JPH01150582A - Thermal stencil paper and its production - Google Patents

Abstract

PURPOSE:To inexpensively and easily obtain base paper capable of preventing sticking to a thermal head and developing excellent printing durability at the time of printing, by forming a resin layer from a polymerization product of a thermoplastic resin containing an addition polymerizable monomer. CONSTITUTION:In thermal stencil paper wherein a thermoplastic resin layer 2 is laminated to one surface of a support 1, the resin layer 2 is composed of a polymerization product of a thermoplastic resin containing an addition prolymerizable monomer. The thermoplastic resin layer 2 containing the addition polymerizable monomer is formed to the surface of a surface smooth film 3 and the porous support 1 is laminated to the surface of the resin layer 2 and, after the polymerization of the monomer, the surface smooth film 3 is released to prepare thermal stencil paper. The addition polymerizable monomer is pref. used in a ratio of about 5-30pts.wt. per 100pts.wt. of the thermoplastic resin and, when the amount of the monomer is below the range of about 5-30pts.wt., it is difficult to achieve the purpose and, when said amount exceeds said range, the thermal perforation of the resin layer is lowered. The support can be sufficiently bonded to the thermoplastic resin layer and the sticking to the thermal head is prevented by adding a surfactant to make it possible to omit the formation of a sticking preventing layer.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a thermal mimeograph base paper and a method for producing the same, and more specifically, an object of the present invention is to provide a high-performance thermal mimeograph base paper and an economical method for producing the same.

(Prior Art) Conventionally, mimeograph printing has been widely used as a simple printing method, and this method uses a thermoplastic film layer laminated on the surface of a suitable support such as paper as a heat-sensitive mimeograph base paper. Printing is performed using a thermal head or the like, the thermoplastic film layer is heated and melted to form image-shaped perforations, and printing is performed on a printing material such as paper by passing printing ink from the support side.

(Problem to be solved by the invention) The thermal mimeograph base paper used in the conventional thermal mimeographing method described above is generally made by laminating a thin thermoplastic film layer of several micrometers on the surface of a porous support such as paper using an adhesive or the like. It is formed by
There are the following problems.

(1) Since the adhesive layer is also required to be thermoplastic so that it can be perforated by heat, strong adhesives such as thermosetting adhesives cannot be used, and therefore sufficient adhesive strength cannot be obtained. or,
For the same reason, during printing, the adhesive strength is reduced by the solvent components in the printing ink, and the thermoplastic film layer is peeled off by a thermal head etc., resulting in printing defects and other printing durability problems.

(2) Since an organic solvent solution or emulsion of a thermoplastic resin is usually used as the adhesive, a drying process and an aging process are required, resulting in high process costs.

(3) As a result of using a porous material such as paper as a support, when the adhesive pressure is increased to sufficiently adhere the two, the surface irregularities of this porous material are transferred to the surface of the thin thermoplastic film layer, and printing Sometimes, the uneven shape causes non-uniformity of the image.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to overcome the above-mentioned drawbacks and to economically provide an excellent heat-sensitive mimeograph base paper.

(Means for solving problems) The above objects of the present invention are achieved by the following present invention.

That is, the present invention consists of two inventions, the first of which is a heat-sensitive mimeograph base paper comprising a thermoplastic resin layer laminated on one side of a porous support, the resin layer comprising a tetrapolymerizable monomer. A second invention is a heat-sensitive mimeograph base paper characterized by being made of a polymerization product of a thermoplastic resin containing:
Forming a thermoplastic resin layer containing an addition polymerizable polymer on the surface of a film with a smooth surface, laminating a porous support on the surface of the resin layer, and peeling off the smooth surface film after polymerizing the monomer. This is a method for producing a thermal mimeograph base paper characterized by the following.

