JPH0338142Y2 - - Google Patents

Description

[Detailed explanation of the idea]

[Industrial Application Field] The present invention relates to a package for a diazo thermosensitive recording material. In particular, in a heat-sensitive recording material in which a recording layer containing a diazo compound, a coupling component, and a coloring aid is provided on a fixable support, at least one of the diazo compound, coupling component, and coloring aid is an organic solvent. The present invention also relates to a package optimal for diazo-based heat-sensitive recording materials contained in microcapsules (except when three types are contained in the same microcapsule). [Prior Art] In recent years, thermal recording methods (1) do not require development;
(2) If the support is paper, the paper quality is similar to ordinary paper. (3) Easy to handle. (4) High color density. (5) The recording device is simple and inexpensive. (6) Because it has advantages such as no noise during recording, it is rapidly becoming popular in fields such as facsimiles and printers. As the heat-sensitive recording material used in this heat-sensitive recording method, a leuco color-forming heat-sensitive recording material, which is excellent in color density and color development speed, is mainly used. Leuco color-forming heat-sensitive recording materials have the disadvantage that they develop color when handled or heated after recording, or when solvents are attached to them, staining the recorded image, and they also have the disadvantage of being discolored by the plasticizer in the cellophane tape. There is. A method for improving the drawbacks of this leuco coloring type heat-sensitive recording material and stopping color development in unnecessary areas after thermal recording is disclosed in JP-A-57-123086, JP-A-57-125092, etc. . This uses a diazo-based heat-sensitive recording material consisting of a diazo compound, a coupling component, and an alkali generator or a color-forming aid, and then irradiates it with light to decompose the unreacted diazo compound and stop color development. be. However, this diazo-based heat-sensitive recording material also undergoes gradual pre-coupling during storage, and undesirable coloring (fogging) may occur. To counter this problem, Japanese Patent Application Laid-Open No. 57-4414,
No. 57-142636 discloses that either the coupling component or the coloring aid is made into a non-polar wax-like substance or encapsulated with a hydrophobic polymeric substance (Japanese Patent Laid-Open No. 1982-192944). known to isolate. The present invention can be suitably used for the above-mentioned various diazo-based heat-sensitive recording materials, but in particular, at least one of the diazo compound, coupling component, and color development aid is microencapsulated together with an organic solvent, and the remaining components are added to the support. This package is ideal for fixing type diazo heat-sensitive recording materials coated on top.
The diazo-based heat-sensitive recording material for which the package of the present invention is most suitable can destroy conventional microcapsules by heat or pressure to separate the reactive substances contained in the core of the microcapsules and the reactive substances outside the microcapsules. Rather than causing a coloring reaction upon contact, the reactive substance present in the core and outside of the microcapsule is caused to react by passing through the microcapsule wall by heating. In this case, when an organic solvent coexists, color fog during storage is dramatically reduced, and color development speed and color density are dramatically increased. In this case, the microcapsule wall does not need to be melted by heat; rather, the higher the melting point of the wall, the better the shelf life. The diazo thermosensitive recording material that is most suitable for the package of the present invention will be explained in detail. After dissolving or dispersing the diazo compound as the core material in an organic solvent, the core material containing the reactive substance and the organic solvent is microencapsulated with a wall material produced by polymerization methods such as interfacial polymerization, external polymerization, and internal polymerization. Preferably.
Preferred wall materials are polyurethane, polyurea, polyamide and polyester. The organic solvent used for the core material is an insoluble high boiling point solvent.
The boiling point is preferably 180°C or higher, and specific examples include phosphoric acid esters, phthalic acid esters, other carboxylic acid esters, fatty acid amides, etc. Specific compounds include dibutyl phthalate, diethyl phthalate, dibutyl maleate, phosphorus, etc. Ester solvents such as tricresyl acid are particularly preferred. The diazo compound is a diazonium salt represented by the general formula ArN ₂ ⁺ x ^- , which can develop a color by causing a coupling reaction with a coupling component, and can be decomposed by light. (In the formula, Ar represents a substituted or unsubstituted aromatic moiety, N ₂ ⁺ represents a diazonium group, and x _- represents an acid anion.) Specific examples of diazonium compounds that form salts include 4-diazo -1-dimethylaminobenzene, 4-diazo-1-diethylaminobenzene,
4-Diazo-1-dipropylaminobenzene, 4
-diazo-1-methylbenzylaminobenzene,
4-Diazo-1-dibenzylaminobenzene, 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-morpholino-2,5-diethoxybenzene, 4-diazo-1-morpholino-2,5-dibutoxybenzene, 4-diazo-1-anilinobenzene , 4-diazo-1.-tolylmercapto-
2,5-diethoxybenzene, 4-diazo-1,
Examples include 4-methoxybenzoylamino-2,5-diethoxybenzene. A specific example of an acid anion is C _o F _2o+1 COO ^-
(n represents 3 to 9), CmF _2n+1 SO ₃ ^- (m is 2
~8), (ClF _2l+1 SO ₂ ) ₂ CH ^- (l represents 1 ~ 18
), etc. A known document regarding diazo-based thermosensitive recording materials is "Thermal sensitizers and thermal color development in diazo-based thermosensitive recording media" by Hiroji Sato of NTT Corporation, which is described in Nippon Kagaku Shishi 1985, (11) p. 2111-2115. There are "characteristics". Conventionally, packaging materials for photographic light-sensitive materials (including diazo photographic light-sensitive materials, etc.) are typical examples of packaging materials that require light-shielding properties, such as the above-mentioned packaging for diazo heat-sensitive recording materials. It was hot. Various types of packaging materials for photographic materials have been widely put into practical use, and various performances are required depending on the intended use. Packaging materials that completely block light are used as packaging materials for photographic materials that lose their quality value when exposed to light. In this case, the required properties are gas barrier properties, light blocking properties, moisture proofing properties, physical strength (breaking strength, tear strength, impact puncture strength, gelbo test strength, friction strength, etc.), heat sealability (heat seal strength, hot tack properties, etc.) , contaminant sealing properties, etc.), antistatic properties, flatness, sliding properties, etc. It is difficult to combine these properties in a single film material, and conventionally, the fifth
As shown in the figure, high-pressure low-density polyethylene (hereinafter referred to as LDPE) with carbon black, pigments, etc.
LDPE light-shielding film layer 5 (shown as ), as shown in Figure 6,
A composite laminate film in which a flexible sheet layer 6 such as cellophane and an LDPE light-shielding film layer 5 are laminated, and a composite in which a light-shielding flexible sheet layer 7 with light-shielding properties and an LDPE film layer 8 are laminated as shown in No. 7. The laminated film is hot. In addition, as shown in FIG. 8, a metal foil light shielding layer 9 such as an aluminum foil is attached to an LDPE light shielding film layer 5 via an adhesive layer 4.
There was one in which a flexible sheet layer 6 was further laminated via an adhesive layer 4. The inventor of the present invention has conducted extensive research to improve packaging materials for photosensitive materials, and has already developed a material with improved physical strength by combining two layers of uniaxially stretched film (Japanese Patent Laid-Open No. 57-6754). Disclosed. In addition, linear low-density polyethylene (hereinafter L-
Regarding packaging materials using resin (denoted as LDPE), it must also have at least one layer of a light-shielding film consisting of a polyethylene polymer and 1% or more of a light-shielding substance, with 50% or more of the total ethylene-based polymer being L-LDPE. have already disclosed something (JP-A-Sho
