JPS60244336A - Preparation of non-aqueous microcapsule composition - Google Patents

Abstract

PURPOSE:To obtain a high performance microcapsule, by treating a hydrophobic core substance containing a melamine/formaldehyde resin precondensate having predetermined formaldehyde substitution degree, an alkylation degree and hydrophobicity under a predetermined condition. CONSTITUTION:A hydrophobic core substrance containing a melamine/formaldehyde resin precondensate with a formaldehyde substitution degree of 40-100%, an alkylation degree of 80-100% and hydrophobicity of 4-16 is prepared. This hydrophobic core substance is emulsified with an aqueous medium and the resulting emulsion is treated under a polycondensation promoting condition. The microcapsule obtained by treatment is dispersed in a non-aqueous medium.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a microcapsule composition, and particularly to a method for producing a non-aqueous microcapsule composition.

Microcapsules are suitable for stably retaining unstable substances (reactive substances, liquid substances, etc.), such as medicines, agricultural chemicals, foods and beverages, fragrances, dyes, liquid crystals, temperature-indicating materials, adhesives, fuels, etc. It is applied to. The most well-known use is pressure-sensitive copying paper, which has been used for over 30 years.

Conventionally known methods for producing microcapsules include the coacervation method (for example, U.S. Pat. No. 2,800,457).
No. 2800458), interfacial polymerization method (e.g., Japanese Patent Publication No. 38-19574, Japanese Patent Publication No. 42
-446, Special Publication No. 42-771, Special Publication No. 49-45
133 etc.), 1n-situ polymerization method (
For example, Japanese Patent Publication No. 36-9168, Japanese Patent Publication No. 51-907
No. 9, 6 methods shown in JP-A No. 53-84881, etc.)
etc. are known, and a large number of technologies have been developed.

Specifically, the microcapsules produced in this manner are coated on a support such as paper or film, or used as powder capsules. Fragrances, liquid crystals, electronics.

Microcapsules containing a color-donating agent or a ligand compound are usually produced in an aqueous medium, and after being made into a coating solution as it is or by adding an auxiliary agent, they are coated on a support such as paper with an air knife, and then coated with a roll. It is smeared by methods such as coating or blade coating, or printed by methods such as silk screen, flexography, or gravure.

However, when applying or printing a microcapsule coating liquid dispersed in an aqueous medium using a coating machine or a printing machine, a large machine with a long drying zone is required to evaporate the aqueous medium, and a large number of machines are required. Requires energy. Further, when such a coating liquid is applied to paper, there is a problem that the paper as a support is likely to expand and contract, resulting in wrinkles.

The use of non-aqueous microcapsule compositions that use an organic medium instead of water is one way to solve the above problems. 49-32717
No. 56-115371, No. 56-144996, No. 57-144788, No. 57-191088,
Flexographic, gravure or offset type inks are described in No. 58-191771 and the like. In addition, Japanese Patent Publication No. 1972-12255, No. 57-53196,
No. 3-13.5720, No. 54-150212, No. 5
No. 7-117337, No. 58-14' 1255, etc. describe true melt type inks, and JP-A-52
No. 136016, No. 53-435718, etc. describe electron beam or ultraviolet curing inks. Of course,
Letterpress inks are also already known.

However, these nonaqueous microcapsule compositions that have been developed so far have any of the following drawbacks, and there is still room for improvement.

■ Because the solvent resistance of the capsule membrane is poor, the core material is extracted depending on the medium used.

■ Due to the strong hydrophilic nature of the capsule surface, it cannot be sufficiently dispersed in hydrophobic media.

■ Because of the water-soluble polymer used as an emulsifier during capsule manufacturing, or because the capsule membrane itself has adhesive properties, pJ [capsules tend to stick to each other during mist drying, resulting in giant capsules.

Therefore, a capsule coating liquid prepared by dispersing the powder capsules in a medium and coated on a support is extremely easily destroyed.

■ Because the mechanical strength of the capsule membrane is weak, those coated with the capsule coating liquid on a support are extremely susceptible to destruction.

■゛ Because the thermal strength of the capsule membrane is poor, part of the core material flows out of the capsule during application.

■ A portion of the core substance flows out of the capsule during the formation of the capsule membrane, and therefore only a capsule coating liquid containing the core substance that is not encapsulated can be obtained.

The present inventors conducted extensive research in view of the current situation, and as a result, by using a specific microcapsule, they succeeded in obtaining an extremely high-performance non-aqueous microcapsule composition that does not have any of the above-mentioned drawbacks.

In the present invention, after emulsifying a hydrophobic core material containing a melamine-formaldehyde resin initial condensate having a degree of formaldehyde substitution of 40 to 100%, a degree of alkylation of 80 to 100%, and a degree of hydrophobicity of 4 to 16 in an aqueous medium, , is a method for producing a non-aqueous microcapsule composition, which is characterized by dispersing microcapsules obtained by processing under polycondensation-promoting conditions in a non-aqueous medium.

The melamine resin initial condensate used in the present invention must be completely or partially dissolved in the hydrophobic core material, and the degree of formaldehyde substitution, alkyl The degree of hydrophobicity and hydrophobicity are adjusted.

