JP3033360B2 - Ink for making heat sensitive stencil sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink for preparing a heat-sensitive stencil sheet which is suitable for use in preparing a heat-sensitive stencil sheet.

[0002]

2. Description of the Related Art Conventionally, heat-sensitive stencil printing has been widely used as a simple printing method. In recent years, it has become popular mainly in ordinary households due to the simplicity of the printing method. The principle of this heat-sensitive stencil printing is to use a heat-sensitive stencil sheet in which a thermoplastic film is bonded to the surface of a porous support.
A manuscript paper drawn with carbon ink is brought into close contact with the thermoplastic film of Example 1 and irradiated with infrared light. The infrared rays are absorbed by the carbon ink on the original, and the infrared energy is transmitted to the thermoplastic film as heat energy, and the film is melted and heat-sensitive with holes formed in the original paper drawn with the carbon ink. A stencil sheet is made, and printing is performed by passing ink through the holes of the stencil sheet. In general, at home or the like, in order to draw a manuscript on manuscript paper, an aqueous carbon ink in which carbon black is dispersed with a resin of styrene-acrylic acid, a copolymer of styrene-maleic acid and a salt thereof, or the like is used. Commercial writing instruments and the like used were used.

[0003]

However, conventionally,
When using the above-mentioned commercially available water-based carbon ink writing implement,
The dispersing resin added to the ink covered the writing coating surface. Therefore, the carbon in the coating film cannot absorb infrared rays sufficiently, and even if the carbon absorbs infrared rays sufficiently, the energy in the film is dissolved as heat energy to dissolve the resin in the coating film. Spend to do. As a result, the thermal energy absorbed by the stencil sheet is reduced, so that a heat-sensitive stencil sheet having a hole having a desired shape (a sheet having good stencil making properties) cannot be obtained, and a portion not printed. Had the problem that a problem occurred. In addition, since the resin coats the surface of the writing film, there is also a problem that the solvent component in the handwriting is difficult to volatilize.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a method for producing
Of water, a water-soluble organic solvent, is coated by a surfactant
At least comprising the heat-sensitive stencil sheet creation aqueous ink and a dispersed carbon black Te to it is an gist.

Hereinafter, the present invention will be described in detail. In the present invention, water is used as a main dispersion medium, and its use amount is preferably 30 to 90% based on the total amount of the ink.

The water-soluble organic solvent is used for the purpose of moisturizing and / or preventing freezing, and examples thereof include methanol, ethanol, propanol, isopropanol, butanol, and the like. Isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3 butylene glycol
3-methyl-1,3-butanediol, 2-methyl-2,4-pentaneddiol, thiodiglycol, ethylene glycol monomethyl ether, ethylene glycol
Monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether,
Ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether , Formamide, N, N dimethylformamide, N-methyl-2-pyrrolidone, sorbit, sorbitan, acetin, glycerin and the like. These can be appropriately selected and used alone or in combination with another. Is preferably 1 to 50% by weight.

[0007] Carbon black is used as a colorant and a heat energy medium. Conventionally known carbon blacks can be used, and specific examples thereof include Spec.
ial Black 6, S170, S610, 5, 4, 4A, 550, 35, 250, 1
00, Printex 150T, U, V, 14
0U, 140V, 95, 90, 85, 80
75, 55, 45, P, XE2, L6, L, 300, 30, 30, 35, 25, 20
0, A and G (all made by Degussa Japan Co., Ltd.)
# 2400B, # 2350, # 2300, # 2200
B, # 1000, # 950, # 900, # 850, #M
CF88, MA600, MA100, MA7, MA1
1, # 50, # 52, # 45, # 44, # 40, # 3
3, # 32, # 30, CF9, # 20B, # 4000B
(Mitsubishi Chemical Industries, Ltd.), MONARCH 1
300, 1100, 1000, 900, 88
0, 800, 700, MOGUL L, REGAL
400R, 660R, 500R, 330R, 300R, 99R, ELFTEX 8, 12, BL
ACK PEARLS 2000 (above, manufactured by Cabot Co. LTD, USA), Raven 7000, 575
0, 5250, 5000, 3500, 200
0, 1500, 1255, 1250, 120
0, 1170, 1060, 1040, 103
5, 1020, 1000, 890H, 890,
850, 790, 780, 760, 500,
450, 430, 420, 410, 22, 16, 16, 825 Oil Beads, H2
0, C, Conductex 975, 900, and SC (all manufactured by Colombian Carbon Japan Ltd.) and the like. The above-described carbon black can be used alone or in combination with other carbon blacks, and the amount of the carbon black varies depending on the concentration of the ink coating film, the amount of infrared absorption, and the like. The film density tends to increase and the amount of infrared absorption tends to increase), but is preferably 2 to 20% by weight based on the total amount of the ink.