58-132555). [Problems to be solved by the invention] However, the packaging materials that have been used for conventional heat-sensitive recording materials, diazo-based photosensitive materials, photographic photosensitive materials, etc., as described above, are used as packaging materials for diazo-based heat-sensitive recording materials. Since these packaging materials contain a layer of plastic, such as a 50/100 um thick polyethylene film layer, they may be exposed to heat and moisture when placed in sunlight or exposed to high temperatures during transportation or storage. There was a problem in that the coupling gradually progressed and coloring occurred. The object of the present invention is to solve the above-mentioned problems and provide a package for a diazo-based heat-sensitive recording material that has excellent heat insulation properties and good release of moisture inside the package to the outside at high temperatures. [Means for Solving the Problems] In order to achieve the above object, the present invention constitutes a package by overlapping two separate sheets of paper. In other words, a single layer of light-shielding paper with a density of 0.7 to 1.0 g/cm ³ , a thickness of 30 to 200 μm, and a moisture permeability of 50 g/m ² for 24 hours or more is used on the inner surface, and white, yellow, silver, or light colored paper is used on the outer surface. When colored, the density is 0.7~1.0g/cm ³ and the thickness is 20~
A single layer of light-reflecting paper with a thickness of 150 μm and a moisture permeability of 50 g/m ² for 24 hours or more is stacked, and the density of the paper is 0.7 to 1.0 g/m ³ and the thickness is a stack of light-shielding paper and light-reflecting paper. The diazo heat-sensitive recording material is wrapped in a wrapping paper having a diameter of 50 to 250 μm and a moisture permeability of 50 g/m ² for 24 hours or more. The wrapping paper is made up of a layer of light-shielding paper and light-reflecting paper. This superposition creates a double structure in which the light-shielding paper and the light-reflecting paper, which are separate from each other, are not glued together. The above-mentioned light-shielding paper refers to paper colored with light-absorbing colors such as black, red, and blue using dyes, pigments, metal powders, etc., and the most preferable paper for the present invention is 1.
It is a black light-shielding paper colored with ~15% by weight carbon black. Carbon black is preferred because it is inexpensive, contains few impurities, and has excellent light-shielding properties. The density of the light-shielding paper is 0.7 to 1.0 g/ ^cm3 , preferably 0.8 to 1.0, to ensure light-shielding properties, moisture permeability, and physical strength.
0.95g/ ^cm3 , thickness is 30-200μm, preferably 50
~120 μm, and the water vapor permeability is required to be 50 g/m ² ·24 h or more, preferably 100 g/m ² ·24 h or more. The light-reflecting paper is white, yellow, lightly colored, or silver-colored paper with a density of 0.7 to 1.0 g/cm ³ , preferably 0.8 to 0.95 to ensure printability, moisture permeability, and physical strength.
g/ ^cm3 , thickness 20~150μm, preferably 30~
90μm, moisture permeability 50g/ ^m2・24h or more, preferably
Characteristics of 100g/m ² for 24 hours or more are required. Light reflective papers include unbleached kraft paper, semi-bleached kraft paper, bleached kraft paper, double-glazed kraft paper, double-glazed kraft paper, pure white wrapping paper, pure white roll paper, S-roll paper, G-roll paper, and single-glazed bleached kraft paper. paper, veined kraft paper, duostress paper, baryta base paper, kurpatsk paper, single-gloss kraft paper, thin imitation paper, high-quality paper,
Examples of shoji paper, art base paper, and light-shielding paper include colored paper obtained by adding a coloring substance to the above-mentioned light-reflecting paper, colored wood-free paper, light-shielding base paper for photographs, and the like. In particular, pure white roll paper and double-sided bleached kraft paper are preferred as the light-reflecting paper, and as the light-shielding paper, paper colored black with carbon black for use as light-shielding base paper for photography is preferred. In addition, in order to ensure light-shielding properties, physical strength, and moisture permeability, wrapping paper made by laminating light-shielding paper and light-reflecting paper has a density of 0.7 to 1.0 g/cm ^{3 and a thickness of 50 to 50 g/cm 3} .
250 μm and a moisture permeability of 50 g/m ² for 24 hours or more. [Function] In the heat-sensitive recording material package of the present invention, the two sheets of paper, the light-shielding paper and the light-reflecting paper, block external temperature and light, and the diazo-based heat-sensitive recording material is heated to 50°C or higher, and the packaging When the humidity inside becomes high, the moisture inside the package is allowed to permeate and released to the outside. Therefore, the quality of the stored diazo thermosensitive recording material is always kept stable. [Example] The product 1 of the present invention corresponds to the embodiment shown in FIG. In this figure, reference numeral 1 denotes a light-shielding paper provided on the inner surface;
Reference numeral 2 denotes a light-reflecting paper provided on the outer surface, which is stacked one on top of the other so that there is a space 3 between them. Then, the above light-shielding paper 1
For this purpose, black paper with a density of 0.92 g/cm ³ and a thickness of 75 μm, consisting of 67% by weight of hardwood pulp (L material), 27% by weight of softwood pulp (N material), and 6% by weight of carbon black, was used. In addition, the light reflective paper 2 has a density of 0.89.
White bleached kraft paper of g/cm ³ and thickness of 67 μm was used. The product 2 of the present invention also corresponds to the embodiment shown in FIG. Light-shielding paper 1 has the same composition as product 1 of the present invention and has a density of 0.93.
A black paper with a density of 0.90 g/cm ³ and a thickness of 55 μm was used as the light ^- reflecting paper 2. Comparative product 1 is similar to the embodiment of FIG. Instead of the light-shielding paper 1, an LDPE light-shielding film layer 5 containing 3% by weight of carbon black with a thickness of 50 μm is provided, and the light-reflecting paper 2 has a density of 0.89 g/cm ³ and a thickness of 67 μm.
The same white bleached kraft paper as in Product 1 of the present invention was used. Comparative product 2 corresponds to the embodiment shown in FIG. This embodiment is constructed by laminating a light-shielding paper 1 and a light-reflecting paper 2 with an adhesive layer 4. The light-shielding paper 1 and the light-reflecting paper 2 are the same paper as the product 1 of the present invention,
For the adhesive layer 4, an extrusion laminate adhesive layer of LDPE resin was used. Conventional product 1 corresponds to the embodiment shown in Fig. 5, and is made of LDPE
As the light-shielding film layer 5, a film having a thickness of 70 μm and containing 3% by weight of carbon black was used. Conventional product 1 corresponds to the embodiment shown in FIG. 6, and the flexible sheet layer 6 has a density of 0.87 g/cm ³ and a thickness.
An extrusion laminate film layer containing 3% by weight of carbon black was used as the LDPE light-shielding film layer 5 using 80 μm bleached kraft paper. The packaging form of wrapping paper as described above is the second method.
This will be explained based on the diagram and FIG. FIG. 2 is a perspective view showing a bag-type packaging form;
A light-shielding paper 1 and a light-reflecting paper 2 are glued together at both ends to form a bag shape. FIG. 3 is a perspective view showing a packaged state of the diazo thermosensitive recording material. In the figure, reference numeral 10 is a diazo thermosensitive recording material, and this recording material 10 has a width of
It is wound around a paper core 11 having a diameter of 210 mm and an inner diameter of 3 inches. Next, the above-mentioned present invention products 1 to 2, comparative products 1 to 2,
2. Wrap a band-shaped diazo thermosensitive recording material in the wrapping paper of conventional products 1 and 2 as shown in Figure 3, and place it in a constant temperature bath at 55℃ for 42 hours.The coloration (fog) is determined as the Macbeth concentration. Ta. The results are shown in the table below.

