JPH10119452A - Base paper for thermal stencil printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To eliminate charging with electricity, to attain excellent carrying properties and to realize printing properties of high fineness and a high picture quality by a method wherein a thin layer containing an alkylammonium sulfonate is provided on one surface of a polyester film whereon a porous substrate is not bonded. SOLUTION: An unoriented polyester film is obtained by extruding polyester being a copolymer of polyethylene terephthalate, ethylene terephthalate and ethylene isophthalate, or the like, onto a cast drum by a T-die extrusion method and by cooling it by the drum kept at a prescribed temperature. A porous substrate being unoriented nonwoven fabric is put on the unoriented polyester film and they are subjected to thermocompression bonding between heating rolls. Moreover, a thin layer containing an alkylammonium sulfonate is provided on one surface of the unoriented polyester film whereon the porous substrate is not bonded. By this method, no wrinkle is formed in a carrying system and the clarity of a print of a high picture quality can be realized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive stencil sheet which is perforated by a thermal head or the like, and more particularly to a heat-sensitive stencil sheet having excellent printing clarity and excellent transportability.

[0002]

2. Description of the Related Art Conventionally, as heat-sensitive stencil printing base paper (hereinafter simply referred to as base paper), thermoplastic resin films such as polyester films and vinylidene chloride films have been used.
There is known a structure in which a porous support made of natural fiber, chemical fiber or synthetic fiber or a thin paper, nonwoven fabric, gauze or the like obtained by mixing them is bonded with an adhesive (for example, see Japanese Patent Application Laid-Open No. SHO 51-51). No. 2513, JP-A-57
182495).

[0003] However, the conventional base paper has the drawbacks that white spots occur in solid black portions and fine characters are blurred. It is considered that the cause of these poor print clarity is that the permeation of the ink is hindered by the adhesive bonding the film and the porous support.

[0004] Various proposals have been made to improve the disadvantages caused by these adhesives. For example, JP-A-58-147396, JP-A-4-23279
In Japanese Patent Application Laid-Open No. 0-210289, a base paper in which the amount of an adhesive to be used is as small as possible is used. A base paper formed by thermocompression bonding has been proposed. However, it has been found that these methods have a problem in that the adhesive strength is insufficient, or that when sufficient adhesive strength is to be obtained, sufficient perforation does not occur and the print density does not increase.

Further, Japanese Patent Application Laid-Open No. Hei 6-305273 discloses that a base paper is obtained by co-drawing an undrawn polyester film and an undrawn polyester fiber. The base paper did not require the use of an adhesive and was excellent in print clarity, but it was found that there was a problem that wrinkles were likely to occur due to charging during transport.

On the other hand, as a method for suppressing the charging of the base paper, a method using a phosphoric acid ester (Japanese Patent Publication No. 6-41234) and a method of providing a nonionic antistatic layer which is liquid at normal temperature (Japanese Patent Application Laid-Open No. 4-336290). Gazette), halogenated fourth
(Japanese Patent Application Laid-Open No. 3-61093), a method using a mixture of a quaternary ammonium chloride type cationic surfactant and a tertiary amine type cationic surfactant (Japanese Patent Application Laid-Open No. 3-61093). Japanese Patent Publication No. Hei 7-61750) has been proposed. However, although these methods showed an effect when a porous support made of natural fibers was used, they were still insufficient for a base paper made of a polyester film and polyester fibers.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a base paper which is free from charging, has excellent transportability, has high definition, and has high-quality printability.

[0008]

Means for Solving the Problems In view of the above problems, the present inventors have conducted intensive studies and as a result, have found that the above problems, ie, the problems of the present invention, can be solved by providing a specific thin layer on the film surface of the base paper. The present invention led to the heading.

That is, the present invention relates to a heat-sensitive stencil sheet comprising a polyester film and a porous support bonded to each other, wherein one side of the polyester film to which the porous support is not bonded is provided with an alkylammonium sulfonate. A heat-sensitive stencil printing base paper provided with a thin layer containing: The term “one side of the polyester film to which the porous support is not bonded” means one side of the polyester film which is to be brought into contact with the thermal head.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester used in the polyester film of the present invention is one containing aromatic dicarboxylic acid, aliphatic dicarboxylic acid or alicyclic dicarboxylic acid and diol as main components. Here, as the aromatic dicarboxylic acid component, for example, terephthalic acid,
Isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,
4'-diphenylsulfone dicarboxylic acid and the like can be mentioned, and particularly, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid and the like can be mentioned. Examples of the aliphatic dicarboxylic acid component include succinic acid, adipic acid, suberic acid, sebacic acid, dodecandionic acid, eicosandioic acid, and dimer acid. Examples of the alicyclic dicarboxylic acid component include 1,4-cyclohexanedicarboxylic acid. One of these acid components may be used alone, or two or more thereof may be used in combination. Further, an oxyacid such as hydroxybenzoic acid may be partially copolymerized. Also,
As the diol component, for example, ethylene glycol,
1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2- Examples thereof include cyclohexane dimethanol, 1,3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, diethylene glycol, triethylene glycol, polyalkylene glycol, and 2,2-bis (4-hydroxyethoxyphenyl) propane. Among them, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol are preferably used. These diol components may be used alone or in combination of two or more.

The polyester used in the polyester film of the present invention is preferably polyethylene terephthalate, a copolymer of ethylene terephthalate and ethylene isophthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyhexaethylene. Methylene-2,6-naphthalate, copolymer of butylene terephthalate and ethylene terephthalate, copolymer of butylene terephthalate and hexamethylene terephthalate, copolymer of hexamethylene terephthalate and 1,4-cyclohexane dimethylene terephthalate, ethylene Copolymers of terephthalate and ethylene-2,6-naphthalate and blends thereof can be mentioned. Particularly preferred for improving the perforation sensitivity, a copolymer of ethylene terephthalate and ethylene isophthalate, polyhexamethylene terephthalate, hexamethylene terephthalate and 1,4-cyclohexane dimethylene terephthalate,
Copolymers of ethylene terephthalate and ethylene-2,6-naphthalate can be exemplified.

The polyester according to the present invention can be produced by the following method. For example, a method in which an acid component is directly esterified with a diol component, and then the product of this reaction is heated under reduced pressure to remove the excess diol component and polycondensate to produce a dialkyl acid. There is a method of using an ester, performing a transesterification reaction between the ester and a diol component, and then performing polycondensation in the same manner as described above. At this time, if necessary,
A metal compound can be used as a reaction catalyst, and a phosphorus compound can be used as a heat stabilizer.

The polyester of the present invention may optionally contain a flame retardant, an antioxidant, an ultraviolet absorber, a pigment, a dye, an antifoaming agent such as polysiloxane, and the like.

Further, the following slipperiness imparting method can be adopted. For example, a method of blending inorganic particles such as clay, mica, titanium oxide, calcium carbonate, kaolin, talc, wet or dry silica, alumina, zirconia, organic particles containing acrylic acid, styrene, etc., a polyester polymerization reaction There are a method using so-called internal particles for precipitating a catalyst and the like to be added sometimes, and a method using a surfactant.

The polyester film of the present invention is preferably a biaxially stretched film, and its thickness is determined by the sensitivity and the like required for the base paper.
μm, more preferably 0.3 to 2 μm, particularly preferably 0.5 to 1.8 μm.

There are the following methods for obtaining a biaxially stretched film. For example, polyester is extruded onto a cast drum by a T-die extrusion method, and is cooled by a drum maintained at a constant temperature to obtain an unstretched film. An unstretched film having a desired thickness can be produced by adjusting the slit width of the die, the discharge amount of the polymer, and the rotation speed of the cast drum. At this time, a so-called electrostatic application casting method in which static electricity is applied to the polymer to increase the adhesion to the drum may be used.

The biaxial stretching method includes a sequential biaxial stretching method and a simultaneous biaxial stretching method.
Any of the axial stretching methods may be used. In the case of the sequential biaxial stretching method, stretching is generally performed in the longitudinal direction and then in the transverse direction, but may be performed in the opposite direction. The stretching temperature is preferably between the glass transition temperature of the polyester film and the elevated crystallization temperature. The stretching ratio is not particularly limited, and is determined by the type of the polymer for the film to be used, the sensitivity required for the base paper, and the like, but is preferably 2 to 8 times each in the vertical and horizontal directions, and more preferably 3 to 8 times. Appropriate. After biaxial stretching, the film may be stretched longitudinally or horizontally, or vertically and horizontally again.

Further, heat treatment may be performed after the biaxial stretching. The heat treatment temperature is not particularly limited and is determined depending on the type of the polymer used.
° C, more preferably 80-170 ° C, particularly preferably 9 ° C
0 to 150 ° C., and the time is suitably about 0.5 to 60 seconds.

The orientation parameter of the polyester film of the present invention is preferably 3 to 10, more preferably 3.5.
-8, particularly preferably 4-7. If the orientation parameter of the polyester film is less than 3, the sensitivity may be lowered, and if it exceeds 10, the sensitivity is saturated and the meaning becomes poor. The orientation parameter in the present invention is determined by laser Raman spectroscopy.

The melting point of the film of the present invention is 140 to 24.
0 ° C is preferred, more preferably 150 to 215 ° C, and particularly preferably 150 to 200 ° C.

The film of the present invention preferably has a crystal melting energy of 12 to 46 J / g, more preferably 1 to 46 J / g.
It is 7 to 35 J / g. If it is less than 12 J / g, there is a possibility that the uniformity of perforation may be reduced or curling may occur. If it exceeds 46 J / g, the sensitivity may decrease.

The porous support of the present invention refers to a porous support made of natural fiber, synthetic fiber, or the like, which is permeable to printing ink and does not substantially undergo thermal deformation under heating conditions under which a film is perforated. Things. The porous support is preferably a polyester nonwoven fabric.

For the adhesion between the film and the porous support, a method of bonding with an adhesive can be used as long as the perforation characteristics of the film are not hindered. However, when the porous support is mainly a polyester nonwoven fabric, the adhesive is used. Adhering without any intervening is more preferable because the printing clarity is improved. As a method of bonding the polyester nonwoven fabric to the film without the use of an adhesive, there is also a method of thermally fusing the film and the polyester nonwoven fabric, but it is difficult to make the adhesive strength and sensitivity incompatible with each other,
The method of overlapping and co-stretching with a polyester nonwoven fabric during the production process of the film is particularly preferable.

The polyester constituting the preferable nonwoven fabric in the present invention is a polyester containing an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid and a diol as main components, similarly to the film. Preferably, polyethylene terephthalate, polyethylene-2,
Examples thereof include 6-naphthalate, poly-1,4-cyclohexane dimethylene terephthalate, and a copolymer of ethylene terephthalate and ethylene isophthalate. When drilling, it is particularly preferable because it is difficult to thermally deform,
Polyethylene terephthalate, polyethylene-2,6-
Naphthalate. The polyester of the film and the nonwoven fabric need not be exactly the same, and the melting point of the film is more preferably lower than the melting point of the nonwoven fabric, and particularly preferably the melting point of the film is at least 10 ° C. lower than the melting point of the nonwoven fabric.

The polyester nonwoven fabric constituting a preferred base paper in the present invention is obtained by using the above polyester and unstretched nonwoven fabric having a low orientation obtained by a direct melt spinning method such as a melt blow method or a spun bond method. Particularly, those formed by stretching are particularly preferable.

In the melt blow method, when the molten polyester polymer is discharged from the die, hot air is blown from the periphery of the die to make the discharged polymer finer, and then the unstretched nonwoven fabric is arranged at an appropriate position. It is manufactured by spraying and collecting on a formed net conveyor to form a web. Since the web is sucked together with the hot air by the suction device provided on the net conveyor, the individual fibers are collected before they are completely solidified. That is, some of the fibers of the web are collected in a fused state. The degree of fusion of the fibers can be adjusted by changing the collection distance between the base and the net conveyor. Further, by changing the polymer discharge amount, hot air temperature, hot air flow rate, conveyor moving speed, and the like, it is possible to arbitrarily set the fiber orientation of the unstretched nonwoven fabric, the basis weight of the web, and the diameter of the single fiber. As the fiber spun by the melt blow method, it is particularly preferable to use a fiber which is finely fined by hot air pressure and solidified in a non-oriented or low-oriented state.
The fibers constituting the undrawn nonwoven fabric are preferably substantially continuous. Further, the polymer discharged from the die can be solidified in a low-crystalline state close to an amorphous state by rapidly cooling from a molten state to a room temperature atmosphere.

Similarly, in the spunbonding method, the unstretched nonwoven fabric is pulled by an air ejector on a polymer discharged from a die, and the obtained filaments collide with a collision plate to spread the fibers, and are collected in a conveyor shape. It is manufactured by forming a web. By changing the polymer discharge amount and the conveyor speed, the basis weight of the web can be arbitrarily set. Further, the molecular orientation state of the filament can be arbitrarily adjusted by adjusting the pressure and the flow rate of the ejector. By reducing the spinning speed by reducing the pressure and the flow rate, a web having a low degree of molecular orientation can be obtained. Further, by adjusting the cooling rate of the discharged polymer, a web having low crystallinity can be obtained. When manufacturing by the spun bond method,
The unstretched polyester nonwoven fabric used for obtaining the base paper of the present invention is preferably spun at a spinning speed of 1500 m / min or less, more preferably 1000 m / min or less,
Especially preferably, it is 800 m / min or less.

The crystallinity of the unstretched polyester nonwoven fabric used in the present invention is preferably 20% or less, more preferably 10% or less, and particularly preferably 5% or less.

The unstretched polyester nonwoven fabric used in the present invention is most preferably unstretched. However, even if it is stretched, it is preferable that the stretch ratio is low and the degree of orientation is low. The birefringence (Δn) is preferably 0.03 or less, more preferably 0.02 or less, and particularly preferably 0.01 or less.

The base paper of the present invention is obtained by laminating an unstretched nonwoven fabric on the above unstretched film between heating rolls, thermocompression bonding, and biaxially stretching to obtain a bonded state without an adhesive. That is, it is most preferable that the unstretched polyester nonwoven fabric is thermocompression-bonded to an unstretched polyester film obtained by extrusion casting before the longitudinal stretching step. The temperature for thermocompression bonding is preferably between the glass transition temperature of the film and the temperature-rise crystallization temperature.

Next, a base paper can be obtained by stretching and heat treatment in the same manner as for the film.

The base paper obtained by the heat treatment may be once cooled to about room temperature, and then aged at a relatively low temperature of 40 to 90 ° C. for about 5 minutes to 1 week.
The use of such aging is particularly preferable because curling during storage of the base paper or in the printing press can be suppressed.

The average fiber diameter of the single yarn constituting the polyester nonwoven fabric of the present invention is usually 1 to 20 μm, preferably 2 to 1 μm.
It is 5 μm, more preferably 3 to 12 μm.

The crystallinity of the polyester nonwoven fabric of the present invention is preferably 15% or more, more preferably 20% or more.
% Or more, particularly preferably 25% or more.

The basis weight of the porous support constituting the stencil of the present invention is preferably 1 to 30 g / m ^2, more preferably 2 to 20 g / m ^2, particularly preferably 3~16g
/ M ² .

The base paper of the present invention has a thin layer containing an alkyl ammonium sulfonate on one side of the film which is to come into contact with the thermal head. Even with alkylammonium salts, chlorides and bromides are not preferred because they have insufficient antistatic effects and corrode the thermal head.
The alkyl ammonium sulfonate is preferably a compound represented by the following formula (1).

RR ₁ R ₂ R ₃ N—SO ₃ —R ₄ (1) wherein R is an alkyl group having 1 to 22 carbon atoms, R ₁ , R ₂ ,
R ₃ is the same or different alkyl group, hydrogen or hydroxyalkyl group, and R ₄ is an alkyl group or alkylaryl group.

The alkyl ammonium may be any as long as it has at least one alkyl group, and preferably has a hydroxyalkyl group in addition to the alkyl group. Examples thereof include tetraethylammonium, tetrabutylammonium, triethylhydroxyethylammonium, tributylhydroxyl. Ethyl ammonium, triethyl hydroxybutyl ammonium, tributyl hydroxybutyl ammonium, diethyl dihydroxyethyl ammonium, dibutyl dihydroxyethyl ammonium, diethyl dihydroxybutyl ammonium, dibutyl dihydroxybutyl ammonium, ethyl trihydroxyethyl ammonium, butyl trihydroxyethyl ammonium, stearyl trihydroxyethyl ammonium , Ethyl Hydroxybutyl ammonium, butyl trihydroxybutyl ammonium, stearyl trimethyl-hydroxybutyl ammonium.
As the sulfonic acid, those having an alkyl group or an alkylaryl group are preferable, for example, hexylsulfonic acid, octylsulfonic acid, dodecylsulfonic acid, stearylsulfonic acid, hexylbenzenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid,
And stearylbenzenesulfonic acid.

These alkylammonium sulfonates are used in combination with a release agent comprising a silicone oil, a silicone resin, a fluorine resin, a wax, a surfactant, etc., in order to prevent fusion during perforation. Is preferably formed. Further, the thin layer may also contain a heat resistant agent, an antioxidant, organic particles, inorganic particles, pigments, dispersing aids, preservatives, defoamers, and the like. The thickness of the thin layer containing the alkyl ammonium sulfonate is preferably from 0.005 μm to 0.4 μm, more preferably from 0.01 μm to 0.4 μm.
4 μm or less.

In the base paper of the present invention, the thin layer containing an alkylammonium sulfonate may be directly coated on the film with an alkylammonium sulfonate or a release agent, but may be dissolved, emulsified or suspended in water or an organic solvent. It is preferable to apply in the state of a turbid coating solution, and then dry or remove the solvent. Before or after stretching the film,
It may be performed at any stage. In order to achieve the effect of the present invention more remarkably, it is particularly preferable to apply before horizontal stretching in the case of sequential biaxial stretching in which horizontal stretching is performed after longitudinal stretching, and before stretching in the case of simultaneous biaxial stretching. . The application method is not particularly limited, but application is preferably performed using a roll coater, a gravure coater, a reverse coater, a bar coater, or the like.

Before the thin layer is provided, if necessary, an activation treatment such as a corona discharge treatment may be applied to the coated surface of the film in air or other various atmospheres.

[Method for Measuring Characteristics] (1) Melting point (° C.) Differential scanning calorimeter RDC220 manufactured by Seiko Instruments Inc.
Using a mold, a 5 mg sample was collected, and the temperature was
It was determined from the peak temperature of the endothermic curve when the temperature was raised at a rate of ° C./min.

(2) Crystal melting energy (ΔHu) Differential scanning calorimeter RDC220 manufactured by Seiko Electronic Industry Co., Ltd.
It is determined from the area at the time of melting using a mold. This area is shifted from the baseline to the absorption side by increasing the temperature, and is the area until the temperature returns to the baseline position when the temperature is further increased.The area from the melting start temperature position to the end position is connected by a straight line. (A) is obtained. I under the same DSC conditions
n (indium) was measured, and this area (b) was determined to be 28.5.
It is calculated by the following equation as J / g.

28.5 × a / b = △ Hu (J / g) (3) Orientation Parameters The orientation parameters were determined by laser Raman spectroscopy. The film is embedded in PMMA resin and wet polished to form a cross section perpendicular to the length or width direction of the film,
For example, "Rama made by Jobin Yvon / Atago Bussan
nor "U-1000I (light source: GLG330 manufactured by NEC)
0 Ar 'laser 514.5 nm, microscope: using a BH-2 type objective lens manufactured by Olympus × 100), irradiating a laser beam perpendicular to the cross section, and polarizing the laser beam in the plane direction of the film and the thickness of the film. 1615c of Raman spectrum by laser light polarized in the vertical direction
^{Assuming that} the peak intensities of the m ^-1 band were I and I _ND , respectively, the ratio I / _IND was used as the orientation parameter of the film.

(4) Fiber Diameter (μm) Ten photographs were taken at an arbitrary magnification of 2000 times with an electron microscope at any ten places of the nonwoven fabric.
The diameters of five fibers were measured, and this was performed for ten photographs, and a total of 150 fiber diameters were measured.

(5) Weight (g / m ² ) A piece of base paper of 20 cm × 20 cm was taken, its weight was measured and converted to the weight per m ² .

(6) Evaluation of printability The prepared base paper was supplied to a printing machine RISOGRAPH (GR275) manufactured by Riso Kagaku Kogyo Co., Ltd., and the whole surface was printed in black on an A4 size by thermal head plate making. Was evaluated by visual judgment. The energy supplied to the thermal head was 40 μJ per dot.

The white spots were judged as ◎ when there were 3 or less white spots, を when there were 4 to 10 white spots, and 11 when white spots were found.
Those having ~ 100 pieces were rated as △, and those having more than 100 blank spots were rated as ×.

◎, △, Δ are practically usable.

(7) Evaluation of Conveyability The produced base paper was supplied to a printing machine lithograph (GR275) manufactured by Riso Kagaku Kogyo Co., Ltd. to perform plate making 100 times continuously, and the presence or absence of wrinkles of the base paper on the plate cylinder was checked. It was determined visually and evaluated as follows.

The base paper on the plate cylinder had no wrinkles at all ◎, wrinkles generated 1-3 times, ○: wrinkles generated 3-5 times Δ, wrinkles generated 6 times or more The result was indicated by x.

◎, △, and Δ are practically usable.

[0053]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1 (Making of unstretched polyester non-woven fabric)
Using a rectangular spinneret having 100 holes, the spinneret temperature was 285.
A polyethylene terephthalate raw material (melting point: 257 ° C., intrinsic viscosity: 0.50) was spun at a temperature of 25 ° C. and a discharge rate of 30 g / min by a melt blow method, and the fibers were collected and wound on a net conveyor at a collecting distance of 15 cm. At this time, the amount of hot air blown from the vicinity of the base was set to 2.7 Nm ³ / min, and the temperature of the web immediately below the base was set to 87 by a suction device provided on the net conveyor.
° C. The fiber weight of the unstretched nonwoven fabric is 140 g /
m ² , average fiber diameter was 9.0 μm, crystallinity was 1%, and birefringence (Δn) was 0.003.

(Film Forming) Next, an ethylene terephthalate-ethylene isophthalate copolymer (isophthalic acid 25%) containing 0.4% by weight of silica having an average particle diameter of 1.5 μm was used.
Mol% copolymerization, melting point 195 ° C., intrinsic viscosity 0.72) was pre-crystallized in an oven at 120 ° C., and then dried under reduced pressure at 150 ° C. for 3 hours in a rotary drier, using an extruder having a screw diameter of 40 mm. Extruded at a T-die die temperature of 270 ° C, cast on a cooling drum having a diameter of 300 mm and a thickness of 13 μm
Was produced.

The above nonwoven fabric is superimposed on the unstretched film, and a roll group consisting of six rolls in which the rotation direction of the adjacent rolls is reversed and a seventh roll rotating in the same direction as the sixth roll is formed. The first roll passed through the sixth roll in a cross-shaped manner so that the film surface came into contact with the non-woven fabric surface of the second roll, and the seventh roll passed through so that the non-woven fabric surface came into contact therewith. At this time, the first roll and the second roll are metal rolls whose surfaces are chrome-plated, and the third to sixth rolls are rolls coated with silicone rubber. ℃,
83 ° C for the second roll, 87 for the third roll
° C, 4th roll is 90 ° C, 5th roll is 8
7 ° C., the sixth roll was 93 ° C., and the seventh roll was 25 ° C. The peripheral speeds of the first to sixth rolls were set to be the same, and a peripheral speed difference was provided between the sixth and seventh rolls, whereby the film was stretched 3.5 times in the longitudinal direction.

Then, an aqueous dispersion composed of 1 part by weight of triethylhydroxyethylammonium dodecylsulfonate, 1 part by weight of dimethyl silicone oil and 98 parts by weight of water was applied on the obtained laminated sheet using a metalling bar to a coating thickness of 9 μm. It applied so that it might become.

Further, it is sent to a tenter type horizontal stretching machine,
Heated to 95 ° C with hot air, stretched 4.0 times in the width direction,
Heat treatment was performed at 110 ° C. for 10 seconds to prepare a heat-sensitive stencil sheet. The orientation parameter of the film portion of the obtained base paper was 5.6, the nonwoven fabric weight was 10 g / m ² , and the average fiber diameter was 4.8 μm. The thickness of the film alone is 0.1.
9 μm, melting point: 195 ° C., crystal melting energy: 24.
It was 7 J / g. (Evaluation Results) As summarized in Table 1, printability was evaluated using the finally obtained base paper. The printed matter printed using this base paper had no white spots and had no wrinkles at all. No transfer occurred and the transportability was good.

Comparative Example 1 A base paper was obtained in the same manner as in Example 1 except that triethylhydroxyethylammonium dodecylsulfonate was not used.

Table 1 summarizes the evaluation results. It can be seen that wrinkles occur and transportability is reduced.

[Examples 2] to [Example 5], [Comparative example 2] and [Comparative example 3] The same procedures as in Example 1 were conducted except that the compounds shown in Table 1 were used instead of triethylhydroxyethylammonium dodecylsulfonate. Base paper was obtained in the same manner as in Example 1.

Table 1 summarizes the evaluation results. When the alkylammonium sulfonate of the present invention was used,
It can be seen that both print clarity and transportability are good.

Example 6 Fabrication of Unstretched Polyester Nonwoven Fabric Pore Diameter 0.35 m
m, using a rectangular spinneret having 100 holes and a spinneret temperature of 2
A polyethylene terephthalate raw material (melting point: 257 ° C., intrinsic viscosity: 0.53) was spun at 85 ° C. at a discharge rate of 30 g / min by a melt blow method, and the fibers were collected and wound on a net conveyor at a collecting distance of 15 cm. . At this time, the amount of hot air blown from the vicinity of the base was set to 2.8 Nm ³ / min, and the temperature of the web immediately below the base was set to 8 by a suction device provided on the net conveyor.
7 ° C. The fiber weight of the unstretched nonwoven fabric is 140 g / m.
^{2. The} average fiber diameter was 9.3 μm, the crystallinity was 2%, and the birefringence (Δn) was 0.004.

(Film Forming) Next, an ethylene terephthalate-ethylene isophthalate copolymer containing 0.4% by weight of silica having an average particle diameter of 1.5 μm (isophthalic acid 14
Mol% copolymer, melting point: 225 ° C., intrinsic viscosity: 0.61) was preliminarily dried in an oven at 120 ° C., and dried in a rotary drier at 175 ° C.
At 275 ° C. using a 40 mm screw diameter extruder.
An unstretched film having a thickness of 13 μm was formed by casting on a cooling drum having a thickness of 13 mm.

The non-woven fabric is superimposed on the unstretched film, and a roll group consisting of five rolls in which adjacent rolls rotate in opposite directions and a seventh roll rotating in the same direction as the sixth roll is formed. The first roll passed through the sixth roll in a cross-shaped manner so that the film surface came into contact with the non-woven fabric surface of the second roll, and the seventh roll passed through so that the non-woven fabric surface came into contact therewith. At this time, the first roll and the second roll are metal rolls whose surfaces are chrome-plated, and the third to seventh rolls are rolls coated with silicone rubber. ℃,
83 ° C for the second roll, 89 for the third roll
° C, 4th roll is 93 ° C, 5th roll is 8
9 ° C., the sixth roll was 93 ° C., and the seventh roll was 25 ° C. Further, the peripheral speeds of the first to sixth rolls were set to be the same, and a peripheral speed difference was provided between the fifth and seventh rolls, whereby the film was stretched 3.5 times in the longitudinal direction.

Next, an aqueous dispersion composed of triethylhydroxyethylammonium dodecylsulfonate, 1 part by weight of dimethyl silicone oil and 98 parts by weight of water was applied to the obtained laminated sheet with a metalling bar to a coating thickness of 9 μm. It applied so that it might become.

Further, it is sent to a tenter type horizontal stretching machine,
Heated to 97 ° C with hot air, stretched 4.0 times in the width direction,
Heat treatment was performed at 120 ° C. for 10 seconds to prepare a heat-sensitive stencil sheet. The orientation parameter of the obtained base paper was 5.8 for the film portion, 4.8 for the nonwoven fabric portion, and 10 g /
m ² , and the average fiber diameter was 5 μm. The thickness of the film alone was 0.9 μm, and the crystal melting energy was 33.1.
J / g. (Evaluation Results) As summarized in Table 1, when the printability was evaluated using the finally obtained base paper, the printed matter printed using this base paper had no white spots and further no wrinkles. It was good without generation.

Example 7 Ethylene terephthalate-ethylene isophthalate copolymer containing 0.4% by weight of silica having an average particle size of 1.5 μm (isophthalic acid copolymer in 25 mol%, melting point 195 ° C., intrinsic viscosity 0.72) ) Was pre-crystallized in an oven at 120 ° C and then dried in a rotary dryer for 15 minutes.
It was dried under reduced pressure at 0 ° C. for 3 hours, extruded at a T-die die temperature of 270 ° C. using an extruder having a screw diameter of 40 mm, and was dried at a temperature of 30 °.
An unstretched film having a thickness of 24 μm was formed by casting on a 0 mm cooling drum.

The unstretched film is rolled into a roll group consisting of six rolls in which the rotation direction of the adjacent rolls is reversed and a seventh roll rotating in the same direction as the sixth roll. However, in the second roll, the nonwoven fabric surface was passed to the sixth roll in a crossing manner so that the nonwoven fabric surface was in contact with the roll, and the seventh roll was also passed so that the nonwoven fabric surface was in contact therewith. At this time, the first roll and the second roll are metal rolls whose surfaces are chrome-plated, the third to sixth rolls are rolls coated with silicone rubber, and the temperature of the roll surface is
The first roll is 80 ° C, the second roll is 83
℃, the third roll is 87 ℃, the fourth roll is 9
0 ° C., the fifth roll was 93 ° C., the sixth roll was 93 ° C., and the seventh roll was 25 ° C. Also, the first
The peripheral speeds of the rolls from the sixth roll to the sixth roll are the same, and a peripheral speed difference is provided between the sixth roll and the seventh roll so that 3.5 rolls in the longitudinal direction.
Double stretching was performed.

Further, it is sent to a tenter type horizontal stretching machine,
Heated to 95 ° C with hot air, stretched 4.0 times in the width direction,
Heat treatment was performed at 110 ° C. for 10 seconds to prepare a heat-sensitive stencil sheet. The orientation parameter of the film portion of the obtained base paper was 5.4. The thickness of the film is 1.7 μm,
Melting point: 195 ° C, crystal melting energy: 25.1 J / g
Met.

(Preparation of base paper) One side of the obtained film was bonded to a thin paper having a basis weight of 10 g / m ² containing manila hemp as a main component using a vinyl acetate adhesive, and dodecyl sulfone was applied to the other side of the film. Triethylhydroxyethylammonium acid and dimethylsilicone oil were applied at a weight ratio of 1: 1 using a bar coater to give a total of 0.10 g / m ² to prepare a base paper.

(Evaluation) The properties of the film and the base paper were evaluated and are shown in Table 1. It can be seen that the base paper has excellent transportability.

Comparative Example 4 Preparation and evaluation of base paper were performed in the same manner as in Example 6 except that dimethyl silicone oil was applied to a concentration of 0.05 g / m ² without using triethylhydroxyethylammonium dodecylsulfonate. went. The results are also shown in Table 1, but the transportability was insufficient.

[0074]

[Table 1]

[0075]

According to the present invention, the above-mentioned structure is provided.
The following effects are obtained. That is, there is no generation of wrinkles in the transport system in the apparatus at the time of use, and the obtained printed matter has print clarity.

Claims (4)

[Claims] 1. A heat-sensitive stencil printing paper comprising a polyester film and a porous support bonded to each other, on one side of the polyester film to which the porous support is not bonded, a thin layer containing an alkylammonium sulfonate. Base paper for heat-sensitive stencil printing, characterized in that: 2. The heat-sensitive stencil printing paper according to claim 1, wherein the porous support is a polyester non-woven fabric. 3. The heat-sensitive stencil sheet according to claim 1, wherein the polyester film and the porous support are adhered to each other without using an adhesive. 4. The heat-sensitive stencil sheet according to claim 1, wherein the orientation parameter of the polyester film portion determined by laser Raman spectroscopy is 3 to 10.