JPH02171294A - Film for thermosensitive stencil and stencil paper - Google Patents

Abstract

PURPOSE:To increase the resolution of printed matter by providing a layer of specific silicon oil for preventing a sticking phenomenon on a surface where thermally plastic film comes in contact with a thermal head and preventing thermal fusion without reducing perforation sensitivity during plate manufacturing. CONSTITUTION:A layer for preventing a sticking phenomenon is formed which epoxy-modified silicon oil is used, as a constituent component, on a surface where film comes in contact with a thermal head. This film is thermally plastic film, preferably of copolymerized polyester but which substantially differs in quality. The epoxy-modified silicon oil used as a useful component should preferably be as outlined in (I). Thus the film becomes more resistive to a sticking phenomenon with a thermal head, and the high resolution of an image by thermosensitive stencil printing is ensured.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides J
:Relates to heat-sensitive stencil films and In (paper) suitable for making stencil blanks, and more specifically to extrusion, casting, etc.
IS/1. By providing a tL layer to prevent heat fusion with T I + without reducing the hole sensitivity during plate making, we have developed a film for thermal stencil printing and 1-kyo paper that improves the resolution of stamp 1111 objects. Related.

[Prior art] Digital plate making using a thermal head (hereinafter referred to as the TH method) and a method in which infrared rays or chilenon flash light is applied to the front side (hereinafter referred to as the flash method), which are methods of creating a heat-sensitive stencil original, are already well known. Are known.

In particular, compared to electrostatic copying (1 (C)), the T1-1 method is cheaper in printing costs (~) when producing a large number of copies, and is capable of high-speed printing. It is rapidly becoming popular in shops, etc. However, in the 1 yam 1 method, the head and the heat-sensitive stencil paper film (hereinafter abbreviated as ?l') are thermally fused together (a stick) and the perforated area is Problems such as enlargement and deformation of the print head (this causes the characters on the printed matter to become thick or blurred), as well as tearing and peeling of the film, have occurred. The surface temperature usually reaches about 300 to 500 °C within a few milliseconds, and as a result, the J'\Tsudo and film 6J1 almost always stick instantly.In this case, the head heats up. If heat fusion occurs in even a small part of the element, unlike the flash method, the head (heating part) and the film are constantly moving relative to each other, so the above-mentioned problems can occur. It happens.

Recently, high-speed plate making, low energy plate making, and high resolution!
For the purpose of slimming, films with improved perforation sensitivity (hereinafter referred to as high-sensitivity films) have been proposed (with
362-282983, etc.). A commercially available 1-Fl digital plate making machine uses a heat-sensitive stencil base paper made by laminating a commercially available crystallized polyester film of about 2 μTn (melting point: 245 to 260°C) and a porous support such as Kyokucho paper. (
Hereinafter, since the base paper (approximately 1) is used, the energy (perforation energy) applied to the paper 1-1 is specially increased as a means of achieving sufficient perforation. When you press base paper made with high-sensitivity film on a Hatake Energy plate-making machine like this, the stick is strong. A similar usage method has also been considered. One example is laminating a highly sensitive film with a porous support. A single thick film (about 5 μm or less) can be used as a printing base plate (base paper without a support). In that case, it is also possible to temporarily adhere the mount, make a plate using TI (for example, TH such as Word Brolly, Legal I Linter, etc.), and then peel it off to use as an original plate.In that case, if the stick problem is solved, The solid area caused by the support has a good feeling of dirt and scratches, and it is possible to perform high-quality medium-sized paper with the advantages of conventional paper. However, it has been confirmed that the thicker the film usually becomes, the more the heat fusion with the film tends to become stronger (see Japanese Patent Application Laid-Open No. 48398/1983).

