JP2835251B2 - Diazo type recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material using a photosensitive diazo compound, and more particularly to a diazo type recording material having excellent preservability of recorded images.

[0002]

2. Description of the Related Art Copying materials utilizing the photosensitivity of diazo compounds are widely used because they are inexpensive, and are roughly classified into the following three types. The first type is a type known as a wet development type in which a photosensitive layer having a diazo compound and a coupling component as main components is provided on a support. After exposure, development is performed using an alkaline solution.

The second type is a type known as a dry development type, which is different from a wet development type in that development is performed with ammonia gas. The third type is known as a heat development type. In addition to a type containing an ammonia gas generating agent such as urea capable of generating an ammonia gas by heating in the photosensitive layer, the photosensitive layer includes Activating a diazo compound and a coupling component by heating and melting, using a type containing an alkali salt of a compound that loses properties as an acid upon heating, such as trichloroacetic acid, as a coloring aid, using a higher fatty acid amide. There are types used.

[0004] The wet type has problems in maintenance and management such as troublesome replenishment and disposal due to the use of a developing solution, and the large size of the apparatus. In addition, it has drawbacks such as that it is not possible to make additions and that the copied image cannot withstand long-term storage. In addition, in the case of the dry type, as in the case of the wet type, it is necessary to replenish the developing solution, and in addition, it is necessary to provide a gas suction device to prevent the generated ammonia gas from leaking to the outside. In addition, there is a drawback such as a strong ammonia smell immediately after copying.

On the other hand, the heat developing type has a maintenance advantage that a developing solution is unnecessary unlike the wet type or the dry type, but the developing temperature is as high as 150 ° C. to 200 ° C. In addition, if the temperature control is not performed within the range of about ± 10 ° C., the development will be insufficient or the color tone will be changed. Therefore, in order to obtain a good image, the cost of the apparatus must be increased. was there. Also, in order to withstand such high-temperature development, the diazo compound used must also have high heat resistance, but such a compound is often disadvantageous for forming a high image density.

Therefore, conventionally, low-temperature development (90 ° C. to 1
(30 ° C.), but there is a drawback that the shelf life of the material itself is reduced. Therefore,
At present, the thermal development type has not yet occupied the mainstream of the diazo copying system, although the maintenance advantages are expected to be sufficiently higher than those of the wet type and the dry type. By the way, in order to obtain a desired color density by heating a material provided with a layer containing a diazo compound, a coupling component and a color development aid on a support,
It is necessary that each component is instantaneously melted, diffused, and reacted by heating to produce a coloring dye.

In this case, if a recording material is designed such that a high density image can be obtained by sufficiently developing a color even at a low heating temperature, it is natural that the color development reaction occurs even during storage at room temperature before copying. Progresses little by little, and the background portion, which must be white, is colored, causing background contamination. The above problem that is seemingly incompatible is that the diazo compound is contained in microcapsules in a copying material provided with a heat-developable photosensitive layer containing a diazo compound, a coupling component and a color-forming auxiliary on a support. This has been substantially solved (JP-A-59-91438).

[0008]

However, in this case, however, there is a disadvantage that the density of the image portion decreases with time, and the storability of the recorded image becomes insufficient. Accordingly, an object of the present invention is to provide a diazo type recording material having better preservability of recorded images than ever before.

[0009]

The object of the present invention is to provide a photosensitive diazo compound encapsulated in microcapsules on a support, a coupling component which reacts with the diazo compound by heating to form a color, and This has been achieved by a diazo type recording material provided with a recording layer containing a compound represented by Chemical Formula 1 and / or Chemical Formula 2.

[0010]

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However, R ₁ and R in Chemical Formula 1 and Chemical Formula 2
₂ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group which may have a substituent or a halogen atom, and at least _one of R ₁ and R ₂ One is not a hydrogen atom, M is Zn, C
a, Mg, Ba, Ni, Co, Mn, Fe, Cu are metal atoms selected from the group consisting of:

The diazo compound used in the present invention is selected from known diazo compounds such as photodegradable diazonium salts, diazosulfonates and diazoamino compounds, which form a color by causing a coupling reaction with a coupling component and decompose by light. Can be appropriately selected and used. In the present invention, among these diazo compounds, particularly from the viewpoint of photosensitivity and image density, the general formula ArN ₂ ⁺
X ^- it is preferable to use a diazonium salt represented by (wherein, Ar represents an aromatic moiety substituted or unsubstituted, N ₂ ⁺ represents a diazonium group, X ^- represents an acid anion.).

