CA1195791A - Radiation curable growth controlling printing ink compositions for chemically embossing heat-foamable material - Google Patents
Radiation curable growth controlling printing ink compositions for chemically embossing heat-foamable materialInfo
- Publication number
- CA1195791A CA1195791A CA000423882A CA423882A CA1195791A CA 1195791 A CA1195791 A CA 1195791A CA 000423882 A CA000423882 A CA 000423882A CA 423882 A CA423882 A CA 423882A CA 1195791 A CA1195791 A CA 1195791A
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- Canada
- Prior art keywords
- radiation curable
- printing ink
- growth
- foam
- controlling
- Prior art date
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Abstract
ABSTRACT
The present invention is directed to a solventless, radiation curable growth-controlling printing ink composition for chemically embossing heat-foamable material, which composition comprises from about 5% to about 99% of a radiation curable vehicle, about 1% to about 25% of a foam-controlling chemical agent, about 0.1%
to about 95% of a pigment, and about 0.1% to about 15% of a photoinitiator. The ink composition of the invention provides a film surface which is non-tacky, non-crocking and non-blocking, which exhibits good adhesion both to the foamable material and to a wear layer, and which provides an effectively embossed flooring product, using commercial equipment.
The present invention is directed to a solventless, radiation curable growth-controlling printing ink composition for chemically embossing heat-foamable material, which composition comprises from about 5% to about 99% of a radiation curable vehicle, about 1% to about 25% of a foam-controlling chemical agent, about 0.1%
to about 95% of a pigment, and about 0.1% to about 15% of a photoinitiator. The ink composition of the invention provides a film surface which is non-tacky, non-crocking and non-blocking, which exhibits good adhesion both to the foamable material and to a wear layer, and which provides an effectively embossed flooring product, using commercial equipment.
Description
l~ ~w 1. Field of the Present Invention:
The present invention relates to foam-controlling print- ¦
ing ink compositions of use for chemically e~bossing of floor, eiling or wall co~e~ings, and like arti~les.
~ .
I
¦ DN-1174 i ', l2. Description of the Prior Arto ¦ r`hemical embossing techniques have been used widely in ¦the manufacture of floor, ceiliny and wall coverings, as described in U.S. Pat~ 3,293,094 and 3,293,108, to ~airn, et al. Such chemical embossing techniques normally have involved coating a base material with a substantially uniform layer of a resinous material. The resinous material includes a foaming or blowing agent uniformly dispersed therein, and which is adapted, upon subsequent heating, to decompose and to liberate gaseous decompo-¦ sition products to expand and create a foamed, blown resinous ' product.
~ One aspect of such chemical embossing techniques has j comprised the printing of selected, predetermined areas of thesurface of the heat-foamable resinous material, prior to the heating, with a solvent foam-growth-controlling printing ink ; composition which is capable of affecting and changing the degree of foam-growth of those selected, predetermined areas, when the heat-foamable resinous materials are subsequently heated to the required elevated temperature.
Such solvent foam-growth-controlling printing ink compo- !
sitions have contained either: (l) agents for inhibiting or suppr~ssing the decomposition of the foaming or blowing agents to thus decrease the resulting expanding gaseous action on the foamable resinous materials and to correspondingly decrease the foam-growth in the selected, predetermined areas to which-hhey , are applied; or (2) agents for cataly7ing or accsleratiny the ¦ decomposition of the foaming ~r `blowi~g agents to thus increase ,1' 1 75~ 1 , D~-1174 , '.
the resulting gaseous action on the foamable resinous materials and to correspondingly increase the foam-growth in the selected, predetermined areas to which they are applied, ll As a consequence, the surface of the resulting, foamed ¦l or blown resinous materials have been given an embossed or relief i i pattern effect containing relatively higher areas or lands and i relatively lower areas or valleys, thus providing excellent sur- ~
face interest. `¦
¦¦ The solvent foam-growth-controlling printing ink compo-! sitions have thus contained both: ~1) the foam-growth-controlling' . agents, and (2) the pigme~ts, ink, dyes or other coloring materials, whereby the resulting embossed or relief pattern effects have been I made to coincide very accurately and very preci,sely with the ink-¦l printing pattern, thus creating excellent visual and tactile effects which are in substantially perfect alignment and registry , at all times.
A number of organic solvent-based foam-growth-controlling printing ink compositions as described in said patents, have been j used previously in such chemic~ embossing manufacturing techni-ques, and have proved to be relatively successful therein. How-ever, organic ~ -based printing inks are relatively expensive, are usually very difficult to remove or clean from printing equipment, are occasioDall~,not adaptable for use with conventionai commercial printing equipment, are often ~lammable or have relatively low flash points which are unfortunately conducive to dangerous or hazardous conditions, fre~uently cause significant waste, ecological, or pollution problems, and sometimes require ' costly and time-consuming solvent-recovery programs.
