CA1109258A - Process for the production of novel radiation curable microcapsular coating compositions - Google Patents
Process for the production of novel radiation curable microcapsular coating compositionsInfo
- Publication number
- CA1109258A CA1109258A CA305,776A CA305776A CA1109258A CA 1109258 A CA1109258 A CA 1109258A CA 305776 A CA305776 A CA 305776A CA 1109258 A CA1109258 A CA 1109258A
- Authority
- CA
- Canada
- Prior art keywords
- hydrophobic
- emulsion
- hydrophilic
- wall
- radiation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
Landscapes
- Color Printing (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Paints Or Removers (AREA)
Abstract
Abstract of the Disclosure This invention relates to a process for producing a radiation curable coating composition containing microcapsules having a hydrophobic liquid core comprising the following steps: An emulsion containing droplets of a hydrophobic emulsion component dispersed in a hydrophilic emulsion component is prepared. The hydrophobic emulsion component comprises a hydrophobic li-quid. The hydrophobic emulsion component additionally contains a first wall-forming material capable of reacting by condensation polymerization with a second wall-forming material to form a polymeric capsule wall. The first wall-forming material is soluble in the hydrophobic emulsion component. The poly-meric capsule wall is substantially insoluble in the hydrophilic and the hydro-phobic emulsion components. The hydrophilic emulsion component comprises an emulsifier dispersed in a radiation curable hydrophilic liquid. The radiation curable hydrophilic liquid comprises water and at least one radiation curable polar compound. The emulsion additionally contains the second wall-forming material. The emulsion is subjected, with stirring, to temperature conditions for a period of time sufficient to react the first and second wall-forming materials to form a dispersion of microcapsules in the hydrophilic emulsion component. The microcapsules have capsule walls substantially impermeable to the hydrophilic and the hydrophobic emulsion components. The radiation curable dispersion so produced can be coated on a paper substrate and set by subjecting the dispersion on the paper substrate to radiation for a period of time suffi-cient to polymerize the radiation curable hydrophilic liquid to a tack-free resinous film on the paper substrate. The radiation is a combination of ultraviolet and infra-red radiation. The invention further relates to a radiation curable coating composition containing microcapsules. The microcapsules have a hydrophobic liquid core and are dispersed in a radiation curable hydrophilic liquid. The radiation curable hydrophilic liquid comprises a polar radiation curable com-pound and water. The radiation curable coating composition additionally contains a photoinitiator.
Description
Z~i8 Background of the Invention Field of the Invention;
This invention relates to the production of radiation curable microcapsu-lar coating co~positions. In particular, it relates to the production of micro-capsules containing a hydrophobic liquid core by polycondensation polymerizationof tw~ w~ forming materials in a hydrophilic liquid continuous phase wherein the hydrophilic liquid cc~orises a polar radiation curable compound. In one em}od1ment of this invention, the encapsulated hydrophobic liquid contains a chromogenic material soluble in the encapsulated hydrophobic liquid. A disper-sion of these microcapsules containing a chramcgenic material can be coated on a substrate and cured by radiation to give a pressure-sensitive carbonless ccpy ` sheet having a transfer coating.
` Prior Art:
The production of microcapsules containing an encapsulated oily (hydropho-i ~
~ 15 bic) liquid wherein the microcapsule walls are produced b~ a polycondensation reaction of polyisocyanate and a second w~ forming material is described in U. S. Patent No. 3,796,669 to Kiritani et al~ Both the polyisocyanate ~all-;:~
~` forming ma~rial and the second wall-forming material are mlxed with oily liquid.
m e mixed oily liquid is dispersed into an aqueous continuous phase and the tem~2rature is raised to initiate the reaction on the surface of the oil drops to encapsulate the oil drops with the reaction produc~ of the polyisocyanate and second wa~l-fo~ming material. A catalyst for the reaction may also be added to the oily liquid.
A number of patents disclose the production of microcapsules using inter-facial condensation polymerization of two or m~re reactants to form the micro-capsule walls. Typical of ~hese c~re:
U. ~. Patent 3,429,827 (1969) to Ruus U. S. Patent 3,432,427 (1969) to Xan et al U. S. Patent 3,464,926 (1969) to Vande~aer et al U. S. Pat nt 3,492,380 (1970) to Santo et al U. S. Patent 3,575,882 (1971) to Vandegaer et al U. S. Pat~nt 3,577,515 (1971) to Vande~aer ~ ~ ~ 3 ~
U. S. Patent 3,607,776 (1971) to Santo et al U. S. Patent 3,726,804 (1973) to Matsukawa et al U. S. Patent 3,875,074 (1975) to Vassiliades et al It is im?ortant to note that none of the above listed patents or U. S.
Patent 3,796,669 to Kiritani disclose the in situ preparation of the micro~ap-sules in a radiation curable hydrophilic liquid contai~ing a radiation curable polar compound.
Carbonless copy paper, briefly stated is a standard type of paper wher2in during manufacture the backside o~ the paper substrate is coated with ~hat is referred to as a CB or transfer coating, the CB coating containing one or ~ore chrcmcgenic materials, generally in capsular form. At the same time the front ; side of the paper substrate is coated during manufacture with what is referred to as a CF coating, ~hich contains one or more chrcmogenic materials capable of producing a color with encapsulated CB chromogenic material. Both the chromogenic materials remain in the coatings on the respective back and front surfaces of the paper in substantially colorless form. Ihis is ~rue until the CB and CF coatings are brought into overlying relationship and sufficient pres-sure, as by a typewriter, is applied to rupture -the CB coating to release the encapsulated chrcmogenic material. At this ~ime the chrQmogenic material con-tacts the CF coating and reacts with the chromogenic material therein to ~orm a colored image. Carbonless copy paper has proved to ~e exceptionally valuable image transfer ~dia for a variety of reasons~ only one of which is the fact that until a CB coating is placed next to a CF coating both the CB and CF coat~
ings are in an inactive state as the coreactive elements are not in contact ~ith one another until pressure is applied. Patents r~lating to carbonless copy paper products are:
U. S. Patent 2,712,507 (1955) to Green U. S. Patent 2,730,456 (1956) to Green et al.
U. S. Patent 3,455,721 (1969) to Phillips et al.
U. S. Patent 3,466,184 (1969) to Bowler et al.
U. S. Patent 3,672,935 (1972) to Miller e-t al.
U. S. Patent 3,720,623 (1973) to Cartmell et al.
A disadvan-tage of coated paper products such as carkonless transfer papers stems from the necessit~ of applying a liquid coating ccmposition con-taining the color forming ingredients during the rnanufacture process. In the application of such coatings, volatile organic solvents are sometimes used which then in turn requires evaporation of excess solvent to dry the coating thus producing volatile solvent vapors. An alternate method of ooating involves the application of the color forming ingredients in an aqueous slurry reguiring removal of water by drying. Both methods suffer from serious disadvantages.
In particular, the organic solvent coating method necessarily involves the , prc~uction of generally volatile solvent vapors, creating both a health and fire hazard in the surrounding en~ironment. When using an aqueous solvent system the large amounts of water must be evaporated since the microcapsule ooatings currently used cc~mercially generally comprise 60% to 85% water.
This invol~es the expenditure of significant a~ounts of energy and further necessitates a separate drying step which rli!~res the use of cc~plex and expensive apparatus to continuously dry a substrate whi~h has been coated with such aqueous coating ccmpositions.
Radiation curable coating ccmpositions and methods of producing these co~lpositions are ~7ell known, although their use is not well known in the produc-tion of carkonless papers. In general, patents concerned with the production and application of liquid resin campositions containins no volatile solvent which are subsequ~ntly polymerized by free radical radiation to a solid film are:
Z~
U. S. Patent 3,551,235 (1970) to Basse~ir e-t al.
U. 5. Patent 3,551,246 (1970) to Bassemir et al.
,! U. S. Patent 3,551,311 (1970) to Nass et aL.
,,:
U. S. Patent 3,558,387 (1971) to Bassemir et al.
U. S. Patent 3,661,614 (1972) to Bassemir et al.
' U. S. Patent 3,720,534 (1973) to Macaulay et al.
U. S. Patent 3,754,966 (1973) to Newman et al.
: .
; ~ U. S. Patent 3,772,062 (1973) to Shur et al.
U. S. Patent 3,772l171 (1973) to Savageau et al.
U. S. Patent 3,801,329 (1974) to Sandner et al.
U. S. Patent 3,819,496 (1974) to Roskott et al.
U. S. Patent 3,847,768 (1974) to Kagiya et al.
U. S. Patent 3,847,769 (1974) to Garratt et al.
These CQmpositiQns generally also contain a pigm~nt or dye. Such resin compositions are useful for protective coatings and fàst drying inks. U. S.
Patent 3,754,966 describes the production of an ink releasing dry transfer element which can be used as a carbon paper or typewriter ribbon. Additionall~
it is known to use such radiation in the formation and hardening of microcaps~Les although none of these microcapsules are kno~n to have utility in the car~onlesspaper environment. Patents knc~ to use radiation in the preparation of-micro--capsules æ e:
; U. S. Patent 3,242,051 (1966) to Hiestand et al.
U. S. Patent 3,265,630 (1966) to Jensen U. S. Patent 3,405,071 (1968) to Reyes U. S, Patent 4,021,364 (1977) to Speiser et al.
