KR20110068836A - Fluorescent lamp - Google Patents

Abstract

PURPOSE: A fluorescent lamp is provided to reduce damage of a liquid crystal by reducing the ultraviolet ray intensity with a wavelength to less than 310nm. CONSTITUTION: A light projecting part is formed at an upper part of a liquid crystal panel(30) in order to emit an ultraviolet ray. A pair of outer electrodes are arranged on an exterior of an airtight container. A fluorescent material layer in which the fluorescent substance is laminated is formed at an inner wall of the airtight container with a light transmissivity. The fluorescent material layer uses the cerium activation magnesium barium aluminate based fluorescent substance. The sealant(32) is covered between two sheets of substrate(31) in a frame shape.

Description

Fluorescent Lamps {FLUORESCENT LAMP}

This invention relates to the lamp for light sources used for manufacture of a liquid crystal panel, and especially the fluorescent lamp used in the liquid crystal panel manufacturing process which enclosed the liquid crystal containing a photoreactive substance inside.

The liquid crystal panel is a structure in which a liquid crystal is enclosed between two light transmitting substrates (glass substrates), and a plurality of active elements (TFTs) and liquid crystal driving electrodes are formed on one glass plate, and an alignment film is formed thereon. Forming. On the other glass substrate, a color filter, an alignment film, and a transparent electrode (ITO) are formed. And liquid crystal is enclosed between the alignment films of both glass substrates, and the circumference is sealed with the sealing compound.

In the liquid crystal panel of such a structure, an alignment film is for controlling the liquid crystal alignment which orientates a liquid crystal by applying a voltage between electrodes.

Conventionally, the control of the alignment film has been performed by rubbing, but recently, a new orientation control technique has been attempted (see Patent Document 1).

It mixes the liquid crystal which has the orientation which orientates by voltage application between the 1st glass substrate in which a TFT element was installed, and the 2nd glass substrate which opposes the said 1st glass substrate, and the monomer which produces superposition | polymerization in response to light. The material is encapsulated, the light is applied while applying voltage to the liquid crystal panel to polymerize the monomer, and the pretilt angle is imparted to the liquid crystal molecules by fixing the direction of the liquid crystal (ie, approximately 1 molecular layer of the surface layer) in contact with the glass substrate. It is.

According to this method, since the projection having the slope required for giving the pretilt angle is conventionally unnecessary, the manufacturing process of the liquid crystal panel can be simplified, and in the final product, the shadow caused by the projection disappears, so that the aperture ratio As a result, the manufacturing cost and manufacturing time of the liquid crystal panel can be reduced as a result, and the backlight can be saved in power.

With reference to FIG. 11, the liquid crystal orientation control technique by this polymer is demonstrated.

In the panel 90, electrodes 92 made of ITO or the like are formed on each surface of the light-transmissive substrate 91 made of glass, and a sealing agent (not shown) is applied and formed on the periphery thereof. Liquid crystals are injected between the substrates 91. In this liquid crystal, an ultraviolet curable monomer 93 is added to a negative liquid crystal having negative dielectric anisotropy at an appropriate ratio.

By applying a voltage and irradiating ultraviolet rays to this panel 90, the orientation regulation of a liquid crystal is performed.

As shown in Fig. 11A, when no voltage is initially applied, the liquid crystal molecules 94 are oriented vertically, and the monomer 93 is also present along the liquid crystal molecules in a monomer state. Here, when a voltage is applied as shown in (b), the liquid crystal molecules 94 are inclined in the direction of the fine pattern of the pixel electrode, and the monomers 93 are tilted as described above. When ultraviolet irradiation is carried out as shown in (c) in this state, the monomer 93 is polymerized with an inclination. In this way, when the monomer 93 polymerizes with the inclination, the orientation of the liquid crystal molecules 94 is regulated.

In the manufacturing technology of the liquid crystal panel which performs this new orientation control, both parts of the panel in a final product are largely concerned about whether superposition | polymerization of a monomer is completed, and, if an uncured monomer remains, Burning of the liquid crystal panel occurs, which causes a defect.

For this reason, as known from patent document 1 etc., the two-step ultraviolet irradiation process which divided | segmented the irradiation of ultraviolet-ray into plural steps is used. Specifically, as shown in FIG. 12, in the (A) primary irradiation step, ultraviolet rays are irradiated onto the liquid crystal layer in a state where a voltage is applied to the liquid crystal layer containing the liquid crystal material and the photopolymerizable monomer. (B) In a secondary irradiation process, an ultraviolet-ray is irradiated in a voltage free state. As a result, in the state where the molecular orientation of the liquid crystal material is inclined in the primary irradiation step, the monomer in the vicinity of the alignment film is polymerized to form a polymer layer, and the inclination direction of the liquid crystal molecules in the secondary irradiation step is stored in the polymer. By passing through such a process, the monomer which remain | survives in a liquid crystal material superpose | polymerizes completely and a monomer disappears.

