JP2002127628A - Master for thermal stencil printing and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a master for thermal stencil printing and the manufacturing method of the same, having a porous resin film consisting of a resin on one side of a thermoplastic resin film and having boring sensitivity capable of effecting surely the aimed boring through a thermal head. SOLUTION: The master for thermal stencil printing having at least the porous resin film, constituted by applying a fluidized body on the thermoplastic resin film and drying the same, comprises hollow fillers in the porous resin film. In this case, a synthetic resin solution under solubilized condition, obtained by mixing the synthetic resin into a plurality of solvents having different solubilities, is applied on the thermoplastic resin film and is dried.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a master for heat-sensitive stencil printing which is made by irradiating flash light or infrared light by a halogen lamp, a xenon lamp, a flash bulb or the like, pulsating irradiation with a laser beam or the like, or perforating and making a plate by a thermal head. It is about the method.

[0002]

2. Description of the Related Art Conventionally, a thermosensitive stencil master in which porous thin paper made of natural fibers or synthetic fibers alone or as a mixture is adhered with an adhesive is used as an ink-permeable support on a thermoplastic film. However, the master for thermal stencil printing using a porous thin paper made of such fibers as a support has the following problems. (1) By laminating the porous thin paper and the film using an adhesive, the adhesive accumulates like a bird's web between the fibers of the porous thin paper, and it is difficult for the thermal head to pierce at that portion, The passage of ink is hindered, and printing unevenness is likely to occur. (2) The fibers of the porous tissue paper themselves impede the passage of ink,
Printing unevenness is likely to occur. (3) The smoothness of the film surface is reduced due to the fiber texture of the porous thin paper, the adhesion to the thermal head is poor, and an unperforated portion is formed, so that printing unevenness occurs. Several proposals have been made to improve these problems, but none have been satisfactory. For example, Japanese Patent Application Laid-Open No. 3-193445 proposes using thin paper made of synthetic fibers having a fineness of 1 denier or less as a porous support, but it cannot be said that it is sufficient for solving the above-mentioned problem. In JP-A-62-198459,
There has been proposed a method of forming a porous support by printing a radiation-curable resin pattern having a substantially closed shape on a thermoplastic film by gravure, offset, flexo, or the like. However, in the printing method, the line width of the resin pattern is set to 50 μm.
It is difficult to do the following, and the printed portion cannot be perforated, resulting in printing unevenness. JP-A-3-240596 discloses a dispersion comprising a water-dispersible polymer and colloidal silica applied to the surface of a thermoplastic film, dried, provided with a porous support, and printed with a low-viscosity ink jet ink. A way to do that has been proposed. However, according to this method, the pore diameter of the porous layer is small, and the conventionally used printing ink for stencils has poor ink passage, so that a sufficient printing density cannot be obtained. On the other hand, JP-A-54-33117 proposes a heat-sensitive stencil master consisting essentially of a thermoplastic film without using a porous support. According to this method, the thermal shrinkage is high, and a film having a film thickness of 3 μm or less has good perforation by a thermal head and excellent print quality. When a thick film is used to improve conveyance, the perforation by the thermal head is reduced, and printing unevenness occurs.

[0003] The present inventors have previously proposed a thermosensitive stencil master in which a porous resin film is provided on one side of a thermoplastic film (JP-A-8-332785, JP-A-7-13).
9918, JP-A-10-24667, JP-A-7-305102). However, a porous resin film formed by applying and drying a fluid on a thermoplastic film has a lower porosity and a lower thermal insulation than thin paper used conventionally for lamination with a film. The diameter of the hole pierced by the head is higher than the conventional master, but tends to be smaller. This means that the thermal sensitivity has decreased, which is not a favorable tendency. Further, it is difficult to increase the stiffness only with the resin film in the heat-sensitive stencil master, and the present inventors disclosed in JP-A-10-147075 and JP-A-10-236011, A thermosensitive stencil master has been proposed which has a porous resin film made of a resin on one surface of a thermoplastic resin film and further has a porous fiber film made of a fibrous substance laminated on the surface. However, even with these masters, the problem that the diameter of the hole formed by the thermal head is small has not been solved.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances of the prior art, and has a heat-sensitive resin having a porous resin film made of a resin on one surface of a thermoplastic resin film. It is an object of the present invention to provide a stencil printing master having a piercing sensitivity capable of reliably performing a desired piercing with a thermal head and a method of manufacturing the same.

[0005]

According to the present invention, there is provided a thermosensitive stencil master in which a porous resin film is provided on one side of a thermoplastic film, wherein a hollow filler is internally added to the porous resin film,
It enhances the heat insulation effect and enhances the perforation sensitivity. The present invention is effective regardless of the presence or absence of the porous fiber membrane laminated on the porous resin membrane. The “porous resin film” in the present invention refers to a porous film formed by, for example, precipitating a resin dissolved in a solvent. In addition, "porous fiber membrane" refers to natural fibers such as cotton and hemp, polyester, vinylon,
It means a film formed of a thin paper made of a fibrous substance such as synthetic fiber such as acrylic.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments of the present invention. In the present invention, as the thermoplastic resin film, for example, polyester, polyamide, polypropylene, polyethylene, polyvinyl chloride,
A conventionally known material such as polyvinylidene chloride or a copolymer thereof is used, but a polyester film is particularly preferably used from the viewpoint of perforation sensitivity. The polyester used for the polyester film preferably includes polyethylene terephthalate, a copolymer of ethylene terephthalate and ethylene isophthalate, and a copolymer of hexamethylene terephthalate and cyclohexane dimethylene terephthalate. Particularly preferably, for improving the perforation sensitivity, a copolymer of ethylene terephthalate and ethylene isophthalate, a copolymer of hexamethylene terephthalate and cyclohexane dimethylene terephthalate, and the like can be given. The thermoplastic resin film in the present invention, if necessary, a flame retardant,
A heat stabilizer, an antioxidant, an ultraviolet absorber, an antistatic agent, an organic lubricant such as a pigment, a dye, a fatty acid ester, a wax, or an antifoaming agent such as a polysiloxane can be added. Further, lubricity can be imparted as required. There is no particular limitation on the method of imparting lubricity, but, for example, clay, mica, titanium oxide, calcium carbonate, kaolin, talc, inorganic particles such as wet or dry silica, acrylic acid, organic particles containing styrene and the like as constituents And the like, a method using internal particles, a method of applying a surfactant, and the like.

[0007] The thickness of the thermoplastic resin film in the present invention is usually preferably 0.1 µm to 5.0 µm,
More preferably, it is 0.1 μm to 3.0 μm. If the thickness exceeds 5.0 μm, the piercing property may decrease,
If the thickness is less than 0.1 μm, the film-forming stability may deteriorate or the printing durability may decrease.

The hollow filler in the present invention is a plastic microcapsule having a closed hollow structure using a resin as a shell wall. By embedding the hollow filler in the porous resin film, the heat insulating property of the master for heat-sensitive stencil printing is enhanced, and the heat generated from the thermal head can be effectively used for perforation. The content of the hollow filler is basically air, but a volatile liquid such as a liquefied hydrocarbon may be held in the filler. In this case, there is an advantage that the heat insulating property of the support of the master is easily maintained for a long period of time because the hollow filler does not easily wither over time. The type of resin that composes the shell wall of the hollow filler does not matter,
When used in the master for heat-sensitive stencil printing of the present invention, a thermoplastic resin is preferred in that the perforation sensitivity is not easily reduced, and a thermoplastic resin having a softening point of 50 ° C to 150 ° C is particularly preferred. As such a thermoplastic resin, for example, vinylidene chloride, acrylonitrile, and a copolymer thereof are often used. If the softening point of the thermoplastic resin is lower than 50 ° C., the shell wall of the hollow filler is broken at the time of perforation, and not only the heat insulating effect is not obtained, but also the softened shell wall adheres to the thermal head and the thermal head itself is damaged. The drilling ability may be reduced. When the temperature exceeds 150 ° C., the hollow filler may easily hinder the perforation of the film. The effect of internally adding a hollow filler to the porous resin film of the master for heat-sensitive stencil printing can be expected not only to improve the perforation sensitivity but also to increase the strength of the porous resin film and the bending rigidity. The improvement in printing strength of the heat-sensitive stencil master is expected by the improvement in strength, and the improvement in bending stiffness is expected to improve transportability in the printing press.

