JPS6140196A - Heat-sensitive stencil paper - Google Patents

Abstract

PURPOSE:To enable to obtain excellent perforability and releasability, by a method wherein a releasable layer provided on the surface of a heat-sensitive stencil paper is formed of a material in which solid or liquid fine particles are incorporated as dispersoid in a film of a thermosetting solicone or a thermoplastic silicone having a softening or melting point of not lower than 200 deg.C. CONSTITUTION:A thermoplastic film and a porous base are adhered to each other by an adhesive, and a coated layer of a releasing agent is provided on the surface of the film. A mixture of a thermosetting silicone or a thermoplastic silicone having a softening or melting point of not lower than 200 deg.C with a liquid or solid additive is used as the releasing agent. Since the liquid or solid additive is dispersed in the coated silicone film, the tensile strength and elongation of the silicone film are extremely low, resulting in that the silicone film is broken or perforated by the heat generated from an original or by a breaking force generated when the thermoplastic film is melted or contracted by the heat. Accordingly, a heat-sensitive stencil paper having excellent releasability and perforability can be obtained. In addition, since the amount of the releasing agent applied can be increased, excellent releasability can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a heat-sensitive stencil paper, and more particularly to a heat-sensitive stencil paper that is excellent in both perforation and releasability.

(Prior Art) Conventionally, when making a plate using heat-sensitive stencil paper, the original and the film surface of the heat-sensitive stencil paper are brought into close contact, and infrared rays or xenon flash light is applied from the porous support side of the heat-sensitive stencil paper. is irradiated to generate heat in the black image area of the original, the film of the heat-sensitive stencil paper is melted and perforated by the heat, and then the original and the heat-sensitive stencil paper are separated.

When perforating the film of the heat-sensitive stencil paper by heat,
There is a drawback that the film and the original are fused together, and when they are peeled off, the film is damaged or the original is damaged. In order to prevent these drawbacks, a release agent is applied to the surface of the film that contacts the original to make it easier to separate the film from the original. As such a release agent, for example, water-soluble silicone oil is known (Japanese Unexamined Patent Publication No. 58-92595), but since such silicone oil does not form a film, its performance as a release agent is poor. Heat-sensitive stencil paper that uses silicone oil as a release agent is used because when the film surface of the base paper is touched by hand, the silicone oil falls off and the releasability of that area deteriorates, and the document and silicone oil come into direct contact. , it also has the disadvantage of contaminating the manuscript.

On the other hand, thermoplastic silicone, which softens and melts at low temperatures (below 200°C), has also been used as a release agent (Japanese Patent Publication No. 30570/1982), but in this case, the film softens due to the heat generated from the original. Since the silicone is melted and in direct contact with the original, it easily adheres to the original, and the softened and molten silicone rapidly cools and solidifies between the original and the film surface, resulting in poor releasability.

On the other hand, room temperature curing type (thermosetting type) silicone (silicone resin or silicone rubber) has also been used as a release agent (Japanese Patent Laid-Open No. 153697/1983).

This silicone is extremely resistant to heat and does not easily soften or melt due to heat, but it does thermally decompose above a certain temperature, and when thermosetting silicone is used as a release agent for heat-sensitive stencil paper, the coating amount If there is a lot of heat generated from the original, the thermosetting silicone will not completely decompose, and in this case, silicone resin has high tensile strength and silicone rubber has a large elongation, so the heat generated from the original will cause the thermosetting silicone to decompose completely. The silicone coating will not be torn by the destructive force generated when the plastic film is thermally melted or thermally shrunk.
As a result, there is a drawback that the perforability becomes very poor.

For this reason, when conventionally using thermosetting silicone, an extremely thin silicone film must be formed.
This causes serious problems in that the releasability is poor and coating spots are likely to occur.

As detailed above, a heat-sensitive stencil paper coated with a release agent that is excellent in both perforation and releasability has not yet been obtained.

(Problems to be Solved by the Invention) An object of the present invention is to eliminate the drawbacks of the above-mentioned prior art and provide a heat-sensitive stencil paper coated with a silicone release agent that has excellent perforation and release properties. It's about doing.