Conventionally, in the ultraviolet irradiation step, a fluorescent lamp that emits light in the ultraviolet region near the wavelength of about 300 to 40 Onm region called black light is used.

Patent Document 1: Japanese Unexamined Patent Publication No. 2008-134668

Radiated light from black light contains a relatively large amount of ultraviolet light having a short wavelength (for example, a wavelength of less than 310 nm). However, when ultraviolet rays having a wavelength of 310 nm or less are irradiated to the liquid crystal display panel, the liquid crystal is damaged, which causes a new problem that the reliability of the liquid crystal display panel is lowered. In order to cut the light of an unnecessary wavelength range, a filter is simply provided, but since a fluorescent lamp is a diffused light source, it is usually necessary to use the filter of absorption characteristic. However, in order to reliably shield light with a wavelength of 310 nm or less, part of the spectral light near 310 nm, for example, around 310 to 340 nm is also absorbed. That is, light in the wavelength range contributing to the polymerization of the monomer is inevitably absorbed. As a result, the light of the wavelength range required for superposition | polymerization cannot be irradiated efficiently, a polymerization rate falls, the ultraviolet irradiation time becomes long, and the problem that a mass productivity worsens arises.

The problem to be solved by the present invention is to form a liquid crystal layer by filling a liquid crystal composition containing a polymerizable monomer between two substrates provided with an electrode, and to polymerize the monomer while applying a voltage to the substrate, thereby providing liquid crystal molecules. In the manufacturing process of the liquid crystal display device which prescribes the inclination direction of this invention, it is providing the light source lamp which radiates the ultraviolet-ray which can be used suitably in the polymerization process of the said monomer, Specifically, the ultraviolet intensity | strength of wavelength shorter than 310 nm in the spectrum is provided. It is an object of the present invention to provide a fluorescent lamp having the maximum energy peak at 310 to 380 nm as small as possible.

In order to solve the said subject, the fluorescent lamp which concerns on this invention is equipped with the following characteristics.

(One)

In the fluorescent lamp used in the manufacturing process of the liquid crystal panel containing a photoreactive substance, in the fluorescent substance layer formed in the inside of a light emitting tube, any one of magnesium barium aluminate, gadolinium yttrium, and magnesium lanthanum aluminate is mother crystal | crystallization. as it will be characterized in that it comprises a phosphor activated by Ce ^{3 +.}

(2)

Moreover, the said phosphor is characterized by including cerium activated magnesium barium aluminate whose general formula is represented by following Formula.

Ce _x (Mg _{1 -y-z} , Ba _{y -z} ) Al ₁₁ 0 _{19- (3 (1-x) + 2z) / 2}

(Where 0.6≤x≤0.8)

(3)

The phosphor further includes cerium-activated gadolinium phosphate in which the general formula is represented by the following formula.

(Y _{1- x} , Gd _x ) PO ₄ : Ce

(Where 0.1≤x≤0.5)

(4)

The said phosphor further contains the cerium activated magnesium aluminate lanthanum whose general formula is represented by following Formula.

(La _{1- x} , Ce _x ) MgAl ₁₁ 0 ₁₉

(Where 0.07≤x≤0.12)

(5)

The phosphor further comprises cerium and lanthanum activated magnesium barium aluminate in which the general formula is represented by the following formula.

_{(Ce 0 .8, La x)} (Mg 0 .8, Ba 0 .1) Al 11 O 18 .6 + 3x

According to the present invention, since the ultraviolet light intensity of the wavelength of 310 nm or less can be reduced in the wavelength of the light emitted from the fluorescent lamp without damaging the light intensity between 321 and 350 nm, the short wavelength ultraviolet light in the vicinity of 300 nm which damages the liquid crystal. The fluorescent lamp which can make intensity | strength small, can carry out polymerization of a monomer reliably, reducing the damage to a liquid crystal, and can be used suitably for the manufacturing process of the liquid crystal panel which enclosed the liquid crystal containing a photoreactive substance inside. Can provide.