Specific examples of the diazonium salt include 4-diazo-1-dimethylaminobenzene, 4-diazo-1-
Diethylaminobenzene, 4-diazo-1-dipropylaminobenzene, 4-diazo-1-methylbenzylaminobenzene, 4-diazo-1-dibedylaminobenzene, 4-diazo-1-ethylhydroxyethylaminobenzene, 4- Diazo-1-diethylamino-3-methoxybenzene, 4-diazo-1-dimethylamino-2-methylbenzene, 4-diazo-1-benzoylamino-
2,5-diethoxybenzene, 4-diazo-1-morpholinobenzene, 4-diazo-1-morpholino-2,5-
Diethoxybenzene, 4-diazo-1-morpholino-
Examples thereof include 2,5-dibutoxybenzene, 4-diazo-1-toluylmercapto-2,5-diethoxybenzene, and 4-diazo-1,4-methoxybenzoylamino-2,5-diethoxybenzene.

Specific examples of the acid forming the diazonium salt include C _n F _{2n + 1} COOH (n is an integer of 1 to 9) and C _m F _{2m + 1} SO ₃ H (m is 1 to 9). , Boron tetrafluoride, tetraphenylboron, hexafluorophosphoric acid, aromatic carboxylic acid, and metal halides such as zinc chloride and tin chloride.

The coupling component used in the present invention is one which forms a dye by coupling with a diazo compound under a basic atmosphere, and specific examples thereof include resorcin, phloroglucin, and 2,3-dihydroxynaphthalene-6. Sodium sulfonate, 1-hydroxy-2-naphthoic acid morpholinopropylamide, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene,
2,3-dihydroxy-6-sulfanylnaphthalene,
2-hydroxy-3-naphthoic acid morpholinopropylamide, 2-hydroxy-3-naphthoic acid anilide, 2-
Hydroxy-3-naphthoic acid-2′-methylanilide,
2-hydroxy-3-naphthoic acid ethanolamide, 2
-Hydroxy-3-naphthoic acid octylamide, 2-hydroxy-3-naphthoic acid-N-dodecyl-oxy-propylamide, 2-hydroxy-3-naphthoic acid tetradecylamide, acetanilide, acetoacetanilide, benzoylacetanilide, 1- Phenyl-3-methyl-5-pyrazolone, 1- (2 ′, 4 ′, 6′-trichlorophenyl) -3-benzamido-5-pyrazolone, 1- (2 ′, 4 ′, 6′-trichlorophenyl)-
3-anilino-5-pyrazolone, 1-phenyl-3-phenylacetamido-5-pyrazolone and the like.

An image of any color tone can be obtained by using two or more of these coupling components in combination. In the present invention, for the purpose of promoting the coupling reaction by making the system basic during thermal development, it is preferable to add a basic substance that acts as a color-forming aid, if necessary. As such a basic substance, a water-insoluble or water-insoluble basic substance or a substance that generates an alkali by heating is used.

Specific examples of the basic substance include inorganic and organic ammonium salts, organic amines, amides, urea and thiourea and derivatives thereof, thiazoles, pyrroles, pyrimidines, piperazines, guanidines, indoles,
Examples include nitrogen-containing compounds such as imidazoles, imidazolines, triazoles, morpholines, piperidines, amidines, formamidines, and pyridines. These basic substances can be used in combination of two or more.

In the present invention, a phenol derivative, a naphthol derivative, an alkoxy-substituted benzene, an alkoxy-substituted naphthalene, a hydroxy compound, an amide compound, A sulfonamide compound or the like can be added. These compounds reduce the melting point of the coupling component or the basic substance or improve the heat permeability of the microcapsule wall, and as a result, function as a color-forming aid, thereby obtaining a high color-forming density. .

The coloring aid in the present invention includes a heat-fusible substance. Here, the heat-fusible substance is a substance which is solid at normal temperature and melts by heating and has a melting point of 50 ° C. to 150 ° C., and is a substance which dissolves a diazo compound, a coupling component or a basic substance. Specific examples of the heat-fusible substance include fatty acid amides, N-substituted fatty acid amides, ketone compounds, urea compounds, esters, and the like.

Specific examples of the salicylic acid compound represented by the formula (3) used in the present invention include those represented by the following formulas (5) to (17).

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[0021]

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[0022]

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Specific examples of the salicylic acid compound represented by Chemical Formula 4 include the following Chemical Formulas 18 and 19.

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These salicylic acid compounds represented by Chemical Formula 3 or Chemical Formula 4 may be used alone or in combination. The amount of the salicylic acid compound used is from 0.01 to
It is preferably 0.5 g / m ² . 0.01 g / m
The ² or less, no effect to improve the storage stability of the recorded image, and the heat sensitivity is reduced When it is 0.5 g / m ² or more is not preferable.