It is significant to note that the encapsuLated materials disclosed in any of the above patents do not include oil solutions of colorless dyes. It is particularly significant in view of the fact that the radiation cured coating ofthe instant invention mu~st be compatible with the reaction of CB and CF chrcmo-genic ma-~erials to form a color in order to have utility in the car onless paper environment. Such color forming reactions are g~erally of a sensitive or delicate nature and are not generally ccmpatible with the compositions found in the prior art. For instance, it is known that certain color precursors currently used in the commercial production o~
carbonless transfer sheets will undergo a color change when exposed to ultraviolet radiation.
The present invention provides a radiation cura~le liquid coating composition for use in the manufacture of micro-capsule coated papers, said liquid coating composition being characterized by being curable by radiation to a dry, solid, tack-free resin, said ra~iation being a combination of ultra-violet radiation and infra-red radiation, said li~uid coating composition being further characterized by containing micro-capsules having a hydrophobic core material, said microcapsules being dispersed in a radiation curable hydrophilic liquid, said hydrophilic liquid comprising water and at least one polar radiation curable compound, said liquid coating composition additionally containing a photoinitiator.
The microcapsular coating compositions of the instant invention have a significantly lower water content than the -~
microcapsular coating compositions currently used in the prepa-ration of carbonless transfer papers. For example, prior art coating compositions containing gelatin are seldom applied at a water content below 80% (20% solids). In comparison with a microcapsular coating composi~ion con~aining 40% water (60%
solids) produced by the process of this invention, the amount of water necessary to be evaporated from the prior art compo-sitions is 6 times the amount to be evaporated from the coating compositions of this invention. By using the coating composi-tions of this invention, a substantial reduction in heat energy used in drying can be realized. Another advantage is that by using available sources of ultraviolet radiation which also contains infra-red radiation such as the radiation from a mercury vapor lamp the microcapsular coating compositions may be cured in one combined polymerization and drying step, thus ,,/~, ~,~ ..,,;, ~
eliminating the need for additional or separate drying.
This invention relates to a process for producing a liquid coating composition for use in the manufacture of ~i pressure-sensitive carbonless transfer papers, said li~uid ` coating composition being characterized by being curable by radiation to a dry, solid, tack-free resin, said radiation being a combination oE ultraviolet radiation and infra-red . radiation and said liquid coating composition being further characterized by containing microcapsules having a hydrophobic `~ 10 core material, comprising the steps of:
~ a) preparing an emulsion containing droplets of hydrophobic ~
emulsion component dispersed in a hydrophilic emulsion compo-nent, said hydrophobic emulsion component comprising a hydro-phobic liquid, said hydrophobic emulsion component additionally containing a first wall-forming material capable of reacting by condensation polymerization with a second wall-forming material to form a polymeric capsule wall, said first wall-forming material being soluble in said hydrophobic emulsion component, said polymeric capsule wall being substantially insoluble in said hydrophilic and said hydrophobic emulsion components, said hydrophilic emulsion component comprising an emulsifier dispersed in a radiation curable hydrophilic liquid, said radiation curable hydrophi]ic liquid comprising water and at least one radiation curable polar compound, said emulsion additionally containing said second wall-f~rming materials;
b~ subjecting said emulsion, with mixing, to temperature con-ditions for a period of time sufficient to substantially com~
pletely polymerize said first and second wall-forming materials thereby forming a dispersion of microcapsules in said hydro-philic emulsion componen~, said microcapsules having capsulewalls substantially impermeable to said hydrophilic and said hydrophobic emulsion components; and c) adding a photoinitiator to said dispersion of microcapsules.
i8 .:
DETAILED DESCRIPTION OF THE INVENTION
~` The coating compositions produced by the process ~ of this invention are essentially dispersions of microcap-'~ sules containing a hydrophobic liquid core material in a ` radiation curable hydrophilic liquid as a continuous phase.
The dispersions of microcapsules are prepared in situ in the radiation curable hydrophilic liquid by a condensation poly-merization reaction of a first wall-forming material and a second wall-forming material. The coating compositions can be applied as a coating to a substrate such as paper or plastic film and can be cured by radiation to a tack-free resinous film. If the mi~rocapsules contain a chromogenic material, the coated pape~ is useful as a pressure-sensitive carbonless transfer CB paper. For purposes of this inven-tion, the term "chromogenic" shall be understood to refer to materials such as color precursors, color developers, and color formers.
The coating composition can contain additional materials which function as photoinitiators. Addition of these materials depends upon the particular method of curing ; the microcapsular coating. Filler materials can also be added to modify the properties of the cured film. Although the product and process o~ this invention are useful in the manufacture of a variety of microencapsulated products, such as, for example, microencapsulated flavors, foods, pharma-ceuticals, insecticides and the like, the preferred use of the process and product of this invention is in the produc-tion of a pressure-sensitive carbonless transfer sheets such as is described in commonly-assigned U. S. Patent 4,091,122 issued on May 23, 1978.
The hydrophobic liquids useful in the process o~
this invention are the non-polar oils and solvents. In the preferred use of this invention, i.e. to prepare pressure-Y~ ) , _g_ Z~
sensitive carbonless transfer sheets, the preferred hydro-phobic liquids are monoisopropybiphenyl (MIPB), chlorinated paraffins, alkylnaphalenes, kerosene, petroleum naphtha and mixtures thereof.
The chromogenic materials useful in the practice of this invention are the electron-donor type color precur-sors. These include the lactone phthalides, such as crystal violet lactone, and 3,3-bis-(1'-ethyl-2-methylindol-3'yl) phthalide, the lactone fluorans, such as 2-dibenz.ylamino-6-10 diethyl- ................. ~
~ t -9a-~":
amlno-fluoran and 5-diethylc~mino-1,3-dimethylfluoran, the lactone xanthenes, the leucoauramines, the 2-(omega substituted vinylene)-3,3-disubsti-tuced-3-H
indoles and 1,3,3-trialkylindolinospirans. Mixtures of these color precursors can be used if desired. The color precursors are soluble in the hydrophobic liquid and are preferably present in such solutions, somet~mes referred to as carrier oil solutions, in an a~Dunt of from about 0.5% to about 20.0% based on the weight of the oil solution, and the most preferred range is ~rom about
This invention relates to the production of radiation curable microcapsu-lar coating co~positions. In particular, it relates to the production of micro-capsules containing a hydrophobic liquid core by polycondensation polymerizationof tw~ w~ forming materials in a hydrophilic liquid continuous phase wherein the hydrophilic liquid cc~orises a polar radiation curable compound. In one em}od1ment of this invention, the encapsulated hydrophobic liquid contains a chromogenic material soluble in the encapsulated hydrophobic liquid. A disper-sion of these microcapsules containing a chramcgenic material can be coated on a substrate and cured by radiation to give a pressure-sensitive carbonless ccpy ` sheet having a transfer coating.
` Prior Art:
The production of microcapsules containing an encapsulated oily (hydropho-i ~
~ 15 bic) liquid wherein the microcapsule walls are produced b~ a polycondensation reaction of polyisocyanate and a second w~ forming material is described in U. S. Patent No. 3,796,669 to Kiritani et al~ Both the polyisocyanate ~all-;:~
~` forming ma~rial and the second wall-forming material are mlxed with oily liquid.
m e mixed oily liquid is dispersed into an aqueous continuous phase and the tem~2rature is raised to initiate the reaction on the surface of the oil drops to encapsulate the oil drops with the reaction produc~ of the polyisocyanate and second wa~l-fo~ming material. A catalyst for the reaction may also be added to the oily liquid.
A number of patents disclose the production of microcapsules using inter-facial condensation polymerization of two or m~re reactants to form the micro-capsule walls. Typical of ~hese c~re:
U. ~. Patent 3,429,827 (1969) to Ruus U. S. Patent 3,432,427 (1969) to Xan et al U. S. Patent 3,464,926 (1969) to Vande~aer et al U. S. Pat nt 3,492,380 (1970) to Santo et al U. S. Patent 3,575,882 (1971) to Vandegaer et al U. S. Pat~nt 3,577,515 (1971) to Vande~aer ~ ~ ~ 3 ~
U. S. Patent 3,607,776 (1971) to Santo et al U. S. Patent 3,726,804 (1973) to Matsukawa et al U. S. Patent 3,875,074 (1975) to Vassiliades et al It is im?ortant to note that none of the above listed patents or U. S.
Patent 3,796,669 to Kiritani disclose the in situ preparation of the micro~ap-sules in a radiation curable hydrophilic liquid contai~ing a radiation curable polar compound.
Carbonless copy paper, briefly stated is a standard type of paper wher2in during manufacture the backside o~ the paper substrate is coated with ~hat is referred to as a CB or transfer coating, the CB coating containing one or ~ore chrcmcgenic materials, generally in capsular form. At the same time the front ; side of the paper substrate is coated during manufacture with what is referred to as a CF coating, ~hich contains one or more chrcmogenic materials capable of producing a color with encapsulated CB chromogenic material. Both the chromogenic materials remain in the coatings on the respective back and front surfaces of the paper in substantially colorless form. Ihis is ~rue until the CB and CF coatings are brought into overlying relationship and sufficient pres-sure, as by a typewriter, is applied to rupture -the CB coating to release the encapsulated chrcmogenic material. At this ~ime the chrQmogenic material con-tacts the CF coating and reacts with the chromogenic material therein to ~orm a colored image. Carbonless copy paper has proved to ~e exceptionally valuable image transfer ~dia for a variety of reasons~ only one of which is the fact that until a CB coating is placed next to a CF coating both the CB and CF coat~
ings are in an inactive state as the coreactive elements are not in contact ~ith one another until pressure is applied. Patents r~lating to carbonless copy paper products are:
U. S. Patent 2,712,507 (1955) to Green U. S. Patent 2,730,456 (1956) to Green et al.
U. S. Patent 3,455,721 (1969) to Phillips et al.
U. S. Patent 3,466,184 (1969) to Bowler et al.
U. S. Patent 3,672,935 (1972) to Miller e-t al.
U. S. Patent 3,720,623 (1973) to Cartmell et al.
A disadvan-tage of coated paper products such as carkonless transfer papers stems from the necessit~ of applying a liquid coating ccmposition con-taining the color forming ingredients during the rnanufacture process. In the application of such coatings, volatile organic solvents are sometimes used which then in turn requires evaporation of excess solvent to dry the coating thus producing volatile solvent vapors. An alternate method of ooating involves the application of the color forming ingredients in an aqueous slurry reguiring removal of water by drying. Both methods suffer from serious disadvantages.