1 is an explanatory diagram showing an ultraviolet irradiation device equipped with a fluorescent lamp according to the present invention.
2 is an explanatory diagram of a fluorescent lamp according to the first embodiment of the present invention.
3 is a diagram showing a spectrum having a wavelength of 250 to 450 nm of each fluorescent lamp of the first embodiment, the conventional example, and the comparative example.
4 is a diagram showing a relationship between the relative value of the accumulated intensity of light and the cerium concentration in the damage wavelength region and the effective wavelength region of the fluorescent lamp according to the first embodiment.
5 is a diagram showing a spectrum having a wavelength of 250 to 450 nm of each fluorescent lamp of the second embodiment, the conventional example, and the comparative example.
It is a figure which shows the relationship between the relative value of the accumulated intensity of light, and gadolinium concentration of the damage wavelength range and effective wavelength range of the fluorescent lamp which concerns on 2nd Embodiment.
FIG. 7: is a figure which shows the spectrum of wavelength 250-450 nm of each fluorescent lamp of 3rd Embodiment, a prior art example, and a comparative example.
It is a figure which shows the relationship between the relative value of the accumulated intensity of light, and the cerium concentration in the damage wavelength region and the effective wavelength region of the fluorescent lamp according to the third embodiment.
9 is a diagram showing a spectrum having a wavelength of 250 to 450 nm of each fluorescent lamp of the fourth embodiment, the conventional example, and the comparative example.
It is a figure which shows the relationship between the relative value of the accumulated intensity of light, and a lanthanum density | concentration of the damage wavelength range and effective wavelength range of the fluorescent lamp which concerns on 4th Embodiment.
FIG. 11 is a view explaining a manufacturing process of a liquid crystal panel in which a liquid crystal containing a photoreactive substance is enclosed.
It is a figure explaining the manufacturing process of the liquid crystal panel which enclosed the liquid crystal containing a photoreactive substance inside.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, embodiment shown below illustrates the ultraviolet irradiation device and fluorescent lamp for liquid crystal manufacture for realizing the technical idea of this invention, and this invention does not identify a fluorescent lamp to the following.

1 is a schematic explanatory diagram of an ultraviolet irradiation device 100 for polymerizing a monomer as a photoreactive substance in a process for producing a liquid crystal panel in which a liquid crystal containing a photoreactive substance is enclosed therein. In the work stage S, the liquid crystal panel 30 carried by an appropriate conveying apparatus, such as a roller, is mounted directly under the light irradiation part. The liquid crystal panel 30 is coated with, for example, a sealing agent 32 in a frame shape between two substrates 31 having light transmittance made of glass, and in an unreacted state therein. The liquid crystal 33 including the photoreactive substance (monomer) is injected and configured.

Each of the board | substrates 31 is provided with the electrode which is not shown in this figure, and each electrode is connected to the mechanism which applies a voltage. Moreover, although not shown here, the ultraviolet irradiation device 34 provided with the mechanism which applies such a voltage is provided.

The light irradiation part 20 for irradiating an ultraviolet-ray is formed in the upper part of the liquid crystal panel 30. The light source is a fluorescent lamp 10, in which a plurality of lamps (five in this drawing) are arranged side by side. In addition, behind the fluorescent lamp, a mirror 21 for reflecting light from the lamp toward the stage is provided.

2 is an explanatory diagram of a fluorescent lamp. (A) is a perspective view, (b) is sectional drawing perpendicular | vertical to the tube axis of a lamp, (c) is axial sectional drawing cut | disconnected by line segment A-A in (b).

The fluorescent lamp 10 which concerns on one Embodiment of this invention is demonstrated in detail. On the inner wall of the transmissive hermetic container 11 made of a dielectric such as glass, a phosphor layer 12 formed by laminating phosphors is formed. A discharge medium made of a rare gas such as xenon is enclosed in the airtight container 11, and a pair of external electrodes 13 and 14 are disposed on the outer surface of the airtight container 11. When a high frequency high voltage is applied between the pair of external electrodes 13 and 14 through the lead wires 15 and 16, a discharge is formed between the walls of the dielectric constituted by the hermetic container 11 to form xenon. The ultraviolet light of 172 nm which is a spectrum is emitted.

The phosphor layer 12 used in the present invention includes a phosphor that emits a long wavelength ultraviolet ray having an emission peak wavelength in a region having a wavelength of 310 to 380 nm when irradiated with such a short wavelength ultraviolet ray, for example, a wavelength of 172 nm ultraviolet light generated from xenon. Doing.

Specific examples of the phosphor include a phosphor in which any one of magnesium barium aluminate, gadolinium yttrium, and magnesium lanthanum is used as the mother crystal, and each mother crystal is revived by cerium (Ce). . In particular, Ce can take trivalent and tetravalent valences, but exists in the present invention as a trivalent cation. Although such fluorescent substance may be mixed and used in an appropriate ratio, since the number of work processes increases, it is preferable to use it independently. Hereinafter, each fluorescent substance is demonstrated in detail based on an Example.

In addition, in the following description, in the manufacturing process of the liquid crystal panel which enclosed the liquid crystal containing a photoreactive substance inside, it demonstrates compared with what is called black light conventionally used for reaction of a photoreactive substance. In addition, there are various kinds of phosphors used as black light. Here, the cerium-activated lanthanum phosphate, which is a general phosphor, will be described as a comparative example. Is called "conventional example 1."

