DE4218999A1 - MICROCAPSLE COLOR COMPOSITION - Google Patents

Description

The present invention relates to a microcapsule color composition and in particular a microcapsule color together composition of the UV-curable type.

Microcapsules that range in particle size from a few microns vary to a few tens of microns, include an inner phase, with a natural or synthetic polymer film is coated, the inner phase z. B. pharmaceutical Fabrics, agricultural chemicals, perfumes, dyes, liquid crystals, thermochromic materials, adhesives, etc. includes. Microcapsules have the big one Advantage that they have the inner phase chemically or physically protect and enable the handling of liquids as whether they were solids. Because of these advantages, micro capsules on a large scale in the fields of pressure sensitive Chen recording materials or sheets or others Products used.

A pressure sensitive recording material or sheet that the color-forming reaction between an electron donating chromogenic material, such as. B. crystal violet lactone, benzyolleukomethylene blue or the like, and one Electron-accepting color developers, such as B. activated Clay, phenolic resin, salts of polyvalent metals with salicylic acid derivatives, served, is well known.

Such a pressure sensitive recording material comprises in general (a) a top sheet, which by coating the Underside of a carrier sheet (sheet-like carrier) with a Dispersion of microcapsules was made, each of which contains a chromogenic material in the core, produced by Coacervation, interfacial polymerization, in situ polymerization tion or similar techniques, (b) a sub-sheet made by Coating the top of a carrier sheet with a Color developer was prepared, and optionally (c) a Middle sheet made by coating one side of a support sheet with the said microcapsule dispersion and other side with the mentioned color developer has been.

A pressure sensitive record is also known  of the so-called self-containing type ("self- contained "), the discrete or mixed layers of the mentioned microcapsules and the color developer composition includes on the same side of a carrier, as well as a System in which a microcapsule layer on the (not be layered) back of the above-mentioned pressure sensitive Self-containing type recording paper becomes. These sheets are either individually or in com combination with the above cover sheet, middle sheet and / or Lower sheet used.

The microcapsule layer of such a pressure sensitive Recording sheet is generally made by coating a carrier sheet with an aqueous microcapsule dispersion made using a large coating apparatus (hereinafter referred to as the "coating method"). A group of methods are also known in which a Microcapsule color composition using a pre-print direction is printed on a carrier sheet, z. B. flexo printing, Gravure printing, screen printing, letterpress printing, offset printing or the like (hereinafter generally referred to as "printing process").

The printing process is for a variety of recordings materials in small quantities are more suitable than the Be stratification process because there are less losses too small batches. The printing process is e.g. B. for the Production of a pressure-sensitive recording sheet suitable for an unusual color (e.g. red) is provided, which is usually manufactured in small quantities becomes.

Furthermore, the printing process allows the application of the Microcapsule coating only on selected Surfaces of the carrier sheet, which is far more economical than the coating process in which an expensive micro capsule coating composition on the entire surface a carrier is applied. A pressure sensitive Recording sheet (a cover sheet or a middle sheet) with a variety of areas, each one different  liche color can be printed by printing on the back of a woodfree paper sheet or the back of one Bottom sheet (base sheet) with microcapsule colors, so are arranged in a predetermined pattern result in different colors. Produced it can also be achieved by partially printing a microcapsule layer on a cover sheet or middle sheet that (with a Microcapsule composition) is completely coated. This can be done using a coating process with a Microcapsule color composition for a color other than that of the microcapsule layer on which the microcapsule color composition to be applied, be made as described in JP-A (Kokai) No. 3 01 360/1989 is. This method therefore allows the production of a Many characteristic products.

So during the printing process using a manufacturing system represents many such favorable features, have Letterpress and offset printing have the disadvantages that oil free from the microcapsules with less effectiveness is set because components other than the microcapsules Cause disability based on the solids content (all solids after drying and hardening the Color) are present in small quantities. This leads to poorer color formation properties. Especially at Use of UV-curable microcapsule compositions This tendency becomes typical in book and offset printing processes clear. To date, they are therefore not for use suitable microcapsule color compositions from UV-curable Type has been developed.

Extensive research has been done to solve these problems operated, and it was found that a microcapsule color composition of the UV-curable type, which has a special, contains ethylenically unsaturated compound, a sheet of high quality that traditionally does not is achieved.  

The present invention relates to a microcapsule color composition which comprises microcapsules, an ethylenically unsaturated compound and a photopolymerization initiator, the composition including, as the ethylenically unsaturated compound, at least one substance which is selected from the group:
a) a liquid polybutadiene / (meth) acrylate,
b) a liquid hydrogenated polybutadiene / (meth) acrylate,
c) a compound of the formula

wherein W represents a hydrogen atom or a methyl group, X and Y are the same and each represent a hydrogen atom, or either X or Y represents a hydrogen atom and the other represents a methyl group, Z represents an unsubstituted or substituted aryl group, and n is an integer of 1 or more means and
d) a compound of the formula

wherein X ^{1 represents} a hydrogen atom or a methyl group, Y ^{1 represents} an unsubstituted or substituted aryl group or alkyl group with not more than 34 carbon atoms.

The microcapsule color composition of the invention has excellent color formation properties. The microcapsule ink composition can be used for flexographic, gravure, Screen printing, letterpress printing, offset printing and other printing processes used and markedly improved properties such as B. color forming ability, especially in the Use in letterpress and offset printing.  

According to a preferred embodiment of the invention comprises the microcapsule color composition of the invention as ethylenically unsaturated compound at least one of the Components of (a), a liquid polybutadiene / (meth) acrylate or (b), a liquid hydrogenated polybutadiene / (meth) acrylate.

According to another embodiment of the invention comprises the microcapsule color composition as the ethylenic unsaturated compound at least one of the components of (c), the compound of formula (I) or (d), the compound of formula (II).

There are 2 types of polybutadienes, one with 1,2 bonds, the other with 1,4 bonds. The liquid polybuta dien / (meth) acrylate (a) is manufactured by chemical Modification of a functional group liquid polybutadiene with a (meth) acryloyl group. The liquid hydrogenated polybutadiene / (meth) acrylate (b) manufactured by chemical modification of a function liquid hydrogenated polybutadiene containing a group, (which was made by hydrogenating a liquid Polybutadiene) with a (meth) acryloyl group. The one functional group-containing liquid polybutadiene or liquid hydrogenated polybutadiene can be obtained by adding a functional group to a liquid polybutadiene or liquid hydrogenated polybutadiene corresponding to various conventional methods. If e.g. B. Maleic anhydride by means of an ene addition reaction is added, one contains a maleinmodierter liquid Polybutadiene. By reacting with an epoxidation agent you get an epoxidized liquid polybutadiene or a epoxidized liquid hydrogenated polybutadiene. The procedure the addition of functional groups is not special crucial; Different conventional methods can be used be applied. As a liquid hydrogenated polybuta dien / (meth) acrylate becomes liquid hydrogenated 1,2-polybuta diene / (meth) acrylate preferred.

Preferred examples of liquid polybutadiene / (meth) acrylate  and of liquid hydrogenated polybutadiene / (meth) acrylate, the as component (a) or (b) is used, for. B.

• i) a liquid polybutadiene / (meth) acrylate, 2-Hy droxyethyl / (meth) arcylate and the hydroxyl group of a hydro xyl-containing liquid polybutadiene with 2,4-tolylene di isocyanate is subjected to a urethane addition reaction;
• ii) a liquid polybutadiene / (meth) acrylate by esterifying 2-hydroxyethyl (meth) acrylate and maleic modified polybutadiene, whereby maleic anhydride by En addition reaction is added to the polybutadiene chain;
• iii) a liquid polybutadiene / (meth) acrylate, prepared, by changing the carboxyl group of a carboxyl-containing one liquid polybutadiene and glycidyl acrylate of an epoxy subject to esterification;
• iv) a liquid polybutadiene / (meth) acrylate by esterification of (meth) acrylic acid and an epoxidized Polybutadiene caused by exposure to an epoxidation agent made on a liquid polybutadiene;
• v) a liquid polybutadiene / (meth) acrylate, produced by Implementation of a hydroxyl-containing liquid polybutadiene and (meth) acrylic acid chloride with removal of chlorine water material;
• vi) a liquid hydrogenated 1,2-polybutadiene / (meth) acrylate, prepared by 2-hydroxyethyl (meth) acrylate and the Hydroxy group of liquid hydrogenated 1,2-polybutadiene glycol with 2,4-tolylene diisocyanate in a urethane addition reaction be subjected.