The hollow filler may be subjected to a surface treatment in order to improve its properties, such as improving the dispersibility in a coating solution and the strength of the hollow filler shell wall. Coating with an inert inorganic powder such as calcium carbonate or titanium oxide is often performed. The amount of the hollow filler added to the porous resin film is preferably 0.5% to 10% by weight after drying. If it is less than 0.5%, it is difficult to obtain a heat insulating effect, and
%, The ink permeability of the porous resin membrane tends to be impaired.

The median particle diameter of the hollow filler is 5
It is preferably 0 μm or less. If it is larger than 50 μm, the hollow filler itself may impede the passage of ink during printing, thereby deteriorating the image quality. The shell thickness of the hollow filler is preferably 0.1 μm to 10 μm. If the shell thickness is less than 0.1 μm, the filler is easily broken,
On the other hand, if it exceeds 10 μm, the shell wall of the hollow filler tends to absorb heat at the time of perforation, and the heat insulating effect is reduced.

[0011] A functional thin layer may be present between the thermoplastic resin film and the porous resin film. The definition of the functional thin layer here is as follows. 1. A thin layer that improves the adhesion between the thermoplastic film and the porous resin film. 2. Thin layer to improve curl. 3. A thin layer that improves the rigidity of the master. 4. A thin layer that does not hinder drilling sensitivity or improves drilling performance when drilling a master with a thermal head.

Examples of the resin material constituting the functional thin layer include polyvinyl acetate, polyvinyl butyral, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, styrene-acrylonitrile copolymer and the like. Examples thereof include vinyl resins, polyamides such as polybutylene and nylon, polyphenylene oxide, (meth) acrylate, polycarbonate, polyester resins, polyether resins, polyurethane resins, and copolymers, mixtures, and modified products thereof. Furthermore, various fillers, antistatic agents, stick preventive agents, surfactants, preservatives, defoamers, plasticizers, modifiers, and the like can be used in a range that does not impair the effects of the present invention.

Further, in order to improve the adhesiveness, it is preferable to use a polyisocyanate in addition to the resin.
It is particularly preferable to use a polyester polyol, a polyether polyol, a polyurethane resin and a polyisocyanate in combination. In order to improve the piercing property of the thermal head, it is preferable to use a polyester polyol, a polyether polyol, or a polyurethane resin having a softening point of 40 to 150 ° C. in combination with an isocyanate. Here, the molar ratio of OH group / NCO group is from 1 / 0.1 to 1/20, but may be appropriately selected according to the required characteristics.

In order to lower the softening point of the functional thin layer.
A resin having a low softening point or a plasticizer may be added. The thickness of the functional thin layer after drying is 0.01 μm to 2.0 μm.
μm is preferred, and more preferably 0.1 μm to 1.0 μm. If it is smaller than 0.01 μm, adhesiveness, stiffness,
The effect of improving curling is small, and if it exceeds 2.0 μm, the heat perforation sensitivity is adversely affected. The preferable material of the functional thin layer and the thickness after drying are experimentally determined in consideration of the configuration of the master for heat-sensitive stencil printing or the constituent materials.
When biaxially stretched polyester is used as the film and butyral resin is used as the porous film, polyester, a reaction product of polyol and isocyanate, an isocyanate polymer, etc. can be suitably used as the thin layer.

The porous resin film in the present invention may have a structure having a large number of voids inside and on the surface of the film, and the voids may have a thickness direction in the porous film from the viewpoint of ink permeability. It is desirable to use a continuous structure. In the present invention, the average pore size of the porous resin membrane is generally 2 μm to 5 μm.
0 μm, preferably 5 μm to 30 μm. If the average pore size is less than 2 μm, the ink permeability is poor. Therefore, if a low-viscosity ink is used in order to obtain a sufficient amount of ink passing, a phenomenon occurs in which the printing ink oozes from the side of the printing drum or the rear end of the wound master during printing. In addition, the porosity in the porous resin film is often low, and it is easy to hinder perforation by the thermal head. On the other hand, when the average pore size exceeds 50 μm, the effect of suppressing the ink by the porous resin film is reduced,
At the time of printing, the ink between the print drum and the film is excessively extruded, causing problems such as back stains and bleeding. That is, if the average pore size is too small or too large, good print quality cannot be obtained. In particular, when the average pore diameter of the voids in the porous resin film is 20 μm or less, the thicker the porous resin film layer, the more difficult it is for the printing ink to pass through. Therefore, the amount of the ink transferred to the printing paper is controlled by the thickness of this layer. can do. If the thickness of the layer is not uniform, printing unevenness may occur. Therefore, it is desirable that the thickness be uniform.

The thickness of the porous resin film of the present invention is 2 μm to
It is 100 μm, preferably 5 μm to 50 μm. 5μ
If it is less than m, the porous resin film hardly remains behind the perforated portion after perforation by the thermal head, and the back transfer of the printed matter is likely to occur without controlling the amount of transferred ink. Also,
The effect of suppressing the amount of ink transferred by the porous resin film is greater as the film is thicker, and the amount of ink transferred to paper during printing can be adjusted by the thickness of the porous resin film. The density of the porous resin film is usually ^{0.01g / cm 3 ~1g / cm 3} , preferably 0.
A ^{1g / cm 3 ~0.7g / cm 3} . Density 0.0
If it is less than 1 g / cm ³ , the strength of the film is insufficient, and the film itself is easily broken. The adhesion amount of the porous resin film is 0.1 g / m ²
３５35 g / m ² , preferably 0.5 g / m ² ２５25 g /
m ^2, in particular ^1g / ^{m 2 ~11g} / m 2 is desirable. An increase in the amount of adherence hinders the passage of ink and degrades the image quality.
becomes difficult to control the ink transfer amount is less than g / m ^2, deteriorating the image prevents the passage of ink exceeds 35 g / m ² in opposite.

Examples of the resin material constituting the porous resin film include polyvinyl acetate, polyvinyl butyral, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, styrene-acrylonitrile copolymer and the like. Examples thereof include vinyl resins, polyamides such as polybutylene and nylon, polyphenylene oxide, (meth) acrylate, polycarbonate, polyurethane, cellulose derivatives such as acetylcellulose, acetylbutylcellulose and acetylpropylcellulose. Each resin may be used in combination of two or more.