In particular, the organic solvent coating method necessarily involves the , prc~uction of generally volatile solvent vapors, creating both a health and fire hazard in the surrounding en~ironment. When using an aqueous solvent system the large amounts of water must be evaporated since the microcapsule ooatings currently used cc~mercially generally comprise 60% to 85% water.
This invol~es the expenditure of significant a~ounts of energy and further necessitates a separate drying step which rli!~res the use of cc~plex and expensive apparatus to continuously dry a substrate whi~h has been coated with such aqueous coating ccmpositions.
Radiation curable coating ccmpositions and methods of producing these co~lpositions are ~7ell known, although their use is not well known in the produc-tion of carkonless papers. In general, patents concerned with the production and application of liquid resin campositions containins no volatile solvent which are subsequ~ntly polymerized by free radical radiation to a solid film are:
Z~
U. S. Patent 3,551,235 (1970) to Basse~ir e-t al.
U. 5. Patent 3,551,246 (1970) to Bassemir et al.
,! U. S. Patent 3,551,311 (1970) to Nass et aL.
,,:
U. S. Patent 3,558,387 (1971) to Bassemir et al.
U. S. Patent 3,661,614 (1972) to Bassemir et al.
' U. S. Patent 3,720,534 (1973) to Macaulay et al.
U. S. Patent 3,754,966 (1973) to Newman et al.
: .
; ~ U. S. Patent 3,772,062 (1973) to Shur et al.
U. S. Patent 3,772l171 (1973) to Savageau et al.
U. S. Patent 3,801,329 (1974) to Sandner et al.
U. S. Patent 3,819,496 (1974) to Roskott et al.
U. S. Patent 3,847,768 (1974) to Kagiya et al.
U. S. Patent 3,847,769 (1974) to Garratt et al.
These CQmpositiQns generally also contain a pigm~nt or dye. Such resin compositions are useful for protective coatings and fàst drying inks. U. S.
Patent 3,754,966 describes the production of an ink releasing dry transfer element which can be used as a carbon paper or typewriter ribbon. Additionall~
it is known to use such radiation in the formation and hardening of microcaps~Les although none of these microcapsules are kno~n to have utility in the car~onlesspaper environment. Patents knc~ to use radiation in the preparation of-micro--capsules æ e:
; U. S. Patent 3,242,051 (1966) to Hiestand et al.
U. S. Patent 3,265,630 (1966) to Jensen U. S. Patent 3,405,071 (1968) to Reyes U. S, Patent 4,021,364 (1977) to Speiser et al.
It is significant to note that the encapsuLated materials disclosed in any of the above patents do not include oil solutions of colorless dyes. It is particularly significant in view of the fact that the radiation cured coating ofthe instant invention mu~st be compatible with the reaction of CB and CF chrcmo-genic ma-~erials to form a color in order to have utility in the car onless paper environment. Such color forming reactions are g~erally of a sensitive or delicate nature and are not generally ccmpatible with the compositions found in the prior art. For instance, it is known that certain color precursors currently used in the commercial production o~
carbonless transfer sheets will undergo a color change when exposed to ultraviolet radiation.
The present invention provides a radiation cura~le liquid coating composition for use in the manufacture of micro-capsule coated papers, said liquid coating composition being characterized by being curable by radiation to a dry, solid, tack-free resin, said ra~iation being a combination of ultra-violet radiation and infra-red radiation, said li~uid coating composition being further characterized by containing micro-capsules having a hydrophobic core material, said microcapsules being dispersed in a radiation curable hydrophilic liquid, said hydrophilic liquid comprising water and at least one polar radiation curable compound, said liquid coating composition additionally containing a photoinitiator.
The microcapsular coating compositions of the instant invention have a significantly lower water content than the -~
microcapsular coating compositions currently used in the prepa-ration of carbonless transfer papers. For example, prior art coating compositions containing gelatin are seldom applied at a water content below 80% (20% solids). In comparison with a microcapsular coating composi~ion con~aining 40% water (60%
solids) produced by the process of this invention, the amount of water necessary to be evaporated from the prior art compo-sitions is 6 times the amount to be evaporated from the coating compositions of this invention. By using the coating composi-tions of this invention, a substantial reduction in heat energy used in drying can be realized. Another advantage is that by using available sources of ultraviolet radiation which also contains infra-red radiation such as the radiation from a mercury vapor lamp the microcapsular coating compositions may be cured in one combined polymerization and drying step, thus ,,/~, ~,~ ..,,;, ~
eliminating the need for additional or separate drying.
This invention relates to a process for producing a liquid coating composition for use in the manufacture of ~i pressure-sensitive carbonless transfer papers, said li~uid ` coating composition being characterized by being curable by radiation to a dry, solid, tack-free resin, said radiation being a combination oE ultraviolet radiation and infra-red . radiation and said liquid coating composition being further characterized by containing microcapsules having a hydrophobic `~ 10 core material, comprising the steps of:
~ a) preparing an emulsion containing droplets of hydrophobic ~
emulsion component dispersed in a hydrophilic emulsion compo-nent, said hydrophobic emulsion component comprising a hydro-phobic liquid, said hydrophobic emulsion component additionally containing a first wall-forming material capable of reacting by condensation polymerization with a second wall-forming material to form a polymeric capsule wall, said first wall-forming material being soluble in said hydrophobic emulsion component, said polymeric capsule wall being substantially insoluble in said hydrophilic and said hydrophobic emulsion components, said hydrophilic emulsion component comprising an emulsifier dispersed in a radiation curable hydrophilic liquid, said radiation curable hydrophi]ic liquid comprising water and at least one radiation curable polar compound, said emulsion additionally containing said second wall-f~rming materials;
b~ subjecting said emulsion, with mixing, to temperature con-ditions for a period of time sufficient to substantially com~
pletely polymerize said first and second wall-forming materials thereby forming a dispersion of microcapsules in said hydro-philic emulsion componen~, said microcapsules having capsulewalls substantially impermeable to said hydrophilic and said hydrophobic emulsion components; and c) adding a photoinitiator to said dispersion of microcapsules.
i8 .:
DETAILED DESCRIPTION OF THE INVENTION
~` The coating compositions produced by the process ~ of this invention are essentially dispersions of microcap-'~ sules containing a hydrophobic liquid core material in a ` radiation curable hydrophilic liquid as a continuous phase.
The dispersions of microcapsules are prepared in situ in the radiation curable hydrophilic liquid by a condensation poly-merization reaction of a first wall-forming material and a second wall-forming material. The coating compositions can be applied as a coating to a substrate such as paper or plastic film and can be cured by radiation to a tack-free resinous film. If the mi~rocapsules contain a chromogenic material, the coated pape~ is useful as a pressure-sensitive carbonless transfer CB paper. For purposes of this inven-tion, the term "chromogenic" shall be understood to refer to materials such as color precursors, color developers, and color formers.
The coating composition can contain additional materials which function as photoinitiators. Addition of these materials depends upon the particular method of curing ; the microcapsular coating. Filler materials can also be added to modify the properties of the cured film. Although the product and process o~ this invention are useful in the manufacture of a variety of microencapsulated products, such as, for example, microencapsulated flavors, foods, pharma-ceuticals, insecticides and the like, the preferred use of the process and product of this invention is in the produc-tion of a pressure-sensitive carbonless transfer sheets such as is described in commonly-assigned U. S. Patent 4,091,122 issued on May 23, 1978.
The hydrophobic liquids useful in the process o~
this invention are the non-polar oils and solvents. In the preferred use of this invention, i.e. to prepare pressure-Y~ ) , _g_ Z~
sensitive carbonless transfer sheets, the preferred hydro-phobic liquids are monoisopropybiphenyl (MIPB), chlorinated paraffins, alkylnaphalenes, kerosene, petroleum naphtha and mixtures thereof.
The chromogenic materials useful in the practice of this invention are the electron-donor type color precur-sors. These include the lactone phthalides, such as crystal violet lactone, and 3,3-bis-(1'-ethyl-2-methylindol-3'yl) phthalide, the lactone fluorans, such as 2-dibenz.ylamino-6-10 diethyl- ................. ~
~ t -9a-~":
amlno-fluoran and 5-diethylc~mino-1,3-dimethylfluoran, the lactone xanthenes, the leucoauramines, the 2-(omega substituted vinylene)-3,3-disubsti-tuced-3-H
indoles and 1,3,3-trialkylindolinospirans. Mixtures of these color precursors can be used if desired. The color precursors are soluble in the hydrophobic liquid and are preferably present in such solutions, somet~mes referred to as carrier oil solutions, in an a~Dunt of from about 0.5% to about 20.0% based on the weight of the oil solution, and the most preferred range is ~rom about
2% to about 7%.