The liquid polybutadiene / (meth) acrylate and the liquid hydrogenated polybutadiene / (meth) acrylate, as above are known per se and are available on the market. It  any of those described by Shigeru NAKAMURA, "Ap plication and market of UV-EB curing technique ", published light on Sept. 29, 1989, Kabushiki Kaisha CMC, pp. 46-55, below Supervision by Yoneho TABATA, have been used will. Of the liquid polybutadiene / (meth) acrylates and liquid hydrogenated polybutadiene / (meth) acrylates preferably uses those that have an average molecule lar weight from about 500 to about 10,000, preferably about 500 to about 5000, and a viscosity of about 1000 to about 1 000 000 mPas, in particular about 1000 to about 10 000 mPas, exhibit. Furthermore, those preferred by Average 1.5 to 3 (meth) acryloyl groups per molecule exhibit. Generally, the liquid polybuta dien / acrylates and the liquid hydrogenated polybuta dien / acrylate the ability to harden faster UV radiation than the corresponding methacrylates and are therefore preferred.

In the compound of formula (I) used as component (c) in the present invention, preferred examples of unsubstituted aryl groups, referred to as Z, are: a phenyl group, a naphthyl group and the like. Preferred examples of substituted aryl groups are a phenyl group, a naphthyl group and the like, each of which has 1 to 3 substituents, preferably 1 substituent. Examples of such substituents are C ₁ -C ₂₀ alkyl groups (preferably C ₁ -C ₁₂ alkyl groups), halogen atoms, hydroxyl groups and the like. It is preferred that n is an integer from 1 to 20, preferably from 1 to 10.

Examples of preferred compounds of formula (I) are

2-phenoxyethyl (meth) acrylate, 2- (nonylphenoxy) ethyl acrylate,
Phenoxy diethylene glycol (meth) acrylate,
Phenoxypolyethylene glycol (meth) acrylate,
Bromophenoxy diethylene glycol (meth) acrylate,
Butylphenoxy diethylene glycol (meth) acrylate,
Butylphenoxy dipropylene glycol (meth) acrylate,
Hexylphenoxy diethylene glycol (meth) acrylate,
Hexylphenoxy dipropylene glycol (meth) acrylate,
Octylphenoxy diethylene glycol (meth) acrylate,
Octylphenoxy dipropylene glycol (meth) acrylate,
Nonylphenoxy diethylene glycol (meth) acrylate,
Nonylphenoxy dipropylene glycol (meth) acrylate,
Dodecylphenoxy diethylene glycol (meth) acrylate,
Dodecylphenyoxydipropylene glycol (meth) acrylate,
Naphthoxy diethylene glycol (meth) acrylate,
Naphthoxydipropylene glycol (meth) acrylate,
Butylnaphthoxydiethylene glycol (meth) acrylate,
Bromnaphthoxydiethylene glycol (meth) acrylate,
Hydroxyphenoxypolyethylene glycol (meth) acrylate,
Chlorophenoxypolypropylene glycol (meth) acrylate,
Butylphenoxypolyethylene glycol (meth) acrylate,
Butylphenoxypolypropylene glycol (meth) acrylate,
Hexylphenoxypolyethylene glycol (meth) acrylate,
Hexylphenoxypolypropylene glycol (meth) acrylate,
Octylphenoxy polyethylene glycol (meth) acrylate,
Octylphenoxypolypropylene glycol (meth) acrylate,
Nonylphenoxypolyethylene glycol (meth) acrylate,
Nonylphenoxypolypropylene glycol (meth) acrylate,
Dodecylphenoxypolyethylene glycol (meth) acrylate,
Dodecylphenoxypolypropylene glycol (meth) acrylate,
Naphthoxypolypropylene glycol (meth) acrylate, etc.

Of these examples, the polyethylene units or Polypro contain pylene units, preference is given to those in which the polyethylene glycol or propylene glycol is a polymer tion degree from 1 to 20, in particular from 1 to 10.

In the compound of formula (II) used as component (d) in the present invention, preferred examples of unsubstituted aryl groups denoted by Y 1 are a phenyl group, a naphthyl group and the like. Preferred substituted aryl groups are substituted C ₆ -C ₃₄ aryl groups such as. B. a phenyl group, a naphthyl group and the like, each of which is substituted with 1 to 3, preferably 1 to 2, substituents; the substituents are selected from: C ₁ -C ₂₀ alkyl groups (preferably C _i -C ₁₂ alkyl groups), halogen atoms and the like. Preferred substituted or unsubstituted alkyl groups (denoted Y ¹ ) having 34 carbon atoms or less are unsubstituted alkyl groups having 1 to 34 carbon atoms, preferably 2 to 12 carbon atoms, and alkyl groups having 1 to 34 carbon atoms, preferably 2 up to 12 carbon atoms, which are substituted with 1 to 3 halogen atoms, preferably with a halogen atom.

Are suitable as a compound of formula (II)

2-hydroxy-3-phenoxypropyl (meth) acrylate,
2-hydroxy-3- (p-bromophenoxy) propyl (meth) acrylate,
2-hydroxy-3- (o-methylphenoxy) propyl (meth) acrylate,
2-hydroxy-3- (p-methylphenoxy) propyl (meth) acrylate,
2-hydroxy-3- (p-ethylphenoxy) propyl (meth) acrylate,
2-hydroxy-3- (p-propylphenoxy) propyl (meth) acrylate,
2-hydroxy-3- (p-butylphenoxy) propyl (meth) acrylate,
2-hydroxy-3- (o, p-dimethylphenoxy) propyl (meth) acrylate,
2-hydroxy-3-hexylphenoxy) propyl (meth) acrylate,
2-hydroxy-3- (p-octylphenoxy) propyl (meth) acrylate,
2-hydroxy-3- (p-nonylphenoxy) propyl (meth) acrylate,
2-hydroxy-3- (p-dodecylphenoxy) propyl (meth) acrylate,
2-hydroxy-3-naphthoxypropyl (meth) acrylate,
2-hydroxy-3- (butylnaphthoxy) propyl (meth) acrylate,
2-hydroxy-3-ethoxypropyl (meth) acrylate,
2-hydroxy-3-propoxypropyl (meth) acrylate,
2-hydroxy-3-butoxypropyl (meth) acrylate,
2-hydroxy-3-dodecyloxypropyl (meth) acrylate,
2-hydroxy-3- (4-chlorobutoxy) propyl (meth) acrylate, etc.,

of which the acrylates are preferred.

Another ethylenically unsaturated compound which is common in the art can be used together with at least one of the components (a) to (d) according to the invention. Examples of such conventional ethylenically unsaturated compounds include photopolymerizable monomers and photopolymerizable prepolymers. Examples of photopolyme riskable monomers are
Methyl methacrylate, butyl methacrylate, 2-ethoxyethyl acrylate, cyclohexyl methacrylate,
Benzyl methacrylate, trifluoromethyl methacrylate, the potassium salt of 3-sulfo propyl methacrylate,
N- (3-sulfopropyl) -N-methacryloylamido propyl-N, N-dimethylammonium betaine,
Glycidyl methacrylate, allyl methacrylate, dimethylaminoethyl methacrylate,
3-chloro-2-hydroxypropyl methacrylate, benzyl acrylate, cyclohexyl acrylate,
Tetrahydrofury acrylate, 1-methoxycyclododecadienyl acrylate, dicyclopentenyl acrylate,
Dicyclopentenyloxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
2,6-dibromo-4-t-butylphenyl acrylate, ethylene glycol diacrylate, ethylene glycol di methacrylate,
Polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxydiethylene glycol acrylate,
Propylene glycol di acrylate, propylene glycol dimethacrylate, polypropylene glycol di acrylate,
Polypropylene glycol dimethylacrylate, 1,2-butanediol diacrylate, 1,2-butanediol dimethacrylate,
1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate,
1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate,
Neopentyl glycol diacrylate, glycerol dimethacrylate, glycerol methacrylate acrylate,
Trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate,
Pentae rythrittetraacrylat, hydroxypivalic acid neopentylglycol ester diacrylate,
2,2-bis [4- (acryloyloxydiethoxy) phenyl] propane,
Hydroxypivalic acid neopentyl glycol ester caprolactone adduct diacrylate,
Hydroxypivaldehyde trimethylolpropane acetal diacry lat, diallyloxydiacryloyloxycyclohexane,
Trimethylolpropane-propyleneoxy adduct triacrylate,
Dipentaerythritol ester of (lower) fatty acid and acrylic acid,
Dipentaerythritol-Caprolak clay adduct acrylate, dioctyl-2-acryloyloxyethyl phosphate and the like.
Examples of suitable photopolymerizable prepolymers are polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, oligoacrylate, alkyd acrylate, polyol acrylate and the like.

The polyester acrylates can be made by first submitted a polyester and this is then acrylated.  