(Means for Solving the Problems) In order to achieve the above object, the present inventors have conducted various studies and found that by dispersing liquid or solid additives into a silicone film, the perforation and releasability can be improved. The present invention was achieved by discovering that an excellent heat-sensitive stencil paper can be obtained.

The present invention relates to a heat-sensitive stencil paper in which a thermoplastic film and a porous support are bonded together using an adhesive, and a release agent coated layer is provided on the surface of the film, using thermosetting silicone or This heat-sensitive stencil paper is characterized by having a release agent coated layer in which solid or fluid fine particles are formed as a dispersion in a thermoplastic silicone coating.

Examples of the thermoplastic film used in the present invention include films of polyester, polypropylene, vinylidene chloride-vinyl chloride copolymer, and the like.

As the porous support, for example, porous thin paper mainly made of natural fibers such as Manila hemp, kozo, and mitsumata, synthetic fibers such as polyester, polyvinyl alcohol, and polyacrylonitrile, and semi-synthetic fibers such as rayon is used.

Adhesives include vinyl acetate resin, acrylic resin,
Polyester resin or the like is used.

In the present invention, thermosetting silicone or
A mixture containing a thermoplastic silicone that softens and melts as described above and a liquid or solid additive is used as a release agent.

Additives used in the present invention include waxes, silicone oils, surfactants, higher fatty acid esters such as dioctyl phthalate, and higher aliphatic alcohols such as isostearyl alcohol and stearyl alcohol.

Examples of surfactants include sorbitan fatty acid esters, glycerin or polyglycerin fatty acid esters,
Propylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, ethylene oxide derivative of glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether,
Examples include polyoxyethylene alkyl phenyl ether, polyoxyethylene castor oil or hydrogenated castor oil derivatives, amine or amide derivatives, and the like.

The mixing ratio of these additives is preferably 0.5 to 50% by weight, particularly 1 to 40% by weight, based on the solid content of the silicone.

The release agent used in the present invention can be obtained by dissolving or dispersing the silicone and the additive in an organic solvent, or directly mixing or dispersing the silicone in the silicone.

As the organic solvent, for example, toluene, n-hexane, methyl ethyl ketone, etc. are used.

When producing the heat-sensitive stencil paper of the present invention, it is desirable to bond the thermoplastic film and the porous support together with an adhesive and dry them, and then apply a release agent to the surface of the film. A release agent may be applied during or after molding the film, and the film may be bonded to a porous support.

The amount of release agent applied is usually 0.05 to 0.5g dry weight.
/nf (thickness approximately 0.05 to 0.5μ).

(Effects of the Invention) In the present invention, since liquid or solid additives are dispersed in the silicone film, the tensile strength and elongation of the silicone film are extremely weak, and as a result, heat generated from the original and The silicone coating is easily broken and perforated by the destructive force generated when the thermoplastic film is melted or shrunk by nuclear heat, making it possible to obtain a heat-sensitive stencil paper with excellent releasability and perforation properties. Furthermore, since the amount of the release agent applied can be increased, excellent releasability can also be obtained.

(Example) Example 1 Vinyl acetate resin (product name Bond KE150, Konishi (
Co., Ltd.) was dissolved in methyl ethyl ketone, and the solid content concentration was 1.
A 0% adhesive solution was prepared. Using this adhesive solution, a polyester film with a thickness of 2μ and a weight of 9.3g/n
A heat-sensitive stencil paper was prepared by laminating the film with thin paper made of Manila hemp.

Separately, silicone rubber (product name: Toray Silicone Rubber S)
E5004, manufactured by Toray Silicone Co., Ltd.) and 0.5 parts of wax (trade name: Hoechstwa Nox OP, manufactured by Hoechst Co., Ltd.) were added to a mixed solution of 30 parts of toluene and 67 parts of n-hexane. A release agent was prepared by melting.

Next, the release agent was applied onto the surface of the polyester film of the heat-sensitive stencil paper using a wire bar, the solvent was dried at 50° C., and the mixture was left at room temperature for 3 days to obtain the heat-sensitive stencil paper of the present invention. When the coating amount of the release layer was measured, it was 0.
．． It was 3g/nl.