In addition, the general formula of the cerium activated lanthanum phosphate phosphor is as follows.

General formula of cerium-activated lanthanum phosphate phosphor: (La, Ce) PO ₄

[Embodiment 1]

In the fluorescent lamp according to the first embodiment, the phosphor layer 12 mainly uses cerium-activated magnesium barium aluminate (Ce-Mg-Ba-Al-O) -based phosphors. The phosphor layer 12 is a phosphor in which the general formula is represented by the following formula (1), and the molar ratio x of cerium (Ce) is in the range of 0.6 to 0.8.

Formula (1): Ce _x (Mg _{1 -y-z} , Ba _{y -z} ) Al ₁₁ 0 _{19- (3 (1-x) + 2z) / 2}

In Formula (1), Ce which is an activating metal element ideally exists as a trivalent cation. By setting the molar ratio of cerium in the range of x = 0.6 to 0.8, ultraviolet light in an area effective for the production process of a liquid crystal panel in which a liquid crystal containing a photoreactive substance is enclosed therein can be increased.

Hereinafter, this embodiment is demonstrated in detail with reference to an Example.

(Comparative Example 1)

As a phosphor with little ultraviolet radiation having a wavelength of 310 nm or less, particularly a wavelength of 300 nm or less, a cerium-activated barium aluminate-magnesium phosphor (abbreviated CAM phosphor) shown in the following formula (2) is generally known.

Formula (2): CeMgAl ₁₁ 0 ₁₉

In addition, in Formula (2), the number-of-moles of cerium (Ce) is 1.

The emission spectrum waveform of the wavelength 250-450mn range of the fluorescent lamp using this CAM fluorescent substance of Formula (2) is shown by the curve of the comparative example 1 in FIG. In addition, the prior art example 1 in this figure is a cerium activated lanthanum phosphate phosphor light emission spectral waveform. Thus, the peak value of the emission spectrum in the curve of the comparative example 1 is in the vicinity of wavelength 360-370 nm, and it responds to reaction of a photoreactive substance in the manufacturing process of the liquid crystal panel which enclosed the liquid crystal containing a photoreactive substance inside. It was confirmed that the intensity of the spectral region used (wavelengths 321 to 350 nm; referred to as "effective wavelength band") was large.

However, the strength of the effective wavelength band is considered to be room for improvement, and the present inventors have a wavelength of 310 to 380 nm based on the phosphor of cerium-activated magnesium barium aluminate (Ce-Mg-Ba-A1-0). Tried to increase the ultraviolet light of the station.

In addition, in this verification, in the manufacturing process of the liquid crystal panel which enclosed the liquid crystal containing a photoreactive substance inside, the spectral region used for reaction of a photoreactive substance, ie, an effective wavelength band (wavelength 321-350 nm), and a liquid crystal Is divided into a spectral range (wavelength 300 to 310 nm; hereinafter referred to as a "damage wavelength band") and a spectral range (wavelengths 311 to 320 nm) between them, and the amount of accumulated light in each region is determined according to the prior art. It was done in comparison with that of black light.

(Comparative Examples 2 and 3)

First, a part of magnesium which is a divalent metal ion in the general formula (formula (1)) of a CAM fluorescent substance is replaced with barium which is a divalent metal ion similarly, without changing the compounding ratio of cerium, and Comparative Example 2 and Comparative Example The fluorescent substance according to 3 was produced. Hereinafter, the general formula of each phosphor is shown.

(Comparative Example _{2) Ce (Mg 0 .95,} Ba 0 .05) Al 11 0 19

(Comparative Example _{3) Ce (Mg 0 .9,} Ba 0 .1) Al 11 0 19

The phosphor according to the fluorescent lamp of Comparative Example 2 is a phosphor produced by substituting magnesium with 0.05 mol of barium and a phosphor of a fluorescent lamp of Comparative Example 3 with 1 mol of barium. In the production of such phosphors, Ce, Mg, Ba, and A1 were mixed in a molar ratio represented by the general formula, and then produced through firing.

Using these phosphors, lamps according to Comparative Example 2 and Comparative Example 3 were produced in accordance with the configuration shown in FIG. 2.

The predetermined voltage was put into the fluorescent lamp produced in this way, it lighted, and the light emission intensity of the lamp was measured. As a result, the addition of barium showed no significant improvement, but it was confirmed that in the fluorescent lamp according to Comparative Example 2, the peak value of the wavelength shifted to the shorter wavelength side than the fluorescent lamp according to Comparative Example 3, and the emission intensity was slightly increased.

(Comparative Example 4)

Subsequently, 0.1 mol of the number-of-moles of barium was employ | adopted in the fluorescent substance substituted by barium, and it tried to change the addition amount of cerium. Here, the molar ratio of cerium was 0.5. In addition, the phosphor was prepared by mixing Ce, Mg, Ba, and A1 in a molar ratio represented by the general formula, and then calcining to produce a fluorescent lamp having the configuration shown in FIG. This fluorescent lamp was turned on and the emission spectrum was verified.

