JPS5883842A - Diazo photosensitive and pressure sensitive material - Google Patents

Abstract

PURPOSE:To obtain a pressure sensitive material capable of forming an image with letters and patterns manually added, by providing on a transparent support a layer contg. diazo compd. and a coupler, either of these microencapsulated in a specified binder resin. CONSTITUTION:A layer containing as main components a diazo compd. as a component (a) and a coupling component or a leuco type dye as a component (b), either of both (a) and (b) microencapsulated, in a binder resin changeable in adhesion by irradiation of an active ray is formed on a transparent support to obtain a pressure sensitive material. All of the diazo copying material generally used can be applied to said diazo compd. Phloroglucin, 2,5-dimethyl-4-morpholinomethylphenol, etc. are used for said coupling component. polyamide epoxy resin, polyvinylidene chloride, etc. are used for said binder resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a diazo-photosensitive pressure-sensitive material, and more particularly to an image-forming material IP# in which a photosensitive pressure-sensitive element made of a specific composition is provided on a transparent support.

The method of providing a layer of a photosensitive composition on a support, exposing it to light and then peeling it off to obtain a relief image or photograph, and the materials used in the method are widely known. There is. One of them is 1, and 11 by light irradiation! It has been proposed that a layer containing a diazo compound and a 111I family is provided on a support to change the balance of adhesion (the adhesion changes due to actinic rays).

The carno black (pigment) added in the -m
At the same time as forming m, heat absorption by light irradiation is made more reliable. And this **forming material K
In the end, the diazo compound is actively thermally decomposed by heat absorption by actinic rays of 1m light through the manuscript, and nitrogen gas is generated, thereby further reducing the I A peeling @ groin forming property that makes it disappear is adopted.

However, when it comes to forming and forming peel-off images using such W4-forming materials, since the material itself uses pigments such as carno black, there is no sensitivity to what is left after peeling. Unable to record pressure. After this peeling, there is a pressure-sensitive record and a pressure-resistance, for example,
(If you want to add more #, you can't do it, which is surprisingly inconvenient.

In addition, Japanese Patent Application Laid-Open No. 52-1s78111 includes (a)
A support with an IC adhesive layer provided thereon and (11) a transparent glass film fK41 with a layer of a photosensitive composition consisting of a diazo compound and a resin are combined to form a hole m.
Great-forming materials have been proposed. However, although this model has the advantage of being able to achieve the same image quality at the same time,
The selection range of the diazo compound and resin used is extremely narrow, and furthermore, the object to be transferred must be a special laminate as shown in the above-○, and the hole is formed using the above-mentioned O11 material and F.
In addition to Q, there are also disadvantages such as 11111 & (D and O images are not 1 in pressure sensitive recording.

The present inventors have developed a method for peeling tii that eliminates the above defects.
As a result of much research and consideration in order to produce in-forming materials, we found that a diazo compound, cassiller (coupling component) or leuco dye.

A photosensitive pressure-sensitive composition mainly consisting of a binder resin whose adhesive properties change with activation light 114C, and microencapsulating either the above-mentioned diazo compound or cassiller (or leuco dye). It was discovered that this can be achieved according to 7t-, and the present invention has been completed based on this knowledge.

That is, the diazo photosensitive pressure sensitive material of the present invention is a layer (photosensitive pressure sensitive layer) containing a diazo compound and a coupling component or a leuco dye as main components in a binder resin whose adhesion changes with actinic rays. It is characterized in that one of the above-mentioned diazo compounds and couplers (or leuco dyes) is microencapsulated and provided on a transparent support.

To explain the present invention in more detail below, even if the photosensitive pressure-sensitive layer provided on the transparent support is a single layer,
It doesn't matter if it consists of two layers. In the case of a single layer, both the diazo compound and the coupling component or leuco dye are combined with a binder resin whose adhesion changes depending on the active light edge (for convenience, this is sometimes referred to as a "heat-modified resin"). In the case of a two-layer type, a layer in which a diazo compound is dispersed in a heat-modified resin is formed on the KFi support side, and on top of that, a layer in which a diazo compound is dispersed in a heat-modified resin is formed. A layer in which the dyestuff is dispersed is formed.

As the diano compound used here, all those used in general diazo copying materials can be applied, and examples include 4-diazo-1-diethylannonese/, 4-diazo-1- diethyl annobenzene,
4-Diazo-1-dizolobylaminobenzene, 4-diazo-1-methylbenzylaminobenzene, 4-sia'/
-1--/”tnjiruadenpenzon, 4-diazo-1
-Ethyl human gastric xyethyl atonobenzene, 4-diazo-1-diethyl annor-3-methoxybenzene, 4-diazo-1-dimethyl 7</-! -Methylbenzene, 4-
Diazo-1-bensylylaino-2,8-jethoxy4
4-diazo-1-morpholino-29,5-jethoxybenzene, 4-diazo-1-morpholino-2,5-dibutoxybenzene, 4-diazo-1-morpholino-2,5-dibutoxybenzene, 4-diazo-1-morpholinobenzene Linobenzene, 4-diazo-1-dimethylannor-3-cardioxybenzene, 4
-diazo-11-tolylmercapto-2,5-diethoxybenzene, 4-diazo-1,4-methoxybenzene)-2,6-jethoxybenzene and other chlorides such as zinc chloride, caddonium chloride or tin chloride Double salts such as sulfuric acid, 4-fluorinated acid, or hexafluorophosphoric acid salts are used.

