JP2787072B2 - Ultraviolet laser light detection method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for detecting an ultraviolet laser beam.

[0002]

2. Description of the Related Art With the development of laser technology, laser light has been used in a wide wavelength range. In recent years, the output of laser light has been increased, and not only information transmission, recording and reproduction, but also material processing technology such as microfabrication essential for semiconductor manufacturing technology, myopia treatment, It has also been used in the medical field, such as the treatment of cataracts. The processing technology using ultraviolet light is not only a semiconductor manufacturing process, but also a process using laser such as laser CVD is a low-temperature process, so there is little damage to the product. Therefore, its use is expanding. Since laser light has a high light intensity and seriously damages eyes, it must be used with caution (Yajima et al., New Laser Handbook, Asakura Shoten, 198
9). As a method for detecting ultraviolet or near-ultraviolet laser light, there is known a method of detecting the amount of light using a photoelectric tube or a pn photodiode and detecting a pattern using silver halide photography. With a laser that emits visible light, such as an argon laser, for example, white paper is inserted into the optical path and the laser light is reflected to adjust the optical axis of the optical system, but the ultraviolet laser light cannot be detected by eyes Therefore, it cannot be easily performed. Therefore, a visible light laser was separately provided in the optical system, and it was necessary to use the laser.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method capable of easily detecting an ultraviolet laser beam.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, an ultraviolet laser characterized in that a silicon-containing polymer compound containing a repeating structural unit represented by the following general formula (1) or (2) in a main chain is used as detection means. A method for detecting light is provided. General formula (1):

Embedded image (Wherein R ¹ and R ² may be the same or different and represent hydrogen or a lower aliphatic group, and R ³ and R ⁴ may be the same or different and represent an aromatic group or a lower aliphatic group. Wherein at least one of R ³ and R ⁴ represents an aromatic group.) General formula (2):

Embedded image (Wherein, R ⁵ and R ⁶ may be the same or different and represent an aromatic group or a lower aliphatic group, but at least one of R ⁵ and R ⁶ represents an aromatic group)

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The ultraviolet laser light detecting means used in the present invention comprises a silicon-containing polymer compound containing a repeating structural unit represented by the above general formula (1) or (2) in the main chain. Things. In the general formula (1), R ¹ and R ² may be the same or different and represent hydrogen or a lower aliphatic group. In this case, the lower aliphatic group preferably has 1 to 6 carbon atoms, preferably Is an alkyl group of 1-4, for example, methyl, ethyl, propyl, butyl and the like. Preferred R ¹ and R ² are hydrogen or methyl. In the general formula (1), R ³ and R ⁴ may be the same or different and are an aromatic group or a lower aliphatic group, and at least one of them is an aromatic group. In the general formula (2), R ⁵ and R ⁶ may be the same or different and are an aromatic group or a lower aliphatic group, at least one of which is an aromatic group. As the aromatic group, use of an aryl group such as phenyl, tolyl, and xylyl is preferred. As the lower aliphatic group, an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl, butyl and the like are used.

In order to obtain the silicon-containing polymer compound,
Ring-opening polymerization of a silicon-containing cyclic compound represented by the following general formula (3) or (4). General formula (3):

Embedded image (Wherein, R ^{1 to} R ⁴ have the same meaning as described above, and n is 2 to 4)
Where n is preferably 2 in consideration of reactivity.) General formula (4):

Embedded image (In the above formula, R ⁵ and R ⁶ have the same meaning as described above, and n is 2
-8, preferably 3-4)