The radiation curable hydr~philic liquids useful in the practice of this invention ccmprise the free radical polymeriza~Le ethylenically unsaturated organic compounds in water solution. These compounds contain at least one terminal ethylenically unsaturated group per molecule. These cc~pounds ar2-radiation curable polar compounds and their aqueous solutions function in part as the continuous hydrophilic phase during the in situ preparat,ion of the microcapsules and as a dispersing medium for the microcapsules and other ingredients of the coating composition prior to the coating operation. They are curable to a solid resin when exposed in the presence of a photoinitiator to ultraviolet radiation containing additionally some infra-red radiation. The cured resin acts as a binder for the microcapsules to a substrate such as pa~er.
E~amples of useful radiation curable polar compounds are N-vinyl-2-pyrrolidonel acrylamide, h~droxyethyl acrylate, hydroxypropyl acrylate~ diaoe tone acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, acrylic acid, polyethylene glycol monoacrylates~ polye-thylene glycol polyacrylates, polyvinyl alcohol acrylate, starch acrylate, cellulose acrylate, quaternary ammonium salt deriva-25 tives of dimethyl2m moeth~l acrylate and methacrylate and muxtures thereof. The abo~e radiation curable polar ocmpounds are liquids. ~owever, solid radiation curable polar com~ounds, such a N-methylol acrylamide, can ke dissolved in ~ater and used as the radiation curable hydrophilic liquid. The preferred polar compounds are ~-methylol acrylamide and hydroxyethyl acryla~e.
Z~8 The first wall-forming material is soluble in and forms a part of a hydraphobic emulsion component. It may be either a polyisocyanate or a polyacid halide compound.
The polyisocyanates useful in this invention are the ali-phatic and aromatic polyisocyanates which include, for example, (a) diisocyanates, such as m-phenylmethane-4,4'-diisocyanate;
(b) triisocyanates, such as toluene-2,4,6-triisocyanate; (c) tetraisocyanates, such as 2,2,5,5- tetraisocyanate; (d) isocyanate prepolymers produced and sold by Mobay Chemical Company, Pitt~burg, Pennsylvania, Mondur C~-75* (75~ of a high molecular weight adduct of toluene isocyanate and 25%
of ethyl acetate produced and sold by Mobay Chemical Company) DesmodurN-100* (a biuret oontaining aliphatic isocyanate also produced and sold by Mobay Chemical Company) and NIAX
SF-50* (a trifunctional aromatic polyurethane prepolymer having a free isocyanate content of 32.5~ made and sold by Union Carbide Corporation, New York, N.Y.). Mixtures of these compounds may be used.
The polyacid halides include terephthalyl dichlo-ride, adipyl di~hloride, 1,3,5-benzenetricarboxylic acid trichloride, oxalyl dibromide, 1,4-benzenedisulfonyl dichlo-ride and 4,4'-biphenyldisulfonyl dichloride~ Mixtures of these compounds may also be used. The preferred first wall-forming materials are NIAX SF-50, ~esmodur N-100 and tereph-thalyl dichloride.
The second wall-forming material can ~e selected from the group consisting of polyols, polythiols, polyamines, acid anhydrides, and polycarboxylic acids and mixtures thereof. The polyols include for example, glycerin, resor-cinol, 1,3-naphthalenediol, bisphenol A/1,3-propylene blycol, 1,5-pentanediol and the like. Examples of polythiols are thioglycol and thioglycol condensates. Polyamines include, for example, p-phenylenediamine, diethylene triamine, * Trade Mark N,N,N',N',-tetrakis-[2-hydroxypropyl) ethylene diamine (Quadrol*-Wyandotte Chemic~l Corp., Wyandotte, Michigan) and phthalamide and the like. Examples of acid anhydrides includ~ maleic anhydride and succinic anhydride. Examples of polycarboxylic acids are malonic acid, succinic acid and terephthalic acid. The preferred second wall-forming materials are Quadrol and diethylene triamine.
A photoinitiator is added to the coating compo-sition to permit curing by ultraviolet radiation. A wide variety of photoinitiators are available which serve well in the system described in this invention. The preferr~d photoinitiators are the benzoin alkyl ethers, such as Vicure 30*, benzoin methyl ether, ~, a azobisisobutyroni-trile, ar a-diethoxyacetophene and ~inc carbonate. Other photoinitiators which can be used are benzophenone, 4,4'-bis-(dimethylamino~benzophenone, ferrocene, xanthone, thi-oxanthane, decabromodiphenyl oxide, pentabromomonochloro-cyclohexane, pentachlorobenzene, benzoin ethyl ether, 2-ethyl anthraquinone, l-~chloroethyl~-naphthalene, desyl chloride, chlorendic anhydride, naphthalene sulfonyl chloride and 2-bromoethyl ethyl ether. The amount of photoinitiator added can be ~rom about 0.2% to about 10 by weight of the coating composition, with a preferred range from about 1% to about 4~ by weight.
Photoinitiation synergists can be added, if desi-red, to the ultraviolet curable coating compositions. Photo-initiation synergists serve to enhance the initiation efficiency of the photoinitiators. The preferred synergists are the chain transfer agents, such as the tertiary alcohol-amines and substituted morpholines, triethanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine and N-methylmorpholine. The amount of photoinitiation synergist added can be from about 0.2% to about 10~ by weight of the * Trade Mark 2~8 coating composition with a preferred range of from abou~ 3 to about 4% by weight.
In the preparation of the dispersion of microcap-sules of this invention, a hydrophobic emulsion component is prepared by dissolvin~ the first wall-forming material in an hydrophobic liquid, as for example, an oil. If the microcapsules are to be used in preparing carbonless copy papers, a chromogenic material i5 dissolved in a carrier oil.
The hydrophilic emulsion component is prepared by dissolvin~ or dispersing an emulsifier and at least one radiation curable polar compound in water. Any of the known emulsifiers can be used including polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose and Triton N-lOl* (Rohm and Haas, Philadelphia, Pa.)O The water from the radiation curable hydrophilic liquid increases the polarity of the hydrophilic emulsion component to a point where the two phases, hydrophobic and hydrophilic are essen-tially insoluble in each other, thus permitting formation 2~ of an emulsion. At this pointr the second wall-forming material sol~ble in the hydrophilic emulsion component can also be dissolved in the hydrophilic emulsion component.
Alternatively, the second wall-forming material can be added to the emulsion formed during the emulsification step. To facilitate mixing the second wall-~orming material may be dissolved in additional radiation curable hydrophilic liquid prior to addition to the emulsion.
Alternatively, the second wall-forming material may be added to the h~drophobic emulsion component. In this case, the second wall-forming material is soluble in the hydrophobic emulsion component. Some second wall-~orming materials, ~or example, diethylene triamine, are soluble in both the hydrophobic and hydrophilic emulsion * Trade Mark -!, . - 13-_ ..
2~8 components. These materials can be added to the hydrophobic and/or hydrophilic emulsion components or to the emulsion formed by the emulsification step.
Preparation of each of these components is easily accomplished by stirring together at room temperature the materials of each component. The Brookfield viscosity of the hydrophilic emu]sion component can be from about 0.5 cps. to about 1,000 cps. The preferred viscosity is about 1 cps. to about 500 cps. a~d the most preferred viscosity is from about 1 cps. to about 50 cops.
The hydrophobic and hydrophilic emulsion compo-nents prepared as above are mixed together with high agita-tion to form an emulsion containing droplets of the hydrophobic emulsion component dispersed in the continuous hydrophilic emulsion component.
The term "soluble" as used herein is intended to describe wall-forming materials which are only partially soluble in and give hazy solutions in the radiation curable hydrophilic liquid as well as those which are completely soluble in the radiation curable hydrophilic liquid.
-13a-After emulsification, the emulsion is stirred for a period of a~out 3 hours to about 16 hours at a temperature of about 0 C to about 70 & , pre-ferably ro~m temperature to about 40& , to allow the firs-t and secorld wall-fonming materials to react and form a dis~ersion of microcapsules having capsule walls which are substantially impermeable to both the hydrophilic and hydrophobic enLlsion components used to form the microcapsules. The microcapsules should be fr~m about 0.1 micron to about 50 microns in diameter.
A preferred range is from about 5 to 15 microns.
After formation of the microcapsules is complete, the photoionitiator is added. m e microcapsular coating compositions prepared according to this invention can contain from about 20~ to about 60%, by weight, wa-ter. The preferred range is from akout 30% to about 50% water. The coating co~lposition of this inv~tion can be applied to a substrate, such as paper or a plastic filn ~y any of the ccmmon paper coating processes such as roll, air knife, or blade coating, or by any of the ccmmon printing processes, such as offset, gravure, or flexographic printing. The rheological properties, particularly, the viscosity of the coating compositions~ can be adjusted for each type of application by proper selection of the type, molecular wei~ht and relative amounts of the liquid radiation curable compounds and the amount of water present.
ThPse coating ccmpositions can be set to a solid film by a cc~bination o ultraviolet radiation and infra-red radiation. A typical ultraviolet source suitable for this t~pe of curing process is a Hanovia 200 watt medium pressure mercury lamp which emits both ultraviolet and infra-red radiation. Polymeri-zation efficiencies of the coating composition æ e dependent on such para~eters as the nature of the radiation curable polar comFounds, atm~sphere in contact with the coating, quantum efficiency of the radiation absorbed, thickness of coating and inhibitory effects of the various materials in the compositiQn.
The ~ater present on the coating composition is e~aporated by the ener~y of the in~ra-red radiation.