The degree of formaldehyde substitution is a value indicating what percentage of the active hydrogens possessed by the amino groups of melamine are substituted by methylol groups, alkoxymethylol groups, and methylene groups, and is expressed by the following formula.

Further, the degree of alkylation is a value indicating what percentage of the methylol group is alkoxylated, and is expressed by the following formula.

The degree of hydrophobicity is the total number of carbon atoms in all alkyl groups per melamine residue, and a melamine resin initial condensate with a degree of hydrophobicity of 5 to 12, more preferably 5 to 8, is a particularly good powder. The melamine resin initial condensate containing hexamethoxyhexamethylolmelamine or triethoxytrimethylolmelamine as a main component is most preferably used because a body capsule can be obtained.

In addition, in the present invention, the average number of nuclei represented by the average number of melamine residues contained in one molecule of the initial condensate is 1 to 1.
An initial condensate having a molecular weight of 0, more preferably 1 to 5 is more preferably used.

Furthermore, in the present invention, one or more other aldehyde resin initial condensates can be used in combination with the melamine resin initial condensate for the purpose of changing the performance of the membrane material. Examples of the initial condensate include phenol formaldehyde resin initial condensate, aminoaldehyde resin initial condensate, and the like.

Examples of the phenol-formaldehyde resin initial condensate include initial condensates obtained by condensing formaldehyde with at least one phenol such as phenol, cresol, xylenol, resorcinol, hydroquinone, pyrocatechol, and pyrogallol.

Examples of the aminoaldehyde resin initial condensate include at least one amine such as urea, thiourea, alkyl urea, ethylene urea, acetoguanamine, benzoguanamine, melamine, guanidine, dicyandiamide, biuret, and cyanamide, and formaldehyde, acetaldehyde, and paraformaldehyde. , hexamethylenetetramine, geltaraldehyde, glyoxal, an initial condensate obtained by condensing at least one aldehyde such as furfural, or an alkylated product or a partially alkylated product thereof, or an anion, cation, or nonionic modified product thereof. Among these, hydrophobic ones can be mentioned.

Although the alkyl group used for etherification is not limited to these, those having 1 to 8 carbon atoms are preferred from the viewpoint of ease of preparation.

In addition, examples of anionic modifiers include sulfamic acid, sulfanilic acid, glycolic acid, glycine, acidic sulfites, phenol sulfonate, taurine, etc., and examples of cationic modifiers include diethylenetriamine, triethylenetetramine, tetraethylene, tetraethylene, etc. Examples include pentamine and dimethylaminoethanol. Furthermore, examples of nonionic modifiers include ethylene glycol, diethylene glycol, etc., and these are used to the extent that the initial condensate does not lose its oil solubility.

In the present invention, when the initial condensate of the melamine resin is dissolved into the hydrophobic core material, if the initial condensate used has insufficient solubility or high viscosity, the hydrophobic core material in which the initial condensate is dissolved may be When the viscosity is high, a low boiling point solvent or a polar solvent may be used in combination. Examples of low boiling point solvents used for this include n-pentane, methylene chloride, ethylene chloride, carbon disulfide, acetone, methyl acetate, chloroform, and methyl. alcohol, tetrahydrofuran,
n-hexasan, carbon tetrachloride, ethyl acetate, ethyl alcohol, n-propyl alcohol, 189-7” propyl alcohol, n 7′ thyl alcohol, 1sO-butyl alcohol, t-butyl alcohol, n-pentyl alcohol, Methyl ethyl'I-), benzene, toluene,
Examples include xylene, ethyl ether and petroleum ether.

As the polar solvent, dioxane, cyclohexanone, methyl isobutyl ketone, dimethylformamide, etc. are used.

In the present invention, it is preferable that the melamine resin initial condensate is used dissolved in the hydrophobic core material, but it is also possible to use it in a dispersed state.

In addition, the blending amount of the melamine resin initial condensate is as follows.

It varies depending on the type of initial condensate used, the type and amount of the hydrophobic core material used, the type and amount of other aldehyde resins used together, the particle size of the capsule, its intended use, etc. - Although it cannot be determined generally, the hydrophobic It is preferably 2 parts by weight or more and 100 parts by weight or less in terms of melamine, and particularly preferably 4 parts by weight or more and 50 parts by weight or less, based on 100 parts by weight of the sex core material.

When the hydrophobic core material used is a solid, the solid is dispersed in an initial condensate or a low boiling point solvent in which the initial condensate is dissolved, and then emulsified in water or a hydrophilic medium.

The conditions for promoting polycondensation in the present invention vary depending on the type of melamine resin initial condensate used and the intended use of the capsule, and cannot be determined unconditionally, but conditions include conditions of 70°C or higher, or conditions of 60°C or higher with a pH of 5.0 or lower. It is preferable to maintain the temperature at 80°C or higher for 2 hours or more, and in particular, if the temperature is maintained at 80°C or higher for 2 hours or more and the PHtil is adjusted with acid at least once during the reaction, capsules with better performance can be obtained. .

