JP5315780B2 - Emulsion ink for stencil printing - Google Patents

Description

  The present invention relates to an emulsion ink for stencil printing, and more particularly to a W / O emulsion ink for heat-sensitive stencil printing.

  As is well known, the stencil printing method uses a stencil printing paper (stencil) having a perforated portion, and moves the ink from one side of the stencil to the other side through the perforated portion of the stencil, thereby making paper or the like This is a method for performing printing on the surface of the substrate. In recent years, rotary stencil printing presses have become more automated with microcomputers and the like, and the operation has become simpler. Accordingly, the use of stencil printing has increased. However, the drying of stencil printing is only penetration drying and evaporation drying, and since no reactive resin can be used so that the ink does not solidify on the machine, the stability, fixing property and touch drying property have been improved so far. Various studies have been made to achieve this.

  For example, an ink using cyclized rubber and cinnamon oil as a vehicle material has been proposed (see Patent Document 1). In addition, in order to improve dryness to touch, inks containing cyclized rubber or polymer rosin modified resin have been proposed (see Patent Documents 2 and 3).

However, the ink using the cyclized rubber and Sin Tung oil disclosed in Patent Document 1 is not a water-in-oil (W / O) emulsion ink but an oil-based ink. When printing on the paper, there was a problem that the drying speed was slow.
In addition, the ink added with the cyclized rubber or the polymer rosin-modified resin has insufficient colorant fixability and drying speed on paper.

Japanese Patent Application Laid-Open No. 2004-101834 Japanese Patent Laid-Open No. 10-81844 JP-A-11-310740

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said problem in the past and to achieve the following objectives. That is, an object of the present invention is to provide an emulsion ink for stencil printing that can improve the fixability of a colorant to paper and the drying speed.

Means for solving the problems are as follows. That is,
<1> In the emulsion ink for stencil printing comprising an oil phase and an aqueous phase, the oil phase is 10% by mass to 90% by mass relative to the emulsion ink for stencil printing, and the water phase is the emulsion ink for stencil printing. In the emulsion ink for stencil printing, wherein the oil phase contains 90% by mass to 10% by mass, and the oil phase contains cyclized rubber and at least one of drying oil and processing oil of the drying oil. is there.
In the emulsion ink for stencil printing of <1>, the oil phase contains a cyclized rubber and at least one of a drying oil and a processing oil of the drying oil. Improvement and improvement of a drying rate can be aimed at. This is because the oil phase contains cyclized rubber, so that the solvent component in the ink selectively permeates the paper, and the oxidative polymerization of at least one of the dry oil having oxidative polymerizability and the processing oil of the dry oil. This is thought to be due to the accelerated reaction.
<2> The emulsion ink for stencil printing according to <1>, wherein the iodine value of the drying oil is 150 or more.
<3> The emulsion ink for stencil printing according to any one of <1> to <2>, wherein the drying oil is tung oil.
In the emulsion ink for stencil printing described in <3>, by using tung oil as the drying oil, the reaction is accelerated due to the specific three-dimensional structure of α-eleostearic acid constituting tung oil, and the fixing property is further improved. To do.
<4> The emulsion ink for stencil printing according to any one of <1> to <3>, wherein the processing oil of the drying oil is a polymerized tung oil obtained by heat-treating tung oil.
In the emulsion ink for stencil printing described in <4>, the fixability is further improved, and the paulownia oil is appropriately polymerized by heating the paulownia oil to become a paulownia polymer oil, which is less volatile and improves odor. Is done.
<5> The emulsion ink for stencil printing according to any one of <1> to <4>, wherein the aqueous phase contains a colorant.
In the emulsion ink for stencil printing of <5>, the drying rate can be further improved when the aqueous phase contains a colorant. This is considered to be due to the fact that the viscosity of the oil phase was lowered due to the water phase containing the colorant. Moreover, since the solvent component and the colorant component do not coexist, it is considered that the detachment of the solvent component from the colorant is promoted.
<6> The emulsion ink for stencil printing according to any one of <1> to <5>, wherein the amount of the cyclized rubber added to the emulsion ink for stencil printing is 3% by mass or more and 9% by mass or less.
In the <6> emulsion ink for stencil printing, the amount of cyclized rubber added to the emulsion ink for stencil printing is 3% by mass or more and 9% by mass or less, thereby further improving the fixability of the colorant to paper. In addition, the water resistance can be improved and the ink cost can be reduced.
<7> The emulsion ink for stencil printing according to <6>, wherein the amount of cyclized rubber added to the emulsion ink for stencil printing is 6% by mass or more and 9% by mass or less.
In the <7> emulsion ink for stencil printing, the drying rate can be further improved by adding 6% by mass or more and 9% by mass or less of the cyclized rubber to the emulsion ink for stencil printing.
<8> The content of any one of <1> to <7>, wherein the addition amount of the drying oil and the processing oil of the drying oil to the emulsion ink for stencil printing is 1% by mass or more and 9% by mass or less. This is an emulsion ink for stencil printing.
In the emulsion ink for stencil printing of <8>, when the addition amount of either a drying oil or a processing oil of the drying oil to the stencil printing emulsion ink is 1% by mass or more and 9% by mass or less, drying is performed. Further improvement in speed and prevention of ink solidification in the open state can be achieved.
<9> The emulsion ink for stencil printing according to <8>, wherein an addition amount of the drying oil and the processing oil of the drying oil to the emulsion ink for stencil printing is 2% by mass or more and 6% by mass or less. .
In the <9> stencil printing emulsion ink, the addition amount of either a drying oil or a processing oil of the drying oil to the stencil printing emulsion ink is 2% by mass or more and 6% by mass or less. It is possible to improve the property and prevent ink solidification in the open state.

  ADVANTAGE OF THE INVENTION According to this invention, the problem in the past can be solved, and the emulsion ink for stencil printing which can aim at the improvement of the fixing property of the coloring agent to paper and the improvement of a drying speed can be provided.

(Emulsion ink for stencil printing)
The emulsion ink for stencil printing of the present invention comprises an oil phase and a water phase, the oil phase is 10% by mass to 90% by mass with respect to the emulsion ink for stencil printing, and the water phase is the emulsion for stencil printing. It is 90 mass%-10 mass% with respect to ink.

<Oil phase>
The oil phase is not particularly limited as long as it contains cyclized rubber and at least one of drying oil and processing oil of the drying oil, and can be appropriately selected according to the purpose. It may further contain a resin, a colorant, a colorant dispersant, an emulsifier, an extender pigment, a gelling agent, an oil component (mineral oil, petroleum solvent, vegetable oil, etc.), an antioxidant, and a dryer.

<< Cyclized rubber >>
There is no restriction | limiting in particular as said cyclized rubber, According to the objective, it can select suitably, For example, ALSYNOL RS47 (made by Colombian Carbon Japan), ALSYNOL RS44 (made by Colombian Carbon Japan), SYNTEX 800 ( Colombian Carbon Japan Co., Ltd.), ALPEX CK 450 (Nihon Cytec Industries Co., Ltd.), ALPEX CK514 (Nihon Cytec Industries Co., Ltd.), and the like. These are synthesized from natural rubber or synthetic rubber. In the case of natural rubber, it is preferable to use a material that has been subjected to deproteinization treatment.
The amount of cyclized rubber added to the emulsion ink for stencil printing is preferably 3% by mass or more and 9% by mass or less, and more preferably 6% by mass or more and 9% by mass or less.

<< Dry oil and processing oil of the dry oil >>
There is no restriction | limiting in particular as said drying oil and the processing oil of the said drying oil, According to the objective, it can select suitably, For example, a linseed oil (linseed oil), sika deer oil, dehydrated castor oil, soybean oil, tung oil ( Cinna Tung Oil) and polymerized oils such as these processing oils and alkyd resins. Among these, polymerized tung oil (polymerized oil obtained by heat-treating the tung oil) is preferable from the viewpoint of odor and stability. This is considered to be because the low molecular weight component is appropriately polymerized and the volatile component is reduced by heat-treating the tung oil. Examples of the polymerized tung oil include China (China) Tung Oil No. 4 (manufactured by Toshin Yushi Co., Ltd.) and China (China) Tung Oil No. 7 (manufactured by Toshin Yushi Co., Ltd.). Examples include boiled oil (manufactured by Nisshin Oillio), flaxseed oil (manufactured by Nisshin Oillio), OOB-DN-H (manufactured by Nisshin Oillio), OOB-DN-W (manufactured by Nisshin Oillio), and the like. .
Moreover, it is preferable that the addition amount of either the said drying oil or the processing oil of the said drying oil with respect to the emulsion ink for stencil printing is 1 mass% or more and 9 mass% or less, and is 2 mass% or more and 6 mass% or less. More preferably.
The iodine value of the drying oil is preferably 150 or more, more preferably 150 to 190.
When the iodine value of the drying oil is less than 150, the effect of fixability and drying speed may be reduced. Examples of the iodine value measuring method include JIS K 0070.