~9z~
The coating weight of the solid film containing the microcapsules can be from about 0.2 pounds to about 12 pounds per 3300 square feet. The preferred coating weight range is from about 4 to about 7 pounds per 3300 square feet.
The following examples further illustrate but do not limit the invention:
Example 1 An aqueous phase (hydrophilic emulsion component) was prepared as follows:
In a 250 ml. beaker with magnetic stirring bar on a magnetic stirrlng hot plate, 40 grams of distilled water, 60 grams of a radiation curable compound, 2-hydroxyethyl acrylate, 0.5 gram of carboxymethyl cellulose (grade 7L2, Hercules, Inc., Wilmington, Delaware) and 0.5 gram of hydroxy-propyl cellulose (Klucel L*, Hercules, Inc.) were mixed to-gether and then heated to 60C until the solid ingredients were dissolved. After cooling the mixture to room tempera-ture, 0.1 gram of Turkey Red Oil (Sulfonated castor oil) and 0.5 gram of trie~hylene tetramine were stirred in.
An oil phase (hydrophobic emulsion component) was prepared as follows:
In an 100 ml. beaker with magnetic stirring bar on a magnetic stirring hot plate, 24 grams of monoisopropyl-biphenyl, 0.83 gram of 3-(N,N-diethylamino-7-(N,N-dibenzyl-amino)fluoran, and 0.08 gram of 2,3-(1'-phenyl-3'-methyl)-7-(N,N-diethylamino)-4-spirophthalidochromene were heated with stirring at 90C for one hour to dissolve the above color precursors. To this solution at room temperature, 3 grams of an aliphatic polyisocyanate (desmodure N-100), 3 grams of an aromatic polyisocyanate (NIAX SF-50) and 0.9 gram of a polyol (Quadrol) were added with stirring until homogeneous.
* Trade Mark ~-~ -15-, , 2~
The oil phase in the 100 ml. beaker was added slowly over a one minute period to the first solution in a Waring Blender on low speed, and stirred for five minutes more. A mint green colored mixture resulted in which capsules 1 to 4 microns in diameter were observed through a 450X microscope. The mixture was placed in a 60C hot water bath for 30 minutes. An off-white disper--15a-.,~ . .
~, ~
i:
resulted, with no apparent chanye in capsule size. 1.5 grams of azobisiso~u-tyronitrile photoinitiator was added, a drawdown was made on 13.5 lb. per 1300 square feet paper rawstock wi-th a No. 16 Mayer rod and exposed to a 200 ~att mercury ultraviolet lamp at a distance of 4 inches for one minute. Ihe coating was smooth and tack-free. When pressure imaged against a kaolin/phenolic resin coated CF sheet, a clear, green image was formed on the CF sheet.
Example 2 The exa~lple above was repeated except that 0.5 gram of polyvinyl alcohol (grade 50-05, E. I. duPont de Nemours & Co., Inc., Wilmington, Del.) was used in place of hydroxypropyl cellulose. Capsules before heat c~ring were 1 to ~
microns as determined by microscopic e~amination of the dispersion. The image formed was clear but not as intense as in Example 1.
Example 3 An aqueous phase was produced by s-tirring together 90 grams of a radia-tion curable ccmpound, N-~ethylol acrylamide (60% solution in water, from Proctor Chemical Company, Salisbury, N.C. 28144), 0.5 gram of a dispersing agent(Triton N-101 - Rohm and Haas Company, Philadelphia, Pennsylvania), 0.8 gram of sodium carbonate (anhydrous) and 9.3 grams of diethylene triamine, An oil solution was prepared by dissolving the following color precur-sors into 19 grams of MIPB (monoisopropylbiphenyl) with heating to 85C: 0.40 gram of crystal violet lactone, 0.10 gram of 3,3-bis(l'-ethyl-2'-methylindol-3-yl) phthalide, 0.17 gram of 2,3-(1'-phenyl-3'-methyl)-7-~N,N-diethylamino)-4-spirophthalidochromene, and 0.05 gram of 3-N,N~diethylamino-7-~N,N-dikenzylamino) fluoran. When the solution was cooled and filtered, 3 grams of terephthaloyl chloride were dissolved. The oil solution was added to the aq~leous phase in a Wari~g Blender operating a high speed over a 30 second period and was stirred for 5 minutes more. Microscopic examination of the fluid, gray muxture skK~
capsules of 2 to 10 micron size. Few agglcmerates were present. A 0.1 gram of benzoin me~hyl ether phoboinitiator was stirred in. m e mixture was coated on 13 Ib./1300 square feet form bond using a No. 16 Mayer rcd and e~posed bD an ultraviolet lamp as in Example 1. When pressure ima~ed against kaolin/phenolic coated CF paper with a ballpoint pen, a purple image was formed.
Example 4 ~n aqueous phase was produced by stirring together 90 grams of a radia-tion curable compound, N-methylol acrylamiae (60~ solution in water, from Proctor Chemical Ccmpany, Salisbury, N.C. 28144), 1.0 gram of a dispersing agent ~Triton N-101 - Rohm and Haas Company, Philadelphia, Pennsylvania), and 1.59 gram of sodium carbonate (anhydrous).
An oil solution contail~ing color precursors was prepared as in EXa~ple
The radiation curable hydr~philic liquids useful in the practice of this invention ccmprise the free radical polymeriza~Le ethylenically unsaturated organic compounds in water solution. These compounds contain at least one terminal ethylenically unsaturated group per molecule. These cc~pounds ar2-radiation curable polar compounds and their aqueous solutions function in part as the continuous hydrophilic phase during the in situ preparat,ion of the microcapsules and as a dispersing medium for the microcapsules and other ingredients of the coating composition prior to the coating operation. They are curable to a solid resin when exposed in the presence of a photoinitiator to ultraviolet radiation containing additionally some infra-red radiation. The cured resin acts as a binder for the microcapsules to a substrate such as pa~er.
E~amples of useful radiation curable polar compounds are N-vinyl-2-pyrrolidonel acrylamide, h~droxyethyl acrylate, hydroxypropyl acrylate~ diaoe tone acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, acrylic acid, polyethylene glycol monoacrylates~ polye-thylene glycol polyacrylates, polyvinyl alcohol acrylate, starch acrylate, cellulose acrylate, quaternary ammonium salt deriva-25 tives of dimethyl2m moeth~l acrylate and methacrylate and muxtures thereof. The abo~e radiation curable polar ocmpounds are liquids. ~owever, solid radiation curable polar com~ounds, such a N-methylol acrylamide, can ke dissolved in ~ater and used as the radiation curable hydrophilic liquid. The preferred polar compounds are ~-methylol acrylamide and hydroxyethyl acryla~e.
Z~8 The first wall-forming material is soluble in and forms a part of a hydraphobic emulsion component. It may be either a polyisocyanate or a polyacid halide compound.
The polyisocyanates useful in this invention are the ali-phatic and aromatic polyisocyanates which include, for example, (a) diisocyanates, such as m-phenylmethane-4,4'-diisocyanate;
(b) triisocyanates, such as toluene-2,4,6-triisocyanate; (c) tetraisocyanates, such as 2,2,5,5- tetraisocyanate; (d) isocyanate prepolymers produced and sold by Mobay Chemical Company, Pitt~burg, Pennsylvania, Mondur C~-75* (75~ of a high molecular weight adduct of toluene isocyanate and 25%
of ethyl acetate produced and sold by Mobay Chemical Company) DesmodurN-100* (a biuret oontaining aliphatic isocyanate also produced and sold by Mobay Chemical Company) and NIAX
SF-50* (a trifunctional aromatic polyurethane prepolymer having a free isocyanate content of 32.5~ made and sold by Union Carbide Corporation, New York, N.Y.). Mixtures of these compounds may be used.
The polyacid halides include terephthalyl dichlo-ride, adipyl di~hloride, 1,3,5-benzenetricarboxylic acid trichloride, oxalyl dibromide, 1,4-benzenedisulfonyl dichlo-ride and 4,4'-biphenyldisulfonyl dichloride~ Mixtures of these compounds may also be used. The preferred first wall-forming materials are NIAX SF-50, ~esmodur N-100 and tereph-thalyl dichloride.
The second wall-forming material can ~e selected from the group consisting of polyols, polythiols, polyamines, acid anhydrides, and polycarboxylic acids and mixtures thereof. The polyols include for example, glycerin, resor-cinol, 1,3-naphthalenediol, bisphenol A/1,3-propylene blycol, 1,5-pentanediol and the like. Examples of polythiols are thioglycol and thioglycol condensates. Polyamines include, for example, p-phenylenediamine, diethylene triamine, * Trade Mark N,N,N',N',-tetrakis-[2-hydroxypropyl) ethylene diamine (Quadrol*-Wyandotte Chemic~l Corp., Wyandotte, Michigan) and phthalamide and the like. Examples of acid anhydrides includ~ maleic anhydride and succinic anhydride. Examples of polycarboxylic acids are malonic acid, succinic acid and terephthalic acid. The preferred second wall-forming materials are Quadrol and diethylene triamine.
A photoinitiator is added to the coating compo-sition to permit curing by ultraviolet radiation. A wide variety of photoinitiators are available which serve well in the system described in this invention. The preferr~d photoinitiators are the benzoin alkyl ethers, such as Vicure 30*, benzoin methyl ether, ~, a azobisisobutyroni-trile, ar a-diethoxyacetophene and ~inc carbonate. Other photoinitiators which can be used are benzophenone, 4,4'-bis-(dimethylamino~benzophenone, ferrocene, xanthone, thi-oxanthane, decabromodiphenyl oxide, pentabromomonochloro-cyclohexane, pentachlorobenzene, benzoin ethyl ether, 2-ethyl anthraquinone, l-~chloroethyl~-naphthalene, desyl chloride, chlorendic anhydride, naphthalene sulfonyl chloride and 2-bromoethyl ethyl ether. The amount of photoinitiator added can be ~rom about 0.2% to about 10 by weight of the coating composition, with a preferred range from about 1% to about 4~ by weight.