In order to adjust the formation, strength, pore size and the like of the porous resin film, it is desirable to add an additive such as a filler to the porous resin film as needed. Here, the filler is a concept including pigments, powders, and fibrous substances. Among them, needle-like fillers are particularly preferable.
Specific examples thereof include mineral silicate fillers such as magnesium silicate, sepiolite, potassium titanate, wollastonite, zonotolite, gypsum fiber, etc., non-oxide needle whiskers, oxide whiskers, and double oxide whiskers. Needle-like artificial mineral filler such as whisker, mica, glass flake,
A plate-like filler such as talc may be used. The pigments include not only inorganic but also organic pigments, or organic polymer particles such as polyvinyl acetate, polyvinyl chloride, and polymethyl acrylate, and zinc oxide, titanium dioxide, calcium carbonate, and silica. The amount of these additives is preferably 5% to 200% based on the resin. If it is less than 5%, the bending stiffness due to the addition of the additive does not increase. Conversely 200
% Or more, the adhesiveness to the film becomes poor. In the porous resin film of the present invention, an antistatic agent, an anti-stick agent, a surfactant, a preservative, an antifoaming agent and the like can be used together within a range that does not impair the effects of the present invention.

Next, a method for forming the porous resin film of the master for heat-sensitive stencil printing of the present invention will be described. The first method for forming a porous resin film is to apply a coating liquid obtained by dissolving and / or dispersing a resin which is well soluble in a mixed solvent of a good solvent and a poor solvent, and to form a porous film in a drying process. To form. In this case, a combination of a good solvent and a solvent that is relatively easy to evaporate at a lower temperature than a poor solvent is required. When one good solvent and one poor solvent are used, respectively, the boiling point of the good solvent must be relatively lower than the boiling point of the poor solvent. The selection of a good solvent and a poor solvent is optional, but in general, the boiling point difference is 15 ° C.
When the temperature is ４０40 ° C., a porous resin film having desired characteristics is easily formed. If the boiling point difference is less than 10 ° C., the evaporation time difference between the two solvents is small, and the formed film is unlikely to have a porous structure. If the boiling point of the poor solvent is too high, drying takes a long time and the productivity is poor.
It is desirable that the temperature is not more than ° C.

The resin concentration in the coating solution varies depending on the material used, but is 5% to 30%. If it is less than 5%, the opening diameter becomes too large, and the thickness of the porous resin film tends to be uneven. Conversely, if it exceeds 30%, it is difficult to form a porous resin film, or even if it is formed, the pore size becomes small and it is difficult to obtain desired characteristics. The average pore size of the porous resin film is affected by the poor solvent in the atmosphere. In general, the higher the ratio to the good solvent, the larger the amount of coagulation and the larger the average pore size. Since the addition ratio of the poor solvent varies depending on the resin and the solvent, it needs to be appropriately determined by experiments. Generally, the pore size of the porous resin film increases as the amount of the poor solvent added increases. If the amount of the poor solvent is too large, the resin precipitates and the coating liquid becomes unstable. In the case of the present invention, the coating solution contains a hollow filler.

The method for forming the second porous resin film is as follows.
It is used when the good solvent and the poor solvent of the resin forming the porous resin film do not mix well with each other.
As disclosed in JP-A-235885, W /
A fluid mainly composed of an O-type emulsion is applied on a thin layer,
A method in which water is formed as a hole through which ink passes after drying, and a resin (which may contain fillers, emulsifiers, and other additives) in a solvent forms a structure. It is. Also in this method, formation of a porous membrane,
In order to adjust the strength, the size of the pore diameter, the stiffness, and the like, an additive such as the filler can be added to the porous film, if necessary, in addition to the hollow filler. Among them, needle-like, plate-like, or fibrous fillers are particularly preferable. W
/ O type emulsion is relatively lipophilic for the formation of H
A surfactant having an LB (Hydrophiric-Lyophiric Balance) of 4 to 6 is effective. However, when a surfactant having an HLB of 8 to 20 is used in the aqueous layer, a more stable and uniform W / O emulsion can be obtained. The use of a polymeric surfactant is also one of the methods for obtaining a more stable and uniform emulsion. Addition of a thickener such as polyvinyl alcohol or polyacrylic acid to an aqueous system is effective for stabilizing the emulsion. However, the method for forming the porous resin film of the present invention is not limited to the method exemplified above. As a method of applying the coating solution for forming a porous resin film of the present invention to a thermoplastic resin film, a commonly used coating method such as a blade, a transfer roll, a wire bar, a reverse roll, a gravure, and a die can be used. However, there is no particular limitation.

As the porous fiber membrane in the present invention,
Mineral fiber such as glass, sepiolite, various metals, animal fiber such as wool and silk, natural fiber such as cotton, manila hemp, mulberry, mitsumata, pulp, regenerated fiber such as soup and rayon, and synthesis of polyester, polyvinyl alcohol and acrylic Thin paper such as fibers, semi-synthetic fibers such as carbon fibers, and inorganic fibers having a whisker structure are exemplified. In this case, it is necessary to select an appropriate thickness of the fibrous substance depending on the perforated diameter of the thermoplastic resin film, the thickness of the film, and the like, but the diameter is 20 μm or less, preferably 1 μm to 10 μm. If the diameter is smaller than 1 μm, the tensile strength is weak, and if the diameter is larger than 20 μm, ink passage is hindered and so-called white spots due to fibers appear on the image. The length of the fibrous substance is 0.1 mm to 10 mm.
mm, more preferably about 1 mm to 6 mm. If it is shorter than 0.1 mm, the tensile strength becomes weak, and if it is longer than 10 mm, uniform dispersion becomes difficult.
The basis weight of the porous fibrous layer in the present invention is usually preferably ^{3g / m 2 ~20g / m 2} , more preferably 5 g / ^{m 2}
１５15 g / m ² . If the basis weight is more than 20 g / m ² , the ink permeability will be reduced and the image clarity will be reduced.
If the basis weight is less than 3 g / m ² , sufficient strength as a support may not be obtained. The porous fiber layer made of a fibrous substance in the present invention may be a papermaking paper made of short fibers, may be a nonwoven fabric or a woven fabric, or may be a screen gauze. Papermaking paper is preferably used from the viewpoint of cost and the like.

The adhesive strength between the thermoplastic resin film and the porous resin film of the master for thermosensitive stencil printing of the present invention, and when a porous fiber film is provided, the adhesive strength between the porous resin film and the porous fiber film. Is preferably at least 1.4 N / m, and more preferably at least 2.8 N / m. If the adhesive strength is less than 1.4 N / m, peeling occurs during handling and transport, causing not only wrinkles but also elongation during printing, peeling, and tearing. The upper limit of the adhesive strength is not particularly limited as long as ink passage is not hindered.

In the present invention, the adhesive used for laminating the porous fiber membrane is preferably in a state of high viscosity so as not to block the pores of the porous resin membrane from the ink-permeable surface, and is preferably used. The viscosity until the adhesive is completely cured is 1
00 cps or more, and more preferably 300 cps or more. According to the present invention, as a method of manufacturing a master for thermosensitive stencil printing when a porous fiber layer is bonded, a coating liquid for forming a porous resin film on one surface of a thermoplastic resin film is applied. After at least the outermost surface layer of the porous resin film is dried and formed into a film, it is preferable to bond the porous resin film to the porous fiber layer to which the adhesive has been applied. If the porous fiber membrane is laminated before the formation of the porous resin film, the formation of the porous resin film is inhibited, and a desirable porous film cannot be obtained. Since the adhesive may block the pores of the porous resin film, it is preferable to apply the adhesive to the porous fiber film.

In order to form a porous resin film having excellent ink permeability, which is the object of the present invention, a thermoplastic resin is preferably used. In this case, if a solvent-type adhesive is used as the adhesive, the porous resin film is eroded and the pores are closed, so it is preferable that there is no solvent at least at the time when the porous resin film and the porous fiber film are laminated. From this side, a solventless adhesive or an aqueous / emulsion adhesive is used. In order to obtain the adhesive strength of the present invention and to satisfy the above conditions, a polyurethane-based adhesive is preferable. As the polyurethane-based adhesive, a solventless polyurethane adhesive capable of obtaining a desired adhesive strength with a small amount of adhesion is used.
In addition, since a porous fiber membrane containing inexpensive natural fibers is preferably used, in the case of a water-based / emulsion-type polyurethane adhesive, the porous fiber layer expands and contracts at the time of application, and the curl and the like are deteriorated. Also, a solventless polyurethane adhesive is used.