<< Resin >>
The resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include rosin resins such as rosin, polymerized rosin, hydrogenated rosin, rosin ester, rosin polyester resin, hydrogenated rosin ester; Modified alkyd resin, rosin modified maleic acid resin, rosin modified phenolic resin, rosin modified resin such as rosin modified petroleum resin; maleic acid resin; phenol resin; petroleum resin; rubber derivative resin; terpene resin; alkyd resin; These resins may be used alone or in combination of two or more. Typical examples of these resins include T (Tamanol) -340, T-352, T-353, T-354, T-361, T-381, T-387, T-392, T manufactured by Arakawa Chemical Co., Ltd. -396, T-400, T-403, T-407, KG-836, KG-846, KG-1861, KG-1816, KG-1834, KG-1845, KG-1847, KG-1848, KG-2212 And rosin-modified phenolic resin.

  The weight average molecular weight of the resin is preferably 40,000 to 160,000, more preferably 70,000 to 160,000, from the viewpoint of fixability, printability, and ink cost. Furthermore, it is preferable that these resins have a tolerance of 1 g / g or more (1 g or more of 0 solvent can be compatible with 1 g of resin) with respect to Nisseki 0 solvent. In addition, the amount of resin used in the case of adding a resin to the oil phase is preferably 2% by mass to 50% by mass of the oil phase from the cost of ink and printing suitability, and 5% by mass to 20% by mass. Is more preferable. These resins may be used alone or in combination of two or more.

<<<< Alkyd Resin >>>>
The said alkyd resin contains fats and oils, a polybasic acid, and a polyhydric alcohol. Examples of the fats and oils include non-drying oils or semi-drying oils having an iodine value of 80 or less, such as coconut oil, palm oil, olive oil, castor oil, rice bran oil, cottonseed oil, soybean oil, and linseed oil (linseed oil) ), Alkyd resins made of a dry oil having an iodine value of 80 or more, such as oil deer oil, tung oil (Chinese tung oil), and the like can also be used for the purpose of improving the fixability. The addition amount of the alkyd resin is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass to 6% by mass with respect to the emulsion ink for stencil printing.

<< Colorant >>
The colorant is not particularly limited and may be appropriately selected depending on the intended purpose. Known pigments and disperse dyes having various color tones, for example, carbon blacks such as acetylene black, channel black, and furnace black, aluminum Metal powders such as powder and bronze powder, petals, inorganic pigments such as yellow lead, ultramarine, chromium oxide and titanium oxide, azo pigments such as insoluble azo pigments, azo lake pigments and condensed azo pigments, metal-free phthalocyanine pigments and copper phthalocyanine Phthalocyanine pigments such as pigment, anthraquinone, quinacridone, isoindolinone, isoindoline, dioxazine, selenium, perylene, perinone, thioindigo, quinophthalone, metal complexes, etc. Pigments, organic pigments such as acid or basic dye lakes, diazo dyes Oil-soluble dyes such as anthraquinone dyes, fluorescent pigments.

The use of a dye as the colorant is problematic in terms of light resistance, but for the purpose of supplementing the color, a dye is added to the phase containing the insoluble colorant, the phase not containing the insoluble colorant, or both phases. Also good.
The colorant may be added to the oil phase, the water phase, or both the oil phase and the water phase, or may be added alone or in combination of two or more, but at least in the water phase It is preferable to add.
The average particle size of the insoluble colorant dispersed in the oil phase or the aqueous phase is preferably 0.05 μm to 10 μm, and more preferably 0.1 μm to 1.0 μm.
The amount of the insoluble colorant added to the emulsion ink for stencil printing can be added according to the required amount, but is usually 2% by mass to 15% by mass.

<<< Carbon black >>>
Regarding carbon black, when added to the oil phase, it is preferable to use acidic carbon black having a pH of less than 5, and when added to the aqueous phase, pH of 5 or more, preferably pH 6 to 10, more preferably pH 7 is used. It is preferred to use ˜9 alkaline carbon black. However, carbon black having a pH of 6 to 10 may be added to the oil phase, and carbon black having a pH of less than 5 may be added to the aqueous phase, or two or more carbons having different pHs may be used in combination.
Examples of the carbon black include MA-100, MA-7, MA-70, MA-77, MA-11, # 40, # 44 (Mitsubishi Chemical Corporation) Raven1100, Raven1080, Raven1255, Raven760, Raven410 (Colombia) For example).

<<< Fluorescent pigment >>>
The fluorescent pigment is not particularly limited and may be appropriately selected depending on the intended purpose, and is obtained by dissolving or dyeing fluorescent dyes that develop various hues during or after bulk polymerization of a synthetic resin. This is a so-called synthetic resin solid solution type obtained by pulverizing and refining the colored block resin. Examples of the synthetic resin carrying the dye include fluorescent pigments carrying melamine resin, urea resin, sulfonamide resin, alkyd resin, polyvinyl chloride resin and the like on the dye.

<< Colorant Dispersant >>
The colorant dispersant is not particularly limited as long as it does not inhibit the formation of the emulsion, and can be appropriately selected according to the purpose. Examples thereof include nonionic surfactants for emulsifiers and water-soluble polymers. May be.
Examples of the colorant dispersant include sorbitan fatty acid esters such as sorbitan sesquiolate, polyglycerin fatty acid esters such as hexaglycerin polyricinoleate, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene alkyl ether. , Nonionic surfactants such as polyoxyethylene alkylamine / fatty acid amide, alkylamine polymer compound, aluminum chelate compound, styrene-maleic anhydride copolymer polymer compound, polycarboxylic acid ester polymer Compound, aliphatic polycarboxylic acid, amine salt of high molecular polyester, ester type anionic surfactant, long chain amine salt of high molecular weight polycarboxylic acid, long chain polyaminoamide and high molecular acid polyester Salt, polyamide compound, phosphate ester surfactant, alkyl sulfocarboxylate, sulfonate, α-olefin sulfonate, dioctyl sulfosuccinate, polyethyleneimine, alkylolamine salt, alkyd resin, etc. Examples thereof include resins having an insoluble colorant-dispersing ability, and other examples include ionic surfactants and amphoteric surfactants as long as they do not impair the storage stability of the ink. Specific examples include Solspers series (S3000, S5000, S9000, S13240, S13940, S16000, S17000, S20000, S24000, S26000, S27000, S28000, S31845, S31850, S32750, S41090, manufactured by Nippon Lubrizol Corporation. , S53095, etc.), Ajinomoto Fine Techno Co., Ltd. Plainact AL-M, Ajisper series (PB711, PM821, PB821, PB811, PN411, PA111, etc.), Surf Products series manufactured by Air Products (GA, TG, CT-221, CT-121, etc.), Nissin Chemical Industry Olfin PD series (001, 002W, 003, 004, 005, etc.), Nikko Chemicals TMGS-15, TMGO-15, Decaglyn series (1-L, 1-M, 1-O, etc.), TL-10, TP-10, TO-10, TI-10, BL-21, BC-15TX BC-23, BC-30TX, BC-40TX, BS-20, BO-10TX, TAMNS-10, TAMNS-15, TAMNO-5, TAMNO-15, TDMNS-8, OTP-100, OTP-75, etc. Can be mentioned.
These dispersants may be added alone or in admixture of two or more. The amount of the colorant dispersant other than the polymer and the resin is preferably 40% by mass or less of the mass of the colorant, and 2% by mass to 35% by mass. % Is more preferable. Alkyd resins are particularly effective for the dispersion stability of insoluble colorants when high molecular weight resins are added, but the amount of resin added when using alkyd resins alone or in combination with other dispersants is insoluble. It is preferable that it is 0.05 or more with respect to the coloring agent 1.
In addition, since the high molecular weight surfactant used for dispersing the colorant has the effect of improving the emulsification stability of the ink, it can be added to the oil phase as necessary even when the oil phase does not contain a colorant. It's okay.
0.01 mass%-5 mass% are preferable, and, as for the addition amount with respect to the emulsion ink for stencil printing of the said surfactant, 0.1 mass%-1.0 mass% are more preferable.

<< Emulsifier >>
The emulsifier is not particularly limited and may be appropriately selected depending on the purpose, and is used for the purpose of forming a water-in-oil emulsion. An anionic surfactant, a cationic surfactant, an amphoteric surfactant, Any nonionic surfactant may be used, and a low molecular weight surfactant or a high molecular weight surfactant may be used in combination as long as it has an effect on stability. Among them, nonionic surfactants are preferable, for example, sorbitan fatty acid esters such as sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate. Polyoxyethylene sorbitan fatty acid esters such as ate, (poly) glycerin fatty acid esters such as glyceryl monostearate, decaglyceryl trioleate, hexaglycerin polyricinoleate, polyoxyethylene sorbit fatty acid ester, polyoxyethylene glycerin vegetable oil fatty acid ester, etc. Polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether Examples include polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine / fatty acid amide, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene castor oil / hardened castor oil, and higher alcohol. It is added to prepare an emulsion having high storage stability. The amount of the emulsifier added to the emulsion ink for stencil printing is usually preferably 0.5% by mass to 15% by mass, and more preferably 1% by mass to 6% by mass.