(Function) By forming the thermoplastic resin layer of the heat-sensitive mimeograph base paper from a thermoplastic resin containing an addition-polymerizable monomer, the support and the thermoplastic resin layer can be sufficiently adhered to each other without providing an adhesive layer. In a preferred embodiment, by including a surfactant in the resin layer, it is possible to prevent adhesion of thermal heads, etc., without providing a separate anti-adhesion layer, and it is possible to produce base paper that exhibits excellent printing durability during printing at low cost and easily. can be provided to

(Preferred Embodiments) Next, the present invention will be described in more detail by citing preferred embodiments.

FIG. 1 is a diagram schematically showing a cross section of a heat-sensitive mimeograph base paper according to the first aspect of the present invention, and FIGS. Yes, 5th
The figure shows another embodiment of the thermal mimeograph base paper of the present invention.

As shown in the first figure, the thermal mimeograph base paper of the first aspect of the present invention has a thermoplastic resin layer 2 laminated on one side of a support 1. The second invention is characterized in that it is made of a polymerized product of a thermoplastic resin containing a thermoplastic resin, and the second invention is characterized in that it is made of a polymerized product of a thermoplastic resin containing a thermoplastic resin, as shown in FIGS. 2 to 4. Forming the plastic resin layer 2 (Fig. 2), the resin layer 2
The porous support 1 is laminated on the surface (Fig. 3), and after the monomer is polymerized, the surface smooth film 3 is peeled off (Fig. 4).

The support 1 used in the present invention needs to be porous so that the printing ink used during printing can pass through it, and examples include various types of paper, especially coarse paper such as Japanese paper, rayon, vinyl , synthetic paper made of chemical fibers such as polyester, acrylonitrile, and mixed paper of chemical fibers and natural fibers, etc., which are used as supports for conventional heat-sensitive mimeograph base paper, can be used in the present invention, and are not particularly limited. For example, paper, synthetic paper, mixed paper, etc. having a basis weight of about 8 to 12 g/rn' are advantageously used.

The thermoplastic resin layer 2 laminated on the surface of the support 1 is, for example, polyvinyl chloride, vinyl chloride-vinylidene chloride copolymer, polyester, polyolefin such as polyethylene or polypropylene, polystyrene, or polyvinyl acetate. , ethylene-vinyl acetate copolymer system, chlorinated polypropylene system, polyacrylic acid ester system, terpene system, coumaron system, indene system, SBR, ABS, polyvinyl ether system, polyurethane system, polyvinyl butyral, acetal system such as polyvinyl acetal, and This layer is made by adding an addition polymerizable monomer to a thermoplastic resin such as a cellulose derivative resin and polymerizing it.

Examples of addition-polymerizable monomers include (meth)acrylic esters, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, vinyl heterocyclic compounds, N-vinyl compounds, styrene, (meth)acrylic acid, Monofunctional monomers such as crotonic acid and itaconic acid; for example, diethylene glycol di(meth)acrylate,
Triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Tris[β
-(meth)acryloyloxyethyl] isocyanurate and other difunctional or higher functional compounds, and the like. If these polyfunctional monomers are used in large amounts, the resin layer will become highly crosslinked and the thermal perforability of the resin layer will decrease, so they should not be used in large amounts. When used in a small amount, for example, 10% by weight or less, preferably 5% by weight or less in Kaneko Tsumar, excellent adhesion to the support and printing durability can be achieved without interfering with the thermal perforability of the resin layer. be able to.

The addition polymerizable monomer as described above is preferably used in a proportion of about 5 to 30 parts by weight per 100 parts by weight of the thermoplastic resin.If the amount is less than the above range, it will be difficult to achieve the purpose of the present invention; If the Ilt exceeds 100%, the thermal perforability of the resin layer decreases, which is not preferable.

Furthermore, in addition to the above components, wax-based polymers and oligomers with relatively low melting points, such as polyethylene glycol, polypropylene glycol, paraffin, aliphatic polyester, and rosettes, are added to improve the heat-melting properties of the formed resin layer. Brex, polyethylene sebacate,
It is also preferable to add polyethylene adipate etc.
These waxes can also be used in place of the above thermoplastic resin.