The polymerization reaction of the cyclic compound of the general formula (3) can be carried out according to a conventionally known method. In the polymerization reaction in this case, the reaction temperature is 100 to 400.
C., preferably 150 to 300 ° C., and the reaction pressure is 10 ⁻⁴ atm to 50 kg / cm ² G, preferably 10 ^−4.
Atmospheric pressure is a pressure of 10 kg / cm ² G. Further, a catalyst or a solvent can be present in the polymerization reaction system.
As the catalyst, a copper catalyst is used. Examples of such a catalyst include copper copper, metallic copper, copper powder, copper wire, copper filament, and other metallic copper; copper alloys represented by bronze, brass, and white copper; chlorides Monovalent copper compounds such as cuprous, cuprous bromide, cuprous oxide, and trimethylsilylmethyl copper (Me ₃ SiCH ₂ Cu); cupric chloride, cupric bromide, cupric oxide, nitric acid Divalent copper compounds such as copper, copper sulfate, cupric acetate, copper naphthenate, copper (II) oleate, copper (II) acetylacetonate, bisethylenediamine copper (II) chloride, and tetraamine copper (II) sulfate And other various copper compounds. As the solvent, a high boiling point solvent such as diphenyl ether and diphenyl sulfone is used.
The amount used is 100 to 5000 parts by weight, preferably 500 to 10 parts by weight, per 100 parts by weight of the silicon-containing cyclic compound.
The ratio is 00 parts by weight. After the completion of the polymerization reaction, the polymerization product is washed with a chlorinated hydrocarbon such as ethylene chloride or an aromatic hydrocarbon such as toluene to remove unreacted silicon-containing cyclic compounds. The polymerization reaction of the cyclic compound represented by the general formula (3) is described in (NSNametkin,
VMVdovin, V.Zavyalov, Akad.Nauk SSSR., 162,824 (196
5); VAPoletaev, VMVdovin, NSNametkin, Akad, Nau
k SSSR., 208,1112 (1973); Masashi Murakami 2nd Symposium on Polymer Science and Technology for Industrial Science and Technology, Proceedings p-9
9 (1994)).

On the other hand, the polymerization reaction of the cyclic compound of the general formula (4) can also be carried out according to a conventionally known method.
In the polymerization reaction in this case, the reaction temperature is 100 to
The reaction pressure is 300 ° C., preferably 150 to 250 ° C., and the reaction pressure is normal pressure to 50 kg / cm ² G, preferably normal pressure to
The pressure is 10 kg / cm ² G. Further, a catalyst or a solvent can be present in the polymerization reaction system. As the catalyst, a compound containing an alkali metal or an alkaline earth metal is used. Examples of such a catalyst include alkyl lithium, alkoxy lithium, lithium silanolate, lithium hydroxide, and potassium silanolate. As the solvent, a high boiling point solvent such as diphenyl ether and diphenyl sulfone is used. The amount used is 100 to 100 parts by weight of the silicon-containing cyclic compound.
The ratio is 1000 parts by weight, preferably 200 to 500 parts by weight. After the completion of the polymerization reaction, the polymerization product is washed with a chlorinated hydrocarbon such as ethylene chloride or an aromatic hydrocarbon such as toluene to remove unreacted silicon-containing cyclic compounds. The polymerization reaction of the cyclic compound represented by the general formula (4) is described in MKLee, DJ Meier, J. Polymer.
4,4882 (1993).

The addition amount of the catalyst used in the polymerization reaction is one of the factors controlling the molecular weight and molecular weight distribution of the polymer, and is appropriately determined in consideration of these factors.
For example, when obtaining a polymer having a high molecular weight, the addition concentration is lowered, and when obtaining a polymer having a low molecular weight, the addition amount is increased. Generally, the amount of the added catalyst can be used in a molar ratio of 1/100000 to 1/5 in terms of a molar ratio to 1 mol of silicon atoms in the silicon-containing cyclic compound, and 1/10000 to 1 / 50
Is more preferable in consideration of polymerization conditions. Further, in terms of parts by weight, the amount of the added catalyst can be used in an amount of between 1/1000 parts and 20 parts with respect to 100 parts of the silicon-containing cyclic compound, and the polymerization conditions are defined as 1/100 parts to 2 parts. It is more preferable when it is considered.