In the method of the present invention, if the hydrophobic core material containing the melamine resin initial condensate can be emulsified in water or a hydrophilic medium, it is not necessary to use an emulsifier, but an emulsifier is used to facilitate emulsification. Anionic, nonionic, cationic, amphoteric polymers, low molecular weight emulsifiers, etc. are preferably used.

The anionic polymer may be natural or synthetic, such as -coo-, -so;, -opo
Examples include those having a knee group, etc., specifically gum arabic, carrageenan, sodium alginate, pectic acid,
Natural polymers such as gum tragacanth, almond gum, agar, carboxymethyl cellulose, sulfated cellulose,
Sulfated methylcellulose, carboxymethyl starch, phosphorylated starch, powder, semi-synthetic polymers such as lignin sulfonic acid, maleic anhydride copolymers (including hydrolyzed ones),
Acrylic acid-based, methacrylic acid-based or crotonic acid-based polymers and copolymers, vinylbenzenesulfonic acid-based or 2-acrylamido-2-methyl-propanesulfonic acid-based polymers and copolymers, and darning polymers. Examples include synthetic polymers such as partial amides or partial esters of polymers and copolymers, carboxy-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, and phosphoric acid-modified polyvinyl alcohol.

More specifically, examples of maleic anhydride copolymers (including hydrolyzed ones) include methyl vinyl ether-maleic anhydride copolymers, ethylene-maleic anhydride copolymers, and vinyl acetate-maleic anhydride copolymers. Polymer, methacrylamide-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, and the like.

Examples of the acrylic acid copolymer, methacrylic acid copolymer, or crotonic acid copolymer include methyl acrylate-acrylic acid copolymer (hereinafter referred to as "copolymer"), ethyl acrylate-acrylic acid , methyl acrylate-methacrylic acid, methyl methacrylate-acrylic acid, methyl methacrylate-methacrylate, methyl acrylate-acrylamide-acrylic acid, acrylomtril-acrylic acid,
Acrylonitrile-methacrylic acid, hydroxyethyl acrylate-acrylic acid, hydroxyethyl methacrylate-methacrylic acid, vinyl acetate-acrylic acid, vinyl acetate-methacrylic acid, acrylamide-acrylic acid, acrylamide-meccrylic acid, meccrylamide-acrylic acid, Examples include copolymers such as methacrylamide-methacrylic acid and vinyl acetate-crotonic acid.

Examples of vinylbenzenesulfonic acid copolymers or 2-acrylamido-2-methyl-propanesulfonic acid copolymers include methyl acrylate-vinylbenzenesulfonic acid (or salts thereof) copolymers, and vinyl acetate-vinylbenzenesulfonic acid copolymers. Polymer, acrylamide-vinylbenzenesulfonic acid copolymer, acrylmorpholine-vinylhenzenesulfonic acid copolymer, vinylpyrrolidone-vinylbenzenesulfonic acid copolymer, vinylpyrrolidone-2-acrylamide-2-methyl-propane Examples include sulfonic acid copolymers.

The nonionic polymer may also be natural or synthetic, and includes, for example, one having an -OH group.

Specific nonionic semi-synthetic polymers include hydroxyethyl cellulose, methyl cellulose, pullulan (non-crystalline, easily water-soluble polymer polyj/1M made from starch by microbial fermentation method), soluble starch, Examples include oxidized starch.

Further, as a synthetic product, polyvinyl alcohol can be mentioned.

Examples of cationic polymers include cation-modified polyvinyl alcohol, and examples of amphoteric polymers include gelatin.

Examples of low-molecular emulsifiers include anionic, cationic, nonionic, and amphoteric emulsifiers, but anionic ones are preferred, and among them, organic sulfuric acids having a total carbon number of 1 to 14 are preferred. Alternatively, Li“+Na”+K++NH4+ salts of organic phosphoric acids are preferable, and specifically, sodium tonylsulfonate, sodium henzenesulfonate, sodium benzenesulfinate, sodium p-toluenesulfonate, and sodium p-toluenesulfinate. , sodium p-vinylbenzenesulfonate, sodium p-i-amylhenzenesulfonate, sodium naphthalene-α-sulfonic acid, naphthalene-β-sulfonic acid sorter, 2-methylnaphthalene-
Sodium 6-sulfonate, sodium 2,6-dimethylnaphthalene-8-sulfonate, sodium 2,6-dimethylnaphthalene-3-sulfonate, 1-naphthol-
Examples include sodium 4-sulfonate, sodium benzene-m-disulfonate, funnel oil, sodium diphenyl phosphate, sodium phenylphosphonate, sodium di-n-butyl phosphate, sodium di-amyl phosphate, and the like.

In the method of the present invention, it is preferable to use one or more of the various emulsifiers mentioned above, but in particular, when a polymer emulsifier and a low-molecular emulsifier are used in combination, capsules with extremely high performance can be obtained. This is a preferred embodiment.

Emulsifiers such as those mentioned above can be added at 0.01% in water or a hydrophilic medium.
The content is preferably 0.1% or more from the viewpoint of ease of preparing 8 parts of the emulsion and stabilization of the emulsion. Particularly, a content in the range of 0.3 to 10% is preferable because capsule preparation is extremely easy. The upper limit of the amount to be used is determined by the viscosity of the system, the capsule preparation device, etc., but it is generally desirable to keep it to 20% or less.