Furthermore, in the present invention, a small amount of a known chain transfer agent such as a mercaptan compound is added to the resin layer to control the increase in molecular weight or crosslinking during curing of the resin layer, and to control the crosslinking of the resin layer after curing. Good thermal perforability can also be maintained.

In addition, surfactants such as lithium, potassium, sodium, and calcium such as stearic acid, palmitic acid, lauric acid, and oleic acid are added to prevent the above-mentioned resin layer from sticking to the thermal head, etc., and to improve slipperiness. , fatty acid metal salts such as metal salts such as barium and aluminum, phosphate ester type surfactants, polyoxyethylene type surfactants, mono- and dialkyl phosphates, tri(polyoxyethylene alkyl ether) phosphates, etc. A surfactant may be added in an amount of about 0 to 70 parts by weight per 100 parts by weight of the resin. Further, by adding such a surfactant, the releasability of the surface-smooth film 3 in the manufacturing method of the present invention, which will be described later, is also improved, which is preferable.

The thermoplastic resin layer 2 made of the above components has a thickness of 20 μm or less, preferably 10 μm or less, and optimally 1 to 5 μm so that perforations can be easily formed by heating means such as a thermal head. be.

Next, a preferred method for producing the heat-sensitive mimeograph base paper of the present invention will be described.

In the manufacturing method of the present invention, as a first step, as shown in the second figure, a resin layer 2 is formed on the surface of a film 3 having a smooth surface using a thermoplastic resin containing the above-mentioned addition polymerizable monomer. The resin layer 2 may be formed by extrusion coating of a thermoplastic resin containing 1,000 ml or by laminating a film made of these resins, but the preferred method is to prepare a coating solution containing the necessary components using an appropriate solvent and apply it. This is a method of engineering. As the solvent, any conventionally known ink or paint solvent such as methyl ethyl ketone, toluene, xylene, etc. can be used. Further, the solid content of the coating liquid is preferably about 5 to 30% by weight in consideration of coating properties.

The application methods themselves include blade coating method, gravure coating method, knife coating method, reverse roll coating method, spray coating method,
Any method such as an offset gravure coating method or a kiss coating method may be used, and is not particularly limited.

If the coating amount is too large, the thermal perforation property during plate making will deteriorate, and if it is too small, a problem will arise in uniformity, so it is preferable to use an amount that produces a film thickness within the above-mentioned range.

The surface smooth film 3 used above is polyethylene,
Any conventionally known plastic film such as polypropylene, polyvinyl chloride, polyester, polyamide, cellophane, etc. can be used as is, and since these films are temporary carriers for the resin layer 2, the thickness may be arbitrary, but - in terms of number. The thickness is 10 to 100 μm. Incidentally, it is also preferable that the surfaces of these films 3 are subjected to a peeling treatment in advance.

In the present invention, the resin layer 2 is formed on the film 5 by the method described above, and after the solvent is evaporated, the support 1 is laminated on the surface thereof. At this time, since the resin layer 2 is in an uncured state, the two adhere well.

After adhering the support 1, the addition polymerizable monomer in the resin layer is polymerized. The polymerization method may be thermal polymerization, but it is preferably carried out using ionizing radiation.

As the ionizing radiation used, electron beams and ultraviolet rays are preferably used, but when ultraviolet rays are used, it is necessary to incorporate a photopolymerization initiator into the resin layer.

When using an electron beam, the electron beam may be irradiated from any part of the laminate, and when using ultraviolet rays, at least one of the support 1 and the film 3 should be transparent. is necessary, and irradiates from the transparent side.

Conventional techniques can be used as is for radiation irradiation; for example,
In the case of electron beam curing, it is emitted from various electron beam accelerators such as Kotscroft-Walton type, Bumpgraph type, resonant transformer type, insulated core transformer type, linear type, electrocurtain type, Dynamidron type, and high frequency type. An electron beam or the like having an energy of 50 to 1,000 ev, preferably 100 to 300 KeV is used, and in the case of ultraviolet curing, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, etc. are used. Ultraviolet light emitted from a light source is used.