[0010] By the polymerization reaction, a solid silicon-containing polymer compound is obtained. This polymer contains a repeating structural unit represented by the general formula (1) or (2) in its polymer chain. The molecular weight of the polymer compound is not particularly limited as long as it is a molecular weight that gives a solid polymer compound. The melting point of this polymer is usually 100 ° C. or higher, preferably 200 ° C. or higher. In addition, a silicon-containing polymer compound containing a repeating structural unit represented by the general formula (1) in the main chain thereof was subjected to a dynamic viscoelasticity measurement apparatus (RDS-II, manufactured by Rheometrics Co., Ltd.).
Complex viscosity measured using a parallel plate)
At a frequency of 1 rad / sec and a temperature of 370 ° C., 10
It is 0 to 100,000 poise, and in view of moldability, it is preferable to use a polymer compound having 100 to 20,000 poise. On the other hand, the complex viscosity of the silicon-containing polymer having the repeating structural unit represented by the general formula (2) in the main chain is as follows: frequency 1 rad / sec, temperature 270
At 100C, it is 100 to 100,000 poise. In consideration of moldability, it is preferable to use a polymer compound having 100 to 20,000 poise.

The silicon-containing polymer compound used as the ultraviolet laser beam detecting means in the present invention is excellent in heat resistance, mechanical strength and thermoformability. In the present invention, by irradiating the ultraviolet laser light detecting means comprising the silicon-containing polymer compound with ultraviolet laser light, visible light can be generated and detected.
In this case, the shape of the detecting means may be a solid, and is not particularly limited, and may be any shape such as a powder, a film, a sheet, and a block. Further, the silicon-containing polymer compound can be blended with another polymer and used as a detection means. In such a detection means, the content of the silicon-containing polymer compound is 1% by weight or more, preferably 5% by weight or more.

The ultraviolet laser light that can be detected in the present invention includes, for example, an ultraviolet laser light from KrF (248 nm) or the like. When the ultraviolet laser light is applied to the detecting means according to the present invention, the irradiated portion emits strong blue light. Therefore, an ultraviolet laser beam having a wavelength that cannot be visually recognized can be easily recognized. Furthermore, this light emission is 4-10
Since the observation is performed for about a second, the optical system adjustment including the optical axis adjustment of the laser optical system can be performed while confirming the light emission. Further, in the case of the detecting means of the present invention, since the light emission intensity changes according to the intensity of the irradiation laser light, it also functions as a means for quantitatively measuring the laser light intensity by measuring the light emission intensity. Further, it is well known that the temperature distribution around the ultraviolet laser light, the salinization of the environment such as vibration causes light rays to scatter, fluctuate, refraction, etc., and that the intensity distribution is affected. The means can also be used as a means for obtaining knowledge on these.

The ultraviolet laser light detected by the detecting means of the present invention can be recorded. That is, the light emission intensity of the irradiated portion of the detection means of the present invention changes in accordance with the light intensity previously irradiated. Therefore, in the case of the detecting means of the present invention, information can be recorded by an ultraviolet laser, and the recorded information can be read out as light emission. Here, the reference laser beam for reading is used mainly for reading a record,
It is not always necessary to use the same laser as the laser used for recording. However, if it is difficult to newly provide a laser beam for detection, the output of the laser beam is performed as in normal optical recording and reading. Can be sufficiently reduced.

[0014]

Next, the present invention will be described in more detail by way of examples.

Example 1 1,1,3,3-tetraphenyl-1,3-disilacyclobutane (in the compound of the general formula (3), R ¹ and R ² are represented by the following formulas:
H, R ³ , R ⁴ : phenyl, n: 2) were degassed, sealed in a glass ampoule and heated at 300 ° C. for 16 hours. After cooling, the solid was taken out, pulverized in a mortar, dispersed in toluene, 1,1,3,3-tetraphenyl-1,3-disilacyclobutane was dissolved and removed in toluene, dried, and dried to give white polydiphenylsilyl. Methylene was obtained. This one is 40
Press forming was performed at 0 ° C. under a pressure of 50 kg / cm ² to obtain a film having a thickness of 200 μm. This film was inserted into a holder and set in a laser beam path. An excimer laser of krypton fluoride (wavelength 248 n)
m), a polysilmethylene film was placed at a distance of 1 m from the light source, and a 5 Hz pulse was irradiated at an output of 0.11 W / cm ² for 1 second. Blue light emission was observed during irradiation. When the laser output was set to 0.001 W / cm ² , no visible light emission was observed. The laser output is set to 0.004 W / cm ² , 0.065 W / cm ² , 0.1
The luminescence was recorded in photographs while changing the luminescence intensity to 1 W / cm ² and the luminescence intensity was compared. Based on the emission intensity at 0.004 W / cm ² , the emission intensity at 0.11 W / cm ² is 2-3 times,
It was 1.5-2 times at 0.065 W / cm ² . next,
The time change of the light emission intensity when a pulse of 5 Hz was irradiated at an output of 0.11 W / cm ² was measured. Compared to immediately after the irradiation, it decreased to about 50% after 2 seconds and disappeared after about 10 seconds.