Examples of polyhydric alcohols that are involved in building one of the like polyester can be involved are ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, trimethylol propane, dipropylene glycol, polyethylene glycol (preferably with a molecular weight of about 400), polypropylene glycol (preferably with a molecular weight of about 400) Pentaerythritol, dipentaerythritol and the like. examples for polybasic acids with polyhydric alcohols can be implemented are phthalic acid, adipic acid, Maleic acid, trimellitic acid, itaconic acid, succinic acid, Terephthalic acid, alkenyl succinic acid and the like.

The polyurethane acrylates can be made by an isocyanate group-containing compound such. B. Toluy Lendiisocyanate with a hydroxy group-containing acrylate such as B. 2-hydroxyethyl acrylate. In this case it is it is possible to add an isocyanate group-containing compound use a polyester structure at the center of the molecule and has isocyanate groups at the ends of the molecule which is acrylated.

The epoxy acrylates can be of a bisphenol A type, novolac type and alicyclic type and are classified in essentially by esterification of the epoxy groups of epoxy Resin with acrylic acid to form acryloyl groups poses.

The photopolymerizable prepolymers can be cured after UV curing form a layer themselves and generally have one Viscosity from about 500 to about 200,000 mPa · s. The photopolyme Risable monomers are often mixed with the above photopolymerizable prepolymers used to make the pre polymer for the purpose of reducing the viscosity thereof to dilute. The photopolymerizable monomers have in generally a viscosity of about 1 to about 500 mPa · s.

The photopolymerizable prepolymers have a larger one Effect on the properties of the hardened color together settlement. The photopolymerizable monomers have the  Advantage that the viscosity of the UV curable together reduce settlement and thereby the coating process facilitate.

If components (a) to (d) in combination with a other ethylenically unsaturated ones known in the art customary connection can be used, the ratio the former vary over a wide range, the weight ratio is usually from 95: 5 to 15:85, is preferably from 90:10 to 30:70.

The ethylenically unsaturated compound, the at least one of components (a) to (d) is preferably in one Amount from about 9 to about 95 wt .-%, in particular about 30 to about 90% by weight based on the microcapsule color together settlement, used. The ethylenically unsaturated compound, which comprises at least one of components (a) and (b) preferably in an amount of about 30 to about 95% by weight, more preferably from about 30 to about 90 weight percent based on the Microcapsule color composition used. The ethylenic unsaturated compound, the at least one of the components (c) and (d) is included in amounts from about 9 to about 94% by weight, preferably about 30 to about 90% by weight, based on the microcapsule color composition used.

The ethylenically unsaturated compound, the at least one which comprises components (a) to (d), individually or as Mixture of such compounds, optionally in combination with said other ethylenically unsaturated, on the Specialty common connection, are used. In in any case, the viscosity of the ethylenically unsaturated th compound or a mixture of ethylenically unsaturated th compounds preferably in the range of about 1 to about 10,000 mPas, in particular in the range from about 1 to about 5000 mPas, as with a Brookfield viscometer at 25 ° C and 60 rpm. If the ver bond or a mixture of the compounds with a viscose If more than 100,000 mPa · s is used, the resulting color composition (ink) a substrate in one to a lesser extent and the resulting color may change  worse.

The polymerization initiator useful according to the invention can be a conventional one and include aromatic ones Ketones, quinones, ethers and nitro compounds such as. B. Benzoquinone, phenanthrenequinone, naphthoquinone, diisopropyl phenanthrenequinone, benzoisobutyl ether, benzoin, benzoin methyl ether, furoin butyl ether, Michler's ketone, Michler's Thioke clay, fluorenone, trinitrofluorenone, β-benzoylaminonaphthalene etc. The photopolymerizable initiator is used in an amount from about 1 to about 20 parts by weight, preferably about 1 to about 10 parts by weight, per 100 parts by weight of the ethylenic unsaturated compound.

A sensitizer can be used to control the polymerisa tion to accelerate. Appropriate sensitizers include u. a. Triethanolamine, N-methyldiethanolamine, N, N-dimethyletha nolamine, N-methylmorpholine etc. The sensitizer is used in an amount of about 0 to about 10 parts by weight per 100 parts by weight le of the ethylenically unsaturated compound used.

If the microcapsule color composition of the invention for Manufacture of pressure sensitive recording sheets is usually used as an electron donor Chromogenic material microencapsulated. Suitable electron-ab Giving chromogenic materials include a variety well-known substances, namely dyes on triarylms than base such. B. 3,3-bis (p-dimethylaminophenyl) -6-dime thylaminophthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethyl indol-3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-di methylaminophthalide, 3,3, -Bis (9-ethylcarbazol-3-yl) -6-di methylaminophthalide, etc .; Dyes based on Diphenylmethane such as B. 4,4, -Bis-dimethylaminobenzhydrylben cyl ether, N-halophenyl leucoauramine, N-2,4,5-trichlorophene nylleucoauramine, etc .; Dyes based on thiazine such as e.g. B. Benzoylleucomethylene blue, p-nitrobenzoylleucomethylene blue, etc .; Spiro dyes such as B. 3-methylspirodinaph thopyran, 3-phenylspirodinaphthopyran, 3-propylspirodibenzo  pyran etc., lactam-based dyes such. B. Rhodamine B-aniline lactam, rhodamine (o-chloroaniline) lactam, etc .; Dyes based on fluorane such. B. 3-dimethylamino-7-methoxyfluorane, 3-diethylamino-6-methyl-7-chlorofluoran, 3- (N-ethyl-p-toluidi no) -7-methylfluorane, 3-diethylamino-7-N-methylaminofluorane, 3-diethylamino-7-dibenzylaminofluoran, 3- (N-ethyl-p-toluidi no) -6-methyl-7-phenylaminofluoran, 3-diethylamino-6-methyl 7-phenylaminofluoran, 3- (N-cyclohexyl-N-methylamino) -6- methyl-7-phenylaminofluoran, 3-piperidino-methyl-7-phenylami nofluorane, 3-diethylamino-6-methyl-7-xylidinofluorane, etc .; and Dyes of the infrared series such as B. 3.3, -Bis- (2- (p- dimethylaminophenyl) -2- (p-methoxyphenyl) ethylene-2-yl) 4,5,6,7-tetrachlorophthalide etc. These dyes can be used alone or used in combination.

In general, one of these electron donating chromogenic materials is dissolved in oil and then microencapsulated. The following known substances can be mentioned as examples of such oils:
Vegetable oils such as B. cottonseed oil; Mineral oils such as E.g. kerosene, paraffin, naphthen, chlorinated paraffin, etc .; aromatic hydrocarbons such as B. alkylated biphenyls, alkylated terphenyls, alkylated naphthalenes, diarylethanes, triarylmethanes, diphenylalkanes, etc .; Ethers such as B. dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, dioctyl phthalate, diethyl adipate, dipropyl adipate, di-n-butyla dipate, dioctyl adipate, etc .; and mixtures of these oils.

The electron-donating chromogenic substance is in space the oil in an amount of usually about 2 to 80 parts by weight, preferably about 5 to 50 parts by weight, per 100 parts by weight of the oil added.

The process of microencapsulation can be done in several ways known methods such. B. coacervation, interfacial poly merization, in situ polymerization, etc. can be selected. Although there are different microencapsulation methods, become microcapsules with a capsule wall film from a synthetic resin from the point of view of capsule strength  speed, ease of manufacturing such capsules, etc., prefers. Examples of resins that form microcapsule walls are amino aldehyde resins, polyurea resins, polyurethane resins, Polyamide resins, etc., of which the amino aldehyde resin is preferred becomes.

The microcapsules are coated with an amino aldehyde resin wall film by using in situ polymerization processes at least one amine compound such as. B. urea, thiourea substance, alkylurea, ethyleneurea, acetoguanamine, Benzoguanamine, melamine, guanidine, biuret and cyanamide, and at least one aldehyde compound such as. B. formaldehyde, Acetaldehyde, paraformaldehyde, hexamethylenetetramine, glutaral dehyd, glyoxal and furfural, or using Pre-condensates of amine compounds and aldehydes bindings made. Microcapsules containing melamine formaldehyde contain resin as a wall-forming material (as in USP 41 00 103 described, on the disclosure of which is expressly here are particularly preferred because they are Are solvent-resistant and because of an aqueous dispersion such a microcapsule after removing the aqueous Medium easily delivers powdered microcapsules.

The average particle size of the microcapsules depends of the material used and the thickness of the wall structure ab, but is generally about 1 to about 10 microns. If required, an antioxidant, UV-Ab sorbent, perfume, etc. introduced into the microcapsule will.