As a result, it was found that the peak of the fluorescence shifted to the shorter wavelength side, and the luminescence intensity increased, greatly improving.

Thus, phosphors with varying cerium (Ce) concentrations were also produced.

(Examples 1-3)

As Examples 1-3, the fluorescent substance was manufactured by preparing the value of x in said Formula (2) so that it may become 0.6, 0.7, and 0.8 in order. In addition, cerium concentration of each Example is 0.6 mol, 0.7 mol, 0.8 mol.

Using the obtained fluorescent substance, the lamp of FIG. 2 was comprised, the predetermined voltage was applied, it turned on, and the emission spectrum was verified. As a result, the absolute value of peak intensity increased, and the favorable emission spectrum was obtained. In these Examples 1-3, the liquid crystal containing a photoreactive substance, reducing the integrated intensity | strength until it becomes 1/10 or less compared with the structure of the black light used as the conventional example 1 until the wavelength is 300-310 nm. In the manufacturing process of the liquid crystal panel which enclosed in the inside, it is possible to emit more wavelength of the ultraviolet-ray to wavelength 320-350 nm which is considered especially effective.

3, the emission spectrum waveforms of Conventional Example 1, Comparative Examples 1 to 4, and Examples 1 to 3 are collectively shown. In Table 1 below, the fluorescent substance compositions according to the prior art, the comparative example and the examples, and the integral values of the spectral intensities of the respective lamps having wavelengths of 300 to 310 nm, wavelengths of 311 to 320 nm, and wavelengths of 321 to 350 nm are shown.

In Table 1, the "measured value" column on the left side is an actual measured value of this integrated intensity of the spectrum measured by the spectroscope at a position of 25 mm from the light emitting tube. The right side shows the integrated intensity by the relative value which made the integrated value 100 of each wavelength range in the lamp of the prior art example 1. As shown in FIG.

4, the relative value of the integrated intensity | strength of the comparative example and Example of Table 1 shown above was shown by the coordinate with the relative value as the vertical axis | shaft, and the horizontal axis | shaft as the density | concentration of cerium. The curve (A) shows the effective wavelength band, and the curve (B) shows the damage wavelength band. As can be seen from this figure, the damage wavelength band changes in the vicinity of 10 in the relative value, but the light output in the effective wavelength band is large in the range where the concentration of cerium is 0.6 to 0.8 mol. However, it can be seen that the efficiency decreases when the number of moles of cerium increases to 1 mole.

As can be seen from the above results, all of Examples 1 to 3 can reduce the intensity of the damage wavelength band to the conventional example 1 to 10 or less, and the intensity of the effective wavelength band can be made 80 or more. Therefore, in the above formula, when the value of x is in the range of 0.6 to 0.8, it can be seen that the light emission in the damage wavelength band is small and the light emission in the effective wavelength band is large.

[Embodiment 2]

Then, Embodiment 2 of this invention is described.

The fluorescent lamp according to the present embodiment uses a cerium-activated gadolinium yttrium (Gd-Y-P-0: Ce) -based phosphor as the phosphor layer 12 of the fluorescent lamp shown in FIG. 2. The phosphor layer 12 is a phosphor in which the general formula is represented by the following formula and formula (3), in particular, the molar ratio x of gadolinium (Gd) is in the range of 0.1 to 0.5.

Formula (3) = (Y _{1- x} , Gd _x ) PO ₄ : Ce

(Where 0.1≤x≤0.5)

In the above formula (3), Ce, which is an activated metal element, is ideally present as all trivalent cations. By setting the molar ratio of gadolinium in the range of x = 0.1 to 0.5, a liquid crystal containing a liquid crystal containing a photoreactive substance in a cerium-activated gadolinium yttrium (Gd-Y-P-0: Ce) -based fluorescent substance therein In the manufacturing process of a panel, the ultraviolet light of an effective area | region can be increased.

Hereinafter, this embodiment is demonstrated in detail with an Example.

In addition, also in the following description, the black light which used the cerium activated lanthanum phosphate phosphor as a lamp which concerns on a conventional example is called conventional example 1. As shown in FIG.

(Comparative Example 5)

As a phosphor with little ultraviolet irradiation of wavelength 310 nm or less, especially the wavelength of 300 nm or less, the cerium activating yttrium phosphate (Y-P-0: Ce) fluorescent substance (abbreviated YPC fluorescent substance) shown by following formula (4) is generally known.