<< Extreme Pigment >>
The extender pigment is not particularly limited as long as it adjusts the viscosity of the ink, and can be appropriately selected according to the purpose. For example, clay, silica, talc, clay, calcium carbonate, organic bentonite, sulfuric acid Inorganic fine particles such as barium, titanium oxide, alumina white, diatomaceous earth, kaolin, mica, aluminum hydroxide, and polyacrylate, polyurethane, polyester, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polysiloxane, phenol Examples thereof include organic fine particles such as resins and epoxy resins, or fine particles comprising these copolymers. More specifically, Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd.), Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.), white gloss TDD (manufactured by Shiroishi Kogyo), Gloss O (manufactured by Shiroishi Kogyo Co., Ltd.), NEW D ORBEN (manufactured by Shiroishi Kogyo Co., Ltd.), BEN-GEL (manufactured by Toyoshiro Yoko Co., Ltd.), S-BEN (manufactured by Toyoshun Yoko Co., Ltd.), ORGANITE (manufactured by Toyoshiro Yoko Co., Ltd.) And TIXOGEL series (VP, DS, GB, VG, EZ-100, etc.) (Nissan Gardler Catalyst), OPTIGEL (Nissan Gardler Catalyst).
The extender pigment may be added to the oil phase, the aqueous phase, or both the oil phase and the aqueous phase, and the amount of the extender pigment added is 0.1% by mass to 50% by mass with respect to the emulsion ink for stencil printing. % Is preferable, and 1% by mass to 5% by mass is more preferable.

<< Gelling agent >>
The gelling agent is not particularly limited as long as it has a role of improving the storage stability, fixability, and fluidity of the ink by gelling the resin contained in the oil phase, and is appropriately selected according to the purpose. A compound that coordinates with a resin in the oil phase is preferable. Examples of the compound that coordinates with the resin in the oil phase include organic acid salts and organic chelate compounds containing metals such as Li, Na, K, Al, Ca, Co, Fe, Mn, Mg, Pb, Zn, and Zr. And metal soap oligomers, and more specifically, metal octylates such as aluminum octylate, metal naphthenates such as manganese naphthenate, stearates such as zinc stearate, and ethyl acetoacetate aluminum diisopropylate. And organic chelate compounds such as a rate.
These gelling agents should just add 1 type, or 2 or more types to an oil phase, and the addition amount is 15 mass% or less of the resin in an oil phase, and may be 5 mass%-10 mass%. preferable.

<< Oil component >>
There is no restriction | limiting in particular as said oil component, According to the objective, it can select suitably, For example, vegetable oil etc. are mentioned.

<<< Vegetable oil >>>
The vegetable oil is not particularly limited and may be appropriately selected depending on the intended purpose.For example, soybean oil, rapeseed oil, corn oil, sesame oil, tall oil, cottonseed oil, sunflower oil, safflower oil, walnut oil, Examples include poppy oil and linseed oil, and these may be used alone or in combination of two or more. Moreover, vegetable oil esterified with methyl, butyl, isopropyl, propyl, etc. can also be used as these vegetable oils. These vegetable oils can be used in combination with a drying oil and a processing oil of the drying oil (a vegetable oil used in the present invention). Considering the ink drying property after printing, it is preferable to use what is generally called semi-drying oil having an iodine value of 100 or more.

<<< Oil ingredients other than vegetable oil >>>
Examples of the oil component other than the vegetable oil include petroleum solvents, liquid paraffin, spindle oil, machine oil, lubricating oil, mineral oil, and the like. Synthetic oils can be used in combination as long as safety and storage stability are not impaired.
Examples of paraffinic oils include Diana process oils (PX-32, PX-90, PW-32, PW-90, PW-380, PS-32, PS-90, PS-430, etc.) manufactured by Idemitsu Kosan Co., Ltd. Fresia series (S-32, S-90, P-32, P-90, P-150, P-180, P-430, etc.) and the like can be mentioned.
As the naphthenic oil, the carbon content (CN) of the naphthene component by ring analysis is 30% or more, the carbon content (CA) of the aromatic component is 20% or less, and the carbon content (CP) of the paraffin component is It is a mineral oil that is 55% or less, and Diana process oil (NP-24, NR-26, NR-68, NS-90S, NM-280, etc.) manufactured by Idemitsu Kosan Co., Ltd., Diana Fresia series (G-6, F -9, N-28, N-90, N-150, U-46, U-56, U-68, U-130, U-170, U-260), Sansen Oil series manufactured by Nippon San Oil Co., Ltd. 410, 420, 450, 480, 3125, 4240, etc.).
Highly safe petroleum-based solvents include ExxonMobil's Isopar series (C, E, G, H, L, M, etc.) and Exol (D30, D40, D80, D110, D130, etc.) The AF solvent series (No. 4, No. 5, No. 6, No. 7) manufactured by the company etc. are mentioned.
In consideration of safety, it is preferable to use those oil components whose polycyclic aromatic components, which are aromatic hydrocarbons containing three or more condensed aromatic rings, are less than 3% by mass.

<< Antioxidant >>
When the drying oil or semi-drying oil having a high iodine value is used, it causes an oxidation reaction with oxygen in the air, whereby the drying (solidification) of the oil proceeds, and consequently the emulsion ink for stencil printing containing the vegetable oil. Will also solidify. Fatty acids in vegetable oils when using vegetable oils with a high iodine value (contains many unsaturated bonds) may cause problems such as clogging of the screen and deterioration of image start-up when the ink is solidified. In order to prevent oxidation of linolenic acid, linoleic acid, oleic acid, etc., it is preferable to contain an antioxidant in the oil phase or the aqueous phase.

  The antioxidant is not particularly limited and may be appropriately selected depending on the purpose. For example, amine compounds such as diphenylphenylenediamine and isopropylphenylphenylenediamine, phenolic compounds such as tocopherol and dibutylmethylphenol, Examples include sulfur compounds such as mercaptomethylbenzimidazole, dibutylhydroxytoluene, propyl gallate, and butylhydroxyanisole. The addition amount of the antioxidant is preferably 2% by mass or less of the oil in the ink, and more preferably 0.1% by mass to 1.0% by mass. In addition, you may use antioxidant alone or in mixture of 2 or more types. Addition of the antioxidant prevents oxidation of the binder resin or the like in the oil phase, thereby preventing an increase in the viscosity of the ink. However, when an extremely small amount of antioxidant is added to the vegetable oil content, an appropriate antioxidant effect cannot be expected, and conversely, if a large amount of antioxidant is added to the vegetable oil content at once. It may act as an oxidation accelerator. Therefore, it is preferable to add a synergist to suppress the oxidation of vegetable oil even with a small amount of antioxidant.

<<< Synergist >>>
The synergist itself has almost no antioxidant action, but enhances its action when used in combination with an antioxidant. The synergist is usually a polyfunctional compound which is an acidic substance and has several hydroxyl groups or carboxyl groups. Examples of the synergist include methionine, ascorbic acid, threonine, leucine, milk protein hydrolyzate, norvaline, ascorbyl palmitate, phenylalanine, cystine, tryptophan, proline, alanine, glutamic acid, valine, pancreatic protein pepsin digestion solution, asparagine, Known substances such as arginine, barbituric acid, asphenamine, ninhydrin, propanidin, histidine, norleucine, glycerophosphoric acid, casein trypsin hydrolyzed solution, casein hydrochloric acid hydrolyzed solution can be used, these may be used alone, Two or more kinds may be mixed and used. The addition amount of the synergist is preferably 50% by mass to 150% by mass with respect to the content of the antioxidant.

<< Dryer >>
The dryer is not particularly limited and may be appropriately selected depending on the purpose. Any dryer that promotes oxidative polymerization may be appropriately selected according to the purpose, for example, cobalt Metallic dryers such as manganese, rare earth organic acids, and more specifically, cobalt naphthenate and manganese naphthenate are preferably used. The addition amount of the metal dryer is preferably 0.1% by mass to 5% by mass, and more preferably 0.3% by mass to 1.0% by mass with respect to the total amount of the oil phase.

<Water phase>
There is no restriction | limiting in particular as said aqueous phase, According to the objective, it can select suitably, For example, water, a coloring agent, a coloring agent dispersing agent, water-soluble polymer, o / w resin emulsion, antiseptic | preservative, antifungal agent Water evaporation inhibitor, antifreeze agent, pH adjuster, electrolyte, extender pigment and the like. As these constituent components, known components that do not inhibit the formation of an emulsion are used.