The surfactant is used for dispersing the carbon black in the dispersion medium and for preventing the resin from covering the carbon black surface in the ink coating film. Any material may be used as long as it covers the surface and is uniformly and stably dispersed in the dispersion medium. Examples thereof include oleates, alkyl sulfates, sulfated fatty acid monoglyceride salts, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, isopropylnaphthalenesulfonic acid, dibutylphenylphenolsulfonic acid salts, and polyoxyethylene alkyl ether sulfate. Low molecular anionic surfactants such as salts, N-acyl amino acids and salts thereof, N-acylmethyl taurine salts, alkyl sulfocarboxylates, alkyl hydrochlorides, polyoxyethylene alkyl ether phosphates, and decaglycerin Fatty acid esters,
Hexaglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ester H such as terol, polyoxyethylene alkylphenyl ether, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, fatty acid amide, lanolin derivative of polyoxyethylene or lanolin alcohol or beeswax derivative
Non-ionic surfactant having an LB of 10 or more (HLB of 10
(Less than a non-ionic surfactant cannot be used because it is hardly soluble or insoluble in water as a main solvent). In order to disperse more uniformly and stably, a nonionic surfactant can be suitably used. The above-mentioned surfactants can be used alone or in combination with other surfactants, and the amount thereof is preferably 1 to 25 parts by weight based on the total amount of carbon black.

Further, the dispersion stabilization of carbon black is improved,
Add 2% by weight or less of a polymer dispersion stabilizer for fixing viscosity, a fixing resin for improving fixability to the total amount of the ink, an antiseptic / antifungal agent, a rust inhibitor for preventing metal corrosion, Various additives such as a foaming agent and a leveling agent can be used.

As a method for producing the ink for preparing a heat-sensitive stencil sheet of the present invention, the above-mentioned components are dispersed in an ordinary dispersing machine, for example,
Mixing and grinding with a ball mill, roll mill, sand mill, flow mill, dyno mill, attriser, etc.
If necessary, it can be easily obtained by removing coarse pigment particles by a method such as filtration or centrifugation.

[0011]

The ink for preparing a heat-sensitive stencil sheet in the present invention is obtained by coating and dispersing carbon black with a surfactant. I will not do it. Even if a resin or the like for improving fixability is added, the surface of carbon black is covered with a surfactant,
The resin does not directly physically and / or chemically adsorb to the surface of the carbon black, and it is considered that the affinity between the carbon black and the resin is low. Therefore, it is considered that the resin component easily penetrates into the ink coating film, and thus the resin does not cover the surface of the writing coating film. As described above, carbon black can sufficiently absorb infrared rays, and can sufficiently transmit the energy as heat energy to the stencil sheet. By this action, a heat-sensitive stencil sheet (a sheet having good plate making properties) having holes of a desired shape can be obtained.

[0012]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but "parts" means "parts by weight".

Example 1 MA100 (carbon black, manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) 10.0 parts NIKKOL TL-10 (polyoxyethylene sorbitan fatty acid ester, manufactured by Nikko Chemicals Co., Ltd.) 2.8 parts Proxel XL-2 (1.2-benzisothiazolin-3-one, manufactured by ICI Japan Ltd.) 0.2 part Ethylene glycol 15.0 parts Purified water 72.0 parts After a dispersion treatment for 1 hour using a commercially available Dyno-mill, the resultant was filtered to obtain an ink for preparing a heat-sensitive stencil sheet.