[Table] The evaluation and test methods for the table are as follows. Excellent - Very good Good - Excellent Fair - Within practical limits No improvement required - Problems Impossible - Not practical Thickness - Conforms to JIS P-8118. Moisture permeability - Conforms to JIS Z-0208. Light-shielding property - After packaging the diazo-based heat-sensitive recording material using each packaging material, it is exposed to light of 80,000 lux for one hour, and the light-shielding property is detected and evaluated by the degree of coloring (fogging) of the diazo-based heat-sensitive recording material. LDPE extrusion adhesive layer 4 in the example
And as the LDPE film layer 8, Mirason 14 manufactured by Mitsui Polychemical Co., Ltd. (MI5.1g/10 minutes, density 0.919g/
cm ³ ) and the carbon black used was Mitsubishi Kasei's oil-fired black #44B (average particle size
21mu, PH7.7), and as the LDPE light shielding film layer 5, Nippon Unicar DFD-0111 (MI2.4g/10 minutes,
A density of 0.923 g/cm ³ ) was used, respectively. The above examples show representative examples of preferred embodiments as packaging materials for the diazo thermosensitive recording material of the present invention, but the present invention is not limited thereto, and other light-shielding papers and light-reflecting papers may be used. A combination is possible. [Effects of the invention] The packaging body for the heat-sensitive recording material of the present invention is composed of separate light-shielding paper and light-reflecting paper, which effectively releases moisture inside the packaging to the outside and effectively blocks outside temperature. to prevent the inside from becoming hot,
The occurrence of coloring (fogging) due to pre-coupling is greatly reduced, and the storage stability of the diazo-based heat-sensitive recording material before heat recording is extremely good, and a stable quality state can be ensured.

