eclairage).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical heat-resistant resin plate having excellent heat resistance and capable of controlling brightness without changing the color tone of transmitted light.

It is preferably used as a substrate for an optical filter for a display device, an optical lens, a prism or a transparent partition plate.

[0003]

2. Description of the Related Art Generally, resin materials are lightweight, have impact resistance,
Due to its excellent processability and mass productivity, demand is expanding in all fields as an alternative to inorganic materials. In recent years, a transparent base material used for optical applications is subjected to a treatment such as an antireflection treatment or an antistatic treatment by depositing an inorganic optical thin film as a multilayer film by vapor deposition or ion sputtering. When these processings are usually performed at high temperature, the film characteristics are likely to develop. However, polymethylmethacrylate (PM), which is known as an organic optical material,
MA), polystyrene, polycarbonate, amorphous polyolefin, and polydiethylene glycol bisallyl carbonate have low heat resistance and are subject to process restrictions. Therefore, the intended treatment cannot be performed sufficiently, and therefore their functions are also better than those of inorganic glass. I haven't made something that I am fully satisfied with.

Further, in an optical filter for a CRT, in addition to antireflection to prevent reflection from the surroundings in order to prevent eye fatigue, the contrast is improved to make the screen easy to see. , It is required to prevent glare on the screen.

It is known that a PMMA plate or a polycarbonate plate colored in neutral gray is provided with an antireflection film, but its optical characteristics are not satisfactory as compared with those made of inorganic glass.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an optical system which has heat resistance sufficient to withstand a function imparting treatment step such as antireflection treatment and which has a controlled light amount without changing the color tone of transmitted light. To provide a heat resistant resin plate for use.

[0007]

In order to achieve the above object, the present invention has the following constitution.

That is, the glass transition temperature is 150 ° C. or higher, x is in the range of 0.30 or more and 0.32 or less in the color coordinate system based on CIE (International Commission on Illumination),
y is in the range of 0.31 or more and 0.32 or less, and Y
Is in the range of 30 or more and 60 or less.

The glass transition temperature of the resin plate must be 150 ° C. or higher. This is because, for example, when an inorganic thin film is provided on the resin plate, the resin plate temperature becomes at least 150 ° C. When the glass transition temperature of the resin plate is less than 150 ° C, when a film attachment process is performed,
Deformation of the resin plate may occur. More preferably, it has a glass transition temperature of 180 ° C. or higher. For example, when a magnesium fluoride film is vapor-deposited as an antireflection film, if the film is applied at 150 ° C. or lower, the film is not dense and a satisfactory strength and refractive index cannot be obtained. In this case, the higher the temperature, the easier it is to obtain excellent film characteristics. Even when an ITO (indium tin oxide) film is formed by sputtering, good film characteristics such as high light transmittance and low resistivity can be obtained when the substrate temperature is 150 ° C. or higher.

The glass transition temperature is measured as a temperature at which the temperature dependency of each resin changes greatly, such as a change in specific heat, a change in refractive index, a change in mechanical characteristics, a change in expansion coefficient. There is a large change in thermal properties. Particularly in the present invention, the glass transition temperature is 150.
If the temperature is lower than 0 ° C, the resin plate is severely deformed, so that it cannot be processed at a temperature substantially above the glass transition temperature.

In the present invention, x and y can be obtained by measuring the tristimulus values X, Y and Z based on the CIE color coordinate system, and by the following equation.

X = X / (X + Y + Z), y = Y / (X + Y + Z) Since the luminosity of transmitted light is not changed, x is 0.30 or more and 0.32 or less, and y is 0.31 or more, 0. It must be in the range of 32 or less. If x and y deviate from this range, the transmitted light will obviously be colored and the color tone of the object will change, so it cannot be used.
Especially when used as an optical filter for a CRT,
The color of the screen display may change, and it may be difficult to correctly recognize the color.

The Y value is a value of light transmittance in a wavelength range having a center wavelength of 555 nm and being said to have the highest human visual sensitivity. When the Y value is set to 30 or more and 60 or less, black and white and The color contrast is high, the visibility is improved and the eyes are less tired. If it exceeds 60, the screen will be glaring and cannot be used. If it is less than 30, the visibility is rather deteriorated except for the light having extremely high luminous intensity, which causes eyestrain and therefore cannot be used.

An ultraviolet absorber can be used to cut off light of 400 nm or less, which is highly harmful to the eyes.
Further, a dye for cutting near infrared light of 700 nm or more can be added.