The solvent-free polyurethane adhesive includes a one-component moisture-curable urethane prepolymer obtained by reacting a polyol component such as polyether polyol or polyester polyol having hydroxyl groups at both ends with an isocyanate component, or a polyol component. And a two-part curable adhesive divided into isocyanate components, but are not particularly limited. As the isocyanate component,
Hexamethylene diisocyanate (HMDI), 2,4
Diisocyanate-1-methylcyclohexane, 2,
6-diisocyanate-1-methylcyclohexane, diisocyanatecyclobutane, tetramethylene diisocyanate, o-, m-, and p-xylylene diisocyanate (XDI), dicyclohexylmethane diisocyanate, dimethyldicyclohexylmethane diisocyanate, hexahydrometoxylidene diisocyanate (HXDI) And resinous or alicyclic diisocyanates such as lysine diisocyanate alkyl esters (where the alkyl portion of the alkyl ester preferably has 1 to 6 carbon atoms): toluylene-2,4-diisocyanate (TD1); Toluylene-2,6-diisocyanate, diphenylmethane-4,4-diisocyanate (MDI), 3-methyldiphenylmethane-4,
4'-diisocyanate, m- and p-phenylene diisocyanate, chlorophenylene-2,4-diisocyanate, naphthalene-1,5-diisocyanate, diphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenyl-4,4 '-Diisocyanate, 1,
Aromatic diisocyanates such as 3,5-triisopropylbenzene-2,4-diisocyanate and diphenylether diisocyanate, and mixtures thereof.

The adhesive can be applied by any method such as a blade coating method, a reverse roll coating method, a gravure coating method, a knife coating method, a spray coating method, an offset gravure coating method, a kiss coating method, and a bar coating method. There is no particular limitation. The surface on which the adhesive is applied may be applied to either the porous resin film or the porous fiber film, but it is better to apply the adhesive to the porous fiber film so as not to close the opening of the porous resin film. .

Solventless polyurethane adhesion to porous fiber membrane
When applying an agent, if the viscosity is too high, the fibers will fall off and
Since the processing failure occurs, heating the roll will reduce the viscosity.
It is preferable to apply the coating at a lowering of 3000 cps or less. Further
Preferably, apply between 300 cps and 1500 cps
Preferably. Porosity when viscosity is less than 300 cps
Closes the opening after lamination with the water-soluble resin film to improve ink permeability
Possibility to inhibit, porous above 3000 cps
The fibers of the conductive fiber layer are likely to fall off. Solventless adhesive
When using a heat-sensitive stencil printing roll wound in a roll
Curing is recommended to promote the reaction of the
Good. The curing temperature is preferably 50 ° C or less.
And more preferably 40 ° C. or lower. Over 50 ° C
Shrinkage of the thermoplastic resin film and curl problem
Occur. Cure time until the desired adhesive strength is obtained
There is no particular limitation as long as it is performed. Of the present invention
As an adhesive coating method, use an organic solvent such as ethyl acetate.
After applying the diluted coating liquid to the porous fiber layer and drying,
There is also a method of bonding with a porous resin film, but the environmental
Solvent-free coating is preferred due to solvent problems
No. The amount of adhesion of the above adhesive is the same as the conventional
Master for thermosensitive stencil printing (with thermoplastic resin film and
Consider the effect of perforation inhibition unlike
There is no need to consider this, and if the desired adhesive strength is obtained,
Although not limited to, porous resin membrane and porous
It is sufficient that the pores of the fiber membrane are not closed, and preferably
0.05g / 1m²~ 5.0 g / m²And more preferably
0.1 g / m ²~ 3.0 g / m²Range.

The master for heat-sensitive stencil printing of the present invention uses silicone oil, silicone-based resin, fluorine-based resin, surfactant, antistatic agent to prevent fusing at the time of perforation on one side of the film to be in contact with the thermal head. Agent, heat-resistant agent,
It is desirable to provide a thin layer comprising an antioxidant, organic particles, inorganic particles, pigments, dispersing aids, preservatives, defoamers, and the like.
The thickness of the thin layer for preventing fusion is preferably 0.005 μm or more.
0.4 μm, more preferably 0.01 μm to 0.4 μm
It is. The method of providing the thin layer for preventing fusion is not particularly limited, but it is preferable to apply a solution diluted with water, a solvent, or the like using a roll coater, a gravure coater, a reverse coater, a bar coater, or the like, and then dry.

Hereinafter, a method for measuring the characteristics of the master for heat-sensitive stencil printing of the present invention will be described. Center Particle Size (Median) The center particle size of the hollow filler was measured using a laser diffraction / scattering particle size distribution analyzer LA-700 manufactured by Horiba, Ltd.

Adhesive Strength Adhesive Strength Between Thermoplastic Resin Film and Porous Resin Film When the heat-sensitive stencil master of the present invention has a porous fiber film, only the porous fiber film is peeled from the master. If the master does not have a porous fiber membrane, this operation is unnecessary. Next, a cellophane tape is attached to the surface of the porous resin membrane opposite to the film so that air does not enter. It is measured by a conforming 90-degree peel test. At this time, the measurement is performed by fixing the porous resin film to which the cellophane tape is stuck and pulling the thermoplastic resin film. When the porous fiber membrane alone cannot be peeled off, the measurement is performed by fixing the laminate of the porous fiber membrane and the porous resin membrane without attaching the cellophane tape. Even when a functional thin film is present between the thermoplastic resin film and the porous resin film, the adhesive strength between the thermoplastic resin film and the porous resin film can be increased by the above method without regard to the presence of the functional thin film. It shall be measurable.

Adhesive strength between porous resin film and porous fiber film (only when the heat-sensitive stencil master of the present invention has a porous fiber film) Only the thermoplastic resin film is removed from the heat-sensitive stencil master of the present invention. A cellophane tape is attached to the surface of the porous resin film from which the thermoplastic resin film has been peeled off so that air does not enter, and measurement is performed by a 90-degree peeling test in accordance with JIS K 6854-1. At this time, the measurement is performed by fixing the porous resin film to which the cellophane tape is stuck and pulling the porous fiber film. When only the thermoplastic resin film cannot be peeled off, the measurement is performed by fixing the laminate of the thermoplastic resin film and the porous fiber membrane without attaching the cellophane tape.

Evaluation of printability The prepared master was manufactured by Ricoh Co., Ltd. “Preport JP4”.
000 "(thermal head resolution 400 dpi), and 50 mm x 50 mm
plate making using a manuscript with black solid
0 sheets were printed. Perforation sensitivity: ◎ for those with the master film part perfectly perforated by the thermal head and a large perforation diameter, も の for those that are perforated completely normally, ○ for those that are perforated but partially reduced in perforation diameter, Those that are not partially perforated are indicated by x. Image quality: The printed matter was evaluated by visual judgment, and a black solid part with conspicuous white spots was evaluated as x, and an intermediate level between ○ and x and a level practically manageable was evaluated as Δ. Set-off: A set having no set-off was evaluated as 、, a set-off having a level that could not withstand double-sided printing was evaluated as x, and a medium having a set-off level that could be used in practical use was evaluated as Δ.