[Brief explanation of the drawing]

Fig. 1 is a partial sectional view of a wrapping paper according to an embodiment of the present invention, Fig. 2 is a perspective view showing a bag-type packaging form, and Fig. 3 is a perspective view showing a packaging form of a band-shaped diazo heat-sensitive material. It is a diagram. FIG. 4 is a partial sectional view of a comparative packaging material, and FIGS. 5 to 8 are partial sectional views of conventional packaging materials. 1... Light-shielding paper, 2... Light-reflecting paper, 3... Between,
4... Adhesive layer, 5... LDPE light-shielding film layer, 6
...Flexible sheet layer, 7... Light-shielding flexible sheet layer, 8... LDPE film layer, 9...
Metal foil light-shielding layer, 10... paper-wrapped core, 11... diazo thermosensitive recording material.

Claims (1)

[Scope of claims for utility model registration] (1) The inner surface has a density of 0.7 to 1.0 g/cm ³ and a thickness of 30 to
A single-layer light-shielding paper with a diameter of 200 μm and a moisture permeability of 50 g/m ² for 24 hours or more, with a white, yellow, silver, or light color on the outer surface, a density of 0.7 to 1.0 g/cm ³ , and a thickness of 20 to
A single layer of light-reflecting paper with a diameter of 150μm and a moisture permeability of 50g/ ^m2 /24 hours or more is stacked, and the density of the paper is 0.7 to 1.0g/
^m3 , thickness 50-250μm, moisture permeability 50g/ ^m2・24
1. A package for a heat-sensitive recording material, characterized in that a diazo-based heat-sensitive recording material is wrapped in a wrapping paper that is longer than 1 hour. (2) The heat-sensitive recording material package according to claim 1, wherein the light-shielding paper contains 1 to 15% by weight of carbon black.