Resin plates include N-methylmaleimide, N-
Butyl maleimide, N-phenyl maleimide, No-methyl phenyl maleimide, Nm-methyl phenyl maleimide,
Np-methylphenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, N-
p-hydroxyphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-
Methoxyphenyl maleimide, No-chlorophenyl maleimide, Nm-chlorophenyl maleimide, Np-chlorophenyl maleimide, No-carboxyphenyl maleimide, Np-carboxyphenyl maleimide, Np-nitrophenyl maleimide, N-ethyl maleimide, N-cyclohexyl maleimide, N-isopropyl Maleimide such as maleimide, or n-bornyl methacrylate, iso-
Methacrylates such as bornyl methacrylate, tricyclodecanyl methacrylate and adamantyl methacrylate are preferably used as a constituent of the resin for the purpose of increasing the glass transition temperature. It is also preferable to use a heat resistant resin such as polysulfone or polyarylate.

The polymerizable composition that can be used is not particularly limited as long as it satisfies the above claims, and it may be a monomer or a mixture of several kinds of monomers. It may be a mixture of a polymer and a monomer. Further, a curing agent, a curing accelerator, a radical-generating initiator, an ultraviolet absorber, an antioxidant, an antistatic agent, a dye, a weather resistance stabilizer, a fragrance, a plasticizer and the like may be added. Specific examples of the monomer include aromatic vinyl monomers, olefin vinyl monomers, acrylic monomers, methacrylic monomers, allyl monomers, fumarate monomers, Examples include maleimide-based monomers, epoxy-based compounds, urethane-based compounds and the like. A mixture of a maleimide monomer and a methacrylic monomer or a styrene monomer is preferably used for applications requiring optical properties and heat resistance. Polymerized moldings obtained from such polymerizable compositions may be thermoplastic or thermosetting. Among them, those obtained by three-dimensionally crosslinking with a polyfunctional monomer are preferable. As the polyfunctional monomer, a polyfunctional maleimide,
Aromatic polyfunctional monomer, polyhydric alcohol di-, tri-,
Examples thereof include tetra- (meth) acrylates, diallyl compounds, dienes, polyfunctional monomers having a polycyclic ring skeleton having a phosphazene skeleton, and the like. A monomer or the like is preferable. Also,
When the resin is produced by a cast polymerization method, for example, a difunctional monomer such as divinylbenzene, diallyl phthalate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or bismaleimide is used as a copolymerization component. It is preferable.

Epoxy resin, urethane resin and the like may be used by molding by cast polymerization.

In the present invention, x is 0.30 or more,
A dye is added so that y is 0.32 or less and y is 0.31 or more and 0.32 or less. The dye that can be used is not particularly limited as long as it satisfies the above claims, but an oil-soluble dye is preferably used. The dye may be one kind or a mixture of several kinds. Specific examples of the dyes include monoazo dyes, metal complex salt type monoazo dyes, disazo dyes, anthraquinone dyes, phthalocyanine dyes, triallylmethane dyes and the like.

In the case of cast polymerization, a polymerizable dye can be added to the monomer composition for polymerization, and in the case of a thermoplastic resin, the dye can be mixed and then molded.
Further, in the case of a resin that can be solution cast polymerized, a dye can be added to the solution for molding. Furthermore, a method of dyeing after molding the heat-resistant resin plate can also be adopted. It is also possible to laminate various heat resistant substrates or films to form a composite substrate.

The optical heat resistant resin plate of the present invention is preferably used as a substrate for an optical filter such as a display device, an optical lens, a prism or a transparent partition plate.

[0021]

The present invention will be described in more detail with reference to the following examples. The invention is not limited to these examples.

The plate thickness used in the examples is JIS
It was measured with a contact type dial gauge IDA-112M manufactured by Mitutoyo Corporation based on the method defined in K6911.

The glass transition temperature is JIS K-7121.
Metller DS based on the method specified in
It was measured by C30.

CIE tristimulus values and x and y are SM color computer (SM-3-C, manufactured by Suga Test Instruments Co., Ltd.).
H) was measured and calculated.

Example 1 A glass plate having a size of 300 mm × 300 mm and a thickness of 5 mm and a gasket made of soft vinyl chloride were used to form a cell so that the distance between two glass plates was 2 mm. In this, 106.0 g of N-isopropylmaleimide, 74.0 g of styrene, 20.0 g of divinylbenzene, 0.2 g of azobisisobutyronitrile as a polymerization initiator, and as a dye, PS Black ME manufactured by Mitsui Toatsu Dyes Co., Ltd. -1
0.020g, PS Red GG 0.010g,
PS Blue RR 0.006 g, TINUVIN-900 manufactured by CIBA-GEIGY as an ultraviolet absorber
Inject 1.0 g of mixed and dissolved monomer mixture,
After polymerizing in a water bath at 0 ° C for 2 hours, it was polymerized in air at 180 ° C for 2 hours to obtain a resin plate. The characteristic values of the obtained resin plate are shown in Table 1.

The obtained resin plate was transparent and colored in gray. Moreover, there was no discomfort in the change in the color tone of the transmitted light.