The microcapsules made as described above are generally in the form of an aqueous dispersion sion before. The microcapsules are either in semi-dry Condition after filtration or in dry condition after Air drying, surface drying, fluid bed drying, Air suspension drying, spray drying, vacuum drying, Freeze drying, infrared drying, dielectric drying, Ultrasonic drying, powder drying or the same dispersed in a non-aqueous carrier and  if necessary, supplemented with various auxiliary substances and result in a finished microcapsule color composition. The Microcapsules can also be used in such a non-aqueous Carrier can be dispersed by either the above aqueous dispersion of the microcapsules with the non-aqueous Carrier mixed and the water under reduced pressure is removed, as in JP-A (Kokai) No. 1 35 718/1978 has been described, or by said dispersion of Filtered off microcapsules and with a water-miscible, non-aqueous carrier is washed.

The amount of microcapsules in the microcapsule color together settlement is generally from about 5 to about 80% by weight, preferably about 10 to about 40 wt .-%, based on the Color composition. Unless the ethylenically unsaturated Compound comprises at least one of components (a) and (b), the amount of the microcapsules is preferably about 5 to about 60% by weight, in particular about 10 to about 40% by weight, based on the color composition. If the ethylenic unsaturated compound at least one of components (c) and (d), the amount of the microcapsules is preferable about 5 to about 80% by weight, more preferably about 10 to about 40% by weight, based on the color composition.

As a dye carrier for use in the invention Microcapsule color composition can not only do the above mentioned ethylenically unsaturated compound, but given If necessary, various other substances such. B. Solution medium with high or low boiling point, resins, waxes and Oils can be used additionally, either individually or in a mixture.

Examples of high-boiling solvents are ethylene glycol, Diethylene glycol, triethylene glycol, polyethylene glycol (preferred with a molecular weight of about 400), propylene glycol, dipropylene glycol, 2,3-butylene glycol, methyl cellosolve, Ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol etc. The high boiling solvents are preferably in  an amount of 0 to about 40 wt .-%, based on the color composition, used.

Examples of low-boiling solvents are methanol, ethanol, n-propanol, iso-propanol, n-butanol, ethyl acetate, propyl acetate, butyl acetate, acetone, methyl ethyl ketone, benzene, toluene, Xylene, etc. The low boiling solvents are preferred in an amount of 0 to about 40 wt .-%, based on the Color composition used.

The above resins include rosin, among others gum, rosin, shellac, ester gum, rosin pen taerythritol ester, polymerized rosin pentaerythritol ester, maleic acid resin, maleic modified rosin penta erythritol ester, rosin dimer, rosin modified Phenolic resin, butanol-modified urea resin, butanol modified melamine resin, terpene resin, terpene-phenolic resin, Soy modified alkyd resin, polyamide resin, polyvinyl acetate, acrylic resin, polyvinyl chloride, vinyl chloride-vinyl acetate Copolymer, ethylene-maleic anhydride copolymer, styrene Maleic anhydride copolymer, methyl vinyl ether-maleic acid hydride copolymer, isobutylene-maleic anhydride copolymer, modified polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, ethyl cellulose, nitrocellulose, hydroxypropyl cellulose, cellulose acetate propionate, cellulose acetate butyrate etc. The resin is preferably used in an amount of 0 to 40 wt .-%, based on the color composition used.

The above waxes include beeswax, spermacetus, Lanolin, candella wax, carnauba wax, wood wax, rice wax, Montan wax, ozokerite, paraffin wax, microcrystalline wax, Montan wax derivatives, paraffin wax derivatives, microcrystalline Wax derivatives, castor wax, opal wax, low molecular weight Polyethylene, distearyl ketone, caprylic acid amide, stearic acid amide, ethylene-bis-stearic acid amide, stearic acid, behenic acid, Stearyl alcohol, destearyl phosphate, etc. The wax is preferred in an amount of 0 to 20 wt .-%, based on the Color composition used.

The above oils include various vegetable oils  such as B. linseed oil, safflower oil, soybean oil, castor oil, etc .; treated oils such as B. dehydrated castor oil, polymeric fixed oil, oil treated with paint, vinyl oil, urethane oil, etc .; and Mineral oils such as B. machine oil, spindle oil, etc. The oil is preferably in an amount of 0 to about 40% by weight on the color composition used.

The dye carrier of the invention, which is the ethylenic contains unsaturated compound which contains at least one of the Components (a) to (d) and optionally high-boiling or low boiling solvents, resins, waxes, oils and the The same includes, in an amount of about 9 to about 95 parts by weight, preferably about 30 to about 90 parts by weight, per 100 parts by weight of the color composition used.

The microcapsule color composition of the invention can if required stiffening materials such. B. Cellulose Pulp ver, starch particles, synthetic resin particles, etc., white Pigments such as B. titanium oxide, surface-treated titanium oxide, zinc oxide, calcium carbonate, aluminum hydroxide etc., thixotropic agents such. B. colloidal silica, metal soap (Aluminum stearate, aluminum octanoate, etc.), sodium palmitate, Aluminum chelate (aluminum diisopropylate monoacetoacetate-ethyl etc.), organic amine-modified concrete, thixotropic Polyamide resin, etc., color desensitizers for suppression the color formation reaction and similar desensitizers, Antioxidants, fluorescent brighteners, plasticizers, Dyes, etc. included. Of these substances, titanium becomes oxide or surface treated titanium oxide preferably ver applies because these can prevent the printed part becomes transparent. Furthermore, the addition of the thixotropic By means such. B. colloidal silica is particularly preferred, the so-called "sagging" (i.e. leakage of paint from a Ink container of the printing device) and ink veil ver avoid.

If at least one as an ethylenically unsaturated compound liquid polybutadiene / (meth) acrylate and / or liquid  hydrogenated polybutadiene / acrylate is used before trains that at least one of these acrylates in combination with an ethylenically unsaturated compound of less Viscosity or in combination with a high or low boiling solvent, oil or the like is used, and not at least one of the ones that serve as color carriers (Meth) acrylate, used alone because the resulting Color composition better color-forming ability if used as a color composition for a print sensitive recording sheet is used. It will be in generally preferred at least one of the liquid Polybutadiene / (meth) acrylate and the liquid hydrogenated Polybutadiene / (meth) acrylate with at least one ethylenic unsaturated compound or with a high or low you which solvent, oil or the like to use so the resulting mixture has a viscosity of about 1 to about 5000 mPa · s.

The microcapsule color composition of the invention is usually made by using microcapsules and other auxiliary Substances are introduced into a carrier and the mixture with a propeller stirrer, an ultrasonic mill, a ball mill, a three-roll mill or the like completely is mixed.

The appropriate viscosity of the color composition is Range of at least 3000 mPa · s (25 ° C), preferably about 5000 to about 30,000 mPa · s, measured with a viscometer from Brookfield type at 25 ° C and 60 rpm. The viscosity of less than 3000 mPa · s leads to the possible occurrence of "sagging" (i.e. Leakage of color from the dye container) when Book printing process and color veils in offset printing drive, and it can also cause difficulties in safe driving Perform the procedure.

The microcapsule color composition thus obtained is applied to a carrier sheet by means of letterpress (letterpress) or offset printing processes, generally in an amount of 1 to 10 g / m ² , preferably in an amount of 2 to 6 g / m ² , based on dry weight. The color composition according to the invention can also be used as a printing ink for screen printing and other printing processes.

The carrier sheet for such printing processes includes other wood-free paper, synthetic paper, foils, Art paper, coated paper, cast paper, lightweight coated paper, pressure sensitive Recording paper (cover, middle and base sheets, paper self-contained type) etc., a.

The microcapsule color composition of the invention based on a carrier sheet is printed in with UV light irradiated conventionally to effect curing. Even though the conditions of UV radiation are not particularly limited are, if only the printed microcapsule color together setting is cured, it is preferred to use UV radiation using a high pressure mercury lamp, metal halogen lamp or the like to perform.

The carrier sheet on which in this way the microcapsule color composition has been applied and hardened, before partial as cover sheet or middle sheet for a print sensitive recording material can be used. The The middle sheet comprises a layer of the micro according to the invention Capsule color composition on one side of the carrier sheet and an electron-accepting color developer layer on the other side of the carrier sheet.

Carrier sheets with an electron-accepting color winder (i.e., an acceptor) are coated and in Combination with the mentioned cover sheet or middle sheet can be used of different types and include a wide range of conventional carriers that are not particularly critical. Preferred execution shapes of such carrier sheets are described below.

The color developer (acceptor) layer, the following can also be used to produce the middle sheet,  which is a layer of the microcapsule color according to the invention composition on the one hand and such Includes acceptor layer used on the other hand will.

The coating composition to form an acceptor Layer contains an acceptor, an adhesive and given if additives. Examples of common adhesives are Starch, casein, gum arabic, carboxylmethyl cellulose, Polyvinyl alcohol, styrene-butadiene copolymer latex, latex based on Vinylacet, etc. Include suitable additives Zinc oxide, magnesiumocid, titanium oxide, aluminum hydroxide, Calcium carbonate, magnesium sulfate, calcium sulfate and the like inorganic pigments, plastic pigments, binder pigments and similar organic pigments, and auxiliaries like them conventionally for pressure sensitive recording sheets be used.