The salicylic acid compound may be added to any location inside the microcapsule, outside the microcapsule, or on the microcapsule wall, and may be added at two or more locations. In particular, it is preferable to add the basic substance to the same place as the place where the basic substance is added. In the present invention, it is preferable to use 0.1 to 10 parts by weight of the coupling component and 0.1 to 20 parts by weight of the coloring aid with respect to 1 part by weight of the diazo compound. In addition, the diazo compound is 0.05 to 5.0.
g / m ² .

The microcapsules of the present invention are prepared by emulsifying a core substance and then forming a wall of a polymer substance around the oil droplets. The reactant that forms the polymeric substance is added inside the oil droplet and / or outside the oil droplet. Specific examples of the polymer substance include polyurethane, polyurea, polyamide, polyester, polycarbonate, urea-formaldehyde resin, and melamine resin. Two or more polymer substances can be used in combination. Preferred polymeric substances are polyurethanes, polyureas, polyamides, polyesters, polycarbonates, more preferably polyurethanes and polyureas. As the physical properties of the polymer substance, a polymer substance that does not melt at the temperature during thermal recording and has a melting point of 150 ° C. or more is preferable.

The microcapsules can be prepared from an emulsion containing at least 0.2% by weight of the component to be microencapsulated. The microcapsules used in the present invention are:
After dissolving the diazo compound and the coupling component together with the monomer for forming the capsule wall in a non-aqueous solvent having a low boiling point, the microcapsules containing substantially no solvent, such as those obtained by distilling off the solvent during the polymerization reaction. Preferably, there is.

The polymer forming the microcapsule wall can be obtained by polymerizing the corresponding monomer by the method described above. The amount of the monomer used is such that the average particle size of the obtained microcapsule is 0.3 to 12 μm. Is determined so that the wall thickness becomes 0.01 to 0.3 μm. By enclosing the diazo compound in the microcapsules produced in this way, the contact between the diazo compound and the coupling component at room temperature can be prevented more than ever.

The coupling components, basic substances, and other color-forming auxiliaries not contained in the microcapsules used in the present invention are preferably used as a solid dispersion with a water-soluble polymer by a sand mill or the like. Preferred water-soluble polymers include water-soluble polymers used when preparing microcapsules (for example, JP-A-59-19).
0886). In this case, the coupling component and the coloring aid are added to the water-soluble polymer solution at 5 to 40% by weight, respectively. The size of the dispersed particles is preferably 10 μm or less.

The coating liquid of the present invention can be applied by a well-known coating method such as bar coating, blade coating, air knife coating, gravure coating, doctor coating, slide coating, roll coating coating, spray coating, dip coating, curtain coating and the like. And Yuji Harazaki, "Coating Engineering" 2
It is applied by a method described on page 53 (published by Asakura Shoten in 1973). The photosensitive layer of the present invention is set so that the solid content after coating and drying is 2.5 to 30 g / m ² .

In the recording material of the present invention, a diazo compound, a coupling component, a basic substance and the like may be contained in the same layer as described above, but the recording material has a laminated structure in which it is contained in another layer. You can also. Further, after providing an intermediate layer as described in JP-A-61-54980 on a support, a photosensitive layer can be applied. A protective layer can be further provided on the photosensitive layer.

When an image is formed on the recording material of the present invention, an imagewise exposure corresponding to the original is performed to decompose the diazo compound in the exposed portion, and then the entire recording material is heated to heat the unexposed portion of the diazo compound. To obtain a colored image by reacting with a coupler, or beforehand, heat recording like an image using a hot pen or thermal head, and then irradiating the entire surface of the recording material with light to decompose the diazo compound in the uncolored part Establish.

For the imagewise exposure corresponding to the original, it is easy to perform close contact exposure if it is a transparent original, but other methods, for example, exposure by scanning light may be adopted. As a light source for exposure, various fluorescent lamps, xenon lamps, mercury lamps and the like are used. In this case, it is preferable that the emission spectrum of the light source substantially coincides with the absorption spectrum of the diazo compound used. Further, as a heating means in the step of heating and developing the entire surface of the photosensitive layer of the recording material, an infrared ray, a high frequency wave, a heat block, a heat roller and the like can be used.

[0034]

As described above in detail, the diazo type recording material of the present invention containing the salicylic acid compound represented by the above formulas (3) and (4) is not necessarily clear, but the storage stability of the density of the recorded image is not clear. Is improved over the prior art.

[0035]

EXAMPLES Examples will be shown below, but the present invention is not limited by these examples. “Parts” indicating the amount of addition represents “parts by weight”.

Embodiment 1 3 parts of the diazonium salt prepared in Capsule liquid (Chemical formula 20) was added to and dissolved in 13 parts of ethyl acetate.