For this reason, a large number of special accommodation applications have been filed to date that use the T-stick anti-L1 method as one of the targets. They are coated with fatty acid metal salts.
No. 1), one with an A-barcode layer of phosphate ester type surfactant (Special Publication No. 111-125897), and one with a silicone release layer (solid) (1).
4 (Japanese Patent Application Laid-Open No. 60-97891, etc.), a plate-making machine equipped with a means for applying a fluid lubricant such as silicone oil (Japanese Patent Application Laid-Open No. 60-1M068, 1983)
-30295) etc. However, the perforation sensitivity (
EC down I! It is not possible to form perforations that are close enough to produce high-crystalline printing. In addition, the heat-generating part of the TH gets dirty, and the stick prevention effect is unstable in terms of warp and +I, so the bank-like shape has not been able to give sufficiently satisfactory results.

Also, especially for high-sensitivity films ^] - Nerusen - (
No effective Sudic city prevention law has been found in areas with high temperatures.

[Problem to be solved by the invention] The problem of heat fusion when creating a heat-sensitive stencil plate is the problem of “1-1
method (between film-11 and 1), flash method (film rv<
TH) occur together. However, in the case of the flash method, there is no relative movement between the film and the document to be thermally fused, so even if there are some fusion points, they will peel off after cooling, so it is not a problem, but as mentioned above, T I- In method 1, heat fusion becomes a minor problem. In addition, the energy required for perforation (J/Jl) is generally said to be smaller in the 1-1 method than in the flash method, and the film is used to prevent sticking.
When a layer is provided, the perforation sensitivity of the film is greatly influenced by the material of the layer and its adhesion amount.

Therefore, it is of great practical importance to provide a small amount of stably preventive layer that can prevent the stick or the head from sticking to the stick without reducing the perforation sensitivity of the film.

Therefore, silicone oil is considered first, but although silicone oil shows high mold release properties and is stable against temperature, it is used as an agent to prevent sticking with the head during T I-I "A version". There are not many examples of this.

Silicone oil is generally liquid at room temperature, so if you apply it to base paper and store it in layers, it may cause damage to the type of paper (especially in the case of D-rolled base paper) or porous paper such as Tengucho paper. The silicone oil "transfers" to the adhesive support (Japanese Unexamined Patent Publication No. 61-29b098) and the stick prevention effect is reduced. For this reason, a method has been proposed in which a coating means 1i is provided in the plate making machine (Japanese Unexamined Patent Publication Nos. 63-30295).

In addition, as an example of using water-soluble silicone oil as a stick preventive agent, a comparative example in JP-A No. 131298/1983 in Specification Co., Ltd. shows that even when an ether-modified silicone oil is used in a polyester film, the stick preventive effect is sufficient. It is also confirmed that the anti-stick effect is not sufficient in Comparative Example 2 of the present application.

[Means and effects for solving the problem] As a result of intensive research aimed at solving the above-mentioned problem, the present inventors discovered that among silicone oils, a particular silicone oil exhibits a remarkable anti-stick effect. The present invention has been achieved.

That is, the present invention provides a film for heat-sensitive stencils which is made by a thermal head, characterized in that a stick prevention layer containing 1-boxy-modified silicone oil as a constituent is present where the film is in contact with the thermal head. In a heat-sensitive stencil sheet made by film and thermal head, the film is a laminate of a porous support, and the surface of the ilm in contact with the thermal head is coated with epoxy-modified silicone oil as a constituent component. It is a heat-sensitive stencil paper that is characterized by the presence of layers.

The film used in the present invention is a film formed by an extrusion method, a casting method, etc., and includes polyester (preferably copolymerized polynisder), nylon (preferably copolymerized nylon), polyolefin, polystyrene,
Examples include vinyl chloride-based, acrylic acid derivative-based, ethylene/vinyl alcohol-based, and polycarbonate-1/based copolymers. Preferably, the perforation feeling of the film is improved (one effect is that the thermoplastic resin constituting the film is substantially amorphous). It is preferable that the film has a crystallinity of up to 15%.More preferably, the film is at a substantially amorphous level.Here, the film at a substantially amorphous level means: ■When the raw material has a melting point that is barely visible even with the DSC method (when measured at a heating speed of 10℃/min); There are cases where crystallization is suppressed, etc. The former (■) is preferable.