Evaluation of printing durability The created master was manufactured by Ricoh Co., Ltd. “Preport JP4”.
000 ", and plate making and printing were performed by a thermal head plate making method using a manuscript having 6-point characters and 50 mm x 50 mm solid black. The printing speed was 3,000 sheets as standard. If an abnormal image such as X occurred, there is no defect in the image, but if the master peels off the film after printing, or if the porous fiber membrane peels off, there is no abnormality in the master. Those that could not be done were marked with ○.

Evaluation of Conveyability In the evaluation of printability and printing durability as described above, those which could be conveyed without problems were evaluated as good, those where wrinkles or the like occurred during conveyance, and those where wrinkles occurred during conveyance. Those having no effect on the image were evaluated as Δ.

[0036]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the following, all parts are based on weight.

Example 1 Porous Film Forming Coating Solution 1 Oil Phase Formulation Polyvinyl acetal resin (Sekisui Chemical Co., Ltd. Esrec KS-1) 2.5 (parts) Talc (Nihon Talc Co., Ltd. Micro Ace LG) 2.0 Sorbitan fatty acid ester (Nikko Chemicals Co., Ltd. SO-15) 0.1 Modified silicone oil (Shin-Etsu Chemical Co., Ltd. KF6012) 0.1 Acrylic polymer O / W type emulsion (Joncryl-711) Johnson Polymer 0.2 Hollow Filler (Matsumoto Yushi Pharmaceutical Co., Ltd. F100SSD) 0.024 Ethyl acetate 43.0 Dissolve and disperse the above, and add water (HEC 1% solution) 2
0.0 parts by weight was slowly added with stirring to obtain a cloudy porous film forming coating solution 1. This was dried on a biaxially stretched polyester film having a thickness of 2.0 μm with a gravure roll in an atmosphere of 20 ° C. and 50% RH, and the adhesion amount was 6.0 g.
/ M ² , applied and dried to form a porous resin film and wound up in a roll. Used hollow filler F100
In the SSD, the shell wall was an acrylonitrile copolymer, the median diameter was 5 μm, and the content of hollow filler in the porous resin film was 0.5% by weight. Formulation of anti-fusing agent coating liquid Silicone oil (SF8422 manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 Surfactant (Plysurf A208 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 Toluene 100.0 The surface of the plastic resin film opposite to the porous resin film was coated and dried using a bar coater to obtain a master for heat-sensitive stencil printing of the present invention. The prepared heat-sensitive stencil master was evaluated by the evaluation method described above. Table 1 shows the results.

Example 2 Porous Film Forming Coating Solution 2 Oil Phase Formulation Polyvinyl Acetal Resin (Sekisui Chemical Co., Ltd. Esrec KS-1) 2.5 Talc (Nihon Talc Co., Ltd. Microace LG) 2.0 Sorbitan fatty acid ester (Nikko Chemicals Co., Ltd. SO-15) 0.1 Modified silicone oil (Shin-Etsu Chemical Co., Ltd. KF6012) 0.1 Acrylic polymer O / W emulsion (Johnson Polymer Co., Ltd. Joncryl-711) 0.2 Hollow filler (Matsumoto) Yushi Pharmaceutical Co., Ltd. F100SSD) 0.25 Ethyl acetate 43.0 Dissolve and disperse the above and add water (HEC 1% solution) 2
0.0 parts by weight was slowly added with stirring to obtain a cloudy porous film forming coating liquid 2. This was dried on a biaxially stretched polyester film having a thickness of 2.0 μm with a gravure roll in an atmosphere of 20 ° C. and 50% RH, and the adhesion amount was 6.0 g.
/ M ² , applied and dried to form a porous resin film and wound up in a roll. Used hollow filler F100
In the SSD, the shell wall was an acrylonitrile copolymer, the median diameter was 5 μm, and the hollow filler content in the porous resin film was 5% by weight. Next, the anti-fusing agent coating solution used in Example 1 was applied to the surface of the thermoplastic resin film opposite to the porous resin film using a bar coater and dried to obtain a heat-sensitive stencil master of the present invention. The prepared heat-sensitive stencil master was evaluated by the evaluation method described above. Table 1 shows the results.

Example 3 Formulation of Three Oil Phases for Coating Solution for Forming Porous Film Polyvinyl Acetal Resin (ESLEK KS-1 Sekisui Chemical Co., Ltd.) 2.5 Talc (Micro Ace LG, Nippon Talc Co., Ltd.) 2.0 Sorbitan fatty acid ester (Nikko Chemicals Co., Ltd. SO-15) 0.1 Modified silicone oil (Shin-Etsu Chemical Co., Ltd. KF6012) 0.1 Acrylic polymer O / W emulsion (Johnson Polymer Co., Ltd. Joncryl-711) 0.2 Hollow filler (Matsumoto) Yushi Pharmaceutical Co., Ltd. F100SSD) 0.53 Ethyl acetate 43.0 Dissolve and disperse the above and add water (HEC 1% solution) 2
0.0 parts by weight was slowly added with stirring to obtain a cloudy porous film forming coating liquid 3. This was dried on a biaxially stretched polyester film having a thickness of 2.0 μm with a gravure roll in an atmosphere of 20 ° C. and 50% RH, and the adhesion amount was 6.0 g.
/ M ² , applied and dried to form a porous resin film and wound up in a roll. Used hollow filler F100
In the SSD, the shell wall was an acrylonitrile copolymer, the median diameter was 5 μm, and the hollow filler content in the porous resin film was 10% by weight. Next, the anti-fusing agent coating solution used in Example 1 was applied to the surface of the thermoplastic resin film opposite to the porous resin film using a bar coater and dried to obtain a heat-sensitive stencil master of the present invention. The prepared heat-sensitive stencil master was evaluated by the evaluation method described above. Table 1 shows the results.

Example 4 Formulation of a Coating Solution for Forming a Porous Film 4 Formulation Polyvinyl Butyral (PVB3000-2 manufactured by Denki Kagaku Kogyo Co., Ltd.) 5.0 Isopropyl alcohol 45.0 Hollow filler (F100SSD manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.) 0.56 Water 11.0 After dissolving polyvinyl butyral in isopropyl alcohol, a hollow filler was added, and the mixture was stirred and uniformly dispersed. Further, water was added dropwise while stirring this liquid, and mixed. This is referred to as a coating liquid 4 for forming a porous film. 20 ° C 5
After drying with a gravure roll on a 2.0 μm-thick biaxially stretched polyester film in an atmosphere of 0% RH, application and drying are performed so that the adhesion amount becomes 6.0 g / m ² to form a porous resin film. Then, it was wound into a roll. The hollow filler F100SSD used had a shell wall of an acrylonitrile copolymer with a median diameter of 5 μm, and the content of the hollow filler in the porous resin film was 10% by weight. Next, the anti-fusing agent coating solution used in Example 1 was applied to the surface of the thermoplastic resin film opposite to the porous resin film using a bar coater and dried to obtain a heat-sensitive stencil master of the present invention. The prepared heat-sensitive stencil master was evaluated by the evaluation method described above. Table 1 shows the results.