Photoinitiation synergists can be added, if desi-red, to the ultraviolet curable coating compositions. Photo-initiation synergists serve to enhance the initiation efficiency of the photoinitiators. The preferred synergists are the chain transfer agents, such as the tertiary alcohol-amines and substituted morpholines, triethanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine and N-methylmorpholine. The amount of photoinitiation synergist added can be from about 0.2% to about 10~ by weight of the * Trade Mark 2~8 coating composition with a preferred range of from abou~ 3 to about 4% by weight.
In the preparation of the dispersion of microcap-sules of this invention, a hydrophobic emulsion component is prepared by dissolvin~ the first wall-forming material in an hydrophobic liquid, as for example, an oil. If the microcapsules are to be used in preparing carbonless copy papers, a chromogenic material i5 dissolved in a carrier oil.
The hydrophilic emulsion component is prepared by dissolvin~ or dispersing an emulsifier and at least one radiation curable polar compound in water. Any of the known emulsifiers can be used including polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose and Triton N-lOl* (Rohm and Haas, Philadelphia, Pa.)O The water from the radiation curable hydrophilic liquid increases the polarity of the hydrophilic emulsion component to a point where the two phases, hydrophobic and hydrophilic are essen-tially insoluble in each other, thus permitting formation 2~ of an emulsion. At this pointr the second wall-forming material sol~ble in the hydrophilic emulsion component can also be dissolved in the hydrophilic emulsion component.
Alternatively, the second wall-forming material can be added to the emulsion formed during the emulsification step. To facilitate mixing the second wall-~orming material may be dissolved in additional radiation curable hydrophilic liquid prior to addition to the emulsion.
Alternatively, the second wall-forming material may be added to the h~drophobic emulsion component. In this case, the second wall-forming material is soluble in the hydrophobic emulsion component. Some second wall-~orming materials, ~or example, diethylene triamine, are soluble in both the hydrophobic and hydrophilic emulsion * Trade Mark -!, . - 13-_ ..
2~8 components. These materials can be added to the hydrophobic and/or hydrophilic emulsion components or to the emulsion formed by the emulsification step.
Preparation of each of these components is easily accomplished by stirring together at room temperature the materials of each component. The Brookfield viscosity of the hydrophilic emu]sion component can be from about 0.5 cps. to about 1,000 cps. The preferred viscosity is about 1 cps. to about 500 cps. a~d the most preferred viscosity is from about 1 cps. to about 50 cops.
The hydrophobic and hydrophilic emulsion compo-nents prepared as above are mixed together with high agita-tion to form an emulsion containing droplets of the hydrophobic emulsion component dispersed in the continuous hydrophilic emulsion component.
The term "soluble" as used herein is intended to describe wall-forming materials which are only partially soluble in and give hazy solutions in the radiation curable hydrophilic liquid as well as those which are completely soluble in the radiation curable hydrophilic liquid.
-13a-After emulsification, the emulsion is stirred for a period of a~out 3 hours to about 16 hours at a temperature of about 0 C to about 70 & , pre-ferably ro~m temperature to about 40& , to allow the firs-t and secorld wall-fonming materials to react and form a dis~ersion of microcapsules having capsule walls which are substantially impermeable to both the hydrophilic and hydrophobic enLlsion components used to form the microcapsules. The microcapsules should be fr~m about 0.1 micron to about 50 microns in diameter.
A preferred range is from about 5 to 15 microns.
After formation of the microcapsules is complete, the photoionitiator is added. m e microcapsular coating compositions prepared according to this invention can contain from about 20~ to about 60%, by weight, wa-ter. The preferred range is from akout 30% to about 50% water. The coating co~lposition of this inv~tion can be applied to a substrate, such as paper or a plastic filn ~y any of the ccmmon paper coating processes such as roll, air knife, or blade coating, or by any of the ccmmon printing processes, such as offset, gravure, or flexographic printing. The rheological properties, particularly, the viscosity of the coating compositions~ can be adjusted for each type of application by proper selection of the type, molecular wei~ht and relative amounts of the liquid radiation curable compounds and the amount of water present.
ThPse coating ccmpositions can be set to a solid film by a cc~bination o ultraviolet radiation and infra-red radiation. A typical ultraviolet source suitable for this t~pe of curing process is a Hanovia 200 watt medium pressure mercury lamp which emits both ultraviolet and infra-red radiation. Polymeri-zation efficiencies of the coating composition æ e dependent on such para~eters as the nature of the radiation curable polar comFounds, atm~sphere in contact with the coating, quantum efficiency of the radiation absorbed, thickness of coating and inhibitory effects of the various materials in the compositiQn.
The ~ater present on the coating composition is e~aporated by the ener~y of the in~ra-red radiation.
~9z~
The coating weight of the solid film containing the microcapsules can be from about 0.2 pounds to about 12 pounds per 3300 square feet. The preferred coating weight range is from about 4 to about 7 pounds per 3300 square feet.
The following examples further illustrate but do not limit the invention:
Example 1 An aqueous phase (hydrophilic emulsion component) was prepared as follows:
In a 250 ml. beaker with magnetic stirring bar on a magnetic stirrlng hot plate, 40 grams of distilled water, 60 grams of a radiation curable compound, 2-hydroxyethyl acrylate, 0.5 gram of carboxymethyl cellulose (grade 7L2, Hercules, Inc., Wilmington, Delaware) and 0.5 gram of hydroxy-propyl cellulose (Klucel L*, Hercules, Inc.) were mixed to-gether and then heated to 60C until the solid ingredients were dissolved. After cooling the mixture to room tempera-ture, 0.1 gram of Turkey Red Oil (Sulfonated castor oil) and 0.5 gram of trie~hylene tetramine were stirred in.
An oil phase (hydrophobic emulsion component) was prepared as follows:
In an 100 ml. beaker with magnetic stirring bar on a magnetic stirring hot plate, 24 grams of monoisopropyl-biphenyl, 0.83 gram of 3-(N,N-diethylamino-7-(N,N-dibenzyl-amino)fluoran, and 0.08 gram of 2,3-(1'-phenyl-3'-methyl)-7-(N,N-diethylamino)-4-spirophthalidochromene were heated with stirring at 90C for one hour to dissolve the above color precursors. To this solution at room temperature, 3 grams of an aliphatic polyisocyanate (desmodure N-100), 3 grams of an aromatic polyisocyanate (NIAX SF-50) and 0.9 gram of a polyol (Quadrol) were added with stirring until homogeneous.
* Trade Mark ~-~ -15-, , 2~
The oil phase in the 100 ml. beaker was added slowly over a one minute period to the first solution in a Waring Blender on low speed, and stirred for five minutes more. A mint green colored mixture resulted in which capsules 1 to 4 microns in diameter were observed through a 450X microscope. The mixture was placed in a 60C hot water bath for 30 minutes. An off-white disper--15a-.,~ . .
~, ~
i:
resulted, with no apparent chanye in capsule size. 1.5 grams of azobisiso~u-tyronitrile photoinitiator was added, a drawdown was made on 13.5 lb. per 1300 square feet paper rawstock wi-th a No. 16 Mayer rod and exposed to a 200 ~att mercury ultraviolet lamp at a distance of 4 inches for one minute. Ihe coating was smooth and tack-free. When pressure imaged against a kaolin/phenolic resin coated CF sheet, a clear, green image was formed on the CF sheet.
Example 2 The exa~lple above was repeated except that 0.5 gram of polyvinyl alcohol (grade 50-05, E. I. duPont de Nemours & Co., Inc., Wilmington, Del.) was used in place of hydroxypropyl cellulose. Capsules before heat c~ring were 1 to ~
microns as determined by microscopic e~amination of the dispersion. The image formed was clear but not as intense as in Example 1.
Example 3 An aqueous phase was produced by s-tirring together 90 grams of a radia-tion curable ccmpound, N-~ethylol acrylamide (60% solution in water, from Proctor Chemical Company, Salisbury, N.C. 28144), 0.5 gram of a dispersing agent(Triton N-101 - Rohm and Haas Company, Philadelphia, Pennsylvania), 0.8 gram of sodium carbonate (anhydrous) and 9.3 grams of diethylene triamine, An oil solution was prepared by dissolving the following color precur-sors into 19 grams of MIPB (monoisopropylbiphenyl) with heating to 85C: 0.40 gram of crystal violet lactone, 0.10 gram of 3,3-bis(l'-ethyl-2'-methylindol-3-yl) phthalide, 0.17 gram of 2,3-(1'-phenyl-3'-methyl)-7-~N,N-diethylamino)-4-spirophthalidochromene, and 0.05 gram of 3-N,N~diethylamino-7-~N,N-dikenzylamino) fluoran. When the solution was cooled and filtered, 3 grams of terephthaloyl chloride were dissolved. The oil solution was added to the aq~leous phase in a Wari~g Blender operating a high speed over a 30 second period and was stirred for 5 minutes more. Microscopic examination of the fluid, gray muxture skK~
capsules of 2 to 10 micron size. Few agglcmerates were present. A 0.1 gram of benzoin me~hyl ether phoboinitiator was stirred in. m e mixture was coated on 13 Ib./1300 square feet form bond using a No. 16 Mayer rcd and e~posed bD an ultraviolet lamp as in Example 1. When pressure ima~ed against kaolin/phenolic coated CF paper with a ballpoint pen, a purple image was formed.