In the present invention, so-called acid catalysts commonly used in the field of aminoaldehyde resin production, such as formic acid, acetic acid, citric acid, oxalic acid, valatoluenesulfonic acid, hydrochloric acid, and sulfuric acid, are used to maintain the reaction system acidic. It will be done.

In addition, in the present invention, an initial condensation product of an aminoaldehyde resin such as hexamethoxy to xamethylolmelamine is added to the microcapsule dispersion prepared as described above and reacted to form capsules that are easily dispersed in a non-aqueous medium. You can also get .

In the present invention, the hydrophobic core substance to be encapsulated in the microcapsules is not particularly limited, but the following substances are exemplified.

Animal oils such as fish oil, lard oil, vegetable oils such as olive oil, peanut oil, linseed oil, soybean oil, castor oil, petroleum, mineral oils such as kerosene, xylene, toluene, etc., alkyl-substituted diphenylalkanes, Substituted naphthalene, biphenylethane, methyl salicylate, diethyl adipate, di-n-propyl adipate, di-n-butyl adipate, di-methyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-phthalate - A water-insoluble or substantially water-insoluble liquid such as synthetic oils such as n-butyl and di-n-octyl phthalate, or an electron-donating color former or an electron-accepting color developer in the above synthetic oil. , solutions containing dissolved ligand compounds, organic metal salts, etc., water-insoluble metal oxides and salts, fibrous substances such as cellulose or asbestos, water-insoluble synthetic polymer substances, minerals, pigments, Glasses, perfumes, flavorings, fungicidal compositions, physiological compositions, fertilizer compositions, liquid crystals, temperature-indicating materials, flame retardants, etc.

In the present invention, the aqueous microcapsule dispersion prepared as described above can be used as it is, or after passing through a concentration process such as filtration, through air drying, surface drying,
Fluidized drying, flash drying, spray drying, vacuum drying, freeze drying,
Most of the dispersion medium is removed by means such as infrared drying, high frequency drying, ultrasonic drying, pulverization drying, etc. to form powder capsules, which are then dispersed in a non-aqueous medium to form a non-aqueous microcapsule composition. prepared. Also, JP-A-53-13!
5711, by mixing an aqueous capsule dispersion with a non-aqueous medium and then removing the aqueous medium under reduced pressure. It can also be prepared by filtering the capsule dispersion and then replacing it with a non-aqueous medium.

Although the microcapsules of the present invention are easily dispersed in non-aqueous media, a surfactant can be used to further improve the dispersibility. Examples of the surfactant include sodium alkyl sulfate, Sodium alkylbenzene sulfonate, sodium alkylnaphthalene sulfonate, sodium polystyrene sulfonate
anionic activators such as lithium, sodium lignin sulfonate, sodium oleic acid amide sulfonate, sodium dialkyl sulfosuccinate, sulfated castor oil, dialkyl phosphate, alkyl phosphate, diaryl phosphate, aryl phosphate; halogen Cation activators such as trinotylaminoethyl alkylamide, alkylpyridinium sulfate, alkyltrimethylammonium halide; polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxynyretine alkylphenyl ether, polyhydric alcohol fatty acid ester , polyoxyethylene polyhydric alcohol fatty acid ester, sucrose fatty acid ester, and other nonionic surfactants; amphoteric surfactants such as alkyltrimethylaminoacetic acid, alkyldiethylenetriaminoacetic acid, lecithin, and the like.

The non-aqueous medium used in the present invention may further include resins, capsule protectants, white pigments, desensitizing components (in the case of pressure-sensitive copying paper), ultraviolet absorbers, antioxidants, fluorescent dyes, plasticizers, etc., as required. Agents etc. can also be added.

Specific examples of the fat include rosin (gum rosin, wood rosin, tall oil rosin), natural resins such as Serafuku, copal, Dalman, Giltonite, and zein, hardened rosin,
Ester gum and other rosin esters, maleic acid resins, fumaric acid resins, trimerized rosins, polymerized rosins, rosin-modified phenolic resins, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, cellulose acetate propio Semi-synthetic resins such as nate, cellulose acetate butyrate, nitrocellulose, phenolic resins, xylene resins, urea resins, melamine resins, ketone resins, coumaron/indene resins, petroleum resins, terpene resins, cyclized rubber, chlorinated rubber, alkyd resins , polyamide resin, acrylic resin, polyvinyl chloride, vinyl chloride/vinyl acetate copolymer, polyvinyl acetate, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, methyl vinyl ether-maleic anhydride Mli polymer, Isobutylene
Examples include synthetic resins such as maleic anhydride copolymer, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl butyral (butyral resin), polyvinylpyrrolidone, chlorinated polypropylene styrene resin, epoxy resin, and polyurethane.

These resins are appropriately selected and used depending on the type of non-aqueous medium used, and the method disclosed in, for example, "Printing Ink Technology" CMC Co., Ltd. edition, etc. is suitable. Can be hired.

Specific examples of the capsule protectant include cellose powder, starch particles, microspheres, glass beads, and synthetic resin powder.