Example 5 Porous Film Forming Coating Solution 5 Oil Phase Formulation Polyvinyl Acetal Resin (ESEK KS-1 Sekisui Chemical Co., Ltd.) 2.5 Talc (Nihon Talc Co., Ltd. Microace LG) 2.0 Sorbitan fatty acid ester (Nikko Chemicals Co., Ltd. SO-15) 0.1 Modified silicone oil (Shin-Etsu Chemical Co., Ltd. KF6012) 0.1 Acrylic polymer O / W emulsion (Johnson Polymer Co., Ltd. Joncryl-711) 0.2 Hollow filler (Matsumoto) Oil and Fat Pharmaceutical Co., Ltd. F80S) 0.42 Ethyl acetate 43.0 Dissolve and disperse the above, add water (HEC 1% solution) 2
0.0 parts by weight was slowly added with stirring to obtain a cloudy porous film forming coating solution 5. This was dried on a biaxially stretched polyester film having a thickness of 2.0 μm with a gravure roll in an atmosphere of 20 ° C. and 50% RH, and the adhesion amount was 6.0 g.
/ M ² , applied and dried to form a porous resin film and wound up in a roll. Used hollow filler F80S
Has a shell wall of acrylonitrile copolymer and a median diameter of 25.
μm, the hollow filler content in the porous resin film was 8% by weight. Next, the anti-fusing agent coating solution used in Example 1 was applied to the surface of the thermoplastic resin film opposite to the porous resin film using a bar coater and dried to obtain a heat-sensitive stencil master of the present invention. The prepared heat-sensitive stencil master was evaluated by the evaluation method described above. Table 1 shows the results.

Example 6 Formulation of Coating Solution for Forming Porous Film 6 Polyvinyl Butyral (PVB3000-2, manufactured by Denki Kagaku Kogyo Co., Ltd.) 5.0 Isopropyl alcohol 45.0 Hollow filler (F50E, Matsumoto Yushi Pharmaceutical Co., Ltd.) 0.25 Water 11.0 After dissolving polyvinyl butyral in isopropyl alcohol, a hollow filler was added and stirred. Dispersed uniformly. Further, water was added dropwise while stirring this liquid, and mixed. This is referred to as a coating liquid 6 for forming a porous film. 20 ° C 5
After drying with a gravure roll on a 2.0 μm-thick biaxially stretched polyester film in an atmosphere of 0% RH, application and drying are performed so that the adhesion amount becomes 6.0 g / m ² to form a porous resin film. Then, it was wound into a roll. The hollow filler F100SSD used had a shell wall of vinylidene chloride-acrylonitrile copolymer with a median diameter of 48 μm and a hollow filler content in the porous resin film of 5% by weight. Next, the anti-fusing agent coating solution used in Example 1 was applied to the surface of the thermoplastic resin film opposite to the porous resin film using a bar coater and dried to obtain a heat-sensitive stencil master of the present invention. The prepared heat-sensitive stencil master was evaluated by the evaluation method described above. Table 1 shows the results.

Example 7 The coating solution 2 for forming a porous film used in Example 2 was heated at 20 ° C. and 50% R
2.0 μm thick biaxially stretched polyester in an atmosphere of H
2. After drying with a gravure roll on the film, the adhesion amount is 3.
0 g / m²Coated and dried to form a porous resin film
And wound up in a roll. Hollow filter inside porous resin membrane
The lurr content was 5% by weight. Then the porous fiber
Papermaking paper made of 100% natural fiber (basis weight 10g)
/ M ²Roll with a thickness of 33 μm) heated to 100 ° C.
One-component urethane adhesive using a coater (Takeda Pharmaceutical
Takenate A260, manufactured by Co., Ltd.) at an application amount of 0.2 g / m²When
Rolled so that it becomes rolled, and the porosity of the roll created earlier
Lamination was performed with the resin film surface. Adhesive viscosity during application
Was about 1000 cps. Then used in Example 1
Anti-fusing agent coating liquid for thermoplastic resin film porous resin
Use a bar coater on the side opposite to the membrane and dry.
After winding, this is cured at 30 ° C. for 3 days to give the feeling of the present invention.
A base paper for hot stencil printing was obtained. Heat-sensitive stencil sheet made
Was evaluated by the evaluation method described above. The results are shown in Table 1.
You.

Example 8 The coating liquid 2 for forming a porous film used in Example 2 was heated at 20 ° C. and 50% R
After drying with a gravure roll on a biaxially stretched polyester film having a thickness of 2.0 μm in an atmosphere of H, the adhesion amount was 3.
The resultant was applied and dried so as to be 0 g / m ² to form a porous resin film, and wound up in a roll. The hollow filler content in the porous resin film was 5% by weight. Subsequently, a paper made of two types of polyester fibers having a fineness of 0.2 denier and 1.1 denier (basis weight 8 g / m ² ,
(Thickness: 25 μm) and a two-component reaction type urethane adhesive (Takeda A)
230, isocyanate component: A30, mixing ratio 10:
8) was rolled using a roll coater heated to 70 ° C. so as to have an application amount of 0.7 g / m ^2, and then applied, followed by lamination with the porous resin film surface of the previously prepared roll. The viscosity of the adhesive at the time of application was about 800 cps. Next, the anti-fusing agent coating solution used in Example 1 was applied to the surface of the thermoplastic resin film opposite to the porous resin film using a bar coater, dried and wound up, and then wound at 30 ° C. for 3 days. The cured stencil sheet of the present invention was cured. The prepared heat-sensitive stencil sheet was evaluated by the evaluation method described above. Table 2 shows the results.

Example 9 Functional Thin Layer Coating Solution Polyester resin 30% ethyl acetate solution (Toyobo Co., Ltd. Byron 50AS) 25.0 Ethyl acetate 185 Polyester resin ethyl acetate solution (Toyobo Co., Ltd. Byron 50AS) in ethyl acetate To obtain a functional thin layer coating solution. The above-mentioned functional thin layer coating solution was applied on a biaxially stretched polyester film having a thickness of 2.0 μm and dried at 50 ° C. to obtain a functional thin layer having a thickness of 0.05 μm. Further, the coating liquid 2 for forming a porous film used in Example 2 was further applied thereto.
After drying with a gravure roll in an atmosphere of 0 ° C. and 50% RH, coating and drying were performed so that the adhesion amount was 6.0 g / m ² to form a porous resin film, which was wound into a roll. The hollow filler content in the porous resin film was 5% by weight. Next, the anti-fusing agent coating solution used in Example 1 was applied to the surface of the thermoplastic resin film opposite to the porous resin film using a bar coater and dried to obtain a heat-sensitive stencil master of the present invention. The prepared heat-sensitive stencil master was evaluated by the evaluation method described above. Table 2 shows the results.

Example 10 Formulation of Coating Solution for Forming Porous Film 7 Polyvinyl Butyral (PVB3000-2, manufactured by Denki Kagaku Kogyo Co., Ltd.) 5.0 Isopropyl alcohol 46.0 Hollow filler (F100SSD, Matsumoto Yushi Seiyaku Co., Ltd.) 0.26 Water 12.0 After dissolving polyvinyl butyral in isopropyl alcohol, a hollow filler was added and stirred. Dispersed uniformly. Further, water was added dropwise while stirring this liquid, and mixed. This is referred to as a coating liquid 7 for forming a porous film. 20 ° C 5
After drying with a gravure roll on a 2.0 μm-thick biaxially stretched polyester film in an atmosphere of 0% RH, application and drying are performed so that the adhesion amount becomes 6.0 g / m ² to form a porous resin film. Then, it was wound into a roll. The hollow filler content in the porous resin film is 5% by weight. In the formulation of the coating liquid 7 for forming a porous film, the amount of water is slightly larger than an appropriate amount.
Subsequently, as a porous fiber membrane, a paper made of 100% natural fiber (basis weight 10 g / m ² , thickness 33 μm) was placed at 100 ° C.
A one-part urethane adhesive (Takenate A260 manufactured by Takeda Pharmaceutical Co., Ltd.) was rolled using a heated roll coater so that the coating amount was 0.05 g / m ^2, and then applied. Lamination was performed with the porous resin film surface. The viscosity of the adhesive at the time of application was about 1000 cps. Next, the anti-fusing agent coating solution used in Example 1 was applied to the surface of the thermoplastic resin film opposite to the porous resin film using a bar coater, dried and wound up, and then wound at 30 ° C. for 3 days. The cured stencil sheet of the present invention was cured. The prepared heat-sensitive stencil sheet was evaluated by the evaluation method described above. Table 2 shows the results.