Embedded image A solution of this diazo compound in a 75% by weight ethyl acetate solution of a 1: 3 adduct of trimethylolpropane and xylylenediisocyanate (Formula 21) (manufactured by Takeda Pharmaceutical Co., Ltd .:
(Takenate D110N, trade name) was added and mixed with stirring.

[0037]

Embedded image The diazonium salt and the isocyanate thus obtained in ethyl acetate were mixed with polyvinyl alcohol (PVA).
217E: Kuraray Co., Ltd.) 3.5 parts water 6
The resulting mixture was mixed with an aqueous solution dissolved in 0 parts and emulsified and dispersed to obtain an emulsion having an average particle size of 1.0 μm. Water 2 is added to the obtained emulsion.
0 parts were added, and the mixture was heated to 40 ° C. with stirring to react the isocyanate which is a wall-forming substance for 3 hours.
Microcapsules containing a diazo compound as a core material were obtained at μm. The above encapsulation reaction was performed under reduced pressure of 400 mmHg to 500 mmHg using a water jet pump.

Preparation of coupler dispersion 5 parts of 2-hydroxy-3-naphthoic acid anilide, 5 parts of triphenylguanidine, compound 8 represented by the following formula
And 2 parts of the salicylic acid compound of Chemical Formula 23 were added to 200 parts of a 5% by weight aqueous solution of polyvinyl alcohol, and dispersed with a sand mill for 24 hours to obtain a dispersion having an average particle size of 2 μm.

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Preparation of Coating Solution To 8 parts of the diazonium salt capsule solution obtained as described above, 25 parts of the above coupler dispersion, 2 parts of a 40% by weight calcium carbonate (Univar 70 manufactured by Shiroishi Kogyo) dispersion, and water 0.5 part was added to obtain a coating solution.

Preparation of Recording Material The above coating solution was coated on smooth high-quality paper (76 g / 2 m ² ) using a coating bar so that the dry weight was 5 g / m ^2, and dried at 50 ° C. for 3 minutes. Thus, a recording material was obtained.

Evaluation of storage stability The obtained recording material was heated at 130 ° C. for 5 seconds using a hot plate to develop color, and then at 40 ° C. and a relative temperature of 90%.
(90% RH) in a dark atmosphere, a forced deterioration test was performed for 6 hours, and the color density before and after the test was measured with a Macbeth densitometer. The color density before the test was 1.20, The color density after the deterioration test was 1.17,
Almost no deterioration was observed.

Embodiment 2 FIG. Used in Example 1 (Formula 23)
A recording material was prepared in exactly the same manner as in Example 1 except that the salicylic acid compound of Chemical Formula 24 was used in place of the salicylic acid compound of Chemical Formula 24, and a deterioration test was performed in exactly the same manner as in Example 1.

Embedded image The color density of the obtained recording material before the deterioration test was 1.20.
In contrast, the color density after the deterioration test was 1.16.
Met.

Comparative Example 1 (Formula 2)
A recording material was prepared in exactly the same manner as in Example 1 except that the compound represented by Chemical Formula 25 was used in place of the salicylic acid compound of 3), and a degradation test was performed in exactly the same manner as in Example 1.

Embedded image The color density of the obtained recording material before the deterioration test was 1.20.
In contrast, the color density after the deterioration test was 1.05.
And deterioration was recognized.

Comparative Example 2 Used in Example 1 (Formula 23)
A recording material was prepared in the same manner as in Example 1 except that no salicylic acid compound was used, and a deterioration test was performed in the same manner as in Example 1. The color density of the obtained recording material before the deterioration test was 1.20, whereas the color density after the deterioration test was 0.95, and remarkable deterioration was recognized. The results of the above Examples and Comparative Examples demonstrate the effectiveness of the present invention.

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshiharu Tanaka 200 Onakazato, Fujinomiya City, Shizuoka Prefecture Inside Fujisha Shin Film Co., Ltd. (56) References JP-A-2-90148 (JP, A) Japanese Patent Publication No. 45- 25840 (JP, B1) (58) Field surveyed (Int. Cl. ⁶ , DB name) G03C 1/61 501

Claims (1)

(57) [Claims] 1. A photosensitive diazo compound encapsulated in microcapsules on a support, a coupling component which reacts with the diazo compound by heating to form a color, and is represented by the following chemical formula 1 and / or chemical formula 2. A diazo type recording material provided with a recording layer containing a compound; Embedded image However, R ₁ and R 2 in Chemical Formulas 1 and ₂ represent a hydrogen atom,
An alkyl group having 1 to 8 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group which may have a substituent or a halogen atom, wherein at least one of R ₁ and R ₂ is not a hydrogen atom , M are Zn, Ca, Mg, Ba, N
i is a metal atom selected from the group consisting of Co, Mn, Fe, and Cu.