Examples of the desensitizing component include amino compounds known in the art in the case of leuco-based recording materials, and organic phosphorus-based compounds as described in Japanese Patent Application No. 149414-1983 in the case of iron and chelate-based recording materials. or a compound having an aminocarboxylic acid group.

In addition, white pigments include oxides, hydroxides, carbonates, sulfates, halogen compounds such as aluminum, zinc, magnesium, calcium, and titanium, as well as acid clay, activated clay, acupurgite, zeolite, bentonite, kaolin, and calcined clay. Examples include clays such as kaolin, organic pigments such as melamine resin, and urea resin.

As the non-aqueous medium used in the present invention, those known in the printing industry can be appropriately used, but specific examples include benzene, toluene, xylene, cyclohexane, Hexane, ligroin, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, etc. Boiling point alcohol is preferred, and in order to control drying of the composition, some n-propyl alcohol or isopropyl alcohol or water may be further added, or methyl acetate, ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, etc. may be added. I can do it.

In the case of flexo type and gravure type compositions, a resin is added as a binder. Examples of this resin include the resins mentioned above, including polyvinyl acetate, vinyl chloride,
Vinyl acetate copolymer, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, methyl vinyl ether-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, modified polyvinyl alcohol, polyvinyl butyral, Preferred are polyvinylpyrrolidone, ethylcellulose, nitrocellulose, hydroxypropylcellulose, cellulose acetate propionate, cellulose acetate butyrate, and the like.

The medium for the true melt type composition includes waxes, such as animal waxes such as beeswax, spermaceti wax, and lanolin, candelilla wax, carnauba wax, wood wax, rice wax, and sugarcane wax. vegetable waxes such as, mineral waxes such as montan wax, osichelite, lignite wax, etc.
Petroleum waxes such as paraffin wax and microcrystalline wax, modified waxes such as montan wax derivatives, paraffin wax derivatives, and microcrystalline wax derivatives, hydrogenated waxes such as castor wax and opal wax, low molecular weight polyethylene and its derivatives, Acra wax , synthetic waxes such as distearyl ketone, caproic acid amide, caprylic acid amide, pelargonic acid amide, capric acid amide, lauric acid amide, tridecylic acid amide, myristic acid amide, stearic acid amide, behenic acid amide, ethylene bisstearic acid amide , fatty acid amide waxes such as caproleic acid amide, oleic acid amide, linoleic acid amide, ricinoleic acid amide, and linoleic acid amide, fatty acid based waxes such as stearic acid and behenic acid, alcoholic waxes such as stearyl alcohol, and distearyl phosphoric acid. Phosphate ester waxes such as esters may be used alone or in combination.

Among them, oxidized mineral wax such as Montan wax, amide wax such as ethylene bisstearamide, stearamide, hehenic acid amide, fatty acid wax, phosphate ester wax, and mixtures thereof, with needles of 0.1 to 30. Those having hardness, a melting point of 50°C to 160°C, and a melting range of less than 20°C are preferably used.

In addition, in the present invention, an aromatic hydrocarbon compound having a melting point in the range of 40°C to 200°C may be used in addition to the above-mentioned wax cheek. It is more preferable to use a meltable resin in combination.Also, a good system can be obtained by using an aromatic hydrocarbon compound and a wax in combination, but a more preferable system is when a resin is used in combination with the mixed system. It is.

Specifically, the aromatic hydrocarbon compound is 2.6-
Diitupropylnaphthalene, 1,4.5-drimethylnaphthalene, 2,3.5-)limethylnaphthalene, 2
．． 3-dimethylnaphthalene, 1.3,6.8-tetramethylnaphthalene, 1゜2-di-0-tolylethane, bis-(2,4,5-trimethylphenyl)methane, 1.1
8-diphenyl-occudecane, 1,3-terphenyl, 1,2-p-)lylethane, diphenyl-p-tolylmethane, 1,2-dibenzylbenzene, 3,4-diphenylhexane, 1,2-bis (2゜3-dimethylphenyl)ethane, 4,4'-isopropylidenediphenol, bisresorcinol ethylene ether, 4-tert-butylphenyl salicylate, 2,2-bis(4-acetoxyphenyl)propane, bis(4- acetoxyphenyl) sulfone, terephthalic acid dimethyl ether, terephthalic acid dichlorophenyl ester, terefucuric acid distearylamide, malonic acid ethyl ester 4-methoxyanilide, benzyl mandelate, benzoic acid phenyl ester, benzoic acid 2-naphthyl ester,
2-Hydroxy-3-octylcarbamoylnaphthalene, 4-hydroxybenz? Examples thereof include acid hensyl ester, benzyl p-hensyloxybenzoate, 1,4-bispropionyloxybenzene, and 1,1-dibenzoylmethane.

In addition, examples of the resin include the resins mentioned above, among which cured rosin, ester gum, ethyl cellulose, phenol resin, rosin-modified phenol resin, urea/melamine resin, chlorinated rubber, cyclized rubber, maleic acid resin, petroleum resin, Terpene resins and the like are preferred.

