JPS63116131A - Light source using laser - Google Patents

Abstract

PURPOSE:To convert semiconductor laser light of a wavelength in an IR region to a wavelength in a visible region by combining a semiconductor laser and a specific wavelength conversion element. CONSTITUTION:This light source consists of a semiconductor laser source and a nonlinear optical element which converts the laser beam outputted by said laser source to the laser beam of a short wavelength. Said elements is formed of the compd. expressed by the formula I or the exidation adduct thereof. In the formula, Z<1> denotes an atomic group necessary for forming 5-6 membered arom. rings having >=1 nitro groups as a substituent; Z<2> denotes a pyrrole ring, imdazole ring, pyrazole ring, etc. For example, the compd. expressed by the formula II is made into a single crystal by a solvent evaporation method, etc., and the laser light of the wavelength in the visible region is outputted therefrom by condensing the semiconductor laser beam thereof.

Description

[Detailed description of the invention] "Industrial application field" The present invention relates to a nine yuan source using a laser beam.

More specifically, the present invention relates to a light source that is miniaturized, has a short wavelength, and obtains nine elements.

"Conventional technology" The laser source is used as a heat source or light source, etc.
It is also commonly used as a light source for recording images. For example, recording methods using a laser source include the so-called scanner-based image forming method, in which an original image is scanned and a photosensitive material is exposed to light based on the image signal to form an image, and the so-called optical disc method. Examples include writing to an optical information recording medium.

Conventionally, semiconductor lasers that emit infrared light have been used as lasers for these applications in order to achieve miniaturization. However, using infrared light requires sacrificing the stability of the photosensitive material and the information recording density. Therefore, in order to solve these problems, it is necessary to oscillate at short wavelengths in the visible range as well. Although it is hoped that a semiconductor laser will emerge that can do this, it is difficult to realize this. In addition, a method has been proposed to obtain a laser beam in the visible range by using a semiconductor laser that emits infrared light in combination with a wavelength conversion element made of a nonlinear optical material, but LINbOKM, P
Nonlinear optical elements made of inorganic compounds such as O4, L t I Oa, and B a B z 04 have low wavelength conversion efficiency. - Nito a aniline (MNA), Ko N, N-dimetal aki no! - Nido a acetanilide (DANn, metanitroaniline (
m-NA), L-N-(≠-=)o phenyl)-1-(
Hydroxymethyl)biclizine and the like have the disadvantage that they are strongly colored yellow and have low transmittance for blue light, making it impossible to shorten the wavelength sufficiently.

"Problems to be Solved by the Invention" Therefore, an object of the present invention is to generate a laser beam with a shorter wavelength by combining a semiconductor laser and a wavelength conversion element made of an organic nonlinear optical material with high blue light transmittance. The objective is to provide a light source that uses

"Means for Solving the Problems" The present inventors have developed a nine-light source comprising a semiconductor laser source and a nonlinear optical element that converts the laser beam output from the semiconductor laser source into a short wavelength laser beam.
The present inventors have discovered that the nonlinear optical element can be achieved by using a nonlinear optical element formed using a compound represented by the following general formula (I) or an acid adduct thereof, and have accomplished the present invention.

ゝ-21'' In the formula, 2 represents an atomic group necessary to form a t-membered aromatic ring having at least one nitro group as a substituent. Z2 is pyrrole, which may be substituted or fused. A ring, an imidazole ring, a pyrazole ring, a triazole ring, and 9 represent an atomic group necessary to form a tetrazole ring.

The above acid adduct refers to the compound of general formula (1) with an organic acid (
For example, carboxylic acid, sulfonic acid, etc.) or inorganic acid (for example, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, etc.) are added (usually 7 molecules).

Formed by zl! Examples of heavily-membered aromatic rings include thiazoles, oxazoles, imidazoles, pyridines, pyrimidines, and benzenes.
These may be substituted with the following groups or may be fused.

Examples of the substituent include an alkyl group, an aryl group, a halogen atom, an alkoxy group, an aryloxy group, an acylamino group, a carbamoyl group, a sulfamoyl group, an alkoxy group, an alkyloxycarbonyl group, an alkyloxycarbonyl group, and an alkyloxycarbonyl group. group, aryloquitasulfonyl group, alkylthio group, arylthio group,
Examples include a hydrocarbon group, a thiol group, a carboxy group, a ureido group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, and a nitro group.

Examples of the alkyl group include methyl group, ethyl group,
Isopropyl group, butyl group, t-butyl group, octyl group, t-octyl group, decyl group, hexadecyl group, dodecyl group, --hydroxyethyl group, carboxymethyl group,
Cyanomethyl group, λ-methoxyethyl group, benzyl group,
Cophenylethyl group, trifluoromethyl group, 3-(
-1penzimidazolyl)propyl group, and the like.

Examples of the aryl group include a phenyl group, a dermethylphenyl group, a 3-methoxyphenyl group, and a chlorophenyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkoxy group include methoxy group, butoxy group, -1methoxyethoxy group, benzyloxy group, and -1phenylethoxy group. Examples of the aryloxy group include phenoxy group, --t-butylphenoxy group, and ≠-chlorophenoxy group.