The above degree of crystallinity is determined by the X-ray method, but in a simple manner, the density of the rimple with a fixed crystallinity of 121 is determined by the X-ray method, a calibration curve is obtained, and the density of the sample is measured. The degree of crystallinity may be determined by

Alternatively, it may be determined by the area ratio of dissolution energy using the DSC method.

The film is more preferably made mainly of copolymerized polyester, and is substantially amorphous. Most preferably, the copolyester as a raw material is substantially amorphous. Here, the term "substantially amorphous polyester" refers to commonly commercially available polyester with a crystalline melting point (according to the DSC method) of 2.
Unlike resins mainly composed of so-called high-crystalline polyethylene terephthalate, which is heated at 45 to 260°C, firstly, the raw materials are single polymers and mixed components J, polymers consisting of other polymers and mixed components, or polymers together. In the blended composition form, density method (density measurement is carried out according to JIS-71)
12), the degree of crystallinity is 10% or less, preferably 5% or less, and more preferably the melting point is hardly observed even by the DSC method. fruit? Firstly, amorphous polyester is selected from monomers constituting the polymer, such as terephthalic acid and its isomers, derivatives thereof, aliphatic dicarboxylic acids, derivatives thereof, etc. as acid components. Next, as a glycol (alcohol) component, ethylene glycol, its g4-isolated acid component (polyethylene glycol, etc.) is used.
, alkylene glycols (trimethylene glycol,
tetramethylene glycol, hekyrimedylene glycol, etc.>, aliphatic 11/i group saturated cyclic glycols (cyclobenzene di-A-l, Schiff[1-hexane dimetatool, cyclohexane dialkyl ols, etc.), It is prepared using one or more types of glycol components, such as diols having an aromatic ring, for example, a bisphenol nucleus.Preferably, at least an alcohol component of both components is used. Copolymerized products - (Yes. The following detailed preferred combination is to select terephthalic acid as the main acid component, and optionally contain a small amount (15 mol% or more of F) of isomers (isophthalic acid, phthalic acid). (Also, it may contain ethylene glycol and Schiff [1] as a flucol component. It is a polymerized mixture component mainly composed of hekylene dimethanol. More preferably, as an acid component, a mixture mainly composed of terephthalic acid as above. Choose one, and add ethylene glycol as the alcohol component and 1.4
- Schiff [1] Select one containing hexane dimetatool as the main component, and the ratio of the above two components forming a multi-component among the copolymerized alcohol components is 60
~80 mol%, 1,4-cyclohekyrindimetatool (CIIDM > 40-207 mol%, most preferably 64-75 mol% EG, 36-25 mol% CHDM, most preferably LG is 67-73 mol%, CI-
IDM is 33-27 mol%.

The thickness of the film used in the present invention is preferably 0.5 to 7 μm, more preferably 0.7 to 5 μm, when used by laminating porous supports such as curving paper or polyester gauze.
It is m. In addition, when using dot-shaped perforations that do not require a porous support due to ease of accumulation, simplicity, and high resolution, the workability, operability, and strength of the film, and the strength of the remaining part between the dots and the track etc., 5 to 15 μm, preferably 6 to 13 μm
, more preferably 8 to 1211TrL.

The porous support used in the present invention is made of natural fibers, recycled fibers, synthetic fibers, etc., which are permeable to printing ink and do not deform even when the film is perforated by heating. Thin paper, non-woven paper, woven paper, etc. are listed. In the case of non-woven thin paper, the ratio is 30 to 3 shi/end of eye 1 of 5, preferably 2()
-4 g/rd, more preferably 15-4 g/TIL. In the case of a mesh-like woven irotybe, the number of meshes is 500 to 15, preferably 300 to 50, and more preferably 2! ) O ~ 80 meshes,
An appropriate one may be selected depending on the resolution required for printing. Particularly preferred is a non-woven polyester porous support made of 0.5 to 5 denier polyester fibers, recycled cellulose fibers, or a mixture of both.