Although any irradiation method is useful in the present invention, electron beam irradiation is more preferred for reasons such as the curing speed of the resin layer and the adhesiveness of the resin layer.

After polymerizing the monomer in the resin layer 2 as described above, the smooth surface film 3 is peeled off to obtain the heat-sensitive mimeograph base paper of the present invention.

The thermal mimeograph base paper of the present invention has the basic structure as described above. For example, as shown in FIG. It is also possible to provide an adhesive layer 5 between them.

(Effects) According to the present invention as described above, by forming the resin layer from a thermoplastic resin containing an addition polymerizable monomer, (1) the support and the thermoplastic resin layer can be formed more easily than in the prior art. Sufficient adhesion is possible, and there are no problems such as the thermoplastic resin layer being cut and peeled off during plate making, or the problem that the adhesive strength is reduced by the solvent component in the printing ink and the printing durability is lost.

(2) Also, in a preferred embodiment, a surfactant is added to the resin layer to prevent sticking of thermal heads, etc.
It is also possible to omit the formation of an anti-adhesive layer.

(3) Furthermore, as described above, in the present invention, it is sufficient to simply form a resin layer on the support, so that a base paper for thermal mimeographing with excellent characteristics can be provided easily and at low cost.

(Example of fruit color) Hereinafter, the present invention will be explained in more detail with reference to Examples.

In the text, parts or percentages are based on weight unless otherwise specified.

Example 1 The following resin layer forming ink was applied to the surface of a 25 μm thick polyester film to a solid content of approximately 2 g/rn'' and dried. Thereafter, l1 was applied to the surface of the resin layer.
g/rn' Japanese paper was laminated, and 5 Mrad electron beam was irradiated from the paper side using an electron beam irradiation device manufactured by ESI ■ to polymerize the monomer in the resin layer. Thereafter, the polyester film on the surface was peeled off to obtain a base paper for a thermal mimeograph plate of the present invention.

2, and≦゛ Ink polyvinyl butyral (S-LEC BMS, manufactured by M! Suikagaku) 10 parts acrylic acid ester monomer (Aronix M5700, manufactured by Toagosei) 2 parts surfactant (Gafac R
L-210) 10 parts methyl ethyl ketone
80 copies Recover Reboot 55 using the above base paper
When a printing plate was prepared and printed using 870, the density of the obtained print was high, and the print was excellent in resolution and gradation.

Example 2 A base paper for a thermal mimeograph plate of the present invention was obtained in the same manner as in Example 1, except that the following ink was used instead of the ink in Example 1.

≦ Cellulose acetate propionate (CAP-504
-02, manufactured by Kodak) 50 parts monomer (Kayarad HX-220, manufactured by Nippon Kayaku) 10 parts surfactant (Blysurf 208, manufactured by Dai-Kogyo Yakuhin)
40 parts methyl ethyl ketone 450 parts isopropyl alcohol
450 copies Recover Report 558 using the above base paper
70 to prepare a printing plate and print it. The density of the obtained printed matter was high, and the printed matter was excellent in resolution and gradation.

Example 3 Using the following resin layer forming ink in place of the ink in Example 1, a 2μ ink was similarly applied to a polyester film.
A base paper for a thermal mimeograph plate of the present invention was obtained in the same manner as in Example 1, except that a resin layer of m was formed, and the following ink for forming an adhesive layer was coated thereon to a thickness of 1 μm.

30 parts Monomer (Kayarad PET-30, manufactured by Nippon Kayaku) 5 parts Surfactant (Gafac RL-210) 65 parts Methyl ethyl ketone 450 part toluene
450 parts -'1v≦Polyester-TP219 70 parts Aronix M5700 30 parts Methyl ethyl ketone 400 parts When a printing plate was created and printed using the above-mentioned base paper with Recover Ribot 55870, the density of the obtained printed matter was high and the resolution was high. and the printed matter had excellent gradation.