Examples of the acylamino group include an acetylamino group, a methanesulfonylamino group, a pensylylamino group, and a dermethylbenzenesulfonylamino group. Cal? Examples of the moyl group include carbamoyl group, N-methylcarbamoyl group, N-ethylcarbamoyl group, and N-phenylcarbamoyl group. Examples of the sulfamoyl group include a sulfamoyl group, an N-methylsulfamoyl group, and an N-phenylsulfamoyl group. Examples of the acyloxy group include an acetyloxy group, a piparoyloxy group, an indiyloxy group, and a benzenesulfonyloxy group. Examples of the ureido group include methylureido, etherureido, and phenylureido.

Examples of the pyrrole ring formed by z2 include pyrrole, indole, -monomethylindole,! -Methoxyindole! -human a-xiindole, L-tryptophan carbazole, 3-carboxindole,
Examples include λ,j-dimethylpyrrole. Examples of the indazole ring include imidazole, co-methylimidazole, -1ethylimidazole, coundecylimidazole, cophenylimidazole, co-dademethylimidazole, -1ethyl-methylimidazole, L-histidine, 3, and j-diphenylimidazole. sole, co, #, j -) IJ phenylimidazole, benzimidazole, comethylbenzimidazole, -monomethyl-! -ri a lobenzimidazole, 2-methyl-! , t-dichlorobenzimidazole, comethyl! -chloro-t-cyanobenzimidazole, comelkabutobenzimidazole, and the like. Examples of pyrazole rings include pyrazole, J,! -dimethylpyrazole,! ,! Examples include -diphenylpyrazole, 31-dimethylpyrazole, J-methylpyrazole, and indazole. As a triazole ring /,! , 44-triazole, 'e2e≠-triazole, cork claw/, J, dartriazole, co,
! -dimethyl-/,! , Reference Triazole, J,! -diphenyl/, J,! -triazole, benzotriazole, etc. Examples of the tetrazole ring include tetrazole and J-phenyltetrazole.

Further, the ring represented by 2 may have a substituent (for example, -1-)t- that can form a dimer.

Specific examples of compounds used in the present invention are shown below, but the scope of the present invention is not limited to these.

t YoJ, 44 Yo02No2 NO, NO□ / cL/ /, /! Kot
Ko2NO, ◆゛ko3 Kohiro-2J:
Ko 2 Ko 2
Kotaha υ, N
o2 These compounds can be easily synthesized, for example, according to the following reaction formula (1).

The base used is pyridine, triethylamine, /
, r-diazabisiphe el (, t, lA, O: any organic base such as l-7-undecene, inorganic base such as potassium carbonate, sodium bicarbonate, potassium t-butoxide, sodium hydride, sodium hydroxide). Examples of solvents include hydrocarbons such as n-hexane, tetrahydrofuran, ethers such as !-dimethoxyethane, and N.

Amides such as N-dimethylformamide and N-methylpyrrolidone, sulfur-containing compounds such as dimethylsulfoxide and sulfolane, nitriles such as acetonitrile, and esters such as ethyl acetate are used. Among these, amides, sulfur-containing compounds, and nitriles are preferred. Also, at the reaction temperature -io @c or /! O@C, preferably -o
"C to 10o"c is desirable.

A specific synthesis method is described in the specification of Japanese Patent Application No. Shoti-ISRRμ for compound /,bu,,22.

The fact that the compound represented by the general formula CI) used in the present invention has excellent blue light transmittance is disclosed in the above-mentioned patent application 1972/-1.
It is described in Example 2 of No. 31111.

The nonlinear optical material referred to in the present invention appears when a strong source electric field such as that of a laser source is applied. It is a material that can exhibit nonlinearity between polarization and electric field - nonlinear optical effect.Nonlinear optical effects include second-order effects such as λ-th harmonic generation, elemental mixing, parametric oscillation, optical rectification, There is the Pockels effect, etc., and the seventh effect is J High All! There are many effects such as generation, Kerr effect, optical bistability, and original mixing, but there are also higher-order effects. In the present invention, the purpose of using a nonlinear optical material is to convert the source of a semiconductor laser having a wavelength in the infrared region to a wavelength in the visible region. , original mixing, parametric oscillation, and third harmonic generation are important.

Using a semiconductor laser and a nonlinear optical material, there are known forms of the nonlinear optical material (or wavelength conversion element) such as a single crystal optical waveguide type and a fiber type. As an optical waveguide type, JP-A-Sho! /-/4C.

-r number, JP-A-1993-101,77, JP-A-KAI! A planar waveguide as described in Kohl J, Cort No., JP-A-70-1999-/Reference, Koh-No., % Kaisho tO-! 7,12! The buried waveguide type described in JP-A No. 1,0-//J, JP-A No. 02J, and also JP-A No. 1979-1999! 0.334
There is a tapered waveguide described in No. 4. Tokukaisho is the fiber type! There is one that satisfies the phase matching condition of the incident laser wave and the converted laser wave described in No. 7-Co// and /CoJ.