Example 4 ~n aqueous phase was produced by stirring together 90 grams of a radia-tion curable compound, N-methylol acrylamiae (60~ solution in water, from Proctor Chemical Ccmpany, Salisbury, N.C. 28144), 1.0 gram of a dispersing agent ~Triton N-101 - Rohm and Haas Company, Philadelphia, Pennsylvania), and 1.59 gram of sodium carbonate (anhydrous).
An oil solution contail~ing color precursors was prepared as in EXa~ple
3 and 3 grams of terephthaloyl chloride were dissolved therein. The oil solution was added to the aqueous phase in a Waring Blender operating at high speed over a 30 second period and was stirred for 3 minutes more~ To the Waring Blender mixture, 6.19 grams of diethylene triamine was added over a 15 seoond period and the speed was reduced to low speed for 5 minutes re. Microsoopic examina-tion of the fluid, light pink mixture showed capsules of approximately 2 to 10micron size. Few agglcmerates were present. 0.1 gram of kenzoin methyl ether photoinitiator was stirred in. The ~ux~ure was coated on 13 Ib./1300 square feet form bond using a No. 16 Mayer rod and exposed to an ultraviolet lamp as in Example 1. When pressure imaged against kaolin/phenolic coa-ted CF paper with a ballpoint pen, a purple image was formed.
i
i
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for producing a liquid coating composition for use in the manufacture of pressure-sensitive carbonless transfer papers, said liquid coating composition being characterized by being curable by radiation to a dry, solid, tack-free resin, said radiation being a combination of ultraviolet radiation and infra-red radiation and said liquid coating composition being further characterized by containing microcapsules having a hydrophobic core material, com-prising the steps of:
a) preparing an emulsion containing droplets of hydrophobic emulsion component dispersed in a hydrophilic emulsion component, said hydrophobic emulsion component comprising a hydrophobic liquid, said hydrophobic emulsion component additionally contain-ing a first wall-forming material capable of reacting by conden-sation polymerization with a second wall-forming material to form a polymeric capsule wall, said first wall-forming material being soluble in said hydrophobic emulsion component, said polymeric capsule wall being substantially insoluble in said hydrophilic and said hydrophobic emulsion components, said hydrophilic emulsion component comprising an emulsifier dispersed in a radiation curable hydrophobic liquid, said radiation curable hydrophilic liquid comprising water and at least one radiation curable polar compound, said emulsion additionally containing said second wall-forming material;
b) subjecting said emulsion, with mixing, to temperature conditions for a period of time sufficient to substantially completely poly-merize said first and second wall-forming materials thereby forming a dispersion of microcapsules in said hydrophilic emulsion component, said microcapsules having capsule walls substantially impermeable to said hydrophilic and said hydrophobic emulsion components; and e) adding a photoinitiator to said dispersion of microcapsules.
a) preparing an emulsion containing droplets of hydrophobic emulsion component dispersed in a hydrophilic emulsion component, said hydrophobic emulsion component comprising a hydrophobic liquid, said hydrophobic emulsion component additionally contain-ing a first wall-forming material capable of reacting by conden-sation polymerization with a second wall-forming material to form a polymeric capsule wall, said first wall-forming material being soluble in said hydrophobic emulsion component, said polymeric capsule wall being substantially insoluble in said hydrophilic and said hydrophobic emulsion components, said hydrophilic emulsion component comprising an emulsifier dispersed in a radiation curable hydrophobic liquid, said radiation curable hydrophilic liquid comprising water and at least one radiation curable polar compound, said emulsion additionally containing said second wall-forming material;
b) subjecting said emulsion, with mixing, to temperature conditions for a period of time sufficient to substantially completely poly-merize said first and second wall-forming materials thereby forming a dispersion of microcapsules in said hydrophilic emulsion component, said microcapsules having capsule walls substantially impermeable to said hydrophilic and said hydrophobic emulsion components; and e) adding a photoinitiator to said dispersion of microcapsules.
2. The process of claim 1 wherein said radiation curable polar compound has at least one terminal ethylenic group per molecule.
3. The process of claim 1 wherein said hydrophobic emulsion component includes a chromogenic material, said chromogenic material being a color precursor of the electron-donor type.
4. The process of claim 1 wherein said first wall-forming material is an oil soluble compound selected from the group consisting of poly-isocyanates and polyacid halides.
5. The process of claim 2 wherein said polar compound having said at least one terminal ethylenic group per molecule is selected from the group consisting of N-vinyl-2-pyrrolidone, acrylamide, N-methylol-acrylamide, hydroxyethyl acrylate, hydroxypropyl acrylate, diacetone acrylamide, 2-acryl-amido-2-methylpropanesulfonic acid, acrylic acid, polyethylene glycol monoacrylates, polyethyleneglycol polyacrylates, polyvinyl alcohol acrylate, starch acrylate, cellulose acrylate, quaternary ammonium salt derivatives of dimethylaminoethyl acrylate and methacrylate and mixtures thereof.
6. The process of Claim 1 wherein said second wall-forming material is selected from the group consisting of polyols, polythiols, polyamines, polycarboxylic acids and mixtures thereof.
-19a-
-19a-
7. The process of claim 1 wherein said liquid coating composition contains between about 20% to about 60% by weight of water.
8. A process for producing a liquid coating composition for use in the manufacture of pressure-sensitive carbonless transfer papers, said liquid coating composition being characterized by being curable by radiation to a dry, solid, tack-free resin, said radiation being a combination of ultraviolet radiation and infra-red radiation, said liquid coating composition being further characterized by containing microcapsules having a hydrophobic core material, comprising the steps of:
a) preparing an emulsion containing droplets of a hydrophobic emulsion component dispersed in a hydrophilic emulsion component, said hydrophobic emulsion component comprising a chromogenic material in a hydrophobic liquid, said chromogenic material being soluble in said hydrophobic liquid, said hydrophobic emulsion component additonally containing a first-wall forming material capable of reacting by condensation polymerization with a second wall-forming material to form a polymeric capsule wall, said first forming material being soluble in said hydrophobic emulsion component, said polymeric capsule wall being substantially insoluble in said hydrophilic and said hydrophobic emulsion compo-nents, said hydrophilic emulsion component comprising an emulsifier dispersed in a radiation curable hydrophilic liquid, said radiation curable hydrophilic liquid comprising water and at least one polar compound selected from the group consisting of N-vinyl-2-pyrrolidone, acrylamide, N-methylolacrylamide, hydroxyethyl acrylate, hydroxypropyl acrylate, diacetone acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, polyethylene glycol monoacrylates, polyethylene glycol polyacrylate, polyvinyl alcohol acrylate, starch acrylate, cellulose acrylate, quarternary ammonium salt derivatives of dimethylaminoethyl acrylate and methacrylate and mixtures thereof, said emulsion additionally containing said second wall-forming material;
b) subjecting said emulsion, with stirring, to a temperature of from about 0°C to about 70°C for a period of time from about 1 hour to about 16 hours, said temperature and said time being sufficient to substantially completely polymerize said first and second wall-forming materials thereby forming a dispersion of microcapsules in said hydrophilic emulsion component, said microcapsules having capsule walls substantially impermeable to said hydrophilic and said hydrophobic emulsion components; and c) adding a photoinitiator to said dispersion of microcapsules.
a) preparing an emulsion containing droplets of a hydrophobic emulsion component dispersed in a hydrophilic emulsion component, said hydrophobic emulsion component comprising a chromogenic material in a hydrophobic liquid, said chromogenic material being soluble in said hydrophobic liquid, said hydrophobic emulsion component additonally containing a first-wall forming material capable of reacting by condensation polymerization with a second wall-forming material to form a polymeric capsule wall, said first forming material being soluble in said hydrophobic emulsion component, said polymeric capsule wall being substantially insoluble in said hydrophilic and said hydrophobic emulsion compo-nents, said hydrophilic emulsion component comprising an emulsifier dispersed in a radiation curable hydrophilic liquid, said radiation curable hydrophilic liquid comprising water and at least one polar compound selected from the group consisting of N-vinyl-2-pyrrolidone, acrylamide, N-methylolacrylamide, hydroxyethyl acrylate, hydroxypropyl acrylate, diacetone acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, polyethylene glycol monoacrylates, polyethylene glycol polyacrylate, polyvinyl alcohol acrylate, starch acrylate, cellulose acrylate, quarternary ammonium salt derivatives of dimethylaminoethyl acrylate and methacrylate and mixtures thereof, said emulsion additionally containing said second wall-forming material;
b) subjecting said emulsion, with stirring, to a temperature of from about 0°C to about 70°C for a period of time from about 1 hour to about 16 hours, said temperature and said time being sufficient to substantially completely polymerize said first and second wall-forming materials thereby forming a dispersion of microcapsules in said hydrophilic emulsion component, said microcapsules having capsule walls substantially impermeable to said hydrophilic and said hydrophobic emulsion components; and c) adding a photoinitiator to said dispersion of microcapsules.