Examples of the medium for electron beam or ultraviolet curable compositions include compounds having one or more vinyl or vinylidene groups, preferably a plurality of vinyl or vinylidene groups, such as acryloyl groups, metallolyloyl groups, allyl groups, unsaturated polyesters, vinyloxy, acrylamide groups, etc. Examples include compounds that have

The most typical examples include reaction products of polyols, polyamines, amino alcohols, etc. and unsaturated carboxylic acids, and reaction products of acrylates or methacrylates having hydroxyl groups and polyisocyanates.

For example, representative compounds include polyethylene glycol diacrylate, propylene glycol dimecacrylate, pentaerythritol triacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, hexanediol diacrylate, 1,2-
Butanediol diacrylate, reaction product of epoxy resin and acrylic acid, reaction product of meccrylic acid, penquerythritol and acrylic acid, condensation product of maleic acid, diethylene glycol and acrylic acid, methyl meccrylate,
Examples include butyl methacrylate and styrene. Regarding these monomers, see JP-A-49-52889 and JP-A-49-52889.
-68641 No. J8-32586, Special Publication No. 1977-
You can also choose from those disclosed in No. 7115 and the like.

When curing by ultraviolet rays, it is preferable to add a photopolymerization initiator to the medium.

Examples of the photopolymerization initiator include aromatic ketones, quinone compounds, ether compounds, and nitro compounds. Specifically, benzoquinone, phenanthrenequinone, naphthoquinone, diisopropylphenanthrenequinone, benzoin butyl ether, benzoin, Examples include furoinbutyl ether, Michler's ketone, Michler's thioketone, fluorenone, trinitrofluorenone, and β-benzoylaminonaphthalene.

Oil is used as the medium for the oxidative polymerization type (letterpress type) composition, and a solvent, wax, dryer, thickener, gelling agent, and thixotropy agent are added as necessary.

Examples of oils include vegetable oils (drying oils such as linseed oil and flower oil, semi-drying oils such as soybean oil, non-drying oils such as castor oil), processed oils (dehydrated castor oil, polymerized oils, maleated oils), Oil 1. Vinylated oil, urethanized oil), mineral oil (machine oil,
spindle oil).

Specific examples of the solvent include high-boiling petroleum solvents (ink oil), diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, and the like.

Example 1 Preparation of Ligand Compound Powder Capsules 25 parts of lauryl gallate and 10 parts of trihensylamine were dissolved in a mixed solution of 50 parts of adipine di-n-butyl, 10 parts of tributyl phosphate, and 40 parts of phenyl cellosolve. To the solution obtained, 62 parts of a solid methoxymethylolated melamine initial condensate (trade name Cynor 350, manufactured by Mitsui Toatsu Chemical Co., Ltd.) containing hexamethoxyhexamethylol melamine as a main component was added and mixed. A phase liquid was obtained.

Separately, in a stirring mixing vessel equipped with a heating device, 0.6 parts of an ethylene-maleic anhydride copolymer (trade name EMA-31, manufactured by Monosand Co., Ltd.) and an ethylene-maleic anhydride polymer copolymer (trade name EMA-31) were placed. -81゜Monosanto) 0.3
1 part to 300 parts of water, add an aqueous solution prepared by heating, and add a 5% aqueous solution of caustic soda to adjust the pH to 4.0.
Further, 0.6 part of funnel oil was added to prepare an aqueous medium for capsule production.

This aqueous medium was heated to 85°C, and the internal phase liquid was emulsified and dispersed therein so that the average particle size was 7.0 μm.
The reaction was carried out at 5°C for 3 hours. Subsequently, this system was stirred to 0
．． Gradually add 1N-hydrochloric acid to bring the pH of the system to 3.2.
The temperature of the system was further raised to 95°C, and the reaction was carried out at 95°C for 5 hours to obtain a milky white capsule dispersion.

The resulting capsule dispersion was suction-filtered, and the paste was further dried to obtain powder capsules mainly consisting of mononuclear capsules.

Preparation of Capsule Ink and Creation of Top Paper After dispersing 25 parts of the above powder capsules in a mixed solution of 50 parts of ethyl alcohol and 21 parts of n-propyl alcohol, 4 parts of ethyl cellulose 14 (manufactured by Vercules) was added thereto. A flexographic capsule ink was obtained by melting.

The above capsule ink was printed on a base paper of 40 g/n using a printing machine so that the ink amount was 4 g/m to obtain a top paper.

Preparation of the bottom paper To an aqueous solution prepared by adding 89 parts of t-butylbenzoic acid, 125 parts of diphenyl phosphate, and 70 parts of sodium laurylbenzenesulfonate to 800 parts of a 5% aqueous solution of caustic soda, add ferric chloride to 500 parts of water. An aqueous solution in which 108 parts of sodium t-butylbenzoate was dissolved was added under strong stirring to form yellow fine particles, and then a 20% aqueous solution of sodium t-butylbenzoate was added to this dispersion. fi, 500 parts were added. Further, 425 parts of TiCl was gradually added to this dispersion under strong stirring to form a pale yellow fine particle dispersion, which was then filtered and washed to obtain a slurry.