Comparative Example 1 Porous film forming coating liquid 8 oil phase formulation Polyvinyl acetal resin (ESLEK KS-1 Sekisui Chemical Co., Ltd.) 2.5 Talc (Nippon Talc Co., Ltd. Microace LG) 2.0 Sorbitan fatty acid ester (Nikko Chemicals SO-15) 0.1 Modified silicone oil (Shin-Etsu Chemical Co., Ltd. KF6012) 0.1 Acrylic polymer O / W emulsion (Johnson Polymer Co., Ltd. Joncryl-711) 0.2 Ethyl acetate 43. 0 or more is dissolved and dispersed, and water (HEC 1% solution) 2
0.0 parts by weight was slowly added with stirring to obtain a cloudy porous film forming coating liquid 8. This was dried on a biaxially stretched polyester film having a thickness of 2.0 μm with a gravure roll in an atmosphere of 20 ° C. and 50% RH, and the adhesion amount was 6.0 g.
/ M ² , applied and dried to form a porous resin film and wound up in a roll. The porous resin film of Comparative Example 1 does not include a hollow filler. Next, the anti-fusing agent coating solution used in Example 1 was applied to the surface of the thermoplastic resin film opposite to the porous resin film using a bar coater and dried to obtain a heat-sensitive stencil master of Comparative Example. The prepared heat-sensitive stencil master was evaluated by the evaluation method described above. Table 2 shows the results.

Comparative Example 2 Formulation of 9 Coating Liquid for Forming Porous Film Polyvinyl Butyral (PVB3000-2 manufactured by Denki Kagaku Kogyo Co., Ltd.) 5.0 Isopropyl alcohol 45.0 Water 11.0 After dissolving polyvinyl butyral in isopropyl alcohol, Water was added dropwise with stirring and mixed.
This is referred to as a coating liquid 9 for forming a porous film. This is 20 ℃ 50%
After drying with a gravure roll on a 2.0 μm-thick biaxially stretched polyester film in an atmosphere of RH, application and drying are performed so that the adhesion amount becomes 6.0 g / m ² to form a porous resin film. Rolled up. The porous resin film of Comparative Example 2 does not include a hollow filler. Next, the anti-fusing agent coating solution used in Example 1 was applied to the surface of the thermoplastic resin film opposite to the porous resin film using a bar coater and dried to obtain a heat-sensitive stencil master of Comparative Example. The prepared heat-sensitive stencil master was evaluated by the evaluation method described above. Table 2 shows the results.

Comparative Example 3 Porous film forming coating liquid 10 oil phase formulation Polyvinyl acetal resin (Sekisui Chemical Co., Ltd. Esrec KS-1) 2.5 Talc (Nihon Talc Co., Ltd. Micro Ace LG) 2.0 Sorbitan fatty acid ester (Nikko Chemicals Co., Ltd. SO-15) 0.1 Modified silicone oil (Shin-Etsu Chemical Co., Ltd. KF6012) 0.1 Acrylic polymer O / W emulsion (Johnson Polymer Co., Ltd. Joncryl-711) 0.2 Hollow filler (Matsumoto) Yushi Pharmaceutical Co., Ltd. F100SSD) 0.65 Ethyl acetate 43.0 Dissolve and disperse the above, and add water (HEC 1% solution) 2
0.0 parts by weight was slowly added with stirring to obtain a cloudy porous film forming coating liquid 10. This is 20 ° C 50% RH
After drying with a gravure roll on a biaxially stretched polyester film having a thickness of 2.0 μm in an atmosphere of
g / m ² and applied and dried to form a porous resin film, which was wound into a roll. Used hollow filler F10
In 0SSD, the shell wall was an acrylonitrile copolymer, the median diameter was 5 μm, and the hollow filler content in the porous resin film was 12% by weight. Next, the anti-fusing agent coating solution used in Example 1 was applied to the surface of the thermoplastic resin film opposite to the porous resin film using a bar coater and dried to obtain a heat-sensitive stencil master of Comparative Example. The prepared heat-sensitive stencil master was evaluated by the evaluation method described above. Table 2 shows the results.

Comparative Example 4 Formulation of Coating Solution 11 for Forming Porous Film Polyvinyl Butyral (PVB300-2 manufactured by Denki Kagaku Kogyo Co., Ltd.) 5.0 Isopropyl alcohol 45.0 Hollow filler (F30E, Matsumoto Yushi Pharmaceutical Co., Ltd.) 0.26 Water 11.0 After dissolving polyvinyl butyral in isopropyl alcohol, a hollow filler was added and stirred. Dispersed uniformly. Further, water was added dropwise while stirring this liquid, and mixed. This is referred to as a coating liquid 11 for forming a porous film. 20 ℃
After drying with a gravure roll on a biaxially stretched polyester film having a thickness of 2.0 μm in an atmosphere of 50% RH, application and drying are performed so that the adhesion amount becomes 6.0 g / m ² to form a porous resin film. Then, it was wound into a roll. The hollow filler F30E used had a shell wall of vinylidene chloride-acrylonitrile copolymer, a median diameter of 55 μm, and a hollow filler content in the porous resin film of 5% by weight. Next, the anti-fusing agent coating solution used in Example 1 was applied to the surface of the thermoplastic resin film opposite to the porous resin film using a bar coater and dried to obtain a heat-sensitive stencil master of Comparative Example.
The prepared heat-sensitive stencil master was evaluated by the evaluation method described above. Table 2 shows the results.

Comparative Example 5 Porous Film Forming Coating Solution 12 Oil Phase Formulation Polyvinyl Acetal Resin (ESEK KS-1 Sekisui Chemical Co., Ltd.) 2.5 Talc (Nihon Talc Co., Ltd. Microace LG) 2.0 Sorbitan fatty acid ester (Nikko Chemicals Co., Ltd. SO-15) 0.1 Modified silicone oil (Shin-Etsu Chemical Co., Ltd. KF6012) 0.1 Acrylic polymer O / W emulsion (Johnson Polymer Co., Ltd. Joncryl-711) 0.2 Hollow filler (Matsumoto) Fat and Oil Pharmaceutical Co., Ltd. F80E) 0.25 Ethyl acetate 43.0 Dissolve and disperse the above, and add water (HEC 1% solution) 2
0.0 parts by weight was slowly added with stirring to obtain a cloudy porous film forming coating solution 12. This is 20 ° C 50% RH
After drying with a gravure roll on a biaxially stretched polyester film having a thickness of 2.0 μm in an atmosphere of
g / m ² and applied and dried to form a porous resin film, which was wound into a roll. Used hollow filler F80
In E, the shell wall is an acrylonitrile copolymer having a median diameter of 9
The hollow filler content in the porous resin film was 0% and the weight ratio was 5%. Next, the anti-fusing agent coating solution used in Example 1 was applied to the surface of the thermoplastic resin film opposite to the porous resin film using a bar coater and dried to obtain a heat-sensitive stencil master of Comparative Example. The prepared heat-sensitive stencil master was evaluated by the evaluation method described above. Table 2 shows the results
Shown in

Comparative Example 6 The coating liquid 2 for forming a porous film used in Example 2 was prepared at 20 ° C. and 50% R
After drying with a gravure roll on a biaxially stretched polyester film having a thickness of 2.0 μm in an atmosphere of H, the adhesion amount was 3.
It was applied and dried so as to have a concentration of 0 g / m ² to form a porous resin film, which was wound into a roll. The hollow filler content in the porous resin film was 5% by weight. Saturated polyester adhesive (UE3500, manufactured by Unitika) 15.0 parts by weight Toluene 75.0 parts by weight A coating solution obtained by dissolving and mixing the above was dried using a direct gravure coater to have an application amount of 0.2 g / m ^2. Paper made of 100% natural fiber (basis weight 10g /
m ² , thickness 33 μm), and superposed on the porous resin film surface of the previously prepared roll, and then dried at 50 ° C. Next, the anti-fusing agent coating solution used in Example 1 was applied to the surface of the thermoplastic resin film opposite to the porous resin film using a bar coater and dried to obtain a heat-sensitive stencil master of Comparative Example. The prepared heat-sensitive stencil master was evaluated by the evaluation method described above. Table 2 shows the results.