Comparative Example 1 MA100 (carbon black, manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) 10.0 parts Joncryl J61J (30.5% salt of styrene-acrylic acid copolymer, manufactured by Johnson Polymer Co., Ltd.) ) 9.2 parts Proxel XL-2 (1.2-benzisothiazolin-3-one, manufactured by ICI Japan Ltd.) 0.2 parts Ethylene glycol 15.0 parts Purified water 65.6 Part The above components were blended to obtain an ink for producing a heat-sensitive stencil sheet in the same manner as in Example 1.

Example 2 Special Black 4 (Carbon Black, manufactured by Degussa Japan KK) 12.0 parts NIKKOL PBC34 (polyoxyethylene polyoxypropylene alkyl ether, manufactured by Nikko Chemicals Co., Ltd.) 7 parts Proxel XL-2 0.2 parts Ethylene glycol 8.0 parts Glycerin 8.0 parts Purified water 69.1 parts The above ingredients were blended, dispersed in a commercially available Dyno-mill for 1 hour, filtered and heat-sensitive An ink for producing a stencil sheet was obtained.

Comparative Example 2 Special Black 4 (Carbon Black, manufactured by Degussa Japan KK) 12.0 parts SMA Resin 1440 (27% styrene-maleic acid copolymer, manufactured by ARCO Chemical Co. LTD, USA) 10.0 parts Proxel XL-2 0.2 parts Ethylene glycol 8.0 parts Glycerin 8.0 parts Purified water 61.8 parts For blending the above ingredients and producing heat sensitive stencil sheet in the same manner as in Example 2. An ink was obtained.

Example 3 # 1000 (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) 12.0 parts NIKKOL BC20TX (polyoxyethylene alkyl ether, manufactured by Nikko Chemicals Co., Ltd.) 3.0 parts Aminocol H (keratin) Hydrolyzate, manufactured by Sun Orient Chemical Co., Ltd.) 0.9 part Phenoxyethanol (preservative and fungicide, manufactured by Toho Chemical Industry Co., Ltd.) 0.2 part 1.3-butylene glycol 18.0 parts 65.9 parts of purified water The total amount of carbon black and PBC34 among the above components was added to 20 parts of purified water, and the mixture was stirred uniformly. A solution obtained by mixing and uniformly dissolving the remaining components was added thereto, followed by stirring for 1 hour, followed by filtration to obtain an ink for producing a heat-sensitive stencil sheet.

Comparative Example 3 # 1000 (manufactured by Mitsubishi Kasei Kogyo KK) 12.0 parts SMA Resin 1440 (27% styrene-maleic acid copolymer, manufactured by ARCO Chemical Co. LTD, USA) 10.0 parts Phenoxyethanol (Preservative and fungicide, manufactured by Toho Chemical Industry Co., Ltd.) 0.2 parts 1.3-butylene glycol 18.0 parts Purified water 59.8 parts Carbon black and SMA Resin among the above components
The whole amount of 1440 was added to 20 parts of purified water, and the mixture was stirred uniformly. Then, an ink for producing a heat-sensitive stencil sheet was obtained in the same manner as in Example 3.

Example 4 Special Black 4 (Carbon Black, manufactured by Degussa Japan KK) 10.0 parts NIKKOL BC20TX (polyoxyethylene alkyl ether, Nikko Chemicals KK) 1.5 parts Rheodor TW-S120 (polyoxyethylene sorbitan fatty acid ester, manufactured by Kao Corporation) 1.2 parts Proxel XL-2 0.2 parts Ethylene glycol 9.0 parts Glycerin 6.0 parts Purified water 72. 1 part Of the above components, carbon black, BC20TX, and the entire amount of Rheodor TW-S120 are added to 20 parts of purified water, 3 parts of ethylene glycol, and 2 parts of glycerin, and the mixture is uniformly stirred. 6 times to carry out a pigment dispersion treatment.
To this is added a solution obtained by mixing and uniformly dissolving the remaining components to obtain 1
After stirring for an hour, the mixture was filtered to obtain an ink for producing a heat-sensitive stencil sheet.