<< Colorant >>
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably, For example, the thing similar to the coloring agent added to the said oil phase is mentioned.

<< Colorant Dispersant >>
There is no restriction | limiting in particular as said coloring agent dispersing agent, According to the objective, it can select suitably, For example, the thing similar to the coloring agent dispersing agent added to the said oil phase is mentioned.

<< Water-soluble polymer >>
The water-soluble polymer is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include the following natural or synthetic polymers, which are necessary for the oil phase or the aqueous phase. Added accordingly.
For example, natural polymers such as starch, mannan, sodium alginate, galactan, tragacanth gum, gum arabic, bull run, dextran, xanthan gum, glue, gelatin, collagen, casein; carboxymethylcellulose, hydroxymethylcellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, Semi-synthetic polymers such as hydroxypropylmethylcellulose, hydroxymethyl starch, carboxymethyl starch, dialdehyde starch; neutralized products such as acrylic resin and sodium polyacrylate, alkyl-modified acrylic resin, polyvinylimide, polyvinyl alcohol, polyvinylpyrrolidone N-vinylpyrrolidone and vinyl acetate copolymer, polyethyleneimine, polyamine Rilamide, poly N-alkyl substituted acrylamides such as poly N-acryloylpyrrolidine and poly N-isopropylacrylamide, polyethylene oxide, polyvinyl methyl ether, styrene-maleic anhydride copolymer, styrene-acrylic acid copolymer and alkyl groups thereof As for the partially hydrophobic polymer, and the acrylamide polymer and the acrylic polymer, a copolymer type polymer in which the substituent is partially hydrophobized with an alkyl group may be used. Also, AB or ABA type block copolymers of polyethylene and polypropylene or polybutylene can be used.
These water-soluble polymers may be used alone or in admixture of two or more. It is preferable that 25% by mass or less of water contained in the ink is added, and 0.5% by mass to 15% by mass is added. Is more preferable. These resins preferably have a weight average molecular weight of 2,000 to 1,000,000, more preferably 5,000 to 300,000, and particularly preferably 10,000 to 150,000. .

<< o / w resin emulsion >>
There is no restriction | limiting in particular as said o / w resin emulsion, According to the objective, it can select suitably, A synthetic polymer or a natural polymer may be sufficient. Examples of the synthetic polymer include vinyl acetate, acrylic ester, methacrylic ester, vinyl chloride, ethylene-vinyl acetate copolymer, vinyl acetate-acrylic ester copolymer, styrene-acrylic ester copolymer, and vinylidene chloride. Acrylic ester copolymer, vinyl chloride-vinyl acetate copolymer, urethane and the like can be mentioned. Examples of the natural polymer include polymers that can be added to the oil phase. These may be used in combination of two or more as long as they do not impair the stability of the water-in-oil emulsion ink, and the dispersing method may include a dispersant, a protective colloid, and a surfactant. Further, the synthesis can be carried out by emulsion polymerization, suspension polymerization or soap-free emulsion polymerization. The minimum film-forming temperature of these o / w resin emulsions is preferably 40 ° C. or lower. Moreover, it is preferable that the particle diameter of a resin emulsion is 0.1 micrometer-30 micrometers, and it is more preferable that it is 0.5 micrometer-5 micrometers.

<< antiseptic and fungicide >>
The antiseptic / antifungal agent is not particularly limited and may be appropriately selected depending on the purpose.Prevents bacteria and fungi from growing in the emulsion, and the aqueous phase is used for long-term storage of the emulsion. It is to be added. The addition amount of the antiseptic / antifungal agent is 3% by mass or less, and preferably 0.1% by mass to 1.2% by mass with respect to the water contained in the ink. Examples of the antiseptic / fungicidal agent include aromatic hydroxy compounds such as salicylic acid, phenols, methyl p-oxybenzoate and ethyl p-oxybenzoate and chlorinated compounds thereof, sorbic acid, dehydroacetic acid, MIT ( Thiazoline-based compounds such as methylisothiazoline), BIT (butylisothiazoline), and OIT (octylisothiazoline) are used, and zinc pyrothione, (2-pyridylthio-1-oxide) sodium, bis (2-pyridylthio-1-oxide) and the like are also used. Can be used. These may be used alone or in combination of two or more.

<< Water evaporation inhibitor, antifreezing agent >>
The water evaporation inhibitor and the antifreezing agent can be used together, and the water evaporation inhibitor and the antifreezing agent are not particularly limited and can be appropriately selected according to the purpose. Ethylene glycol, diethylene glycol And glycols such as propylene glycol; lower saturated monohydric alcohols such as methanol, ethanol, isopropanol, butanol and isobutanol; polyhydric alcohols such as glycerin and sorbitol; These chemicals may be added singly or in combination of two or more. The amount of the water evaporation inhibitor and antifreezing agent added is preferably 15% by mass or less of the mass of water in the ink, preferably 4% by mass to More preferably, it is 12 mass%.

<< pH adjuster >>
The pH adjuster is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include those added to the aqueous phase in order to maintain the pH of the aqueous phase at 6-8. Specific examples include ammonia, triethanolamine, sodium acetate, triamylamine, sodium hydroxide and the like. When the pH of the aqueous phase is out of the range of 6 to 8, when the water-soluble polymer for thickener is added, there is a problem that the effect is impaired. In order to keep the pH constant, a buffering agent may be added. Examples of the buffering agent include ethylenediaminetetraacetic acid, Trizma base of Aldrich, 4-morpholinoethanesulfonic acid (MES), and 4-morpholinopropanesulfonic acid. (MOPS). The addition amount of the buffering agent is preferably in the range of about 0.05% by mass to 0.1% by mass of the aqueous phase component.

<< Electrolyte >>
The electrolyte is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a cation such as an alkali metal or alkaline earth metal, citrate ion, tartrate ion, sulfate ion, acetate ion, or chloride ion And anions such as borate ions. Examples of the cation for preventing aggregation of the water-insoluble pigment, extender pigment, o / w resin emulsion, etc. added to the aqueous phase and the stability of the emulsion are monovalent lithium ions, sodium ions, potassium ions, etc. Is preferred. Therefore, the electrolyte added here is preferably lithium sulfate, potassium sulfate, sodium sulfate, sodium citrate, sodium hydrogen phosphate, sodium borate, sodium acetate, sodium chloride, potassium chloride, lithium chloride, etc. The amount is 0.01% by mass to 5% by mass and preferably 0.1% by mass to 2.0% by mass with respect to the aqueous phase. Further, a divalent cation electrolyte may be used in combination as long as the stability of the emulsion and the dispersion stability of the powder are not affected.

<< Extreme Pigment >>
There is no restriction | limiting in particular as said extender pigment, According to the objective, it can select suitably, For example, the same thing as the extender pigment added to the said oil phase is mentioned.

<Other additives>
In the emulsion ink for stencil printing of the present invention, a wax can be added to the oil phase in order to improve separation of the printing paper and the printing drum during printing or to prevent the printing paper from rolling up. Further, triethanolamine, sodium hydroxide or the like can be added to the aqueous phase to further increase the viscosity of the aqueous phase by adding a water-soluble polymer. Furthermore, a rust preventive agent or an antifoaming agent can be added to the aqueous phase to prevent the printing press from being rusted or bubbling by ink during printing. These additives may be added as necessary to known products added to the stencil printing ink, and the amount added may be the same as that of the conventional product.

<Method for producing emulsion ink for stencil printing>
The emulsion ink for stencil printing of the present invention adjusts the oil phase and the water phase in the same manner as in the production of conventional emulsion inks, and gradually adds the water phase to the oil phase using a known emulsifier. The ink may be emulsified.

  For inks that contain a colorant in the oil phase, add a colorant and a colorant dispersant to the oil component, finely disperse them with a commercially available disperser such as a three-roll or bead mill, and apply varnish or emulsifier as necessary. To adjust the oil phase. Furthermore, water, electrolyte, glycerin and other anti-freezing agents, antiseptic / antifungal agents, water-soluble polymers and the like are made uniform using a stirrer to adjust the aqueous phase. The resin is dissolved in the oil component by heating to form a varnish.

  For example, a W / O emulsion ink containing an insoluble colorant in the oil phase is obtained as follows. First, an insoluble colorant dispersion is prepared by kneading the colorant, oil, and insoluble colorant dispersant with three rolls, and the insoluble colorant dispersion is mixed with a surfactant for emulsification, Oil and vegetable oil and varnish such as resin are added to form an oil phase. To this, an aqueous phase composed of water, an antifreezing agent, an antibacterial agent, an electrolyte, a water-soluble resin, etc. is added and emulsified. An emulsion ink is obtained. Moreover, you may add other components, such as extender, as needed. The varnish is obtained by heating and dissolving a resin component in an oil component, and can be obtained by a known method.