The nonlinear optical element of the present invention is formed as an element of the above type using the compound or acid adduct represented by the general formula (1).

The light source of the present invention can be used for various purposes, but when used in an optical recording method, recording materials such as electrophotographic photoreceptors, electrophotographic materials, silver halide photosensitive materials, original discs, Examples include subsequent printing plates or recording materials using photopolymers and the like.

"Effects of the Invention" According to the present invention, by using a combination of a semiconductor laser and a nonlinear optical element formed using the compound represented by the general formula (I) or its acid adduct, optical It became possible to obtain a laser beam with a wavelength of .

"Examples" Next, the present invention will be described in more detail based on Examples. However, the present invention is not limited to these specific examples.

Example 1 A single crystal was obtained by a solvent evaporation method using acetone as a solvent for compound t.

A semiconductor laser is an infrared light source having an oscillation wavelength of 0.3 μm. The infrared light is focused on the crystal of the nonlinear optical element via the SELFOC lens, and a laser source of 01323 μm is output.

Example 2 Compound / is single-crystalized in a glass capillary, and a fiber-based nonlinear element 'f! : Obtained soil.

A semiconductor laser is an infrared light source having an oscillation wavelength of o, r4t μm. The infrared light is focused by a lens and introduced into the input end of the fiber. A laser source of O0≠2μm is emitted from the output end on the opposite side of the fiber.

Example 3 A thin film waveguide type nonlinear optical element was obtained by single crystallizing the compound between two sheets of flat glass sandwiching a 2ff spacer.

A semiconductor laser is an infrared light source having an oscillation wavelength of /Jμm. The infrared light is collected by a lens and then enters the end face of the nonlinear element. Opposite end surface height 0. A laser source of lsJμm is output.

Example 4 The oscillation wavelength i, sμm%/
, Ojμm and O,taμm semiconductor lasers and nonlinear optical elements are each combined with 0.4! pm, 0. j
We have laser light sources with red, green, and blue light of 50 ppm, 0, and eatsm. These laser beams are focused and scanned by a lens and a Galpa scanner, and are sequentially exposed onto a color paper photosensitive material according to the light signal, which then undergoes color development processing steps such as development, fixing, desilvering, and water washing. After drying, a color image corresponding to the input signal was obtained.

Example 5 Using the laser light source obtained in Example 1, the laser source was focused onto an electrophotographic photoreceptor using a collimating lens and a condensing lens. This light is scanned over the photoreceptor by a Galpa scanner. An electrostatic latent image is formed on the electrophotographic photoreceptor in response to this original signal. This photoreceptor is used for developing, transferring,
After going through the electrophotographic process of fusing, a hard copy corresponding to the input signal is obtained on plain paper.

Example 6 Prtc, o, r4tμ of the semiconductor laser of Example J
When using a semiconductor laser that oscillates at a wavelength of m, 0, ≠ 2
A laser source of μm is obtained, this laser source is made into parallel light by a collimator lens, and then passed through a filter to go, r
The e μm element was cut, and only the 0°442 μm element passed through the half prism and was focused as a spot on the cyobtical disk by a condenser lens. The reflected light from the disk passes through the condenser lens again, is reflected by the half prism, is focused by the light receiving lens, passes through the cylindrical lens, enters the photodiode, and is converted into an electrical signal.

Example 7 A photosensitive polymerizable composition was prepared by coating an ethyl alcohol/methyl ethyl ketone solution containing a binder, an unsaturated compound, a photopolymerization initiator, and a sensitizer on an aluminum plate.

Using the nine light sources obtained in Example 1 as a laser light source, the light intensity was varied by controlling the current of the semiconductor laser, the above composition was scanned and exposed with a beam spot diameter of jOμm, and then lightly rubbed in tap water. When dried, a relief image is obtained.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment Showa T/72/72 Mr. Commissioner of the Patent Office, Mr. Kokoro 1,
Indication of the incident: 1939/2016 Patent Application No. 263032 2
, Title of the invention Light source using a laser 3, Person making the amendment - Relationship to the case Patent applicant Subject of the amendment ``Detailed description of the invention'' column in the specification & Contents of the amendment ``Details of the invention'' in the description The description in the "Explanation" section has been amended as follows.

l) Page 1! row "Indazole ring" "Imidazole ring" and correct it.

2) Compound No. 1/Page/4 and correct it.

3) Page 1j, page 1 "Appear." "Appear," and correct it.

4) Page 77, line 7 "Hikari Desk" "optical disk" and correct it.

5) It page, O line "gathering" "Light gathering" and correct it.

Claims (1)

[Scope of Claims] A light source comprising a semiconductor laser source and a nonlinear optical element that converts a laser beam output from the semiconductor laser source into a short wavelength laser beam, in which the nonlinear optical element is expressed by the following general formula (1). ) or an acid adduct thereof. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z^1 represents the atomic group necessary to form a 5- to 6-negative aromatic ring having at least one nitro group as a substituent. . Z^2 may be substituted and fused,
Represents an atomic group necessary to form a pyrrole ring, imidazole ring, pyrazole ring, triazole ring, or tetrazole ring.