The obtained heat-sensitive stencil paper was overlapped with an off-cent printing manuscript and plate-made using a heat-sensitive stencil making machine (trade name: RISOGRAPH FX7200, manufactured by Riso Kagaku Kogyo Co., Ltd.) at a normal manuscript scale of 2.

Next, when the original and the heat-sensitive stencil paper were peeled off, there was little resistance during peeling, and the original could be easily peeled off without damaging the original.

Further, when printing was performed using a stencil printing machine (trade name: Risograph AP7200, manufactured by Riso Kagaku Kogyo Co., Ltd.), a printed matter with a clear image was obtained. These results are shown in Table 1.

Example 2 Silicone rubber (product name Shin-Etsu Silicone KE348T
, manufactured by Shin-Etsu Chemical Co., Ltd.) and 1 part of a surfactant (trade name: Niracol BC-40, manufactured by Nippon Surfactant Co., Ltd.), 30 parts of toluene and 67% n-hexane.
A stripping agent was prepared by dissolving it in a mixed solution of 1.

Next, the release agent was applied with a wire bar onto the polyester film surface of the heat-sensitive stencil paper prepared in Example 1, the solvent was dried at 50°C, and the heat-sensitive stencil paper of the present invention was left at room temperature for 3 days. I got it.

When the coating amount of the release layer was measured, it was 0.31 g/-.

The obtained heat-sensitive stencil paper was overlapped with the off-cent printing manuscript and then passed through a heat-sensitive stencil maker (product name: RISOGRAPH FX7200,
When we peeled off the heat-sensitive stencil paper from a 0-order manuscript made by Riso Kagaku Kogyo Co., Ltd. on a regular manuscript scale of 2, there was little resistance during peeling, and the manuscript was not damaged.
It could be easily peeled off.

Further, when printing was performed using a stencil printing machine (trade name: Risograph AP7200, manufactured by Riso Kagaku Kogyo Co., Ltd.), a printed matter with a clear image was obtained. These results are shown in Table 1.

Example 3 Silicone rubber (product name Toray silicone rubber SE9)
140, manufactured by Toray Silicone Co., Ltd.) 2° 5 parts and silicone oil (trade name Toray Silicone Oil 5H)
200, )-manufactured by Resilicone Co., Ltd.) was mixed to prepare a release agent.

Next, the release agent was applied onto the polyester film surface of the heat-sensitive stencil paper prepared in Example 1 using a roll coater, and the mixture was left at room temperature for 3 days to obtain the heat-sensitive stencil paper of the present invention. When the coating amount of the release layer was measured, it was 0.4 g.
/ af.

The obtained heat-sensitive stencil paper is superimposed on the PPC copy original and heat-sensitive stencil making IIl & (product name: Risograph FX720
0, manufactured by Riso Kagaku Kogyo Co., Ltd.) with a PPC scale of 2. Next, when the original and the heat-sensitive stencil paper were peeled off,
There was little resistance during peeling, and the original could be easily peeled off without damaging it.

Further, when printing was performed using a stencil printing machine (trade name: RISOGRAPH AP?200, manufactured by Riso Kagaku Kogyo Co., Ltd.), a print with a clear image was obtained. These results are shown in Table 1.

Example 4 Silicone rubber (product name Toshiba Silicone TSE37O)
RTV, Toshiba Shi IJ Corn (K) IJ) 2.5 parts and dioctyl butarate 0.5 part, toluene 30
A stripping agent was prepared by dissolving it in a mixed solution of 1 part and 67 parts of n-hexane.

Next, the release agent was applied with a wire bar onto the polyester film surface of the heat-sensitive stencil paper prepared in Example 1, the solvent was dried at 50°C, and the heat-sensitive stencil paper of the present invention was left at room temperature for 3 days. I got it.

When the coating amount of the release layer was measured, it was 0.25 g/-.