  In emulsion inks for stencil printing presses containing a colorant in the water phase, the oil phase is adjusted by uniformizing the varnish component, oil component, emulsifier, and the like with a stirrer. In addition, the colorant is dispersed in water using a low-viscosity dispersing machine such as a colorant, a colorant dispersant, a water-soluble polymer, or a bead mill, and an antifreezing agent such as an electrolyte or glycerin, an antiseptic / antifungal agent, etc. Add as necessary to adjust the aqueous phase.

  For example, a W / O emulsion ink containing an insoluble colorant in the aqueous phase is obtained as follows. Insoluble colorant, colorant dispersant, water-soluble polymer, antifreeze agent, antibacterial agent, premixed and dispersed using bead mill to form an aqueous phase. This aqueous phase is prepared in advance The emulsion ink for stencil printing can be obtained by stirring and mixing in an oil phase comprising vegetable oil, surfactant for emulsification, varnish, and the like and emulsifying. Moreover, you may add other components, such as extender, as needed.

  An emulsion ink for a stencil printing press containing a colorant in an oil phase and an aqueous phase is obtained by preparing an emulsion ink for a stencil printing press from an oil phase containing a colorant and an aqueous phase containing a colorant. It is done.

  For example, emulsion inks for stencil printing presses that contain insoluble colorants in both the oil phase and the water phase produce insoluble colorant dispersions for the oil phase and the water phase, and the water phase is stirred in the oil phase. By mixing and emulsifying, an emulsion ink for stencil printing is obtained. Moreover, you may add other components, such as an extender, as needed.

The viscosity of the emulsion ink for stencil printing presses can be adjusted by the stirring conditions and is not particularly limited as long as it is suitable for the system, but the viscosity at a shear rate of 20 s ⁻¹ is preferably 2 to 40 Pa · s. , Preferably 10 to 30 Pa · s.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1
7. Raven 760 (manufactured by Columbian) as a pigment, 7.0 parts by mass of PVP K-30 (manufactured by BASF) as a water-soluble polymer, glycerin as a cryoprotectant (manufactured by Kao) 0 part by mass, 0.1 part by mass of methyl p-oxybenzoate (manufactured by Kanto Chemical Co., Ltd.) as an antibacterial agent, 0.1 part by mass of magnesium sulfate (manufactured by Kanto Chemical Co., Ltd.) as an electrolyte, and 56.8 ion-exchanged water A mass part was added, and after premixing, it was dispersed using a bead mill to obtain an aqueous phase. Furthermore, the emulsion was prepared as an emulsion ink for stencil printing by mixing and emulsifying a water phase in an oil phase prepared in advance. The oil phase is 10.0 parts by mass of Sansen 310 (manufactured by Sun Oil Co., Ltd.) as oil, 5.0 parts by mass of AF-5 (manufactured by Nippon Oil Corporation) as a petroleum solvent, and soybean as a vegetable oil solvent. 5.0 parts by mass of methyl ester (manufactured by Toei Chemical Co., Ltd.), 2.0 parts by mass of ALPEX CK514 (manufactured by Nippon Cytec Co., Ltd.) as cyclized rubber, China Tung Oil No. 4 as vegetable oil (manufactured by Toshin Oil & Fat Co., Ltd., Tung Oil ( Processing oil of iodine value 155 to 175)) 2.0 parts by mass, sorbitan monooleate (manufactured by Kao Corporation) as an emulsifier 4.0 parts by mass.

  Using the obtained emulsion ink for stencil printing, evaluation of rubbing stains, evaluation of drying speed, evaluation of water resistance, evaluation of open storage stability of ink, and evaluation of ink cost, which will be described later, were performed. The results are shown in Table 1.

(Evaluation of rubbing dirt)
0.5 g of ink was placed on an LT tester (manufactured by Taniguchi Ink Co., Ltd., automatic color developing machine Type LT-2) and kneaded for 10 seconds, and then a solid image of 20 mm × 20 mm was printed on Ricoh Type 6200 PPC paper to obtain a sample. After 24 hours, paper was set on a clock meter, and evaluation was made based on how dirty the paper was when it was reciprocated 10 times. The degree of dirt in the evaluation was evaluated using four grades based on the color difference between Lab and paper.
A: Color difference is less than 0.80 B: Color difference is 0.80 or more and less than 1.10 Δ: Color difference is 1.10 or more and less than 1.40 ×: Color difference is 1.40 or more

(Dry rate evaluation)
A masking paper tape (manufactured by Nitto Denko) was applied after 1 hour of printing with the LT tester, and after applying pressure, the amount of colorant transferred to the tape when peeled was measured using a Macbeth densitometer. It was evaluated with.
A: Density is less than 0.15 O: Density is 0.15 or more and less than 0.25 Δ: Density is 0.25 or more and less than 0.35 x: Density is 0.35 or more

(Evaluation of water resistance)
A sample was obtained by printing a solid image of 20 mm × 20 mm on Ricoh Type 6200 PPC paper using a commercially available Ricoh stencil printing machine Satelio A650. After 24 hours, the smeared portion of the ink when the printed sample was traced with a finger wetted with water was measured with a Macbeth densitometer, and evaluated based on the stain density in four stages.
A: Density is less than 0.10 B: Density is 0.10 or more and less than 0.12 B: Density is 0.12 or more and less than 0.16

(Evaluation of open storage stability of ink)
After the ink was applied thinly on a glass plate, the change of the ink surface when left in a room temperature environment was evaluated.
◎: No change after standing for 1 week ○: Film formation by 4-5 days Δ: Film formation by 2-3 days x: Film formation by 1 day

(Evaluation of ink cost)
The cost of the ink was evaluated by the ratio of the oil phase that greatly affects the cost.
A: Oil phase is less than 30% by weight,
○: Oil phase is 30 wt% or more and less than 40 wt%,
Δ: The oil phase is 40 wt% or more and less than 50 wt%,
X: Oil phase is 50% by weight or more

(Comparative Example 1)
The amount of AF-5 (manufactured by Nippon Oil Corporation) as a petroleum solvent added to the oil phase was changed from 5.0 parts by mass to 6.0 parts by mass, soy methyl ester (Toei Chemical Co., Ltd.) as a vegetable oil solvent. The amount added to the oil phase is 5.0 parts by mass to 6.0 parts by mass, and Sina Tung Oil No. 4 as vegetable oil (manufactured by Toshin Yushi Co., Ltd., processed oil of Tung Oil (Iodine Value 155 to 175)) Except that the oil phase was not added to the oil phase, a stencil printing emulsion ink was prepared in the same manner as in Example 1, and the stencil printing emulsion ink thus prepared was used to evaluate rubbing stains and dry speed. Evaluation of water resistance, evaluation of open storage stability of ink, and evaluation of ink cost were performed. The results are shown in Table 1.

(Comparative Example 2)
The amount of ion-exchanged water added to the water phase is changed from 56.8 parts by mass to 57.8 parts by mass, and the amount added to the oil phase of Sansen 310 (manufactured by Sun Oil Co., Ltd.) as oil is changed from 10.0 parts by mass. Change to 12.0 parts by mass, and change the amount of AF-5 (manufactured by Nippon Oil Corporation) as a petroleum solvent to the oil phase from 5.0 parts by mass to 6.0 parts by mass. The amount of soybean methyl ester (Toei Chemical Co., Ltd.) added to the oil phase was changed from 5.0 parts by mass to 3.0 parts by mass, and ALPEX CK514 (manufactured by Nippon Cytec Co., Ltd.) as a cyclized rubber was added to the oil phase. Except for not making the emulsion ink for stencil printing in the same manner as in Example 1, using the prepared emulsion ink for stencil printing, evaluation of rubbing dirt, evaluation of drying speed, evaluation of water resistance, Evaluation of ink open storage stability and ink The cost was evaluated. The results are shown in Table 1.

(Example 2)
The amount of ion-exchanged water added to the water phase is changed from 56.8 parts by mass to 54.8 parts by mass, and the amount of Sansen 310 (manufactured by Sun Oil Co., Ltd.) as oil added to the oil phase is changed from 10.0 parts by mass. Change to 4.0 parts by weight, and change the amount of AF-5 (manufactured by Nippon Oil Corporation) as a petroleum solvent to the oil phase from 5.0 parts by weight to 10.0 parts by weight. The amount of soybean methyl ester (Toei Chemical Co., Ltd.) added to the oil phase was changed from 5.0 parts by mass to 6.0 parts by mass, and ALPEX CK514 (made by Nippon Cytec Co., Ltd.) as a cyclized rubber was added to the oil phase. A stencil printing emulsion ink was prepared in the same manner as in Example 1 except that the addition amount was changed from 2.0 parts by weight to 4.0 parts by weight. Using the stencil printing emulsion ink thus prepared, Evaluation of rubbing dirt, evaluation of drying speed, evaluation of water resistance, Evaluation of open storage stability of ink and cost of ink were performed. The results are shown in Table 2.