When the above-mentioned heat-sensitive stencil film and base paper are plate-made using a commercially available printing machine, a high-energy serial type used in facsimiles, etc., the film surface does not stick. If not treated, GI stick ring (heat melts) in most cases.
occurs.

As mentioned above, use the flash method! Heat fusion using the 3 method and heat fusion using the Tl-1 method cannot be handled in the same way. In the T I-1 method, the thermal element of the thermal head and the film move relative to each other under heating, so even the slightest fusion point can be a problem. Particularly in the present invention, a highly sensitive film is preferably used. Since the high-sensitivity film uses an amorphous or low-crystalline material, it tends to become sticky during perforation and melting, and the melted polymer tends to aggregate and form a lump, making it difficult to stick.

Furthermore, as mentioned above, the present invention also targets base paper that does not require a support, and because it does not use a porous support, it is sensitive to sticks on a 1:1 basis. Furthermore, as shown in (e) above, a porous support mainly composed of, for example, 0.5 to 5 denier polyester fibers is preferred in the present invention. In this case, as well as eliminating the need for the support, a clear printed matter can be obtained by pressing the printer without causing stickiness. However, the support is not stiff, and when stickiness occurs, the paper rips and the image becomes distorted), causing troubles such as paper jams in the plate-making machine. When using a high-speed film, C is not particularly necessary.

The present inventors investigated the production of a printing original plate (film perforation) using the -11-1 method and found the following important points: First, the stick prevention agent The material is spread thinly and handled, does not transfer during storage, does not bleed through during film processing, and does not get scraped during plate making. Secondly, it is necessary for the formation of the stick prevention layer to be effective with minimal hanging.

Based on the above findings, we arrived at the stick prevention method of the present invention. In the present invention, a king consisting of 7°1 of various materials in the high energy range to the low energy range]
-1 J: Sticking is prevented without reducing the perforation sensitivity of the film, and in order to improve pest control, the adhesive between the support and the film is prevented from decreasing, and the adhesive strength is reduced to the ultimate level. This is particularly effective in cases where the film is perforated accurately, and it is the first time that a base paper can be obtained that allows rapid plate making under +:%T energy. That is, a stick prevention layer containing a specific epoxy-modified silicone oil as a constituent is provided on the film surface in contact with -1.

The outline of the epoxy-modified silicone oil used in the present invention as an effective ingredient is shown in the following formula (1), but it is not limited to this and is listed as a preferred example.

(However, RG; L-CI-13 or IJ-0Ct-13
, Xham+n = 2-2000. ) The stick prevention effect of epoxy modified IJ1 silicone oil is much more effective than that of other silicone oils (for example, dimethyl silicone oil, -[-thyl modified silicone oil, higher fatty acid modified silicone oil, etc.). It is especially effective against polynisder type and ilm. The reason for this is not clear in detail, but the silicone oil has a strong adsorption property to fibers, coatings, etc., and the characteristics of the polymer that constitutes the film (1)
This, together with the surface characteristics of the film, etc., together with the above-mentioned ineffective property near the T I-1 perforation temperature, is thought to provide a remarkable stick prevention effect.

The viscosity of the epoxy-modified silicone oil is not particularly limited, but considering volatilization, tit, and thermal stability, the higher the molecular weight, the higher the molecular weight (therefore, m in the formula (I>),
n is also limited), so the viscosity is also limited. Mechanical slippage in the plate-making machine (bad slippage may distort the image,
Taking into account problems such as paper jams that occur when the base paper is not fed, the adhesive is classified into JIS K-2283 as C ((
The value measured at 1α is preferably 20 to 25°C at 25°C.
1,000,000 cs (Sendestokes), more preferably 50-20,000 cs, most preferably 100-10,0 OOC3.