The obtained heat-sensitive stencil paper was overlapped with the original for offset printing using a heat-sensitive stencil maker (product name: RISOGRAPH FX7200J).
The plate was made by Riso Kagaku Kogyo Co., Ltd. on a normal manuscript scale of 2. Next, when the original and the heat-sensitive stencil paper were peeled off, there was little resistance during peeling (and the original was not damaged;
It could be easily peeled off.

Further, when printing was performed using a stencil printing machine (trade name: Risograph AP7200, manufactured by Riso Kagaku Kogyo Co., Ltd.), a printed matter with a clear image was obtained. These results are shown in Table 1.

Example 5 Silicone resin (trade name: Torre Silicone Resin 5)
A release agent was prepared by dissolving 14.5 parts of R2410 (manufactured by Toray Silicone Co., Ltd.) and 0.1 part of isostearyl alcohol in 85.4 parts of methyl ethyl ketone.

Next, the release agent was applied onto the polyester film surface of the heat-sensitive stencil paper prepared in Example 1 using a wire bar, the solvent was dried at 50°C, and the heat-sensitive stencil paper of the present invention was left at room temperature for 3 days. I got the original paper. The coating amount of the release layer was measured and was 0.31 g/cd.

The obtained heat-sensitive stencil paper was overlapped with the original for offset printing, and a heat-sensitive stencil maker (product name: RISOGRAPH FX7200,
The plate was made by Riso Kagaku Kogyo Co., Ltd. on a normal manuscript scale of 2. Next, when the original and the heat-sensitive stencil paper were peeled off, there was little resistance during peeling, and the original was not damaged.
It could be easily peeled off.

Further, when printing was performed using a stencil printing machine (trade name: Risograph AP7200, manufactured by Riso Kagaku Kogyo Co., Ltd.), a printed matter with a clear image was obtained. These results are shown in Table 1.

Example 6 Silicone rubber (trade name Toray Silicone Rubber SF:
5004, manufactured by Toray Silicone Co., Ltd.) 1 part, silicone resin (trade name: Toray Silicone Resin 5R240)
2. Manufactured by Toray Silicone Co., Ltd.) 1. A release agent was prepared by dissolving 0.0075 parts of LFB, a silicone resin catalyst (trade name Q-1-2407, manufactured by Toray Silicone Co., Ltd.) and 0.5 parts of isostearyl alcohol in 97 parts of n-hexane. did.

Next, the release agent was applied with a wire bar onto the polyester film surface of the heat-sensitive stencil paper prepared in Example 1, the solvent was dried at 50°C, and the heat-sensitive stencil paper of the present invention was left at room temperature for 3 days. I got it. The coating amount of the release layer was measured and was 0.3 g/d.

The obtained heat-sensitive stencil paper was overlapped with the original manuscript, and a plate was made with a heat-sensitive stencil maker (product name: Risograph FX7200, manufactured by Riso Kagaku Kogyo Co., Ltd.) with a normal manuscript opening of 1ik2.
Next, when the original and the heat-sensitive stencil paper were peeled off, there was little resistance during peeling, and the original could be easily peeled off without damaging the original.

Further, when printing was performed using a stencil printing machine (trade name: RISOGRAPH AP?200, manufactured by Riso Kagaku Kogyo Co., Ltd.), a print with a clear image was obtained. These results are shown in Table 1.

Example 7 0.5 part of stearyl alcohol was used instead of 0.5 part of Hoechstowasox OP, 97 parts of n-hexane was used as the solvent, and the process was otherwise carried out in the same manner as in Example 1 to obtain a coating amount of the release layer of 0. A heat-sensitive stencil paper of the present invention having a weight of .32 g/cd was obtained.

Table 1 shows the results of plate making and printing using the obtained heat-sensitive stencil paper in the same manner as in Example 1.

Comparative Example 1 (a) A release agent was prepared by dissolving 0.5 parts of silicone rubber (trade name: Toray Silicone Rubber SE5004, manufactured by Toray Silicone Co., Ltd.) in 99.5 parts of n-hexane.

(b) 1 part of silicone rubber (trade name: Toray Silicone Rubber SE5004, manufactured by Toray Silicone Co., Ltd.)
A stripping agent was prepared by dissolving it in 99 parts of hexane.