(Example 3)
The amount of ion-exchanged water added to the water phase is changed from 56.8 parts by mass to 48.8 parts by mass, and the oil as a petroleum solvent is not added to the oil phase. -5 (Shin Nippon Oil Co., Ltd.) added to the oil phase from 5.0 parts by weight to 16.0 parts by weight to the oil phase of soybean methyl ester (Toei Chemical Co., Ltd.) as a vegetable oil solvent The addition amount of ALPEX CK514 (made by Nippon Cytec Co., Ltd.) as a cyclized rubber to the oil phase is changed from 2.0 parts by mass to 6.0 parts by mass. The emulsion ink for stencil printing was prepared in the same manner as in Example 1 except that the stencil printing emulsion was used, and the stencil printing emulsion ink thus prepared was used to evaluate rubbing dirt, evaluation of drying speed, and evaluation of water resistance. , Evaluation of open storage stability of ink, and ink The strike was evaluated. The results are shown in Table 2.

Example 4
The amount of ion-exchanged water added to the water phase is changed from 56.8 parts by mass to 46.8 parts by mass, and the oil as a petroleum solvent is not added to the oil phase. -5 (Shin Nippon Oil Co., Ltd.) added to the oil phase from 5.0 parts by weight to 16.0 parts by weight to the oil phase of soybean methyl ester (Toei Chemical Co., Ltd.) as a vegetable oil solvent The amount of ALPEX CK514 (manufactured by Nippon Cytec Co., Ltd.) as a cyclized rubber is changed from 2.0 parts by weight to 8.0 parts by weight. The emulsion ink for stencil printing was prepared in the same manner as in Example 1 except that the stencil printing emulsion was used, and the stencil printing emulsion ink thus prepared was used to evaluate rubbing dirt, evaluation of drying speed, and evaluation of water resistance. , Evaluation of open storage stability of ink, and ink The strike was evaluated. The results are shown in Table 2.

(Example 5)
The amount of ion-exchanged water added to the aqueous phase is changed from 56.8 parts by mass to 42.8 parts by mass, and the oil as a petroleum solvent is not added to the oil phase. -5 (Shin Nippon Oil Co., Ltd.) added to the oil phase from 5.0 parts by weight to 16.0 parts by weight to the oil phase of soybean methyl ester (Toei Chemical Co., Ltd.) as a vegetable oil solvent The amount of ALPEX CK514 (manufactured by Nippon Cytec Co., Ltd.) as a cyclized rubber is changed from 2.0 parts by mass to 10.0 parts by mass. The emulsion ink for stencil printing was prepared in the same manner as in Example 1 except that the stencil printing emulsion was used, and the stencil printing emulsion ink thus prepared was used to evaluate rubbing dirt, evaluation of drying speed, and evaluation of water resistance. , Evaluation of ink open storage stability, and ink Evaluation of the cost of The results are shown in Table 2.

(Example 6)
The amount of ion-exchanged water added to the water phase is changed from 56.8 parts by mass to 48.8 parts by mass, and the oil as a petroleum solvent is not added to the oil phase. -5 (Shin Nippon Oil Co., Ltd.) added to the oil phase from 5.0 parts by weight to 16.0 parts by weight to the oil phase of soybean methyl ester (Toei Chemical Co., Ltd.) as a vegetable oil solvent The addition amount of ALPEX CK514 (made by Nippon Cytec Co., Ltd.) as a cyclized rubber to the oil phase is changed from 2.0 parts by mass to 6.0 parts by mass. The amount added to the oil phase of Sina Tung Oil No. 4 (manufactured by Toshin Yushi Co., Ltd., processed oil of Tung Oil (iodine value 155 to 175)) as a vegetable oil is changed from 2.0 parts by mass to 0.5 parts by mass. A stencil printing emulsion ink was prepared in the same manner as in Example 1 except that Using the emulsion ink for stencil printing prepared as described above, evaluation of rubbing stain, evaluation of drying speed, evaluation of water resistance, evaluation of open storage stability of ink, and evaluation of ink cost were performed. The results are shown in Table 3.

(Example 7)
The amount of ion-exchanged water added to the water phase is changed from 56.8 parts by mass to 48.8 parts by mass, and the oil as a petroleum solvent is not added to the oil phase. -5 (Shin Nippon Oil Co., Ltd.) added to the oil phase from 5.0 parts by weight to 16.0 parts by weight to the oil phase of soybean methyl ester (Toei Chemical Co., Ltd.) as a vegetable oil solvent The amount of addition of ALPEX CK514 (made by Nippon Cytec Co., Ltd.) as a cyclized rubber to the oil phase is changed from 2.0 parts by weight to 6.0 parts by weight. The amount of Sina Tung Oil No. 4 (manufactured by Toshin Yushi Co., Ltd., processed oil of Tung Oil (iodine value 155 to 175)) as a vegetable oil is changed from 2.0 parts by mass to 1.0 parts by mass. A stencil printing emulsion ink was prepared in the same manner as in Example 1 except that Using the emulsion ink for stencil printing prepared as described above, evaluation of rubbing stain, evaluation of drying speed, evaluation of water resistance, evaluation of open storage stability of ink, and evaluation of ink cost were performed. The results are shown in Table 3.

(Example 8)
The amount of ion-exchanged water added to the water phase is changed from 56.8 parts by mass to 48.8 parts by mass, and the oil as a petroleum solvent is not added to the oil phase. -5 (Shin Nippon Oil Co., Ltd.) added to the oil phase from 5.0 parts by weight to 16.0 parts by weight to the oil phase of soybean methyl ester (Toei Chemical Co., Ltd.) as a vegetable oil solvent The addition amount of ALPEX CK514 (made by Nippon Cytec Co., Ltd.) as a cyclized rubber to the oil phase is changed from 2.0 parts by mass to 6.0 parts by mass. The amount added to the oil phase of Sina Tung Oil No. 4 (manufactured by Toshin Yushi Co., Ltd., processed oil of Tung Oil (iodine value 155 to 175)) as a vegetable oil is changed from 2.0 parts by mass to 4.0 parts by mass. A stencil printing emulsion ink was prepared in the same manner as in Example 1 except that Using the emulsion ink for stencil printing prepared as described above, evaluation of rubbing stain, evaluation of drying speed, evaluation of water resistance, evaluation of open storage stability of ink, and evaluation of ink cost were performed. The results are shown in Table 3.

Example 9
The amount of ion-exchanged water added to the water phase is changed from 56.8 parts by mass to 48.8 parts by mass, and the oil as a petroleum solvent is not added to the oil phase. -5 (Shin Nippon Oil Co., Ltd.) added to the oil phase from 5.0 parts by weight to 14.0 parts by weight to the oil phase of soybean methyl ester (Toei Chemical Co., Ltd.) as a vegetable oil solvent The amount of ALPEX CK514 (manufactured by Nippon Cytec Co., Ltd.) as a cyclized rubber is changed from 2.0 parts by mass to 6.0 parts by mass. The amount added to the oil phase of Sina Tung Oil No. 4 (manufactured by Toshin Yushi Co., Ltd., processing oil of Tung Oil (iodine value 155 to 175)) as a vegetable oil is changed from 2.0 parts by mass to 8.0 parts by mass. A stencil printing emulsion ink was prepared in the same manner as in Example 1 except that Using the emulsion ink for stencil printing prepared as described above, evaluation of rubbing stain, evaluation of drying speed, evaluation of water resistance, evaluation of open storage stability of ink, and evaluation of ink cost were performed. The results are shown in Table 3.

(Example 10)
The amount of ion-exchanged water added to the water phase is changed from 56.8 parts by mass to 48.8 parts by mass, and the oil as a petroleum solvent is not added to the oil phase. -5 (Shin Nippon Oil Co., Ltd.) added to the oil phase from 5.0 parts by weight to 14.0 parts by weight to the oil phase of soybean methyl ester (Toei Chemical Co., Ltd.) as a vegetable oil solvent The amount of ALPEX CK514 (manufactured by Nippon Cytec Co., Ltd.) as a cyclized rubber is changed from 2.0 parts by mass to 6.0 parts by mass. The amount added to the oil phase of Sina Tung Oil No. 4 (manufactured by Toshin Yushi Co., Ltd., processed oil of Tung Oil (iodine value 155 to 175)) as a vegetable oil is changed from 2.0 parts by mass to 10.0 parts by mass. The emulsion ink for stencil printing was prepared in the same manner as in Example 1 except that Using the prepared emulsion ink for stencil printing, rubbing stain evaluation, drying speed evaluation, water resistance evaluation, ink open storage stability evaluation, and ink cost evaluation were performed. The results are shown in Table 3.