The coating composition to form an acceptor layer can still microcapsules (e.g. oil microcapsules) contain a hydrophobic liquid, but none Contain dye.

Suitable acceptors are e.g. B. inorganic acceptors such as e.g. B. acidic clay, activated clay, attapulgite, zeolite, bento nit, silicon dioxide, aluminum silicate etc. and organic Acceptors such as B. phenol polymers, e.g. B. phenol-aldehyde po polymers and phenol-acetylene polymers, aromatic carboxylic acid derivatives, etc. The organic acceptors are the inorganic rule of light resistance, such as. B. to sunlight, think.

Examples of organic acceptors are salicylic acid, 3-phenyl salicylic acid, 3-cyclohexylsalicylic acid, 3-tert-butyl-5-methylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3-methyl-5-benzylsalicylic acid, 3-phenyl-5- ( α, α-dimethylbenzyl) salicylic acid, 3- (α, α-dimethylbenzyl) -5-methylsalicylic acid, 3,5-dicyclohexylsalicylic acid, 3,5-di- (α-methylbenzyl) salicylic acid, 3,5-di- ( α, α-dimethylbenzyl) salicylic acid, 3- (α-methylbenzyl) 5- (α, α-dimethylbenzyl) salicylic acid, 4-methyl-5-cyclohexylsalicylic acid, 2-hydroxy-1-benzyl-3-naphthoic acid, 3-hydroxy- 5-cyclohexyl-2-naphthoic acid, 3-methyl-5- (iso) nonylsalicylic acid, 3-methyl-5- (iso) dodecylsalicylic acid, 3-methyl-5- (iso) pentadecylsalicylic acid, 3-methyl-5- (α -methylbenzyl) salicylic acid, 3-methyl-5- (α, α-dimethylbenzyl) salicylic acid, 3,5-di-sec-butylsalicylic acid, 3,5-di-tert-butyl-6-methylsalicylic acid, 3-cyclohexyl-5 - (Iso) nonylsalicylic acid, 3- (α-methylbenzyl) -5- (iso) nonylsalicylic acid, 3-isopropyl-5- (iso) nonylsalicylic acid , 3- (Iso) nonylsalicylic acid, 3- (Iso) nonyl-5-methylsalicylic acid, 3- (Iso) nonyl-5-cyclo hexylsalicylic acid, 3- (Iso) nonyl-5- (α-methylbenzyl) salicylic acid, 3- (Iso) nonyl-5- (4, α-dimethylbenzyl) salicylic acid, 3- (Iso) nonyl-5- (α, α-dimethylbenzyl) salicylic acid, 3- (α, α-dimethylbenzyl) -5- (iso ) nonylsalicylic acid, 5- (iso) nonylsalicylic acid, 3- (iso) -nonyl-6-methyl salicylic acid, 3-tert-but-5- (iso) nonylsalicylic acid, 3,5-di (iso) nonylsalicylic acid, 3- ( Iso) dodecylsalicylic acid, 3- (iso) dodecyl-5-methylsalicylic acid, 3- (iso) dodecyl-6-methylsa licylic acid, 3-isopropyl-5- (iso) dodecylsalicylic acid, 3- (iso) do decyl-5-ethylsalicylic acid, 5- (Iso) pentadecylsalicylic acid, 3-cyclohexyl-5- (α-methylbenzyl) salicylic acid, 3-phenyl-5- (α-methylbenzyl) salicylic acid, 3- (α-methylbenzyl) salicylic acid, 3- (α-methylbenzyl) - 5-methylsalicylic acid, 3- (α-methylbenzyl) - 6-methylsalicylic acid, 3- (α-4-dimethylbenzyl) 5-methylsalicylic acid, 3,5-di (α, 4-dimethylbenzyl) salicylic acid, 3- (α, α -Dime thylbenzyl) -6-methyl salicylic acid, 3,5-di (α, α-dimethylbenzyl) salicylic acid, 5- (4-mesitylmethylbenzyl) salicylic acid, 2-hydroxy-3- (α, α-dimethylbenzyl) -1-naphthoic acid, 3-hydroxy- 7- (α, α-dimethylbenzyl) -2-naphthoic acid
and similar aromatic carboxylic acids and the corresponding salts of more valuable metals. Examples of polyvalent metals are magnesium, calcium, zinc, aluminum, iron, cobalt, nickel, etc. These acceptors can be used individually or in combination.

Also suitable as acceptors are those described in JP No. 9309/1965 and 20 144/1967 and described in JP-A No. 14 409/1973 ben have been such. B. 6,6'-methylenebis (4-chloro-m-cresol)  and similar phenolic compounds; Phenolic resins, e.g. B. p-phenylphenol formaldehyde resin and like phenol aldehyde resins, p-tert-butylphenol acetylene resin and like phenol acetylene resins, and the corresponding polyvalent metal salts Phenolic resins; Acid polymers such as B. Maleic Colophoni resin, copolymers of styrene, ethylene or vinyl methyl ether with maleic anhydride; and those described in JP No. 8215/1973, 8216/1973 and 1326/1977 have been described, e.g. B. polymers of aromatic carboxylic acids with aldehyde or Acetylene and polyvalent metal salts of these.

Polyvalent are preferred among these organic acceptors Metal salts of aromatic carboxylic acids. These acceptors can be used in combination.

The coating composition for forming the acceptor layer can normally be prepared by dispersing the acceptor and other component (s) together or separately using a stirring or pulverizing device such as e.g. B. a sand mill, a ball mill, an attritor or the like using water as the dispersion medium or by dissolving them in an organic solvent with subsequent emulsification of the solution in water with an emulsification or dispersion medium such as e.g. B. polyvinyl alcohol and evaporation of the organic solvent by means of steam distillation, followed by the addition of a pigment, binder by means of immobilizing agents, etc. The coating composition for forming the acceptor layer is applied to a base sheet in an amount that is not particularly limited. The amount is usually in the range of about 2 to about 8 g / m ² based on the dry weight.

The coating composition to form the acceptor layer is on a carrier sheet such. B. woodfree paper, coated paper, synthetic paper, film or the same with an air brush coating machine, knife on carrier machine, roller application machine, size press coater Curtain coater, short-term coater or similar  conventional applicators applied to a finished color development sheet for pressure sensitive printing to receive drawing sheets.

The substances in the microcapsules of the invention Microcapsule color composition can be encapsulated not on the elementary components of the pressure sensitive Recording sheet limited, but can also perfumes, liquid crystals, thermochromic materials, anti-rust agents, Anti-moth agents, anti-rodent agents, tackifiers, Include adhesives and so on.

The following examples and comparative examples are intended to Explain the invention in detail, but not be restrict.

In all examples and comparative examples, the parts and percentages by weight unless otherwise stated specified. Furthermore, all ratios are in the Examples and comparative examples based on weight, unless otherwise stated.

Example I-1 Manufacture of microcapsules that donate electrons contain chromogenic materials

In 75 parts of benzyltoluene, 25 parts of 3,3-bis (2-methyl- 1-octyl-3-indolyl) phthalide dissolved with heating to a Obtain solution for the inner phase. This solution was in 200 parts of a 3% aqueous solution of ethylene Maleic anhydride copolymer (trademark "EMA 31", product from Monsanto Co.), which is adjusted to a pH of 6.0 was emulsified and the system was heated to 55 ° C.

Separately, 15 parts of melamine became 45 parts of a 37% added aqueous solution of formaldehyde, and the Reaction was carried out at 60 ° C for 15 minutes to make a to obtain aqueous prepolymer solution.

This prepolymer solution was added dropwise to that above th emulsion was added and the mixture was dripped  wise addition of 0.1 N hydrochloric acid with stirring on a pH adjusted to 5.3. The system was then brought up to 80 ° C warmed and stirred for 1 hour. Then 0.2 N was added dropwise Hydrochloric acid added to bring the pH to 3.5, and the mixture was further stirred for 3 hours. After this Cooling gave a microcapsule dispersion with a average particle size of 3.8 µm.

This dispersion was sent through a filter press and dried to obtain powdery microcapsules.

Preparation of the microcapsule color composition

By mixing the following components, a micro Capsule color composition made:

• - microcapsules that are electron-donating Chromogenic material contained: 100 parts
• - Composition of an ethylenically unsaturated Ver bond [a liquid polybutadiene / acrylate made, by adding 2-hydroxyethyl acrylate and a hydroxyl group liquid polybutadiene with a urethane addition reaction 2,4-tolylene diisocyanate (hereinafter referred to as "liquid polybutadiene / acrylate A", viscosity = 5200 cps, average number of acryloyl groups per Molecule = 1.8): Dipropylene glycol diacrylate = 1: 1] 300 parts
• - Photopolymerization initiator (benzoin methyl ether): 10 parts

Production of a cover page

Using a letterpress printing method, a base paper sheet weighing 40 g / m ^{2 was} printed with the above microcapsule color composition (in an amount of 5.0 g / m ² ), and then the composition was equipped with a UV irradiation device 6 kW high pressure mercury lamp, hardened to obtain a cover sheet.