Next, 1 part of sodium polyacrylate and 1 part of hydroxyethyl cellulose were dissolved in 200 parts of water, and 20 parts of the solid content of the above slurry, 20 parts of titanium oxide, 50 parts of aluminum hydroxide, and 10 parts of tribenzylamine were added to this. After adding and strongly dispersing, carboxy-modified styrene-butadiene copolymer latex (solid content concentration 50%) is added to the dispersion.
A coating liquid was obtained by adding 15 parts of .

The obtained coating liquid was applied to 40g/n (8g/n dry weight) of base paper.
A lower paper was obtained by coating with an air knife coater so as to obtain rd.

When the upper paper was superimposed on the lower paper and printed using a typewriter, an extremely clear colored image was obtained. When the upper paper was treated at 100° C. for 3 hours and then printed on the lower paper using a typewriter, similarly clear colored images were obtained.

Example 2 Preparation of electron-donating color former powder capsules 74 parts of crystal violin tract was mixed with alkylnaphthalene (trade name
MC oil (manufactured by Kureha Chemical Co., Ltd.) was dissolved in 100 parts, the resulting solution was heated to 70°C, and after 1) lil production, Cymel 35
63 parts of solid content of 0 were added and mixed to obtain an internal phase liquid.

A capsule dispersion liquid was obtained in the same manner as in Example 1 except that the above-mentioned internal phase liquid was used, and this was spray-dried to obtain powder capsules.

Preparation of Capsule Ink and Creation of Top Paper 26 parts of the above powder capsules and 3 parts of starch particles were dispersed in a mixed solution of 40 parts of Air JL/7 L/L, 20 parts of isopropyl rutile alcohol, and 6 parts of water. After that, add ethyl cellulose layer 14 to this.
．． 5 parts were added and melted to obtain Gusibia type capsule ink.

The above capsule ink was printed on a 40 g/l base paper using a printing machine at an ink amount of 3 g/rl to obtain a top paper.

Preparation of bottom paper 65 parts of aluminum hydroxide, 20 parts of zinc oxide, 3.5-
Mixture of zinc di(α-methylbenzyl)salicylate and α-methylstyrene/styrene copolymer (melt ratio 80/
20) Add 20 parts (solid content) of carboxy-modified styrene-butadiene copolymer latex to a dispersion obtained by grinding 15 parts of polyvinyl alcohol aqueous solution (solid content) and 300 parts of water in a ball mill for 24 hours. In addition, the prepared color developer coating liquid was smeared on 40 g/m+ paper using an air knife coater so that the solid content was 5 g/d to prepare a base paper.

When the upper paper and lower paper prepared as described above were overlapped and printed using a typewriter, a clear colored image was obtained. Further, after processing the upper paper at 100'C for 3 hours, printing was performed on the lower paper using a typewriter, and similarly clear colored images were obtained.

Example 3 25 parts of powder capsules prepared in exactly the same manner as in Example 2 and 3 parts of polyethylene wax were dispersed in a mixed solution of 40 parts of ethyl alcohol, 18 parts of n-propyl alcohol, and 3 parts of cellosolve. A flexographic capsule ink was obtained by adding and dissolving 7 parts of modified maleic acid resin and 3 parts of nitrocellulose.

The above capsule ink was printed on the back side of a bottom paper prepared in the same manner as in Example 2 using a printing machine in an amount of ink of 3 g/- to obtain an inner paper.

When two sheets of the inner paper were printed using a typewriter, an extremely clear colored image was obtained.

Example 4 30 parts of powder capsules prepared in exactly the same manner as in Example 1 were dispersed in a mixed melt of 65 parts of microcrystalline wax with a melting point of 96°C and a penetration level of 8 and 5 parts of distearyl phosphate. A hot melt capsule ink was obtained.

The obtained ink was applied at 40 g/rr using a hot melt coating machine.
An upper paper was obtained by printing with an ink amount of 7 g/rd on R base paper.

Then, when the obtained upper paper and the lower paper obtained in the same manner as in Example 1 were overlapped and printed using a typewriter, a clear colored image was obtained.

Example 5 30 parts of powder capsules prepared in exactly the same manner as in Example 2 were dispersed in a mixed melt of 65 parts of microcrystalline wax with a melting point of 96 degrees and a penetration degree of 8 and 5 parts of distearyl phosphate. Obtain real melt type ink and apply ink amount 5g/rr on 40g/m base paper using hot melt coating machine.
? I printed it and got the top paper.

Then, when the obtained upper paper and the lower paper obtained in the same manner as in Example 2 were overlapped and printed using a typewriter, a clear colored image was obtained.

Example 6 30 parts of powder capsules prepared in exactly the same manner as in Example 2 were mixed with 30 parts of microcrystalline wax having a melting point of 96 degrees and a penetration level of 8, 1730 parts of 2,6-diisopropyl naphtha, and 5 parts of distearyl phosphate. and 5 parts of an aliphatic hydrocarbon resin (trade name: Tasoquirol 1000, manufactured by Sumitomo Chemical KK) to obtain a true melt type capsule ink.

Next, clay paper was obtained in the same manner as in Example 4 except that this capsule ink was used, and when printed with a typewriter, a colored image more vivid than in Example 4 was obtained.