(Comparative Example 3)
The amount of ion-exchanged water added to the aqueous phase is changed from 56.8 parts by mass to 52.8 parts by mass, and the oil is not added to the oil phase, and the oil-based solvent AF -5 (Shin Nippon Oil Co., Ltd.) added to the oil phase from 5.0 parts by weight to 14.0 parts by weight to the oil phase of soybean methyl ester (Toei Chemical Co., Ltd.) as a vegetable oil solvent Was added from 5.0 parts by mass to 4.0 parts by mass, and ALPEX CK514 (manufactured by Nippon Cytec Co., Ltd.) as a cyclized rubber was not added to the oil phase. For stencil printing in the same manner as in Example 1 except that the amount added to the oil phase of Tung Oil (processing oil with iodine value of 155 to 175) manufactured by the company is changed from 2.0 parts by mass to 10.0 parts by mass. An emulsion ink was prepared and the prepared emulsion ink for stencil printing was used. The ink was used to evaluate rubbing dirt, drying speed, water resistance, ink open storage stability, and ink cost. The results are shown in Table 3.

(Example 11)
The amount of ion-exchanged water added to the water phase is changed from 56.8 parts by mass to 44.8 parts by mass, and the oil as a petroleum solvent is not added to the oil phase. -5 (Shin Nippon Oil Co., Ltd.) added to the oil phase from 5.0 parts by weight to 13.4 parts by weight to the oil phase of soybean methyl ester (Toei Chemical Co., Ltd.) as a vegetable oil solvent The amount of ALPEX CK514 (manufactured by Nippon Cytec Co., Ltd.) as a cyclized rubber is changed from 2.0 parts by weight to 8.0 parts by weight. The amount added to the oil phase of Sina Tung Oil No. 4 (manufactured by Toshin Yushi Co., Ltd., processed oil of Tung Oil (iodine value 155 to 175)) as a vegetable oil is changed from 2.0 parts by mass to 10.0 parts by mass. , Manganese naphthenate (manufactured by Showa Chemical Co., Ltd.) in the oil phase as a dryer Stencil printing was carried out in the same manner as in Example 1 except that 0.1 part by mass of RIKEN E Oil 1000 (d-δ-tocophenol) (manufactured by Riken Vitamin Co., Ltd.) as an antioxidant was added to the oil phase. The emulsion ink for stencil printing was prepared, and the stencil printing emulsion ink prepared above was used to evaluate rubbing stains, dry speed, water resistance, ink open storage stability, and ink cost. went. The results are shown in Table 4.

(Example 12)
7.0 parts by mass of MA-70 (manufactured by Mitsubishi Chemical Corporation) as a pigment (insoluble colorant), 0.5 parts by mass of AL-M (manufactured by Ajinomoto Fine Techno Co., Ltd.) as a pigment dispersant (insoluble colorant dispersant) The pigment dispersion (insoluble colorant dispersion) was adjusted by kneading 15.5 parts by mass of AF-5 (manufactured by Nippon Oil Co., Ltd.) as a petroleum solvent with three rolls. In the body (insoluble colorant dispersion), 6.0 parts by mass of ALPEX CK514 (manufactured by Nippon Cytec Co., Ltd.) as a cyclized rubber, and China Tung Oil No. 4 (manufactured by Toshin Oil & Fat Co., Ltd. 175) processed oil) 10.0 parts by weight and 4.0 parts by weight of sorbitan monooleate (manufactured by Kao Corporation) as an emulsifier (emulsifying surfactant) to obtain an oil phase. .8 parts by weight, glyce as antifreeze 7.0 parts by mass of phosphorus (manufactured by Kao Corporation), 0.1 parts by mass of methyl p-oxybenzoate (manufactured by Kanto Chemical Co.) as an antibacterial agent, and 0.1 parts by mass of magnesium sulfate (manufactured by Kanto Chemical Co., Inc.) as an electrolyte A water phase consisting of parts was added and emulsified to obtain an emulsion ink for a stencil printing machine.

  Using the resulting emulsion ink for stencil printing, as in Example 1, evaluation of rubbing stain, evaluation of drying speed, evaluation of water resistance, evaluation of open storage stability of ink, and evaluation of ink cost were performed. It was. The results are shown in Table 5.

(Comparative Example 4)
The amount of ion-exchanged water added to the water phase is changed from 49.8 parts by mass to 61.3 parts by mass, and AF-5 (manufactured by Nippon Oil Corporation) as a petroleum solvent is not added to the oil phase. Example 12 except that 10.0 parts by mass of Sansen 310 (manufactured by Sun Oil Co., Ltd.) was added to the oil phase and ALPEX CK514 (manufactured by Nippon Cytec Co., Ltd.) as a cyclized rubber was not added to the oil phase. Similarly, an emulsion ink for stencil printing was prepared, and by using the emulsion ink for stencil printing thus prepared, evaluation of rubbing stains, evaluation of drying speed, evaluation of water resistance, evaluation of open storage stability of ink, and ink Evaluation of the cost of The results are shown in Table 5.

(Example 13)
The amount of ion-exchanged water added to the water phase is changed from 56.8 parts by mass to 48.8 parts by mass, and the oil as a petroleum solvent is not added to the oil phase. -5 (Shin Nippon Oil Co., Ltd.) added to the oil phase from 5.0 parts by weight to 14.0 parts by weight to the oil phase of soybean methyl ester (Toei Chemical Co., Ltd.) as a vegetable oil solvent The amount of ALPEX CK514 (manufactured by Nippon Cytec Co., Ltd.) as a cyclized rubber is changed from 2.0 parts by mass to 6.0 parts by mass. In addition, from 2.0 parts by weight of Sina Tung Oil No. 4 (produced by Toshin Yushi Co., Ltd., processed oil of Tung Oil (iodine value of 155 to 175)) as vegetable oil to Tung Oil (Nisshin Oilio Co., Ltd., iodine value of 155 to 175) 8 For stencil printing in the same manner as in Example 1 except for changing to 0.0 parts by mass Emulsion ink is prepared, and the stencil printing emulsion ink prepared above is used to evaluate rubbing stains, dry speed, water resistance, ink open storage stability, and ink cost. It was. The results are shown in Table 6.

(Comparative Example 5)
The amount of ion-exchanged water added to the aqueous phase is changed from 56.8 parts by mass to 54.8 parts by mass, and the oil is not added to the oil phase, and the oil-based solvent AF -5 (Shin Nippon Oil Co., Ltd.) added to the oil phase from 5.0 parts by weight to 14.0 parts by weight to the oil phase of soybean methyl ester (Toei Chemical Co., Ltd.) as a vegetable oil solvent Was added from 5.0 parts by mass to 4.0 parts by mass, and ALPEX CK514 (manufactured by Nippon Cytec Co., Ltd.) as a cyclized rubber was not added to the oil phase. Example 1 except that 2.0 parts by mass of Tung Oil (processed oil of iodine value 155 to 175) manufactured by the company was changed to 8.0 parts by mass of Tung Oil (manufactured by Nisshin Oilio Co., Ltd., iodine value 155 to 175). Prepare emulsion ink for stencil printing in the same way as above, Using the emulsion ink for stencil printing, evaluation of rubbing dirt, evaluation of drying speed, evaluation of water resistance, evaluation of open storage stability of ink, and evaluation of ink cost were performed. The results are shown in Table 6.

(Example 14)
The amount of ion-exchanged water added to the water phase is changed from 56.8 parts by mass to 48.8 parts by mass, and the oil as a petroleum solvent is not added to the oil phase. -5 (Shin Nippon Oil Co., Ltd.) added to the oil phase from 5.0 parts by weight to 14.0 parts by weight to the oil phase of soybean methyl ester (Toei Chemical Co., Ltd.) as a vegetable oil solvent The amount of ALPEX CK514 (manufactured by Nippon Cytec Co., Ltd.) as a cyclized rubber is changed from 2.0 parts by mass to 6.0 parts by mass. 7. From 2.0 parts by weight of Sina Tung Oil No. 4 (manufactured by Toshin Yushi Co., Ltd., processed oil of Tung Oil (iodine value of 155 to 175)) as a vegetable oil to linseed oil (manufactured by Kaneda Corporation, iodine value of 179 to 180) Except for changing to 0 parts by mass, the stencil printing process was performed in the same manner as in Example 1. Prepare Marshon ink, and use the emulsion ink for stencil printing produced above to evaluate rubbing stains, dry speed, water resistance, ink open storage stability, and ink cost. It was. The results are shown in Table 6.