Example 2 A flask equipped with a thermometer, a reflux condenser and a stirrer was charged with hexaphenylcyclotrisiloxane (in the compound of the formula (4), R ⁵ : phenyl, R ⁶ : phenyl, n:
3) Add 25 g and 50 mL of diphenyl ether, and add
Heated to 0 ° C. To this mixture, lithium triphenylsilanoate (0.65 mol) was added, and the mixture was stirred at 170 ° C. for 1 hour. After cooling to room temperature, the organic layer was neutralized with acetic acid, and the precipitated product was collected by filtration, washed with toluene, and dried at 200 ° C. under reduced pressure to obtain 18 g of a white solid polydiphenylsiloxane. This was pressed at 300 ° C. under a pressure of 50 kg / cm ² to obtain a film having a thickness of 200 μm.
The film was sandwiched between holders and set at a distance of 1 m from the light source in the laser beam path. A KrF laser (AQX-150, MPB (Canada)) was used for this.
48 nm wavelength light with an output of 0.11 W / cm ²
When irradiation was performed for 1 second as a pulse having a frequency of Hz, blue light emission was observed during the irradiation. Next, 0.11W /
The time change of the light emission intensity when a pulse of 5 Hz was irradiated with an output of cm ² was measured. Compared to the time immediately after the irradiation, 0.
It decreased to about 50% after 5 seconds and disappeared after about 5 seconds.

[0017]

According to the ultraviolet light detecting method of the present invention, invisible ultraviolet laser light can be visualized and detected as visible light. Further, in the present invention, the detected ultraviolet laser light can be recorded on the detecting means as light intensity or as a pattern. Moreover, the record can be easily read as needed.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideaki Nagai 2-1-1, Tsukikan East, Toyohira-ku, Sapporo-city, Hokkaido In-house Hokkaido Institute of Industrial Technology (72) Inventor Takeshi Okutani Tsukikan, Toyohira-ku, Sapporo, Hokkaido Higashi 2-jo 17-2-1, Hokkaido Institute of Industrial Technology Hokkaido Institute of Technology (72) Inventor Masashi Murakami 603, Yamakita-machi, Ashigagami-gun, Kanagawa Prefecture Dow Corning Asia Co., Ltd. Research and Information Center (72) Inventor Kushibiki Nobuo 603, Kishi, Yamakita-machi, Ashigara-kami-gun, Kanagawa Pref. Dow Corning Asia Co., Ltd. Research and Information Center Examiner Naohide Murata (58) Field surveyed (Int. Cl. ⁶ , DB name) G01J 1/02 G01J 1/58

Claims (1)

(57) [Claims] 1. Detection of ultraviolet laser light, wherein a silicon-containing polymer compound containing a repeating structural unit represented by the following general formula (1) or (2) in its main chain is used as a detection means. Method. General formula (1): (Wherein R ¹ and R ² may be the same or different and represent hydrogen or a lower aliphatic group, and R ³ and R ⁴ may be the same or different and represent an aromatic group or a lower aliphatic group. Wherein at least one of R ³ and R ⁴ represents an aromatic group.) General formula (2): (Wherein, R ⁵ and R ⁶ may be the same or different and represent an aromatic group or a lower aliphatic group, but at least one of R ⁵ and R ⁶ represents an aromatic group)