The additive components that make up the stick prevention layer include:
(2) A substance that does not impair the stick prevention effect of the epoxy-modified silicone oil is selected, and more preferably one that prevents transfer, absorption into the film material, etc., and also enhances the stick prevention effect. That's fine.

These include, for example, solid fine particles (about 5 μm or less) such as silica, talc, carbon, graphite 1~, heptabutene compounds, inorganic substances such as mica, and fatty acids alone.
Surfactants, preferably nonionic surfactants, such as fatty acid Nisdels. Also, there are fine particles of fatty acid amide, resin, etc. (culm of less than 5 μm). In addition, antistatic agents, substances that improve heat transfer 71, and types of silicate:
1-one oil (e.g. 7/mino-modified silicone oil,
Mercapto modified ↑i [silicone oil, ether modified silicone oil, etc.] snow may be added.

Further, the stick prevention layer is a stick prevention layer containing epoxy-modified silicone oil as a constituent component, and preferably has a total weight of 0.0001 to 1.5 g/approx. The limit is the absolute amount of the epoxy-modified silicone oil, which is the active ingredient in the first bottle, and is at least 0.0
001 g/m. This applies even when diluted with the other components mentioned above, especially nonionic surfactants (for example, the upper limit of the dilution ratio is up to about 200 times). In addition, the above-mentioned eyes are limited by the stick prevention performance, stickiness, and decreased sensitivity due to heat being taken away, and generally 1.
It is about 57/77i. Although it varies somewhat depending on the size of the material 1/T that constitutes the stick prevention layer, it is preferably 0.001 to 0.5 g/'rIi, and more preferably 0.005 to 0.3 g/Td. . In short, it is sufficient that the film is uniformly covered with the epoxy-modified silicone oil without any defects or in spots that are effectively spread during plate making.

Furthermore, the method for forming the stick prevention layer includes coating.
There are methods such as spraying, kneading into the polymer constituting the film, bleeding transfer from other layers using coextrusion, adding it to the support side and transferring it to the film side in a roll state.

[Examples] Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto.

Examples 1 to 6 and Comparative Examples 1 to 10 Substantially amorphous copolyester (manufactured by Gose 1-Man Kodak Company, trade name: KODAROP E 1)
G6763 was extruded with a T-die to form a sheet, and the sheet was stretched biaxially at 90°C with a stretch i/- to a size of 3.5×3.5 to 2μ and 5°8.12.
A film of μ tiles was obtained. Among these, a thin paper (manufactured by wet method) mainly made of polyester and iaMt with a thickness of 111 g/m was laminated to a 2μ tile film using a methanol solution of vinyl acetate adhesive to make a heat-sensitive stencil paper. (Base paper A). In addition, the amount of adhesive adhered is 3 after drying.
The concentrations of the solutions were adjusted so that the ratio was 9/rIi, and each solution was used. In addition, for the 5, 8, and 12 μm films, we used 150-mesh polynisdel gauze as a mount for punching by rolling them together without using adhesive, and then peeled them off and used only the film as a base paper. I3, base paper C, base paper 1]
).

These base papers were coated with a solution shown in Table 1 using a wire bar to produce heat-sensitive stencil film and paper.
The film and base paper were evaluated. The second result is
Shown in the table. The R value method is as shown below.