(e) 2 parts of silicone rubber (trade name: Toray Silicone Rubber 5E5004, manufactured by Toray Silicone Co., Ltd.)
A release agent was prepared by dissolving it in 98 parts of hexane.

Next, each of the release agents (a) to (e) was applied with a wire bar onto the polyester film surface of the heat-sensitive stencil paper prepared in Example 1, the solvent was dried at 50°C, and the mixture was left at room temperature for 3 days. did.

When the coating amount of the release layer was measured, it was 0.04 g/nl and 0.1 g/nl in the order of (a), (b) and (C), respectively.
ivy at rrr and 0.19g/ffr.

These heat-sensitive stencil sheets were overlapped with the original manuscript, and a normal manuscript opening was created using a heat-sensitive stencil maker (product name: RISOGRAPH FX7200, manufactured by Riso Kagaku Kogyo Co., Ltd.). The plate was made in 2.

Next, when the original and the heat-sensitive stencil paper were peeled off, there was considerable resistance when the original was peeled off with coating amounts of o, o4g, and /rrrO, and in some cases, the original was peeled off or the base paper was damaged.

Also, the coating amount is 0.1g/n (and 0.19g/rrr
However, with the stencil printing machine (product name: RISOGRAPH FX72
00 (manufactured by Riso Kagaku Kogyo Co., Ltd.), there was some blemish in the printed image, and especially when the coating amount was 0.19 g/rd, it was impossible to read fine letters. These results are shown in Table 1.

Comparative Example 2 (a) A release agent was prepared by dissolving 5 parts of silicone resin (trade name: Toray Silicone Resin 5R2410, manufactured by Toray Silicone Co., Ltd.) in 95 parts of methyl ethyl ketone.

(b) A release agent was prepared by dissolving 10 parts of silicone resin (trade name: Toray Silicone Resin 5R2410, manufactured by Toray Silicone Co., Ltd.) in 90 parts of methyl ethyl ketone.

(C) A release agent was prepared by dissolving 15 parts of silicone resin (trade name: Toray Silicone Resin 5R2410, manufactured by Toray Silicone Co., Ltd.) in 85 parts of methyl ethyl ketone.

Next, each of the # layer agents (a) to (C) was applied using a wire bar onto the polyester film surface of the heat-sensitive stencil paper prepared in Example 1, the solvent was dried at 50°C, and the mixture was left at room temperature for 3 days. I left it alone.

When the coating amount of the release layer was measured, it was found that <a>, (b) and (C) were each 0.1 g/n? in that order. ,0.19g/
The resistance was 0.3 g/rrr.

These heat-sensitive stencil sheets were superimposed on the original manuscript, and a plate was made using a heat-sensitive stencil maker (trade name: RISOGRAPH FX7200, manufactured by Riso Kagaku Kogyo Co., Ltd.) at a normal manuscript scale of 2. Next, when the original and the heat-sensitive stencil paper were peeled off, there was considerable resistance at the time of peeling when the coating amount was 0.1 g/rrr, and in some cases, the original was peeled off or the base paper was damaged.

Also, the coating amount is 0.19g/n? and 0.3 g/
With the RD version, there was little resistance when peeling off, and it was easily peeled off, but it was
7200 (manufactured by Riso Kagaku Kogyo Co., Ltd.), blemishes occurred in the printed image, especially when the coating amount was 0.19 g/n.
In the case of f, it was impossible to read the rope characters. These results are shown in Table 1.

Margin below Table 1 1st courtesy call)

Claims (2)

[Claims] (1) In a heat-sensitive stencil paper in which a thermoplastic film and a porous support are bonded together with an adhesive, and a release agent coated layer is provided on the surface of the film, thermosetting silicone or thermosetting silicone is used, which softens and melts at 200°C or higher. 1. A heat-sensitive stencil paper having a release agent coated layer in which solid or fluid fine particles are formed as a dispersion in a thermoplastic silicone coating. (2) The heat-sensitive stencil paper according to claim 1, wherein the fine particles are at least one selected from wax, silicone oil, surfactant, higher aliphatic alcohol, and higher fatty acid ester.