Formula (4) = YPO ₄ : Ce

In the cerium-activated yttrium phosphate (Y-P-0: Ce) phosphor of the formula (4), the light intensity in the effective wavelength region is, in particular, less than half the efficiency of the conventional example 1. This inventor tried to amplify the ultraviolet light of the wavelength range of wavelength 310-380 nm that the efficiency improves based on this fluorescent substance.

(Comparative Example 6)

First, a part of yttrium (Y) of the phosphor of formula (4) was replaced with gadolinium (Gd) to produce a phosphor, and a fluorescent lamp according to Comparative Example 6 was produced.

(Comparative Example _{6) (Y 0 .95, Gd} 0 .05) PO 4: Ce,

In the phosphor according to the fluorescent lamp of Comparative Example 6, the molar ratio of gadolinium is 0.05 mol and the molar ratio of yttrium is 0.95 mol. In the production of the phosphor, Gd, Y, P, and Ce were mixed at a molar ratio represented by the general formula, and produced through firing. Using this phosphor, a fluorescent lamp according to Comparative Example 6 was produced. A predetermined voltage was applied to the fluorescent lamp thus produced, and the lamp was turned on to obtain an emission spectrum waveform and intensity in the wavelength range of 250 to 450 nm of the emitted light from the fluorescent lamp. This result was shown by the curve of the comparative example 6 in FIG.

(Examples 4-7)

As Examples 4-7, the value of x in said Formula (3) was prepared so that it might become 0.1, 0.2, 0.3, and 0.5, and the fluorescent substance was manufactured. In addition, the cerium concentration is 0.05 mol in all with respect to 0.95 mol of the sum total of yttrium (Y) and gadolinium (Gd).

Using the obtained phosphor, the lamp of FIG. 2 was constructed, and the light emission spectrum was verified by applying a predetermined voltage. As a result, the absolute value of peak intensity increased, and the favorable emission spectrum was obtained. In these Examples 4-7, compared with the structure of the black light used as the conventional example 1, the liquid crystal containing a photoreactive substance, reducing the integration intensity | strength until it becomes 1/10 or less to the wavelength band 300-310 nm. In the manufacturing process of the liquid crystal panel enclosed in the inside, it becomes possible to emit more wavelengths of the ultraviolet-ray to wavelength 320-350 nm which are considered especially effective.

5, the emission spectrum waveforms of Conventional Example 1, Comparative Example 6, and Examples 4 to 7 are collectively shown. In addition, in Table 2 below, the fluorescent substance composition according to the conventional example, the comparative example, and the example, and the integral value of the spectral intensity of each lamp of wavelength 300-310 nm band, wavelength 311-320 nm, and wavelength 321-350 nm which were separate were shown.

The left column of Table 2 is the measured value of this integrated intensity. The right side shows this integrated intensity as a relative value when the integrated value of each wavelength range in the lamp of the prior art example is 100.

6, the relative value of the vertical axis | shaft and the horizontal axis | shaft were represented by the density | concentration of cerium, and the relative value of the integrated intensity of each of the comparative example and the Example of Table 1 shown above was shown by the coordinate. The curve (A) shows the effective wavelength band, and the curve (B) shows the damage wavelength band. As can be seen from this figure, as the number of moles of gadolinium increases, the light output in the effective wavelength band increases. However, at the same time, the relative value of the damage wavelength band also increases with the increase of the light output in the effective wavelength band. Therefore, as addition amount of gadolinium, the range of 0.1 mol-0.5 mol is a practical range. Especially preferred is a case where gadolinium is 0.3 mol.

From the above result, it was confirmed that all of Examples 4-7 can reduce the intensity of the damage wavelength band about the conventional example 1 to 10 or less, and can make intensity of an effective wavelength band larger. Therefore, in the formula (3), when the value of x is in the range of 0.1 to 0.5, it is found that the light emission in the damage wavelength band is small and the light emission in the effective wavelength band is large.

[Embodiment 3]

Then, Embodiment 3 of this invention is described.

The fluorescent lamp according to the present embodiment uses a cerium-activated magnesium-lanthanum (La-Mg-A1: Ce) -based phosphor as the phosphor layer 12 of the fluorescent lamp shown in FIG. 2. The phosphor layer 12 is a phosphor in which the general formula is represented by the following formula and formula (5), and the molar ratio x of cerium (Ce) is in the range of 0.07 to 0.12.

Formula (5): (La _{1- x} , Ce _x ) MgAl ₁₁ 0 ₁₉ (where 0.07≤x≤0.12)

In Formula (5), Ce which is an activating metal element exists ideally as all trivalent cations. By setting the molar ratio of cerium in the range of x = 0.07 to 0.12, the liquid crystal containing the photoreactive substance is enclosed in the cerium-activated magnesium-lanthanum (La-Mg-Al-0: Ce) -based phosphor. When performing the manufacturing process of one liquid crystal panel, the ultraviolet light of an effective area | region can be increased.