Production of oil microcapsules for the base sheet

100 parts of alkyl diphenylethane as an oil for the internal phase were in 200 parts of a 3% aqueous solution of Ethylene-maleic anhydride copolymer (trademark "EMA-31", Product of Monsanto Co.) which has a pH of 6.0 was set, emulsified, and the resulting emulsion was heated to 55 ° C.

Separately, 15 parts of melamine became 45 parts of a 37% added aqueous solution of formaldehyde, and the Reaction takes 15 minutes at 60 ° C to an aqueous Obtain prepolymer solution.

This aqueous prepolymer solution was added dropwise to the The above emulsion was added and the mixture was made up to a pH adjusted to 5.3 by dropwise stirring 0.1 N hydrochloric acid was added. The system was then up Heated 80 ° C and stirred at this temperature for 1 hour. Then 0.2 N hydrochloric acid was added dropwise to make up the Bring the system pH to 3.5, and the mixture was further stirred for 3 hours. After cooling, was obtained a dispersion of microcapsules with an average Particle size of 5.0 microns.

Production of a base sheet

In 300 parts of a 0.2% aqueous solution of polyvinyl alcohol, 60 parts of precipitated calcium carbonate, 10 parts of zinc oxide, 10 parts of a co-melt of zinc 3,5-di (α-methylbenzyl) salicylate and α-methylstyrene -Styrene copolymer (80:20), 10 parts of the oil microcapsules prepared as above, and 10 parts of pulp powder, followed by the addition of 10 parts (calculated as a solid) of tackified starch and 15 parts (calculated as a solid) of carboxy-modified Styrene-butadiene latex dispersed. The mixture was diluted to give a 30% color developer coating composition. This coating composition was applied with an air brush machine to a base sheet of 40 g / m ² in a weight of 7 g / m ² on a dry weight basis.

evaluation

The cover sheets and the base sheets that are in the above be had been produced in the manner described and it was based on it using a electric typewriter with a square shaped flat type of printing, which was designed so that one on the Auf drawing paper a square shaped colored image received, created images, the flat type of printing that Touched recording paper with constant pressure. In the following examples and comparative examples was the same typewriter used. The results were very good sharp color images on the base sheet.

Example I-2

The procedure of Example I-1 was repeated with the Except that a microcapsule color composition is made was made using 300 parts of a composition an ethylenically unsaturated compound (a liquid Polybutadiene / acrylate, made by esterification of 2-hydroxyethyl acrylate and a maleic acid modified Polybutadiene, wherein maleic anhydride attached to the polybutadiene chain had been added using the ene addition reaction (after hereinafter referred to as "liquid polybutadiene / acrylate B"; Viscosity = 3800 mPa · s, average number of acryloyl groups per molecule = 1.8): Dipropylene glycol diacrylate = 1: 1) instead of 300 parts of the composition of the ethylenic unsaturated compound as used in Example I-1 has been. In the same manner as in Example I-1, a Cover sheet produced, images created on the base sheet and rated. The color images obtained were very sharp.

Example I-3

The procedure of Example I-1 was repeated with the Except that a microcapsule color composition is made was made using 300 parts of a composition  the ethylenically unsaturated compound (a liquid Polybutadiene / acrylate, made by using acrylic chloride and a liquid polybutadiene with hydroxyl groups under Ab decomposition of hydrogen chloride was subjected to a reaction, (hereinafter referred to as "liquid polybutadiene / acrylate C" net; Viscosity = 4200 mPa · s, average number of Acryloyl groups per molecule = 2.0): Dipropylene glycol diacrylate = 1: 1) instead of 300 parts of the composition of the ethylenically unsaturated compound as in Example I-1 has been used. In the same way as in the example I-1 a cover sheet was made, pictures on the base sheet generated and evaluated. The color images obtained were very good sharp.

Example I-4

The procedure of Example I-1 was repeated with the Except that a microcapsule color composition is made was made using 300 parts of a composition the ethylenically unsaturated compound (liquid polybuta diene / acrylate A: 2- (p-nonylphenoxy) ethyl acrylate = 1: 1) Place 300 parts of the composition of the ethylenic unsaturated compound according to Example I-1, and the others Add 5 parts of colloidal silica (trademark "AEROSIL 200", product of Nippon Aerosil Co. Ltd.). In the a cover sheet was made in the same manner as in Example I-1 produced and created and added images on the base sheet tet. The images obtained were very sharp. No sagging (e.g. leakage of paint from the paint container) occurred during of the printing process.

Example I-5

The procedure of Example I-1 was repeated with the Except that a microcapsule color composition is made was made using 300 parts of a composition the ethylenically unsaturated compound (liquid polybuta diene / acrylate A: 1,6-hexanediol diacrylate = 1: 1) instead of 300 parts of the composition of the ethylenically unsaturated  Compound as used in Example I-1. In the a cover sheet was made in the same manner as in Example I-1 produced, images created and evaluated on the base sheet. The images obtained were very sharp.

Example I-6

The procedure of Example I-1 was repeated with the Except that a microcapsule color composition is made was made using 300 parts of a composition the ethylenically unsaturated compound (liquid polybuta diene / acrylate A: dipropylene glycol diacrylate: 2- (p-nonylphe noxy) ethyl acrylate = 1: 1: 1) instead of 300 parts of the Composition of the ethylenically unsaturated compound such as it was used in Example I-1. In the same meadow as a cover sheet was produced according to Example I-1, images on the base sheet generated and evaluated. The color images obtained were very sharp.

Example I-7

The procedure of Example I-1 was repeated with the Except that a microcapsule color composition is made was made using 300 parts of polybutadiene / acrylate A instead of 300 parts of the composition of the ethylenic unsaturated compound according to Example I-1. In the same A cover sheet was produced as in Example I-1, Generated and evaluated pictures on the base sheet. Get the Color images were very sharp.

Example I-8

The procedure of Example I-1 was repeated with the Except that a microcapsule color composition is made was made using 240 parts of liquid polybuta diene / acrylate A instead of 300 parts of the composition the ethylenically unsaturated compound according to Example I-1, and further 80 parts of ethanol and 5 parts colloidal silica (trademark "AEROSIL 200", Nippon Aerosil Co. Ltd.). In the same way as after  Example I-1, a cover sheet was made, pictures generated and evaluated on the base sheet. The received Color images were very sharp.

Example I-9

The procedure of Example I-1 was repeated with the Except that a microcapsule color composition is made was made using 200 parts of liquid polybuta diene / acrylate A instead of 300 parts of the composition the ethylenically unsaturated compound as in Example 1- 1, and further 80 parts of ethyl cellosolve and 50 Parts of rosin pentaerythritol ester added. In the a cover sheet was made in the same manner as in Example I-1 manufactured and evaluated. The color images obtained were very good sharp.

Example I-10

The procedure of Example I-1 was repeated with the Except that a microcapsule color composition is made was made using 220 parts of liquid polybuta diene / acrylate B instead of 300 parts of the composition the ethylenically unsaturated compound according to Example I-1, and 100 parts of ethylene glycol was further added. A deck was made in the same manner as in Example I-1 sheet produced, images created on the base sheet and rated. The color images obtained were very sharp.

Example I-11

The procedure of Example I-1 was repeated with the Except that a microcapsule color composition is made was made using 300 parts of a composition the ethylenically unsaturated compound (liquid hydrogenated 1,2-polybutadiene / acrylate, made by 2-hydroxyethyl acrylate and a liquid hydrogenated 1,2-polybutadiene glycol a urethane addition reaction using 2,4-tolylene dii socyanate (hereinafter referred to as "liquid hydrogenated 1,2-polybutadiene / acrylate D ", viscosity  = 4900 mPa · s, average number of acryloyl groups per Molecule = 1.9): Dipropylene glycol diacrylate = 1: 1) instead of 300 parts of the above composition of ethylenic unsaturated compound according to Example I-1. In the same A cover sheet was prepared as in Example I-1 and images were generated and evaluated on the base sheet. The color images obtained were very sharp.

Example I-12

The procedure of Example I-1 was repeated with the Except that a microcapsule color composition is made was hydrogenated using 170 parts of liquid 1,2-polybutadiene / acrylate D instead of 300 parts of Composition of the ethylenically unsaturated compound according to Example I-1, and further 80 parts of propylene glycol and 50 parts of rosin pentaerythritol ester admitted. In the same manner as in Example I-1 a cover sheet is made and pictures on the base sheet generated and evaluated. The color images obtained were very good sharp.