Example 7 iM 40 parts of carnauba wax in form B and 1 part of cylinder oil
5 parts and 15 parts of castor oil were mixed, and 30 parts of powder capsules prepared in the same manner as in Example 2 were further added and dispersed to obtain a true melt type capsule ink.

The obtained ink was coated at 40 g/rd using a true melt coating machine.
The upper paper was obtained by printing on the base paper with an ink amount of 7 g/rd.

Then, when the obtained upper paper and the lower paper obtained in the same manner as in Example 2 were overlapped and printed using a typewriter, a clear colored image was obtained.

Example 8 30 parts of powder capsules prepared in exactly the same manner as in Example 2 were dispersed in 70 parts of an ultraviolet curable medium (trade name: Guicure RX Jume B, manufactured by Dainippon Ink and Chemicals), and
Obtain ultraviolet curable capsule ink and use a printing machine to print 40g/
An amount of ink of 6 g/1rd was printed on rrr base paper and irradiated with ultraviolet rays to obtain a top paper.

Next, the obtained upper paper and the lower paper obtained in the same manner as in Example 2 were overlapped and printed using a Quibwriter, and a clear colored image was obtained.

Example 9 Powder capsule 35 prepared in exactly the same manner as Example 2
The mixture was dispersed in 65 parts of an electron beam curable medium (trade name HX-220, manufactured by Nippon Kayaku Co., Ltd.) to obtain an electron beam curable capsule ink.
m printing and electron beam irradiation to obtain upper paper.

Next, the obtained upper paper and the lower paper obtained in the same manner as in Example 2 were placed one on top of the other, and when printing was performed using a typewriter, a clear colored image was obtained.

Example 10 iM capsule dispersion 3 was prepared in exactly the same manner as in Example 1.
After mixing 5 parts (in terms of solid content) and 65 parts of HX-220 under strong stirring, water was removed while heating under reduced pressure using an evaporator to obtain an electron beam curable capsule ink. 8 g of ink on 40 g/rd paper using printing machine
/rdm printing and electron beam irradiation to obtain upper paper.

Then, when the obtained upper paper and the lower paper obtained in the same manner as in Example 1 were overlapped and printed using a typewriter, a clear colored image was obtained.

Example 11 After filtering the capsule dispersion obtained in the same manner as in Example 1, a flexographic capsule ink was obtained in the same manner as in Example 1, except that 25 parts of the undried capsules were used as a solid content. As a result of printing and evaluation in the same manner as in Example 1, it was found that a product of almost the same quality was obtained.

Example 12 40 parts of powder capsules obtained in the same manner as in Example 1, 2 parts of light oil
Capsule ink for letterpress was obtained by sufficiently mixing 0 parts of linseed oil, 10 parts of linseed oil, and 30 parts of petroleum resin, and printing with an ink amount of 4 g/rrr on 40 g/m base paper using a printing machine to obtain upper paper. .

Next, the obtained upper paper was overlapped with the lower paper obtained in the same manner as in Example 1, and when printing was performed with a typewriter, a clear colored image was obtained.

Example 13 30 parts of powder capsules obtained in the same manner as in Example 2, 45 parts of castor oil, 10 parts of petroleum resin, and 10 parts of paraffin wax were thoroughly mixed to obtain a letterpress ink, and 40 parts of the powder was mixed with a printing machine.
Printed on gZrd base paper with an ink amount of 4 g/rdm,
I got the top paper.

Next, the obtained upper paper was placed on the lower paper obtained in the same manner as in Example 2, and when printing was performed with a typewriter, a clear colored image was obtained.

Example 14 40g of capsule ink prepared in the same manner as in Example 3
/rd base paper was printed at 8 g/d using Soufreel printing to obtain a top paper.

Next, the obtained upper paper was placed on the lower paper obtained in the same manner as in Example 2, and when printing was performed with a typewriter, a clear colored image was obtained.

Patent applicant Kanzaki Paper Co., Ltd.

Claims (1)

Scope of Claims: (11) A hydrophobic core material containing a melamine-formaldehyde resin initial condensate having a degree of formaldehyde substitution of 40 to 100%, a degree of alkylation of 80 to 100%, and a degree of hydrophobicity of 4 to 16 in an aqueous medium. A method for producing a non-aqueous microcapsule composition, which comprises emulsifying the composition into a non-aqueous medium and dispersing the microcapsules obtained by emulsifying the composition in a non-aqueous medium. (2) Initial stage of melamine-formaldehyde resin The manufacturing method according to claim 1, wherein the degree of hydrophobicity of the condensate is 5 to 8. (3) Initial condensation of melamine-formaldehyde resin. Initial condensation in which the product has hexamethoxyhexamethylolmelamine as a main component. The manufacturing method according to claim (2), wherein the melamine-formaldehyde resin initial condensate is an initial condensate containing triethoxytrimethylolmelamine as a main component. (5) The manufacturing method according to claim (1), wherein the non-aqueous medium is an electron beam or ultraviolet curable ink medium. (6) The non-aqueous medium is a true-melt ink medium. A manufacturing method according to claim (1). (7) A manufacturing method according to claim (1), wherein the non-aqueous medium is a flexographic ink medium. (8) The non-aqueous medium is a printing plate. The manufacturing method according to claim 1), which is a medium for ink.