Example 4 The following ink for forming an anti-adhesive layer was applied to the surface of a polyester film to a thickness of 0.1 μm and dried, and then a resin layer of 2 μm was formed using the ink for forming a resin layer below. Except for this, a base paper for a thermal mimeograph plate of the present invention was obtained in the same manner as in Example 1.

5-ton polyester resin (Byron 200, manufactured by Toyobo) 80 parts Aronix M5700 (Toagosei Kaji missing) 30 parts Methyl ethyl ketone 450 parts Toluene
450 parts -m-stop layer ink Polyvinyl butyral (S-LEC BMS, Sekisui Kajika) 30 parts Surfactant (
Gafaq RL-210) 70 parts methyl ethyl ketone 900 parts toluene
900 copies were printed using the above base paper using Ricoh Report 55870 to create a printing plate.
The resulting printed matter had high density and excellent resolution and gradation.

Comparative Example A solution of 10 parts by weight of polyvinyl chloride dissolved in 90 parts by weight of ethyl acetate was applied to the surface of a polyester film with a thickness of 25 μm at a solid content of 2 g/rn'', and dried until adhesiveness remained. Thereafter, Japanese paper of 11 g/m'' was laminated on the surface of the resin layer, and after completely drying, the polyester film was peeled off to obtain a heat-sensitive mimeograph base paper of a comparative example. When a printing plate was created and printed using this base paper with Recover Ribot 55870, the density and printing durability of the printed matter were inferior to those made using the base paper of the present invention. These results were compared with those of Examples to obtain the results shown in Table 1 below. In all examples, printing, printing, and evaluation were performed under the following conditions.

Printing speed 3 m5ec, /1ine Heat ff
i O, I6mJ printing machine: Recover Ribot 5S870
Printing speed 3 speed Density: Macbeth Densitometer 0ptica
l Density (0, 0,) resolution: Evaluation when printing 10 lines/mi of the electrophotographic society test chart.

The O= line can be easily distinguished.

△: Lines are broken or stuck together in some places, but can be distinguished.

× = Unable to distinguish between lines.

Number of sheets printed without crab sticking (heat-sensitive mimeograph base paper performance) 〇〇〇〇〇〇〇〇　Example 1 1.4 0 1,000　Example 2
1.3 0 1,500 Example 3 1.
2 Δ 3,000 Example 4 1,2
0 2,000 Comparative example 1.0
△ 500

[Brief explanation of the drawing]

FIG. 1 is a diagram schematically showing a cross section of a thermal mimeograph base paper of the present invention, FIGS. 2 to 4 are diagrams schematically showing a method of the present invention, and FIG. FIG. 2 is a diagram schematically showing a cross section of a thermal mimeograph base paper according to an embodiment of the present invention. 1; Support 2: Resin layer 3: Film 4; Adhesive layer 5: Anti-adhesive layer Patent applicant Dai Nippon Printing Co., Ltd. Representative Patent attorney Yoshi 1) Katsuhiro Figure 1 Figure 2

Claims (6)

[Claims] (1) A thermosensitive mimeograph base paper comprising a thermoplastic resin layer laminated on one side of a porous support, characterized in that the resin layer is made of a polymerization product of a thermoplastic resin containing an addition polymerizable monomer. Heat-sensitive mimeograph paper. (2) Claim No. 1 in which the resin layer contains a surfactant
) Thermal mimeograph base paper described in item ). (3) A thermoplastic resin layer containing an addition polymerizable monomer is formed on the surface of a film with a smooth surface, a porous support is laminated on the surface of the resin layer, and after polymerizing the monomer, the smooth surface film is formed. A method for producing a thermal mimeograph base paper characterized by peeling. (4) Claim No. 3 in which the resin layer contains a surfactant
) The method for producing a thermal mimeograph base paper as described in item 1. (5) A method for producing a thermal mimeograph base paper according to claim (3), which comprises polymerizing using ionizing radiation. (6) Claim No. 3 (3) Polymerization using an electron beam
) The method for producing a thermal mimeograph base paper as described in item 1.