9. A process for producing a pressure-sensitive transfer paper comprising the steps of:
a) preparing an emulsion containing droplets of a hydrophobic emulsion component dispersed in a hydrophilic emulsion component, said hydrophobic emulsion component comprising a chromogenic material in a hydrophobic liquid, said chromogenic material being soluble in said hydrophobic liquid, said hydrophobic emulsion component additionally containing a first wall-forming material capable of reacting by condensation polymerization with a second wall-forming material to form a polymeric capsule wall, said first wall-forming material being soluble in said hydrophobic emulsion component, said polymeric capsule wall being substantially insoluble in said hydro-philic and said hydrophobic emulsion components, said hydrophilic emulsion component comprising an emulsifier dispersed in a radiation curable hydrophilic liquid, said radiation curable liquid comprising water and at least one radiation curable polar component, said emulsion additionally containing said second wall-forming material;
b) subjecting said emulsion, with mixing, to temperature conditions for a period of time sufficient to polymerize said first and second wall-forming materials thereby forming a dispersion of microcapsules in said hydrophilic emulsion component, said microcapsules having a hydrophobic core material and capsule walls substantially impermeable to said hydrophilic and said hydro-phobic emulsion components;
e) adding a photoinitiator to said dispersion of microcapsules;
d) applying said dispersion of said microcapsules to a paper substrate;
and e) setting said dispersion of said microcapsules by subjecting said dispersion on said paper substrate to radiation for a period of time sufficient to cure said radiation curable hydrophilic liquid to a dry, solid, tack-free resinous film on said paper substrate, said radiation being a combination of ultraviolet radiation and infra-red radiation.
a) preparing an emulsion containing droplets of a hydrophobic emulsion component dispersed in a hydrophilic emulsion component, said hydrophobic emulsion component comprising a chromogenic material in a hydrophobic liquid, said chromogenic material being soluble in said hydrophobic liquid, said hydrophobic emulsion component additionally containing a first wall-forming material capable of reacting by condensation polymerization with a second wall-forming material to form a polymeric capsule wall, said first wall-forming material being soluble in said hydrophobic emulsion component, said polymeric capsule wall being substantially insoluble in said hydro-philic and said hydrophobic emulsion components, said hydrophilic emulsion component comprising an emulsifier dispersed in a radiation curable hydrophilic liquid, said radiation curable liquid comprising water and at least one radiation curable polar component, said emulsion additionally containing said second wall-forming material;
b) subjecting said emulsion, with mixing, to temperature conditions for a period of time sufficient to polymerize said first and second wall-forming materials thereby forming a dispersion of microcapsules in said hydrophilic emulsion component, said microcapsules having a hydrophobic core material and capsule walls substantially impermeable to said hydrophilic and said hydro-phobic emulsion components;
e) adding a photoinitiator to said dispersion of microcapsules;
d) applying said dispersion of said microcapsules to a paper substrate;
and e) setting said dispersion of said microcapsules by subjecting said dispersion on said paper substrate to radiation for a period of time sufficient to cure said radiation curable hydrophilic liquid to a dry, solid, tack-free resinous film on said paper substrate, said radiation being a combination of ultraviolet radiation and infra-red radiation.
10. The process of claim 9 wherein said chromogenic material is a color precursor of the electron-donor type.
11. The process of claim 9 wherein said combination of ultraviolet radiation and infra-red radiation is obtained from a mercury vapor lamp.
12. The process of claim 9 wherein said dry, solid, tack-free film is from about 0.5 pounds to about 12 pounds per 3300 square feet.
13. A radiation curable liquid coating composition for use in the manufacture of microcapsules coated papers, said liquid coating composition being charac-terized by being curable by radiation to a dry, solid, tack-free resin, said radiation being a combination of ultraviolet radiation and infra-red radia-tion, said liquid coating composition being further characterized by con-taining microcapsules having a hydrophobic core material, said microcapsules being dispersed in a radiation curable hydrophilic liquid, said hydrophilic liquid comprising water and at least one polar radiation curable compound, said liquid coating composition additionally containing a photoinitiator.
14. The coating composition of claim 13 wherein said microcapsules have capsule walls comprising a condensation polymerization reaction product of a first wall-forming material and a second wall-forming material.
15. The coating composition of claim 13 wherein said hydrophobic core material is a non-polar oil containing a chromogenic material dissolved therein.
16. A pressure-sensitive carbonless transfer paper prepared by the process of
11. The process of claim 9 wherein said combination of ultraviolet radiation and infra-red radiation is obtained from a mercury vapor lamp.
12. The process of claim 9 wherein said dry, solid, tack-free film is from about 0.5 pounds to about 12 pounds per 3300 square feet.
13. A radiation curable liquid coating composition for use in the manufacture of microcapsules coated papers, said liquid coating composition being charac-terized by being curable by radiation to a dry, solid, tack-free resin, said radiation being a combination of ultraviolet radiation and infra-red radia-tion, said liquid coating composition being further characterized by con-taining microcapsules having a hydrophobic core material, said microcapsules being dispersed in a radiation curable hydrophilic liquid, said hydrophilic liquid comprising water and at least one polar radiation curable compound, said liquid coating composition additionally containing a photoinitiator.
14. The coating composition of claim 13 wherein said microcapsules have capsule walls comprising a condensation polymerization reaction product of a first wall-forming material and a second wall-forming material.
15. The coating composition of claim 13 wherein said hydrophobic core material is a non-polar oil containing a chromogenic material dissolved therein.
16. A pressure-sensitive carbonless transfer paper prepared by the process of
claim 11.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US81155677A | 1977-06-30 | 1977-06-30 | |
| US912,376 | 1978-06-05 | ||
| US05/912,376 US4228216A (en) | 1978-06-05 | 1978-06-05 | Production of radiation curable microcapsular coating compositions, pressure-sensitive transfer paper and its production |
| US811,556 | 1991-12-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1109258A true CA1109258A (en) | 1981-09-22 |
Family
ID=27123491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA305,776A Expired CA1109258A (en) | 1977-06-30 | 1978-06-19 | Process for the production of novel radiation curable microcapsular coating compositions |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS6059874B2 (en) |
| CA (1) | CA1109258A (en) |
| DE (1) | DE2828136A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5610489A (en) * | 1979-07-06 | 1981-02-02 | Fuji Photo Film Co Ltd | Manufacture of pressure-sesitive recording sheet |
| JPS5777589A (en) * | 1980-11-04 | 1982-05-14 | Mitsubishi Paper Mills Ltd | Capsule sheet for non-carbon copying |
| JPS6129903A (en) * | 1984-07-20 | 1986-02-12 | Nippon Steel Corp | Material temperature controller of heat processing furnace |
| JPS6129904A (en) * | 1984-07-20 | 1986-02-12 | Nippon Steel Corp | Material temperature controller of thermal processing furnace |
| JPS6319002A (en) * | 1986-07-11 | 1988-01-26 | Omron Tateisi Electronics Co | Temperature adjusting device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4091122A (en) * | 1976-05-07 | 1978-05-23 | The Mead Corporation | Process for producing pressure-sensitive copy sheets using novel radiation curable coatings |
-
1978
- 1978-06-19 CA CA305,776A patent/CA1109258A/en not_active Expired
- 1978-06-27 DE DE19782828136 patent/DE2828136A1/en active Granted
- 1978-06-30 JP JP53078765A patent/JPS6059874B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6059874B2 (en) | 1985-12-27 |
| DE2828136A1 (en) | 1979-01-11 |
| DE2828136C2 (en) | 1988-06-30 |
| JPS5440711A (en) | 1979-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4162165A (en) | Process for the production of microcapsular coating compositions containing pigment particles and compositions produced thereby | |
| CA1110063A (en) | Process for producing pressure-sensitive copy sheets using novel radiation curable coatings | |
| US4228216A (en) | Production of radiation curable microcapsular coating compositions, pressure-sensitive transfer paper and its production | |
| EP0439874B1 (en) | High solids printing ink to be used in the production of carbonless copy paper | |
| US4112138A (en) | Manifold carbonless form and process for the production thereof | |
| US4139392A (en) | Chromogenic hot melt coating compositions | |
| US4097619A (en) | Manifold carbonless form and process for the continuous production thereof | |
| CA1099101A (en) | Process for the production of a pressure-sensitive carbonless copy sheet using microcapsules formed in situ in a radiation curable binder | |
| EP0392876B1 (en) | Preparing microcapsules | |
| US4404251A (en) | Copying systems, a process for their production, and suitable printing inks for both offset and book printing | |
| US4200667A (en) | Process for producing a pressure-sensitive carbonless copy sheet using microcapsules formed in situ in a radiation curable binder | |
| CA1109258A (en) | Process for the production of novel radiation curable microcapsular coating compositions | |
| CA1107955A (en) | Manifold carbonless form and process for the continuous production thereof | |
| CA2051063C (en) | High solids cb printing ink which produces a black image | |
| US4940739A (en) | Process for making a high solids CB printing ink | |
| US4296947A (en) | Pressure-sensitive transfer sheets using novel radiation curable coatings | |
| US4435340A (en) | Process for preparing microcapsules for pressure sensitive manifold paper | |
| US4161570A (en) | Process for the production of radiation curable coating compositions containing microcapsules | |
| US4230495A (en) | Process for producing a pressure-sensitive carbonless copy sheet using microcapsules formed in situ in a radiation curable binder | |
| US4940738A (en) | High solids CB printing ink containing a protective colloid blend | |
| US4191404A (en) | Process for producing a pressure-sensitive carbonless copy sheet using microcapsules formed in situ in a radiation curable binder | |
| US4071469A (en) | Solvent composition for use in carbonless copy systems | |
| US5132271A (en) | Carbonless copy paper sheet bearing a high solids CB printing ink containing a protective colloid blend | |
| GB1603239A (en) | Coating compositions and their production | |
| US4186115A (en) | Novel radiation curable coating compositions for pressure-sensitive transfer sheets |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |