NL8104428A - ELECTRO-CONDUCTIVE FILM. - Google Patents

Description

, * VO 2U03 0 Electroconductive film.

The invention relates to an electroconductive film. Lake. in particular, the invention relates to an electroconductive film for an electro-sensitive blank used in rotary mimeographic printing or stenciling.

Polyvinyl chloride or a vinyl chloride / vinyl acetate copolymer has heretofore been used as an electroconductive film for an electro-sensitive blank used for rotary mimeographic printing or stenciling (hereinafter referred to as "stencil film"). More specifically, a mixture consisting of polyvinyl chloride or a vinyl chloride / vinyl acetate copolymer with suitable amounts of a plasticizer, stabilizer and conductive material, such as carbon black, is formed into a film with a thickness of 20 - 30 micrometers, after which the film is applied as a stencil film.

Such a stencil film is treated according to the known stencil method using a scanning drum as well as a recording conductive stylus and then used for printing using a known rotary stencil printing machine. This stencil film is widely used even today as a cheap, convenient, easy and light printable material.

Since the conventional stencil film as main starting material comprises vinyl chloride, the formation of hydrogen chloride gas by thermal decomposition of vinyl chloride cannot be avoided in stencilling. As a result, the recording conductive lead and other parts are corroded by formed hydrogen chloride gas, while the operator of the machine experiences the stenciling operation as unpleasant.

Some stencil cutters attach a hydrogen chloride gas capture device to eliminate the aforementioned drawback, but it does not completely solve the problem. Thus, a strong need has always been felt for a stencil film composed of a material other than a vinyl chloride-type material.

Many materials other than a vinyl chloride type material have so far been proposed. For example, polykene type resins such as polyethylene, polypropylene, polyethylene / polypropylene blends, ethylene / vinyl 8104428 * 2 acetate copolymer, copolymer of ethylene with acrylic acid or an acrylic acid ester and an ethylene / vinyl alcohol polymer, cellulose resins such as acetyl cellulose and ethyl cellulose polyacetate-type resins such as polyvinylhutyral have been tested and test products have been prepared from these resin materials.

However, these test products are worse than. the usual products obtained from a vinyl chloride-type material in terms of film strength, resolving power and durability in printing, none of which have hitherto been of practical importance.

It is a main object of the invention to provide a stencil film formed using a material other than a vinyl chloride-type material as a binder, whereby no harmful gas with an unpleasant odor is formed during stenciling and excellent film strength , has resolution and longevity.

The volume-spring setting serves in an electro-sensitive stencil plate. for easy perforation of a stencil

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film by electrical decompositions to be about 1 x 10 to about 1 x 10 -TL cm. It is admitted that in order to realize such a volume spring position, it is necessary to have 15 - 35 parts by weight of an electroconductive substance, normal carbon black, per 100 parts by weight of the resin. to disperse. However, it is difficult to disperse carbon black homogeneously in a resin and a long kneading operation which requires a considerable yielding capacity should be carried out regardless of whether a dry or wet mixing method is used. This problem becomes more pronounced when the target carbon black concentration is higher. In addition, the more filler used, the poorer the quality of the film. Thus, a plasticizer should also be used to somewhat offset the poorer marketability.

It is a second object of the invention to provide a stencil film which is formed from an electroconductive substance and a resin component, for which mixing can be easily carried out and a very uniform distribution of the volume resistance can be obtained because the skate the conductive substance can be homogeneously distributed in the resin component. It is a third object of the invention to provide a stencil film in which the ink resistance is greatly improved.

In a recording strip made of a stencil film 8104428-3, the cartridge formed on the strip is easily deformed by bloating caused by the printing ink, making it difficult to obtain an accurate and clear image copy. To avoid this drawback, one needs a stencil film with a high ink resistance.

Research has shown that when a mixture of two specific linear saturated polyester resins is selected and the mixture is combined with a carbon black grafted polymer, the aforementioned objectives can be achieved. The invention is based on this finding.

More particularly, according to the invention, there is provided an electro-conductive film for an electro-sensitive blank used for rotary stencil printing, which is composed of a resin mixture comprising a carbon black grafted polymer and a mixture of a linear saturated polyester resin I with a molecular weight of 160Q0 - 22000, a glass transition temperature of k6 - U8 ° C and a softening point of 156 - 160 ° C, as well as a linear saturated polyester resin IX with a molecular weight of 20000 - 25000, a glass transition temperature of 3 - 5 ° 0 and a softening point of 112 - 116 ° C.

According to the invention, the carbon black grafted polymer 20 (hereinafter referred to as "GC") is used as an electroconductive material.

GC is prepared by inoculating a vinyl group-containing monomer, such as acrylic acid and / or an acrylic acid ester, on carbon black using GC usually dispersed in a medium with a high affinity for the grafted component. For example, "Graft Carbon HC-501B" (trade name for a product of Byoyu Xogyo Kabushiki Kaisha), which is a suspension with a solids content of kO, is obtained by injecting a graft polymer in aqueous ammonia. dispersion formed by inoculating acrylic acid and butyl acrylate on carbon black, advantageously used in the invention.

A mixture consisting of linear saturated polyester resins I and II with the following different properties is used as a binder.

Linear Saturated Linear Saturated Polyester Resin I Dated Polyester Resin 35 _______________________ Resin II _

Molecular weight 1Ö000 - 22000 20000 - 25000

glass transition temperature k6 - k8 ° C 3 - 5 ° C

softening point 156 - 160 ° C 112.- 116 ° C

8104428 a - ΰ k

Each of the. linear, saturated polyester resins with the aforementioned properties can be used. For example, one can use ethylene terephthalate / ethylene isophthalate copolyester, an ethylene ephthalate / 2,2-bis [U- (beta-hydroxy-ethoxy) phenyl] -propane terephthalate copolyester, a bis-5 (beta-hydroxyethyl) terephthalate / 2,2 -bis- [Ij- (bet a-hydroxyethoxy) phenyl] - propane terephthalate copolyester and a diphenyl terephthalate / diphenyl isophthalate copolyester. As a suitable example of the linear saturated polyester resin I Vylon 103 (trademark of a product of Toyobo Kabushiki Kaisha) is mentioned as well as a typical example of the linear saturated polyester resin II Vylon 530 (also trademark of a product of Toyobo Kabushiki Kaisha).

A polymer compatible with the linear saturated polyester resin, for example nitrocellulose or a xylene resin, can be used in a minor amount in combination with the linear saturated polyester resin as required. The linear saturated polyester resins Γ and II are dissolved or emulsified. used in a solvent. The type of solvent is not particularly critical and any of it. the. Conventional solvents can be used. From a practical point of view, hydrocarbons such as benzene, toluene, methylene chloride, 2-nitropropane, trichloro, dichloropropylene and derivatives thereof are advantageously used, as well as oxygen-containing compounds such as methyl ethyl ketone, cyclohexanone, ethyl acetate, cellulose acetate , dioxane and tetrahydrofuran. Toluene / methyl ethyl ketone, toluene / ethanol, toluene / acetone and tolnene / methyl ethyl ketone / ethyl acetate can be mentioned as practically useful mixing solvents.

In principle, no plasticizer need be used for the resin composition of the invention. However, a plasticizer can be added as needed. A plasticizer can be used according to a known recipe. From a practical point of view, advantageous use can be made of phthalate-type plasticizers such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate and butyl benzyl phthalate, as well as methyl ethyl phthalate, phosphate type plasticizers, such as triphenyl phosphate methyl glycol phosphyl glyphyl glycol phosphyl glycol ethyl phthalylethyl glycol, and butyl phthalyl butyl glycol, maleate-type plasticizers such as diethyl maleate and dibutyl maleate, and fumarate-type plasticizers such as dibutyl fumarate. Nitrocellulose can also sometimes be used as a plasticizer. The amount of plasticizer is not particularly critical, but from a practical point of view, it is preferred to add 5-20 wt.% To the resin composition.

The weight ratio of the linear saturated polyester resin I to the linear saturated polyester resin II 5 is set from a practical point of view "within the range 6 / k - 7/3, but when using a plasticizer this weight ratio range can be extended to 5/5 - 8/2 If the weight ratio of resin I to resin II falls outside said range, the flexibility and strength of the film deteriorate and a good stencil film cannot be obtained.

From a practical point of view, the amount of GP used is set at 10-30 parts by weight, preferably 12-26 parts by weight, per 100 parts by weight of the mixture of the linear saturated polyester resins I and U.

If the amount of GC is less than 10 parts by weight per 100 parts by weight of the mixture of the linear saturated polyester resins I and IX, electric discharge perforation becomes difficult while if the amount of GC is greater than 30 parts by weight per 100 wt parts of the mixture mix the leakage current at the perforation stage increases by electric discharge and hardly a clear perforation pattern can be obtained.

Conventional stabilizers, additives and fillers can be added to the resin composition, provided the properties of the stencil film are not adversely affected. For example, a lubricant, such as calcium stearate, zinc laurate, or bicarbonate, a thermal stabilizer such as an organic tin compound and an organic metal salt of barium, calcium, or zinc, and an antioxidant such as di-tert-butyl hydroxytoluene to the resin composition of the invention. being added.

A stencil film is prepared from the aforementioned resin mixture 30 by casting a solution or emulsion, or a stencil film is prepared by extrusion or blow molding from a solid obtained by removing volatile components from the resin composition.

A masking coating can be applied to the surface of the stencil film of the invention, as is the case with a commercially available stencil film. More specifically, 8104428 'β, a colored layer to facilitate the distinction of a perforated recording image can be obtained by a mixture of an inorganic pigment, such as titanium oxide or zinc oxide, and a resin binder, such as an acrylic resin. a cellulose resin or a polyamide-5 resin, on the surface part. of the movie too. to coat.

As with a conventional stencil film, the stencil film of the invention thus prepared is bonded to a conductive backing.

. paper to form a. electro-sensitive blank, after which this blank is formed into a registration strip by perforation by means of electrical discharge and then used for stencil printing kea.

When the stencil film of the invention is formed into a recording strip, no harmful gas with an unpleasant odor is formed, while the stencil film of the invention further has excellent strength, excellent resolving power and excellent printing stability. and the volume resistance throughout the stencil film is completely uniform. Moreover, the stencil film of the invention has a high ink resistance, which is very favorable from a practical point of view. Torch, the power required to knead the resin composition used to form the stencil film according to the invention is considerably lower and thus the processing time can be shortened. The stencil film according to the invention thus provides very significant energy savings.

The invention will now be described in detail with reference to the following examples which are not intended to be limiting.

Examples. X-XII and comparative examples 1-k

A resin composition as shown in Table A, in a thickness of 20 µm after drying on a polyester film previously coated with a peeler, was coated by the solution casting method using a roller coater to obtain a stencil film. The properties of the stencil film were measured according to the primary evaluation methods described below for stirring. The volume resistance, the tensile strength and. elongations were determined according to the method of J.S. 0-2318 (1975) - The stencil film was bonded to a commercially available electroconductive paper backing and subjected to the perforation test. Originally, a facsimile test 8104428 τ card No. 2 from the Institute of Linage Electronics Engineers of Japan was used, while a registration strip was prepared using a commercial stencil cutter (Rex Rotary Press Model 2202S from Rex Co, Denmark). The perforation properties were evaluated by observing an enlarged photographic image.

In. Comparative Examples 1 and 2, only one type of a linear saturated polyester resin was used, but other procedures were the same as in Examples I and II. The perforation properties were good and the properties of the resulting film 10 were in each of the comparative examples 1 and 2 bad.

In comparative examples 3 and Ij-, the amount of GC used was changed, but the other procedures were the same as in examples I, II and III. The perforation properties in each of Comparative Examples 3 and U were poor.

The ink resistance was tested on each of the films with good perforation properties obtained according to Examples I, IX and III. More specifically, a stencil ink was applied to the entire surface of a recording strip, made by perforation using electric discharges, and the recording strip was left for an additional 2 hours, checking the change of the appearance of the strip and the ink resistance was evaluated.

The rules of the resin compositions, the film reheading conditions, the properties of the films and the results of the primary evaluation are shown in Table A.

In each of the aforementioned examples and comparative examples, it was confirmed that mixing with stirring can be considerably facilitated by the use of GC and that the mixing and kneading treatment can be carried out in a short time with only a small power. In addition, when the film was formed into a recording strip, no unpleasant odor was produced and the operation could be carried out easily and smoothly.

Each of the recording strips obtained from the above stencil films of the invention was subjected to a pressure stage using a commercial rotary press (Duplo Rotation Eress Model 750 from DUPLO Towa Kabushiki Kaisha) and 500 prints were made. Clear prints could always be obtained.

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Note: 1) The properties of Vylon 103 and Vylon 530 are as follows:

Vylon 103 Vylon 530

Molecular weight 18,000 - 20,000 20,000 *> 25,000 5 Glass transition temperature, ° C ^

Melt viscosity (poise) as measured at 200 ° C

by a rotary viscometer 3000 TOO

Soaking point (° C 158 tlU

16 15 10 Volume display (- ^ * - cm) 1 x 10 1 x 10 2) Graft carbon HCT 501B (from Ryoyu Kogyo Kabushiki Kaisha) was used as GC.

Example IV

The stencil film obtained in example. Ill became. laminated! 15 and bonded to an electroconductive surface of an electroconductive paper backing. which was fabricated separately to obtain an electro-sensitive blank for stencils.

The electroconductive paper backing layer was prepared by the following procedure.

20 A. liquid composition as indicated below was uniformly coated after drying in an amount of about 10 g / m on a surface of a wood-free paper weighing about 80 g / m using a roller coater, after which the coating was dried in a continuous drying step using warm air.

Liquid composition components Quantity (parts by weight) ethylhydroxyethylcellulose 500 carbon black 270 methyl ethyl ketone 2150 toluene 100 30 lanolin 100 was 100

The binding of the stencil film to the electroconductive paper backing thus obtained was carried out at a pressure of 200 kg / cm and a temperature of 80 ° C using a laminating press. The peel strength between the electro-conductive paper backing and 8104428

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The laminated film was 2-5 kg / cm. "Determined" at a draw angle of. 90 °.

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The specific volume resistance of the stencil film was 2.5 x 10 cm.

Fifty samples each measuring ^ 70 x 270 mm (the Width size of the Ge st et tener Size standard) were cut from the thus obtained electro-sensitive Blanko for stencilling, while registration strips were made from these samples using of a commercial stencil cutter (Rex Rotary Press Model 2202 S), while facsimile sample card No. 2 from the Institute of Image ELectro-. sneeze Engineers of Japan, newspaper shreds and xerox copies of T0 literature references as originals were used. No unpleasant odor was released at the perforation stage during the electric discharge and the Treatment could be stirred easily and smoothly. Each registration strip was. Attached to a commercial rotary press (Duplo Rotary Press Model 750 from Duplo Towa SaBushiki Kaisha) after which the electroconductive paper support member was removed, and the printing was carried out until about 2000 prints were obtained. Stable clear copied images were always obtained.

8104428

Claims (10)

1. Electroconductive film for an electro-sensitive plate useful for rotatable stencils, which is composed of a resin composition comprising a carbon black copolymer and a mixture of a linear saturated polyester resin of molecular weight. from 16,000 - V. 5 22 QQOy a glass transition temperature of U6 - 1 * 80C and a softening point of -156 - 160 ° C ,. as well as a linear saturated polyester resin II with a molecular weight of 20,000-25,000, a glass transition temperature of 35 ° C and a softening point of 112-116 ° C. Film according to claim 1. characterized in that the carbon black grafted polymer is a polymer obtained by a vinyl group-containing monomer on carbon black. to graft. Film according to claim 1 or 2, characterized in that the carbon black grafted polymer is a polymer obtained by grafting at least one monomer selected from acrylic acid and acrylic acid esters on carbon black. Film according to claims 1 - 3. characterized in that the carbon black grafted polymer is a polymer obtained by using acrylic acid and butyl acrylate. grafting on carbon black, the polymer being used in a state suspended in aqueous ammonia. Film according to claim 1, characterized in that the linear saturated polyester resins are selected from (a) an ethene enteralate / ethylene isophthalate copolyester, (b) an ethylene terephthalate / 2,2-bis- [1 + - (bet a-hydroxy ethoxy) phenyl] -propane-terephthalate copolyester, (c) a bis - (bet a-hydroxyethyl hyl) t erephthalate / 2,2-bis- [U- (bet a-hydroxy-25 ethoxy) phenyl] propaate terephthalate copolyester, (d) a diphenyl terephthalate / diphenyl isophthalate copolyester and (e) a mixture of two or more of the copolyesters (a) - (&). 6. Film according to claim 1, characterized in that the weight ratio of the linear saturated polyester resin I to the linear saturated polyester resin II is in the range 6 / k-7/3. Film according to claim 1, characterized in that the amount of the carbon black-grafted polymer is 10-30 parts by weight per 100 parts by weight of the mixture of the linear saturated polyester resins I and II. 8104428 .............. 13 * 8. Film according to claim 1, characterized in that a plasticizer is used in combination with the linear saturated polyester resins I and H. Film according to claim 1, characterized in that a plasticizer is used in combination with the linear saturated polyester resins I and II and the weight ratio of the linear saturated polyester resin I to the linear saturated polyester resin II in the range from 5/5 - 8/2. The electroconductive film according to claim 1, characterized in that the linear saturated polyester resins are used in a dissolved or emulsified state. 8104428