Example I-13

The procedure of Example I-1 was repeated with the Except that a microcapsule color composition is made was hydrogenated using 300 parts of liquid 1,2-polybutadiene / acrylate D in place of the above setting of the ethylenically unsaturated compound according to example I-1. In the same manner as in Example I-1, a Cover sheet made and pictures were on the base sheet generated and evaluated. The color images obtained were sharp.

Example I-14 Production of a cover page

Using an offset printing method, a base paper sheet weighing 40 g / m ² was printed twice with the microcapsule color composition prepared in the same manner as in Example I-1 (in an amount of 4.0 g / m ² ) and then with a UV irradiation device equipped with a 6 kW high pressure mercury lamp, hardened to produce a cover sheet.

rating

As the cover sheet made as above, and the base sheet, which is in the same manner as in Example I-1 was made, placed on top of each other and with the help of a Typewriter on which images were created was very much received sharp color images on the base sheet.

Comparative Example I-1

The procedure of Example I-1 was repeated with the Except that a microcapsule color composition is made was made using 300 parts of a composition an ethylenically unsaturated compound (pentaerythritol triacrylate: pentaerythritol tetraacrylate = 1: 1) instead of 300 parts of the composition of the ethylenically unsaturated Compound according to Example I-1. In the same way as after Example I a cover sheet was made on the base sheet images were generated and evaluated. The color obtained pictures were so inferior that they were not practical Showed benefits.

Comparative Example I-2

The procedure of Example I-1 was repeated with the Except that a microcapsule color composition is made was made using 300 parts of a composition the ethylenically unsaturated compound (pentaerythritol triacrylate: pentaerythritol tetraacrylate: dipropylene glycol di acrylate = 1: 1: 1) instead of 300 parts of the above Composition of the ethylenically unsaturated compound according to Example I-1. In the same way as in Example I-1 a cover sheet was made and were on the base sheet Images generated and evaluated. The color images obtained  were so inferior that they had no practical use had.

Comparative Example I-3

The procedure of Example I-1 was repeated with the Except that a microcapsule color composition is made was made using 300 parts of a composition the ethylenically unsaturated compound (trimethylolpropane di acrylate: trimethylolpropane triacrylate = 1: 1) instead of 300 Share the composition of the ethylenically unsaturated Compound as used in Example I-1. In the a cover sheet was made in the same manner as in Example I-1 and images were created on the base sheet and evaluated. The color images obtained were so inferior t that they had no practical use.

Comparative Example I-4

The procedure of Example I-1 was repeated with the Except that a microcapsule color composition is made was made using 300 parts of a composition the ethylenically unsaturated compound (trimethylolpropane triacrylate: trimethylol propane diacrylate: dipropylene glycol di acrylate = 1: 1: 1) instead of 300 parts of the composition the ethylenically unsaturated compound, as in example I-1 used. In the same manner as in Example I-1 a cover sheet was made and pictures were taken on the base sheet generated and evaluated. The color images obtained were like this inferior that they had no practical use.

Comparative Example I-5

The procedure of Example I-1 was repeated with the Except that a microcapsule color composition is made was made using 300 parts of 1,6-hexanediol diacrylate instead of 300 parts of the composition of the ethylenic unsaturated compound as used in Example I-1 has been. In the same manner as in Example I-1, a Cover sheet produced and images created on the base sheet  and rated. The color images obtained were so inferior that they were of no practical use.

Comparative Example I-6

The procedure of Example I-1 was repeated with the Except that a microcapsule color composition is made was made using 300 parts of dipropylene glycol diacry lat instead of 300 parts of the composition mentioned ethylenically unsaturated compound as in example I-1 was used. In the same way as in the example I-1 a cover sheet was made and on the base sheet Images created and rated. The color images obtained were so inferior that they were of no practical use.

Example II-1 Preparation of a microcapsule color composition

In 75 parts of benzyltoluene, 25 parts of 3,3-bis (2-methyl- 1-octyl-3-indolyl) phthalide dissolved with heating to a Obtain solution for the inner phase. This solution was in 200 parts of a 3% aqueous solution of ethylene Maleic anhydride copolymer (trademark "EMA 31", product of Monsanto Co.) emulsified, the pH was adjusted to 6.0 and the system was heated to 55 ° C.

Separately, 15 parts of melamine became 45 parts of a 37% given aqueous solution of formaldehyde, and the implementation Tung was carried out at 60 ° C for 15 minutes to an aq to get some prepolymer solution.

This prepolymer solution dropwise became the above Emulsion was added and the mixture was brought to pH adjusted from 5.3 by dropwise adding 0.1 N hydrochloric acid Stirring was added. The system was then heated to 80 ° C and stirred for 1 hour. Then 0.2 N hydrochloric acid was added dropwise added wisely to adjust the pH of the system to 3.5 bring, and the mixture was further stirred for 3 hours. To cooling resulted in a dispersion of microcapsules an average particle size of 3.8 microns.

This dispersion was then passed through a filter press  and dried to give powdery microcapsules. A Microcapsule color composition was prepared by mixing 100 Parts of the microcapsules, 400 parts of a composition of ethylenically unsaturated compound (2- (p-nonylphen oxy) ethyl acrylate: pentaerythritol triacetate = 7: 3), 10 parts Photopolymerization initiator (benzoin methyl ether) and 20 Parts made of titanium oxide.

Production of a cover page

Using a letterpress printing process, a base paper sheet with a weight of 40 g / m ^{2 was} printed with the above microcapsule color composition (in an amount of 5.0 g / m ² ) and then equipped with a UV radiation device equipped with a 6 kW - High pressure mercury lamp, hardened to get a cover page.

rating

After assembling the cover sheet, do the above had been produced with the base sheet, which in the same The manner in which Example I-1 was made were shown in this using an electric typewriter Images were created and you got a lot on the base sheet sharp color images.

Example II-3

The procedure of Example II-1 was repeated with the Except that a microcapsule color composition is made was made using 400 parts of a composition the ethylenically unsaturated compound (p-nonylphenoxy diethylene glycol acrylate: 1,6-hexanediol diacrylate = 5: 5) Place 400 parts of the composition of the ethylenic unsaturated compound as used in Example II-1 has been. In the same manner as in Example II-1, a Cover sheet made and pictures were on the base sheet generated and evaluated. The color images obtained were very good sharp.  

Example II-4

The procedure of Example II-1 was repeated with the Except that a microcapsule color composition is made was made using 400 parts of a composition the ethylenically unsaturated compound (2- (p-nonylphe noxy) ethyl acrylate: 1,6-hexanediol diacrylate = 6: 4) instead of 400 parts of the composition of the ethylenically unsaturated Compound as used in Example II-1. In the a cover sheet was made in the same manner as in Example II-1 and images were created on the base sheet and rated. The color images obtained were completely sharp.

Example II-5

The procedure of Example II-1 was repeated with the Except that a microcapsule color composition is made was made using 400 parts of a composition the ethylenically unsaturated compound (p-butylphenoxy polypropylene glycol acrylate: 1,6-hexanediol diacrylate = 5: 5) Instead of 400 parts of the composition mentioned ethylenically unsaturated compound as described in Example II-1 has been used. In the same way as in Example II-1 a cover sheet was made, pictures on the base sheet generated and evaluated. The color images obtained were very good sharp.

Example II-6

The procedure of Example II-1 was repeated with the Except that a microcapsule color composition is made was made using a composition of ethylenic unsaturated compound (p-nonylphenoxy dipropylene glycol acrylate: p-nonylphenoxypropylene glycol acrylate: polypropylene glycol dimethacrylate = 4: 3: 3) instead of 400 parts of Composition of the ethylenically unsaturated compound, such as it was used in Example II-1. In the same way a cover sheet was prepared as in Example II-1 the base sheet generated and evaluated images. The received Color images were very sharp.  

Example II-7

The procedure of Example II-1 was repeated with the Except that a microcapsule color composition is made was made using a composition of ethyle nisch unsaturated compound (2- (p-nonylphenoxy) - ethyl acrylate: liquid polybutadiene / acrylate B = 6: 4) Place 400 parts of the composition of the ethylenic unsaturated compound as used in Example II-1 has been. In the same manner as in Example II-1, a Cover sheet produced, images generated on the base sheet and evaluated. The color images obtained were very sharp.

Comparative Example II-1

The procedure of Example II-1 was repeated with the Except that a microcapsule color composition is made was made using 400 parts of pentaerythritol triacrylate instead of 400 parts of the composition of the ethylenic unsaturated compound as used in Example II-1 has been. In the same manner as in Example II-1, a Cover sheet produced, images generated on the base sheet and evaluated. The color images obtained were completely inferior significant.