Comparative Example 7 Formulation of Coating Solution 13 for Forming Porous Film Polyvinyl Butyral (PVB3000-2, manufactured by Denki Kagaku Kogyo Co., Ltd.) 5.0 Isopropyl alcohol 45.0 Hollow filler (F100 SSD, Matsumoto Yushi Seiyaku Co., Ltd.) 0.26 Water 13.0 After dissolving polyvinyl butyral in isopropyl alcohol, a hollow filler was added, and the mixture was stirred and uniformly dispersed. Further, water was added dropwise while stirring this liquid, and mixed. This is referred to as a coating liquid 13 for forming a porous film. 20 ℃
After drying with a gravure roll on a biaxially stretched polyester film having a thickness of 2.0 μm in an atmosphere of 50% RH, application and drying are performed so that the adhesion amount becomes 6.0 g / m ² to form a porous resin film. Then, it was wound into a roll. The hollow filler content in the porous resin film was 5% by weight. The formulation of the porous film forming coating liquid 13 contains more water than an appropriate amount. Next, the anti-fusing agent coating solution used in Example 1 was applied to the surface of the thermoplastic resin film opposite to the porous resin film using a bar coater and dried to obtain a heat-sensitive stencil master of the present invention. The prepared heat-sensitive stencil master was evaluated by the evaluation method described above. Table 2 shows the results.

[0054]

[Table 1] * Hollow filler shell wall material: AN indicates acrylonitrile copolymer, and VC-AN indicates vinylidene chloride-acrylonitrile copolymer.

[0055]

[Table 2] Adhesive strength: FP indicates the adhesive strength between the film and the porous resin film, and PT indicates the adhesive strength between the porous resin film and the porous fiber film.

[0056]

According to the first and second aspects of the present invention, a heat-sensitive stencil master having a porous resin film formed by applying and drying a fluid on a thermoplastic resin film has been conventionally used for heat insulation. Insufficient drilling sensitivity due to lack of properties can be greatly improved. According to the third aspect of the present invention, there is provided a heat-sensitive stencil master capable of improving heat insulation and improving perforation sensitivity without impairing good print image quality. According to the invention of claim 4, by using a material having a relatively low softening point for the hollow filler, a heat-sensitive stencil having improved heat insulating properties without causing perforation inhibition due to addition of the hollow filler to the porous resin film. A printing master is provided. According to the fifth aspect of the present invention, it is possible to apply to an ethyl acetate system which is not suitable for the material of the fourth aspect. According to the invention of claim 6, there is provided a master for heat-sensitive stencil printing in which the adhesive strength between the thermoplastic resin film and the porous resin film is improved without adversely affecting the perforation sensitivity and printing quality of the master. . According to the invention of claim 7, since the printing durability is ensured by the laminated porous fiber film, the choice of the resin constituting the porous resin film is wider than when the porous fiber film is not laminated. In addition, since the amount of resin adhered to the porous resin film can be reduced, it is easy to form a porous resin film having high ink permeability. According to the eighth and ninth aspects of the present invention, there is provided a master for heat-sensitive stencil printing which does not cause peeling during plate making or printing. According to the tenth aspect of the present invention, there is provided a heat-sensitive stencil master capable of providing a sufficient adhesive strength between a porous resin film and a porous fiber film without deteriorating good print image quality. The invention of claim 11 is used when a plurality of solvents (good solvent and poor solvent) having different solubilities of the resin forming the porous resin film are mutually soluble. Since organic solvents often dissolve in each other well, the choice of solvents is wide, and as a result, the selection range of resins is also wide. A gourd-shaped porous resin film can be easily formed by arbitrarily changing the mixing ratio of the solvent. Further, productivity can be increased by selecting a solvent that evaporates quickly, such as ether or acetone. According to the twelfth aspect of the invention, an emulsion is formed by selecting a good solvent and a poor solvent that are not mixed with each other. Compared with the eleventh aspect of the present invention, since it does not depend on the solubility of the resin, it is less affected by temperature and humidity, and the reproducibility of the formed film shape is high. Since the flexibility of formulation is high and the range in which a porous resin film can be formed is wide, it is easy to adjust the viscosity of the coating liquid by adjusting the ratio of the oil-water phase, the resin concentration, the resin molecular weight, and the like. Further, in the present invention, the coating liquid generally has a higher viscosity than the invention of the eleventh invention if the solid content concentration is the same.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of an example of a thermosensitive stencil master according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Thermoplastic resin film 2 Porous resin film 3 Porous fiber film 4 Hollow filler 5 Porous resin film void

Claims (12)

[Claims] 1. A thermosensitive stencil master having at least a porous resin film formed by applying and drying a fluid on a thermoplastic resin film, wherein the porous resin film contains a hollow filler. Master for thermal stencil printing. 2. A master for heat-sensitive stencil printing, wherein the hollow filler is contained in the porous resin film in a weight ratio of 0.5% to 10%. 3. The master for heat-sensitive stencil printing according to claim 1, wherein the hollow filler has a median particle size (median) of 50 μm or less. 4. The master for heat-sensitive stencil printing according to claim 1, wherein the hollow filler has a shell wall of a vinylidene chloride-acrylonitrile copolymer. 5. The master for heat-sensitive stencil printing according to claim 1, wherein the hollow filler has an acrylonitrile copolymer as a shell wall. 6. The method according to claim 1, wherein a functional thin layer is provided between the thermoplastic resin film and the porous resin film.
5. The master for heat-sensitive stencil printing according to any one of 5. 7. The method according to claim 1, wherein a porous fiber film made of a fibrous substance is laminated on the surface of the porous resin film provided on one surface of the thermoplastic resin film. Master for thermal stencil printing. 8. The master for heat-sensitive stencil printing according to claim 1, wherein the adhesive strength between the thermoplastic resin film and the porous resin film is 1.4 N / m or more. 9. The master for heat-sensitive stencil printing according to claim 8, wherein the adhesive strength between the porous resin film and the porous fiber film is 1.4 N / m. 10. The master for heat-sensitive stencil printing according to claim 1, wherein the porous resin film and the porous fiber film are bonded with a polyurethane adhesive. 11. The method according to claim 1, wherein the synthetic resin is mixed with a plurality of solvents having different solubilities, and a synthetic resin solution in a solubilized state is applied on a thermoplastic resin film and dried. A method for producing a master for heat-sensitive stencil printing as described in Crab. 12. The heat-sensitive method according to claim 1, wherein a water-in-oil emulsion containing the dissolved synthetic resin is applied on a thermoplastic resin film at a constant thickness and dried. A method for manufacturing a stencil master.