The diazo compound needs to be conjugated to a carbide compound if the coupling component or the leuco dye is not encapsulated.

On the other hand, examples of coupling components or leuco dyes include #i books. That is, the coupling components include resorcinol, phlorogluciol, 2,5-dimethyl-4-morpholinomethylphenol, 3-mono-droxycyanoacetairide, /92 sulfoacetanilide, l-beydiylannnor-8-hytruxinaphthalene. −
13゜6-cisulfonaphthalene, 2,2-dihydroxynaphthalene, 2,7-dihydro Shiimashina7talene-3,6-
Disulfo? Meng soda, 2,3-dihydroxy-6-sulfonic acid sodium, 2,5-dihydroxynaphthalene-6-
Sodium sulfonate, 1-human tetraxinaphthalene-4-sodium sulfonate, 1-amino-3-human sexinaphthalene-3,6-disulfonand, naphthol^a.

naphthol^8-D, 2-human tetraxinaphthalene 7-3-
1) guanide, 2-hydro-sinaphthoic acid morpholinozolovir alide, 2-hydroxyna 7) engineered acid ethanolate, 2-human-friendly xinaphthoic acid-N-dimethylannoprobil alide hydrochloride, 2. Examples include 2',4.4'-tetrahydroxydienyl, 2.2',4.4'-tetrahydrocydiphenyl sulfoxide, and the like.

For p-ico dyes a)) As a 9-phenylmethane type (hereinafter the margin λ b) As a fluorine-based product etc. are listed as representative examples.

If the diazo compound is not encapsulated, these coupling components or the diazo dye must be encapsulated.

Typical examples of heat-modified resins include butterfly, polyand, epoxy resin, and chloride C! Examples include 0 heat softenable IIi fats such as lylidene polyacetic acid-2, polyacrylic acid ester, etc., and the appropriate softening temperature of these is about 80 to ■s'c.

Whether you are encapsulating a diazo compound, a coupling component, or a pigment-based dye, there are many ways to encapsulate the gastric encapsulation method and I! Membrane material Ic
e: Conventionally known 0+1 stage and material (water-soluble wall covering) are used.

As a fM bright support carrying a photosensitive pressure sensitive layer, /9
・Resin films such as ester, poly, adze, polyolefin, ♂yl polymer, cell four, etc. can be opened. The appropriate thickness of this support is about 20 to 2'00μ, and since it only needs to be transparent, it should be colored by adding an appropriate amount of colorant (dye'4+). It doesn't matter if there is. Examples of the dyes include methylene blue, crystal/solet, rhodamine B, fuchsia, organic dyes, azo dyes, anthoquinone dyes, and the like.

To create the diazo photosensitive pressure sensitive material of the present invention,
Prepare a photosensitive pressure-sensitive layer forming solution and apply it with a doctor blade □
Apply with a wire brush, etc. and dry for about 5 to 2 hours.
A photosensitive pressure sensitive layer having a thickness of 0 μm may be provided. As mentioned above, the photosensitive pressure-sensitive layer may be formed as either a single-layer type or a two-layer type.

The appropriate amount of the diazo compound and the coupling component (or Roy's dye P#) in the photosensitive pressure sensitive layer is about 1 to 30 weight - 1 - 30 weight - 1 - 30 weight - of the latter to the entire layer. In addition, the ratio of the former (diazo compound) to the latter (coupling component or sulfate dye) is l:1-1:8.
Approximately 100% is appropriate.

In addition to the above-mentioned components, this photosensitive pressure-sensitive layer also includes the stability of the diazo-sensitive pressure-sensitive material, storage stability, improvement of image color saturation, prevention of discoloration and fading, improvement of brightness of copies, and coating. Citric acid, tartaric acid, oxalic acid, formic acid, isolic acid, and aluminum sulfate for the purpose of improving sexual performance.

Glauber's salt, zinc chloride, chloride! Gnesium, urea, thiourea,
Allylthiourea, naphthalene trisulfo/Il soda,
It is desirable to add glycerin, ethylene glycol, surfactant, etc. It is also desirable that an appropriate amount of a release agent (silicone resin, fluororesin, acrylic resin, etc.) be blended in order to improve releasability. Additionally, if a coupler is used, IIcIc
It is desirable that the photosensitive layer contains an alkali component (whether or not it coexists with the component to be ff-equalized).

Incidentally, as the solvent used for preparing the photosensitive pressure-sensitive layer forming liquid, organic solvents such as toluene, 1,2-dichloroethane, methanol, ethanol, methyl ethyl ketone, and benzene can be used.