Hereinafter, this embodiment is demonstrated in detail with an Example.

In addition, in the following description, the black light lamp which used the cerium activating lanthanum phosphate phosphor as a lamp which concerns on a conventional example is called conventional example 1. As shown in FIG. The number of moles of cerium (Ce) in the cerium-activated lanthanum phosphate phosphor (General Formula: LaPO ₄ : Ce) is 0.05 mol.

(Examples 8-11)

As Examples 8-11, the value of x in said Formula (5) was prepared so that it might become 0.07, 0.09, 0.1, 0.12, and the fluorescent substance was manufactured. Moreover, the number-of-moles of cerium in each Example are 0.07 mol, 0.09 mol, 0.1 mol, 0.12 mol.

Using the obtained phosphor, the lamp of FIG. 2 was constructed, and the light emission spectrum was verified by applying a predetermined voltage. As a result, the absolute value of peak intensity increased, and the favorable emission spectrum was obtained. In these Examples 8-11, compared with the structure of the black light used as the prior art example 1, the liquid crystal containing a photoreactive substance, reducing the integrated intensity | strength until the wavelength becomes 300 or 310 nm until it becomes 2/5 or less. In the manufacturing process of the liquid crystal panel enclosed in the inside, it is possible to emit the wavelength of the ultraviolet-ray up to wavelength 320-350 nm which is considered especially effective more.

In Fig. 7, the emission spectrum waveforms of Conventional Example 1 and Examples 8 to 11 are collectively shown. Table 3 below shows the integrated values of the fluorescence composition according to the prior art and the examples, and the spectral intensities of the respective lamps having wavelengths of 300 to 310 nm, wavelengths of 311 to 320 nm, and wavelengths of 321 to 350 nm.

The left column of Table 3 is the measured value of this integrated intensity. The right side shows this integrated intensity as a relative value when the integrated value of each wavelength range in the lamp of the prior art example is 100.

8, the relative value of the vertical axis | shaft and the horizontal axis | shaft are the density | concentrations of cerium, and the relative value of the integral intensity of each of the comparative example and Example of Table 3 shown above is shown by coordinate. The curve (A) shows the effective wavelength band, and the curve (B) shows the damage wavelength band. As can be seen from this figure, the relative value of the effective wavelength region peaks in the vicinity of the number-of-moles of cerium of 0.1, showing good efficiency of 80 or more even in the relative value. As the intensity of the damage wavelength band, the relative value is changed between 20 and 40. However, by setting the cerium concentration slightly higher at 0.1 to 0.12, it can be suppressed as low as 20 degrees.

From the above result, it was confirmed that all of Examples 8-11 can reduce the intensity of the damage wavelength band about the conventional example 1 to 40 or less, and can make intensity of an effective wavelength band larger. Therefore, in the formula (3), when the value of x is in the range of 0.1 to 0.12, it can be seen that the light emission in the damage wavelength band is small and the light emission in the effective wavelength band is large.

[Embodiment 4]

In the fluorescent lamp according to the fourth embodiment, the phosphor layer 12 mainly uses cerium and lanthanum-activated magnesium barium aluminate (Ce-La-Mg-Ba-A1-0) -based phosphors. The phosphor layer 12 is a phosphor in which the general formula is represented by the following formula (6), in particular, the molar ratio (x) of cerium (Ce) is 0.8, and the molar ratio of lanthanum (La) is 0.06 or less. It does not include).

Equation _{(6): (Ce 0 .8} , La x) (Mg 0 .8, Ba 0 .1) Al 11 O 18 .6 + 3x

In the formula (6), Ce and La which are the activating metal elements are ideally present as trivalent anions. By setting the molar ratio of this cerium to 0.8 and the molar ratio of lanthanum (La) in the range of 0 to 0.06, ultraviolet light in an area effective for the manufacturing process of a liquid crystal panel in which a liquid crystal containing a photoreactive substance is enclosed therein is obtained. You can increase it.

Hereinafter, this embodiment is demonstrated in detail with reference to an Example.

In addition, in description of this embodiment, since the mother crystal of fluorescent substance is the same as the fluorescent substance which concerns on Embodiment 1, about the comparative example, while referring to the content of the said Comparative Example 1-Comparative Example 4, The case where the concentration is 0 is the same as that of the phosphor of Example 3 described above in Embodiment 1, and therefore, the content of Example 3 will be cited and described.

(Examples 12-16)

As Examples 12-16, the fluorescent substance was manufactured by preparing the value of La concentration x in said Formula (6) so that it may become 0.01, 0.02, 0.04, 0.06, 0.10. In addition, the cerium concentration of each Example is 0.8 mol.