(1) Stick rainproofing effect and evaluation of printed matter Each base paper treated as described above was tested using a personal word processor, Word Boy PW70 (manufactured by Xenon, 32 x 3
2-dot printing with 7 tricks and a printing speed of 8.5 characters/sec).
Printing was performed using a stencil printing machine, Risograph AI 7200 (manufactured by Riso Kagaku Kogyo Co., Ltd.) (maximum thermal head surface temperature is approximately 500°C).Printing patterns include numbers, hiragana, Consists of 126 special symbols (JIS size printing of 10.5 points) including kanji and solid parts, sticks occur within the total number of symbols, the holes widen, and the film is cracked, so when printed, the ink Count the number of symbols in which the black part has spread beyond the symbol glue size, and if the percentage of the symbol is less than 2%, it is considered a passing line, 2 to 5% is Δ (failure is below), and 5 to 8
0% was indicated as X, and 80% or more was indicated as XX. Also, if the printed matter is clear, it is O (the clearest one is ◎), if the holes are slightly enlarged and the printing is blurred and the nail brightness is reduced, it is Δ, if there are many sticks and the printed matter is unclear, or if the film is If the perforation was insufficient and the printed matter was difficult to read, it was rated X.

(2) Non-transferability 10 sheets of heat-sensitive stencil paper on which a stick prevention layer was formed as described above were stacked and a 50Ky/rIi sheet was placed on top of them at 35°C.
I left it for a week. After that, measure the lithic prevention effect using the method described above. ○ indicates that there is no change in the lithic preventive effect before and after leaving it, △ indicates that the effect has decreased somewhat, and × indicates that the effect has significantly decreased. And so. Iro,
Items that cause stickiness in 5% or more even before being left unused (
Evaluations of ×, ××: b) were not measured (
(indicated by - in Table 2).

In all Examples, clear printed matter was obtained, and in 11 examples, the non-transferability was also excellent. Especially base paper that does not require a support (base paper B, C, D)
Example 41516, which used the medium, had clear prints, and Examples 4 and 5, which used the medium, had the clearest prints.

As mentioned above, when using epoxy-modified silicone A-yl, it is effective even in a very small amount. 5, etc.), a marked effect is recognized.

Example 7 The above-mentioned KFlol was mixed with oleic acid heptanoglyceride
[σ] Vitamin Co., Ltd. Rikemar OL -100) is 1/1
It was diluted to 0.00 and evaluated by coating it on base paper A as in Examples 1 to 3 above. Coating rr; m is the weight after drying and is 0
．． It was 1g/Trt. As a result, the Sudik city prevention effect, printed matter and non-transferability were ioJ in total using the above-mentioned πf' (+fl+ method. Surprisingly, the epoxy modified 1 (1 series) -n It was effective as mentioned above when diluted to 100%. Also, a surfactant (such as Riquemar OL-100 shown in Example 7)
Not only is it easier to apply uniformly when 2 yen is coexisting, but even when the anti-stick agent is transferred to a porous support (for example, Tenkaicho paper, etc.), there is no phenomenon of repelling printing ink at all.
We were able to reduce the number of test prints.

(Hereinafter in the margin) [Effects of the Invention] According to the present invention, the stick resistance of the thermal head and film has been significantly improved, and it has become possible to achieve high resolution in thermal stencil printing. Further, the heat-sensitive stencil paper of the present invention can be used under a wide plate-making line (from high energy range to low energy range to low energy range, and high-speed plate making at high energy); It can be used for purposes such as unnecessary perforation, etc., and its uses can be expanded.Furthermore, it has many effects such as producing printed matter of higher quality than electrostatic copying (PPC).

Patent applicant Asahi Ka-Seikogyo Co., Ltd. teenager Reason Man

Claims (1)

[Scope of Claims] 1. A heat-sensitive stencil film made by a thermal head, characterized in that a stick prevention layer containing epoxy-modified silicone oil as a constituent is present on the surface of the film in contact with the thermal head. Heat-sensitive stencil film. 2. In a thermal stencil base paper made by a thermal head, a stick prevention layer containing epoxy-modified silicone oil as a constituent is present on the surface of the film in contact with the thermal head in a laminate consisting of a film and a porous support. A thermal stencil paper featuring the following.