Comparative Example 4 Special Black 4 (Carbon Black, manufactured by Degussa Japan Co., Ltd.) 10.0 parts Joncryl J61J (30.5% salt of styrene-acrylic acid copolymer, Johnson Polymer Co., Ltd.) )) 8.5 parts Proxel XL-2 0.2 parts Ethylene glycol 9.0 parts Glycerin 6.0 parts Purified water 66.3 parts Carbon black and Joncryl J61 among the above components
The whole amount of J was added to 20 parts of purified water, 3 parts of ethylene glycol, and 2 parts of glycerin, and the mixture was stirred uniformly, and then the same procedure as in Example 4 was performed to obtain an ink for producing a heat-sensitive stencil sheet.

Example 5 MA100 (carbon black, manufactured by Mitsubishi Kasei Kogyo KK) 9.0 parts NIKKOL SLS (alkyl sulfate, manufactured by Nikko Chemicals KK) 2.1 parts Proxel XL-2 (1. 2-benzoisothiazolin-3-one, manufactured by ICI Japan Ltd. 0.2 part Glycerin 7.0 parts Purified water 81.7 parts Carbon black and NIKKOL SL among the above components
The total amount of S was added to 20 parts of purified water and 3 parts of glycerin, and the mixture was stirred uniformly. After that, the mixture was passed through a roll of three times to perform a pigment dispersion treatment. A solution obtained by mixing and uniformly dissolving the remaining components was added thereto, followed by stirring for 1 hour, followed by filtration to obtain an ink for producing a heat-sensitive stencil sheet.

Comparative Example 5 MA100 (carbon black, manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) 9.0 parts Joncryl J61J (30.5% salt of styrene-acrylic acid copolymer, manufactured by Johnson Polymer Co., Ltd.) 6.9 parts Proxel XL-2 (1.2-benzoisothiazolin-3-one, manufactured by ICI Japan Ltd.) 0.2 parts Glycerin 7.0 parts Purified water 76.9 parts Among them, carbon black, John Krill J6
The total amount of 1J was added to 20 parts of purified water and 3 parts of glycerin, and the mixture was stirred uniformly.

[0023]

The ink for preparing heat-sensitive stencil sheets of Examples 1 to 5 and Comparative Examples 1 to 5 is a commercially available batting-type writing implement S510F.
(Pentel Co., Ltd.) into 2.0 g
Under a condition of 35 ° C. and a humidity of 35%, a postcard size paper (made by Riso Kagaku Kogyo Co., Ltd.) is postcard-sized (one time coating) on a postcard paper, and a heat-sensitive stencil printing machine (RIS) after 10 minutes.
A heat-sensitive stencil sheet for printing was prepared using O-Print Gokko B6 (manufactured by Riso Kagaku Corporation). Further, printing was performed using the heat sensitive stencil sheet and high mesh ink (manufactured by Riso Kagaku Kogyo Co., Ltd.) with the above printing machine. The evaluation method is to determine what percentage of a postcard-size original is printed by equally dividing the area of the postcard into 10 × 10 = 100, visually evaluating each printing rate, and summing them.
It was performed as a substitute for the perforation rate of the stencil.

[0024]

[Table 1]

Since the surface of the handwriting coating film is not coated with the resin, the solvent component in the handwriting is also easy to evaporate .
Heat-sensitive stencil sheet with perforated shape
G) is an ink that can obtain
It is possible to obtain a printed matter with as little as possible .

Claims (1)

(57) [Claims] 1. A water as a main solvent, a water-soluble organic solvent and, at least comprising the heat-sensitive stencil sheet creation Aqueous <br/> ink and a carbon black dispersed is coated with a surfactant.