Using the obtained phosphor, the lamp of FIG. 2 was constructed, and the light emission spectrum was verified by applying a predetermined voltage. As a result, the absolute value of peak intensity increased, and the favorable emission spectrum was obtained. In these Examples 12-16, compared with the structure of the black light used as the prior art example 1, the liquid crystal containing a photoreactive substance, reducing the integrated intensity | strength until it becomes 1/10 or less in wavelength ranges from 300-310 nm. In the manufacturing process of the liquid crystal panel enclosed in the inside, it is possible to emit more wavelengths of the ultraviolet-ray to wavelength 320-350 nm which are considered especially effective.

9, the emission spectrum waveforms of Conventional Example 1, Comparative Examples 1 to 4, and Examples 3 and 12 to 16 are collectively shown. Table 4 below shows the integrated values of the fluorescence intensities of the conventional examples, the comparative examples, and the examples, and the spectral intensities of the respective lamps having wavelengths of 300 to 310 nm, wavelengths of 311 to 320 nm, and wavelengths of 321 to 350 nm.

In Table 4, the "measured value" column on the left side is an actual measured value of this integrated intensity of the spectrum measured by the spectroscope at a position of 25 mm from the light emitting tube. The right side shows this integrated intensity by the relative value which made the integral value of each wavelength range in the lamp of the prior art example 100.

In addition, in FIG. 10, the relative value of the integral intensity of Example 3 of Table 4 and Examples 12-16 shown previously was shown by the coordinate with the relative value as the vertical axis | shaft, and the horizontal axis | shaft as the density | concentration of lanthanum (La). The curve (A) shows the effective wavelength band, and the curve (B) shows the damage wavelength band. As can be seen from this figure, the damage wavelength band is shifted in the vicinity of 10 in the relative value, but the integral value of 320 to 350 nm with respect to the integral value of 300 to 310 nm is obtained in the range of lanthanum concentration of 0 to 0.06 mol. It is understood that the integration intensity of 321 to 350 nm is equivalent to or smaller than that of 3, and the integration intensity of 321 to 350 nm of the conventional example is approximately 50% or more.

As can be seen from the above results, all of Examples 12 to 15 can reduce the intensity of the damage wavelength band to the conventional example 1 to 10 or less, and the intensity of the effective wavelength band can be made 50 or more. Therefore, in the formula (6), when the value of x is in the range of 0 < x? 0.06, light emission in the damage wavelength band is small, and light emission in the effective wavelength band can be increased.

As described above, in the process for producing a liquid crystal panel in which a liquid crystal containing a photoreactive substance is enclosed therein, any one of magnesium barium aluminate, gadolinium yttrium, and magnesium lanthanum alumina is used as the mother crystal, and Ce ³ By constituting a fluorescent lamp using a phosphor containing a phosphor revived by ⁺ , it is possible to increase the light of the wavelength band effective for the reaction of the photoreactive substance, and the fluorescence having a small emission of light in the wavelength range that damages the liquid crystal It can provide a lamp.

100: ultraviolet irradiation device
10: fluorescent lamp
11: airtight container
12: phosphor layer
13, 14: electrode
15, 16: lead wire
20: light irradiation unit
21 mirror
30 liquid crystal panel
31: light transmissive substrate
32: sealing system
33: liquid containing a photoreactive substance
34: mechanism for applying voltage

Claims (5)

In the fluorescent lamp used in the manufacturing process of the liquid crystal panel containing a photoreactive substance,
Characterized in that it comprises a has a phosphor layer formed within the light emitting tube, a magnesium barium aluminate, phosphate, gadolinium, yttrium and aluminate magnesium revived by any one of a lanthanum to Ce ^{3 +} to the parent crystal (付活) fluorescent Fluorescent lamp made with. The method according to claim 1,
The phosphor is a fluorescent lamp comprising a cerium-activated magnesium barium aluminate represented by the general formula:
Ce _x (Mg _{1 -y-z} , Ba _{y -z} ) Al ₁₁ 0 _{19- (3 (1-x) + 2z) / 2}
(Where 0.6≤x≤0.8) The method according to claim 1,
The phosphor includes a cerium-activated gadolinium phosphate in which a general formula is represented by the following formula.
(Y _{1- x} , Gd _x ) PO ₄ : Ce
(Where 0.1≤x≤0.5) The method according to claim 1,
The said fluorescent substance contains the cerium activated magnesium aluminate lanthanum whose general formula is represented by following Formula.
(La _{1- x} , Ce _x ) MgAl ₁₁ 0 ₁₉
(Where 0.07≤x≤0.12) The method according to claim 1,
The phosphor further includes a cerium and a lanthanum activated magnesium barium aluminate in which the general formula is represented by the following formula.
_{(Ce 0 .8, La x)} (Mg 0 .8, Ba 0 .1) Al 11 0 18. _{6 + 3x}
(Where 0 <x≤0.06)

Images