Example III-1 Preparation of a microcapsule color composition

In 75 parts of benzyltoluene, 25 parts of 3,3-bis (2-methyl- 1-octyl-3-indolyl) phthalide dissolved with heating to the solution to get for the inner phase. This solution was in 200 Share a 3% aqueous solution of ethylene maleic acid anhydride copolymer (trademark "EMA 31", product of Monsanto Co.) emulsified, the pH adjusted to 6.0 and the system warmed to 55 ° C.

Separately, 15 parts of melamine became 45 parts of a 37% Solution of formaldehyde added, the reaction was 15 Minutes at 60 ° C and gave an aqueous Prepolymer solution.

This prepolymer solution dropwise became the above Emulsion was added and the mixture was brought to pH  adjusted from 5.3 by dropwise adding 0.1 N hydrochloric acid Stirring was added. The system was then heated to 80 ° C and stirred for 1 hour. Then 0.2 N was added dropwise Hydrochloric acid added to adjust the pH of the system to 3.5 to deliver, and the mixture was further stirred for 3 hours. After cooling, a microcapsule dispersion was obtained an average particle size of 3.8 microns.

This dispersion was then passed through a filter press and dried to give powdery microcapsules. The Microcapsule color composition was prepared by mixing 100 Parts of the microcapsules, 400 parts of a composition of ethylenically unsaturated compound (2-hydroxy-3-phenoxy propyl acrylate: pentaerythritol triacrylate = 7: 3), 10 parts a photopolymerization initiator (benzoin methy lether) and 20 parts of titanium oxide.

Production of a cover page

Using a letterpress printing method, a base paper sheet weighing 40 g / m ^{2 was} printed with the above microcapsule color composition (in an amount of 50 g / m ² ) and then cured with a 6 kW high pressure mercury lamp to produce a cover sheet.

rating

After assembling the cover sheet that in the above manner had been produced, and the base sheet, which in the the same manner as that prepared according to Example I-1, were then pictures using an electrical Typewriter generated and you got on the base sheet very sharp color images.

Example III-2 Production of a cover page

Using an offset printing process, a base paper sheet with a weight of 40 g / m ^{2 was} printed with the microcapsule color composition prepared as in Example III-1 (in an amount of 3.0 g / m ² ) and then with a 6th -KW high pressure mercury lamp hardened to produce a cover sheet.

rating

After the cover sheet that was made as above was, with the base sheet, made in the same way as according to Example I-1, were put together Images using an electric typewriter generated, and you got very sharp on the base sheet Color images.

Example III-3

The procedure of Example III-1 was repeated with the Except that a microcapsule color composition is made was made using 400 parts of a composition the ethylenically unsaturated compound (2-hydroxy-3- (p-no nylphenoxy) propyl acrylate: 1,6-hexanediol diacrylate = 5: 5) Place 400 parts of the composition of the ethylenic unsaturated compound according to Example III-1. In the same A cover sheet was produced as in Example III-1, images created and evaluated on the base sheet. The color images obtained were very sharp.

Example III-4

The procedure of Example III-1 was repeated with the Except that a microcapsule color composition is made was made using 400 parts of a composition the ethylenically unsaturated compound (2-hydroxy-3-dodecyl oxypropyl acrylate: 1,6-hexanediol diacrylate = 6: 4) in place of 400 parts of the composition mentioned the ethylenic unsaturated compound according to Example III-1. In the same A cover sheet was produced as in Example III-1, images created and evaluated on the base sheet. The color images obtained were completely sharp.  

Example III-5

The procedure of Example III-1 was repeated with the Except that a microcapsule color composition is made was made using 400 parts of a composition the ethylenically unsaturated compound (2-hydroxy-3- (p-bu tylphenoxy) propyl acrylate: 1,6-hexanediol diacrylate = 5: 5) Place 400 parts of the composition of the ethylenic unsaturated compound as used in Example III-1 has been. In the same manner as in Example III-1, a Cover sheet produced, images generated on the base sheet and evaluated. The color images obtained were very sharp.

Example III-6

The procedure of Example III-1 was repeated with the Exception that a microcapsule color composition under Using 400 parts of a composition of ethyle nisch unsaturated compound (2-hydroxy-3-phenoxypropyl acrylate: p-nonylphenoxypropylene glycol acrylate: polypropylene glycol dimethylacrylate = 4: 3: 3) instead of 400 parts of the Composition of the ethylenically unsaturated compound, such as it was used in Example III-1. In the same way a cover sheet was prepared as in Example III-1 The base sheet was created and evaluated. The color images obtained were very sharp.

Example III-7

The procedure of Example III-1 was repeated with the Except that a microcapsule color composition is made was made using 400 parts of a composition the ethylenically unsaturated compound (2-hydroxy-3-phen oxypropyl acrylate: liquid polybutadiene / acrylate A = 6: 4) Instead of 400 parts of the composition mentioned ethylenically unsaturated compound as described in Example III-1 has been used. In the same way as in the example III-1 a cover sheet was made on the base sheet Images generated and evaluated. The color images obtained were completely spicy.  

Example III-8

The procedure of Example III-1 was repeated with the Except that a microcapsule color composition is made was made using 400 parts of a composition the ethylenically unsaturated compound (2-hydroxy-3-phenox propyl acrylate: 2- (p-nonylphenoxy) ethyl acrylate: liquid Polybutadiene / acrylate A = 4: 4: 2) instead of 400 parts of the Composition of the ethylenically unsaturated compound, such as it was used in Example III-1. In the same way a cover sheet was prepared as in Example III-1 the base sheet generated and evaluated images. The received Color images were very sharp.

The color density of the entire surface of the sub sheet and each of the pressure sensitive recording sheets (Cover sheet and base sheet) generated images according to the above examples and comparative examples "Macbeth" type RD-914 (product of Macbeth Company). The results are given in Table 1 below.

Table 1 also shows the viscosity of the composition the ethylenically unsaturated compound, the at least one of components (a) to (d), optionally in combination with other ethylenically unsaturated compounds or others Dye carriers (e.g. ethanol, ethyl cellosolve) contains, such as them with a "Brookfield" type viscometer at 25 ° C and 60 rpm was determined.  

Table 1

Claims (10)

1. A microcapsule color composition comprising microcapsules, an ethylenically unsaturated compound and a photopolymerization initiating agent, the composition comprising as the ethylenically unsaturated compound comprising at least one substance which is selected from the group:

• a) a liquid polybutadiene / (meth) acrylate,
• b) a liquid hydrogenated polybutadiene / (meth) acrylate,
• c) a compound of the formula wherein W represents a hydrogen atom or a methyl group, X and Y are the same and each represent a hydrogen atom, or either X or Y represents a hydrogen atom and the other represents a methyl group, Z represents an unsubstituted or substituted aryl group and n is an integer of 1 or more means, and
• d) a compound of the formula wherein X ^{1 represents} a hydrogen atom or a methyl group, Y ^{1 represents} an unsubstituted or substituted aryl or alkyl group with not more than 34 carbon atoms.

2. The microcapsule color composition of claim 1, wherein the liquid hydrogenated polybutadiene / (meth) acrylate liquid hydrogenated 1,2-polybutadiene / (meth) acrylate.   3. Microcapsule color composition after at least one of claims 1-2, characterized in that they as the aforementioned ethylenically unsaturated compound in addition at least one of components (a) to (d), still little another ethylenically unsaturated compound, selected from the group of photopolymerizable Monomers and photopolymerizable prepolymers contains. 4. Microcapsule color composition according to claim 1, characterized characterized in that said ethylenically unsaturated Compound (a) or (b) in an amount of about 30 to about 95% by weight, based on the color composition, is included. 5. Microcapsule color composition according to claim 1, characterized characterized in that the ethylenically unsaturated Compound (c) or (d) in an amount of about 9 to about 94% by weight, based on the color composition, is included. 6. Microcapsule color composition according to claim 1, characterized characterized in that the microcapsules with compound (a) or (b) in an amount of about 5 to about 60% by weight, based on the color composition are. 7. Microcapsule color composition according to claim 1, characterized marked that the microcapsules with compound (c) or (d) in an amount of about 5 to about 80% by weight, based on the color composition. 8. Microcapsule color composition according to at least one of the Claims 1-7, characterized in that the ethyle nisch unsaturated compound has a viscosity of about 1 to about 10,000 mPa · s, determined at 25 ° C.   9. Microcapsule color composition according to at least one of the Claims 1-8, characterized in that the photopoly merization initiators in an amount of about 1 to about 20 parts by weight per 100 parts by weight of the ethyle nisch unsaturated compound is included. 10. Microcapsule color composition according to at least one of the Claims 1-9, characterized in that they continue contains at least one dye carrier, which from the Group of high-boiling solvents, the low boiling solvents, resins, waxes and oils was selected.