Example 2 In Example 1, N-isopropylmaleimide 94.
0 g, N-cyclohexylmaleimide 20.0 g, styrene 66.0 g, divinylbenzene 12.0 g, azobisisobutyronitrile 0.2 g as a polymerization initiator, and Mitsui Toatsu Dyestuff's PS Black ME- as a dye.
1 0.020g, PS Red GG 0.008g,
PS Blue RR 0.006 g, TINUVIN-900 1.0 manufactured by Ciba-Geigy as an ultraviolet absorber
Cell cast polymerization was carried out in the same manner as in Example 1 except that a monomer mixture obtained by mixing and dissolving g was injected to obtain a resin plate. The characteristic values of the obtained resin plate are shown in Table 1.

The obtained resin plate was transparent and colored in gray. Moreover, there was no discomfort in the change in the color tone of the transmitted light.

Example 3 In Example 1, N-isopropylmaleimide 80.
5 g, N-cyclohexylmaleimide 38.5 g, methyl methacrylate 43.0 g, α-methylstyrene 1
8.0 g, divinylbenzene 20.0 g, azobisisobutyronitrile 0.2 g as a polymerization initiator, and Mitsui Toatsu Dye KK PS Black ME-1
020g, PS Red GG 0.008g, PS
BlueRR 0.004g, CI as UV absorber
BA-GEIGY TINUVIN-900 1.0
Cell cast polymerization was carried out in the same manner as in Example 1 except that a monomer mixture obtained by mixing and dissolving g was injected to obtain a resin plate. The characteristic values of the obtained resin plate are shown in Table 1.

The obtained resin plate was transparent and colored in gray. Moreover, there was no discomfort in the change in the color tone of the transmitted light.

Comparative Example 1 In Example 1, as a dye, P manufactured by Mitsui Toatsu Dye Co., Ltd. was used.
S Black ME-1 0.020g, PS Re
Cell cast polymerization was carried out in the same manner as in Example 1 except that 0.020 g of d GG was added to obtain a resin plate. The characteristic values of the obtained resin plate are shown in Table 1.

The obtained resin plate was transparent and colored orange, and the change in the color tone of the transmitted light was uncomfortable.

Comparative Example 2 In Example 1, as a dye, P manufactured by Mitsui Toatsu Dye Co., Ltd. was used.
Cell cast polymerization was carried out in the same manner as in Example 1 except that 0.020 g of S Black ME-1 was added to obtain a resin plate. The characteristic values of the obtained resin plate are shown in Table 1.

The obtained resin plate was transparent and colored in green, and there was a feeling of strangeness in the change in color tone of transmitted light.

Comparative Example 3 A cell was formed by a glass plate having a size of 350 mm × 350 mm and a thickness of 5 mm and a soft vinyl chloride gasket so that the distance between the two glass plates was 2 mm. In this, azobisisobutyronitrile 0.
2g, PS Blac manufactured by Mitsui Toatsu Dye Co., Ltd.
k ME-1 0.020g, PS Red GG
0.010 g, PS Blue RR 0.006 g,
TINUVIN made by Ciba-Geigy Y as an ultraviolet absorber
-900 Methyl methacrylate partial polymer in which 1.0 g was dissolved (viscosity 100 centipoise, polymerization rate 10
%) 200 g, injected at 80 ° C for 1 hour, at 130 ° C for 3 hours
Polymerization was carried out for 0 minutes to obtain a resin plate. The characteristic values of the obtained resin plate are shown in Table 1.

The obtained resin plate was transparent and colored in gray. Further, although the change in the color tone of the transmitted light was not uncomfortable, the glass transition temperature was low at 119 ° C.

[0037]

[Table 1]

[0038]

The optical heat-resistant resin plate obtained by the present invention has heat resistance capable of sufficiently performing a function imparting treatment such as an antireflection treatment, and further, does not change the color tone of transmitted light,
The amount of light can be controlled.

Claims (5)

[Claims] 1. A glass transition temperature of 150 ° C. or higher, C
In the color coordinate system based on IE (International Commission on Illumination), x is
It is in the range of 0.30 or more and 0.32 or less, and y is 0.3.
A heat-resistant resin plate for optics, which is in the range of 1 or more and 0.32 or less and Y is in the range of 30 or more and 60 or less. 2. The heat-resistant resin plate for optics according to claim 1, which contains an ultraviolet absorber. 3. The fluctuation of the light transmittance in the transmission spectrum in the wavelength range of 420 nm to 640 nm is 2
The optical heat resistant resin plate according to claim 1, wherein the heat resistant resin plate is within 0%. 4. The heat-resistant resin plate for optics according to claim 1, wherein the light transmittance in a transmission spectrum at a wavelength of 390 nm is 1 mm or more and 2% or less. 5. The heat resistant resin plate for optics according to claim 1, which is obtained by polymerizing a monomer composition containing an n-alkylmaleimide and a bifunctional monomer.