(Comparative Example 6)
The amount of ion-exchanged water added to the aqueous phase is changed from 56.8 parts by mass to 54.8 parts by mass, and the oil is not added to the oil phase, and the oil-based solvent AF -5 (Shin Nippon Oil Co., Ltd.) added to the oil phase from 5.0 parts by weight to 14.0 parts by weight to the oil phase of soybean methyl ester (Toei Chemical Co., Ltd.) as a vegetable oil solvent Was added from 5.0 parts by mass to 4.0 parts by mass, and ALPEX CK514 (manufactured by Nippon Cytec Co., Ltd.) as a cyclized rubber was not added to the oil phase. Except for changing from 2.0 parts by mass of Tung oil (processed oil of iodine value 155 to 175) manufactured by the company to 8.0 parts by mass of linseed oil (produced by Kaneda, iodine value 179 to 180), Example 1 Similarly, an emulsion ink for stencil printing was prepared and The stencil printing emulsion ink was used to evaluate rubbing stains, drying speed, water resistance, ink open storage stability, and ink cost. The results are shown in Table 6.

(Example 15)
The amount of ion-exchanged water added to the water phase is changed from 56.8 parts by mass to 48.8 parts by mass, and the oil as a petroleum solvent is not added to the oil phase. -5 (Shin Nippon Oil Co., Ltd.) added to the oil phase from 5.0 parts by weight to 14.0 parts by weight to the oil phase of soybean methyl ester (Toei Chemical Co., Ltd.) as a vegetable oil solvent The amount of ALPEX CK514 (manufactured by Nippon Cytec Co., Ltd.) as a cyclized rubber is changed from 2.0 parts by mass to 6.0 parts by mass. Instead of 2.0 parts by mass of Sina Tung Oil No. 4 (manufactured by Toshin Yushi Co., Ltd., processed oil of Tung Oil (iodine value 155 to 175)) as soybean oil (Nisshin Oilio Co., iodine value 114 to 138) Stencil printing in the same manner as in Example 1 except that the content was changed to 8.0 parts by mass. The emulsion ink for stencil printing was prepared, and the stencil printing emulsion ink prepared above was used to evaluate rubbing stains, dry speed, water resistance, ink open storage stability, and ink cost. went. The results are shown in Table 6.

(Comparative Example 7)
The amount of ion-exchanged water added to the aqueous phase is changed from 56.8 parts by mass to 54.8 parts by mass, and the oil is not added to the oil phase, and the oil-based solvent AF -5 (Shin Nippon Oil Co., Ltd.) added to the oil phase from 5.0 parts by weight to 14.0 parts by weight to the oil phase of soybean methyl ester (Toei Chemical Co., Ltd.) as a vegetable oil solvent Was added from 5.0 parts by mass to 4.0 parts by mass, and ALPEX CK514 (manufactured by Nippon Cytec Co., Ltd.) as a cyclized rubber was not added to the oil phase. Except for changing from 2.0 parts by mass of Tung oil (processed oil of iodine value 155 to 175) manufactured by the company to 8.0 parts by mass of soybean oil (manufactured by Nisshin Oilio Co., Ltd., iodine value 114 to 138). In the same manner as in No. 1, an emulsion ink for stencil printing was prepared. Using the produced emulsion ink for stencil printing, evaluation of rubbing stain, evaluation of drying speed, evaluation of water resistance, evaluation of open storage stability of ink, and evaluation of ink cost were performed. The results are shown in Table 6.

  From Tables 1 to 6, Examples 1 to 15 containing both the cyclized rubber and at least one of the vegetable oil and the processed oil of the vegetable oil in the oil phase include the cyclized rubber, the vegetable oil, and the oil phase. Compared with Comparative Examples 1 to 7 that do not contain both of the vegetable oil and at least one of the processed oils, the results of “rubbing dirt” and “drying speed” are superior, so that the oil phase is cyclized. It has been found that when both rubber and at least one of vegetable oil and processed oil of the vegetable oil are contained, fixability of pigment (colorant) to paper and drying speed can be improved.

  From Table 6, Example 9 containing Sina Tung Oil No. 4 in the oil phase and Example 13 containing Tung Oil in the oil phase have better “rubbing stains” results than Example 14 containing linseed oil in the oil phase. Therefore, it was found that when the oil phase contains tung oil or polymerized tung oil, the fixability of the pigment (colorant) to the paper can be further improved.

  From Table 5, Example 10 containing a pigment (colorant) in the water phase has a better “drying speed” result than Example 12 containing a pigment (colorant) in the oil phase. It has been found that the drying rate can be further improved if the phase contains a pigment (colorant).

  From Table 2, Examples 2 to 4 in which the addition amount of the cyclized rubber to the emulsion ink for stencil printing is 4.0% by mass or more and 8.0% by mass or less are the addition amount of the cyclized rubber to the emulsion ink for stencil printing. Compared with Example 1 in which 2.0% by mass, the results of “rubbing stains” and “water resistance” are excellent, and the amount of cyclized rubber added to the emulsion ink for stencil printing is 10.0% by mass. Since the result of “ink cost” is excellent as compared with Example 5, when the addition amount of the cyclized rubber to the emulsion ink for stencil printing is 4.0% by mass or more and 8.0% by mass or less, to the paper It was found that the fixing property of the colorant can be further improved, the water resistance can be improved, and the ink cost can be reduced.

  From Table 2, Examples 3-4 whose addition amount of the cyclized rubber with respect to the emulsion ink for stencil printing is 6.0 mass% or more and 8.0 mass% or less are the addition amount of the cyclized rubber with respect to the emulsion ink for stencil printing. Since the result of “drying speed” is superior to those of Examples 1 and 2 in which is 2.0% by mass to 4.0% by mass, the amount of cyclized rubber added to the emulsion ink for stencil printing is 6. It was found that the drying rate could be further improved when the content was 0% by mass or more and 8.0% by mass or less.

  From Table 3, Examples 3 and 7 to 9 in which the amount of tung oil added to the emulsion ink for stencil printing is 1.0% by mass or more and 8.0% by mass or less are the additions of Sina Tung Oil No. 4 to the emulsion ink for stencil printing. Example 10 in which the result of “drying speed” is superior to Example 6 in which the amount is 0.5% by mass, and the amount of Sina Tung Oil No. 4 added to the emulsion ink for stencil printing is 10.0% by mass Since the “open storage stability of the ink” is superior, the addition amount of either the drying oil or the processing oil of the drying oil to the emulsion ink for stencil printing is 1.0 mass% or more and 8.0 mass%. It was found that the following can further improve the drying speed and prevent solidification of the ink when opened and in the opened state.

  From Table 3, Examples 3 and 8 in which the addition amount of Sin Tung Oil No. 4 with respect to the emulsion ink for stencil printing is 2.0% by mass or more and 4.0% by mass or less are those of Sin Tung Oil No. 4 with respect to the emulsion ink for stencil printing. Compared with Examples 6 and 7 in which the addition amount is 0.5% by mass to 1.0% by mass, the result of “water resistance” is excellent, and the addition amount of Sina Tung Oil No. 4 to the emulsion ink for stencil printing is 8 Compared with Examples 9 and 10 which are 0.0 mass% to 10.0 mass%, the “open storage stability of the ink” is superior, so that the drying oil for the emulsion ink for stencil printing and the processing oil of the drying oil are used. It was found that if any of the addition amounts is 2.0% by mass or more and 4.0% by mass or less, water resistance can be improved and ink solidification can be prevented at the time of opening and in the open state.

Claims (4)

In an emulsion ink for stencil printing comprising an oil phase and an aqueous phase, the oil phase is 10% by mass to 90% by mass with respect to the stencil printing emulsion ink, and the aqueous phase is based on the stencil printing emulsion ink. An emulsion ink for stencil printing, comprising 90% by mass to 10% by mass, wherein the oil phase contains cyclized rubber and polymerized tung oil obtained by heat-treating tung oil . In an emulsion ink for stencil printing comprising an oil phase and an aqueous phase, the oil phase is 10% by mass to 90% by mass with respect to the stencil printing emulsion ink, and the aqueous phase is based on the stencil printing emulsion ink. 90% by mass to 10% by mass, and the oil phase contains cyclized rubber and at least one of drying oil and processing oil of the drying oil, and the addition of the cyclized rubber to the emulsion ink for stencil printing An emulsion ink for stencil printing, characterized in that the amount is 6 mass% or more and 9 mass% or less. In an emulsion ink for stencil printing comprising an oil phase and an aqueous phase, the oil phase is 10% by mass to 90% by mass with respect to the stencil printing emulsion ink, and the aqueous phase is based on the stencil printing emulsion ink. 90% by mass to 10% by mass, and the oil phase contains cyclized rubber and at least one of a drying oil and a processing oil of the drying oil, and the drying oil and the drying property for the emulsion ink for stencil printing An emulsion ink for stencil printing, wherein the addition amount of any of the processing oils is from 1% by mass to 9% by mass. 4. The emulsion ink for stencil printing according to claim 3, wherein the addition amount of either the drying oil or the processing oil of the drying oil to the emulsion ink for stencil printing is 2% by mass or more and 6% by mass or less.