In order to obtain a positive image or a negative ms using the diazo photosensitive pressure sensitive material of the present invention, a suitable transfer material such as plain paper, synthetic paper, cloth, etc. is brought into close contact with the photosensitive pressure sensitive layer, and the opposite side (diazo photosensitive pressure sensitive An original is placed on the transparent support side of the material - this original is preferably a transparent original, and may be placed away from the transparent support, but preferably in close contact with it - and then, after being irradiated with, for example, a Simply peel off the body and the diazo photosensitive pressure sensitive material and apply pressure to each of them.When the diazo photosensitive pressure sensitive material is a two-component diazo copying material and does not contain an alkali component in the photosensitive pressure sensitive layer. must be placed in an alkaline atmosphere.

The formation of the IIL image here can be considered as follows. First, when a light image is irradiated through the transparent support, the bonding force of the knee portion t of the photosensitive pressure sensitive layer with the transparent support is t9, and the bonding force with the transferred object is relatively large. As a result, the exposed portion is transferred to the transfer target. In this case, the bonding force between the diazo-photosensitive pressure-sensitive layer and the transparent support decreases at the same time that the heat-modified resin attached to the transparent support or in the vicinity changes its adhesion when exposed to actinic rays. In some cases, the non-microencapsulated diazo compound present in the vicinity of the transparent support decomposes and generates nitrogen scum, which is considered to be one of the primary contributors to the releasability.

In addition, in the light irradiation for forming 1ris, all the diazo compounds in the ζ region are decomposed and destroyed when the exposed portion hits, so it is necessary to select a uniform light source or an appropriate amount of exposure. To investigate this, the light source used here is one that emits visible or infrared light pI! use is desirable.

As mentioned above, even if the diazo compound is decomposed, the proportion of the diazo compound in the hole-sensitive pressure-sensitive layer transferred to the transfer object is small. Therefore, if this is passed between a pair of pressure rollers, etc., the capsule covering either the diazo compound or the coupling component (or leuco dye) will be destroyed, and these will react and A negative I11 image is formed. In the same manner, a positive image is formed on the original diazo-sensitive pressure-sensitive material.

As described above, buoyant M and F images can be easily obtained using the diazo photosensitive pressure-sensitive material of the present invention; In the same way as with pressure-sensitive paper, write on the transparent support side with, for example, an iron pen or l-pen to form a positive mark on the transfer target, or (2) prior to the pressure operation (however, If the above-mentioned additions are made (it doesn't matter what happens after the original), a hole-in-the-wall drawing and a negative image with karakami characters or added IIL patterns added can be obtained.

Next, 1 part 4 examples will be shown, where all 0 parts are parts by weight.

A mixture consisting of Example 1 was stirred and dispersed for 1 hour while maintaining the temperature at 20°C, and a polyester film (about 50 μm thick)
A diazo photosensitive pressure sensitive material was prepared by coating the mixture on a transparent support and drying with hot air at 30 to 50 η to form a photosensitive pressure sensitive layer having a thickness of 1O to SOμ.

Next, composite a (subject to be transferred) was brought into close contact with this photosensitive pressure-sensitive layer, and a transparent original or one-sided thin original was placed on the transparent support. The synthetic paper and the diazo-sensitive pressure-sensitive material were separated by irradiation for S seconds.

It was observed that the photosensitive pressure-sensitive layer 7 was partially transferred onto the peeled synthetic paper and was about to adhere.

When these were passed through a pair of pressure rolls of 3ul14/d, a black negative image was obtained on the synthetic paper and a black positive image was obtained on the polyester film. LiI payless in shadow forming operation.

When additional writing was performed on the polyester film without applying pressure, an additional image of Fi ink color was obtained on the synthetic paper.

Back Example 2 The mixture was stirred and dispersed for 1 hour while maintaining the temperature at 20°C.
A diazo photosensitive pressure sensitive material was prepared by coating the photosensitive layer on a transparent support (transparent support) and drying with 30 to 50'' Co hot air to form a photosensitive pressure sensitive layer having a thickness of 10 to 30 μm.

Next, a high-quality paper (subject to be transferred) was closely attached to this photosensitive pressure-sensitive Jl, and the marks were added with iron wire from above the transparent support, and then,
After attaching a thin original with a transmissive thickness or a transparent support to the transparent support, it was heated from the original side with a SOOW Φ Senon lamp for 4 hours.
The upper 1×I11 and the diazo-sensitive pressure-sensitive material were peeled off by irradiation for a second. It was observed that a partially transferred photosensitive pressure sensitive field was attached to the peeled high-quality paper.

When these were passed through a pair of pressure rows of 50~/- At, a black negative i corresponding to the original was deposited on the high-quality paper.
ii*, but the polyester film corresponds to the original and the next? A black I[
I got it.

In addition, in the above image forming operation, without applying image exposure and pressure, (D
7Jl Osamu, stop matata and 0ro, black additions on high quality paper *
*was gotten.

Claims (1)

[Claims] 1. A layer containing diazo compound # (&=min) and a coupling component or leuco dye (component b) as main components in a binder resin whose adhesive properties change from activity 11tc is placed on a transparent support. 9. A diazo photosensitive pressure sensitive material, characterized in that either one of the a component and the b component is encapsulated with a microphone.