7~
li DN-1174 I~ l An improved solvent, growth-controlling printing ink composition is described in U.S.Pat. 4,083,907. These compositions employ a~ueous-alcohol as solvents and are advantageous as com-pared to organic solvent inks in that they do not pollute the latmosphere excessively. However, they require a large amount of ¦heat energy to remove the aqueous-alcoholic solvents.
l Accordingly, it would be of considerable advantage to ithe industry to provide a solventless, foam-growth controlling printing ink composition fo~ use with chemical embossing processes, which compositions are particularly adapted to require less heat ¦
energy than in the past which do not create dangerous or hazardous conditions, or cr~ate significant waste, ecological or pollution problems; and which enable the production of commercial embossed i flooring products using economical manufacturing e~uipment and processes.
SUMMA RY OF THE I NVENT I ON
~ The present invention provides a solventless, radiation i curable growth-controlling printing ink composition for chemically embossing heat foamable material, which composition includes abou.
5% to about 99% of 3 radiation curable vehicle, about 1% to about ¦ 25% of a foam-controlling chemical agent about 0.1% to about 95%
i Of a pigment, and about 0.1% to about 15% of a photo initiator~
Such an ink composition is capable of ~eing readily printed onto the foamable materia~ and cured using radiation energy to provide ~ a film surface which is non-tacky, non-crocking and non-blocking, ¦~ and which exhibits good adhesion to both the foamable material i , 4 ~ 9~7~ DN-1174 ¦~ and to the wear layer.. After blowing, effectively embossed floor-~ ing product is formed.
¦ DETAILED DE~CRIPTION OF THE
PREFERRED _MBODIMENTS _F T E INVENTION
The Foam-Growth Controllinq Aqent: ¦
. ~
The radiation curable foam-growth-controlling printing ink compositions for controlling the foam-growth of heat-foamable and expandable resinous materials upon heating lncludes a foam-growth controlling agent which is present in an amount of at least about 1% and normally up to about 25% by weight, based upon the total weight of the printing ink composltion. The amount¦
of the foam-growth controlling agent used will depend upon the ¦ degree of the embossing effect which is desired or re~uired.
¦ Another complete list of suitable foam-growth controlling~
agents is described in the aforementioned Nairn patents~ The preferred commercial foam-controlling agents are trimellitic an-I hydride and benzotriazole, although many others known in the art ¦ may be used as well. Such foam-growth controlling agents must be sufficiently soluble or dispersible in the printing ink compo-sitions and they must be sufficiently stable therein as not to be convertible, through reaction with the radiation curable vehi- ¦
cle, or otherwise, into other chemical forms in which they lose their foam-growth controlling properties and characteristics.
.
!
7~
.
The Radiation Curable Vehicle: `
j The radiation curable vehicle of the printing ink compo- ' I sition of the invention functions to hold the pigment component I of the ink in dispersion and, when cured, as a binder in the ' ¦ resulting film coating. Accordingly, any radiation curable resin I
¦ system which has a suitable viscosity to disperse the pigment and j which forms a flexible coating upon curing which is adharent to both the foam and wear layers may be used. Such reactive resin systems are well known in the art, and are described in such U.S.
patents as 4,100,318; 4,180,615; 3,924,023; 4,122,2~5; 4,309,452;
3,485,732; and 4,196,243~ 1 ¦ Generally the components of a preferred radiation curable¦
vehicle in the printing ink composition of the present invention includes one or more of an unsaturated resin, a re~ctive monomer, ~ ~ f and a multifunctional monomer,and, if desired, an-i~ polymer resin. The unsaturated resins are usually low molecular weight polymers or oligomers containing a functional group which partici-pates in the polymerization process. The unsaturated resins commonly employed herein are compounds which contain polar groups,¦
preferably urethanes. However, polyethers, epoxides, amides and I the like terminated by two or more photopolymerizable ethyleni-i cally unsaturated groups csn be employed.
¦ The reactive monomers preferably includes those contain-ing at least one acrylyl or methacryl group, or are lighter alkyl ! acrylamides and methacrylamides. Illustrative of which one can i mention acrylic acid, methyl acrylate, ethyl acrylate, butyl i acrylate, hexyl acrylate, 2-ethylhe~yl acrylate, butoxyethyl 7~
!. DN-1174 , . .
acrylate, dicyclopentenyl acrylate, isodecyl acrylate, 2-phenox-yethyl acrylate, glycidyl acrylate, 2-ethozyethyl acrylate,
The present invention relates to foam-controlling print- ¦
ing ink compositions of use for chemically e~bossing of floor, eiling or wall co~e~ings, and like arti~les.
~ .
I
¦ DN-1174 i ', l2. Description of the Prior Arto ¦ r`hemical embossing techniques have been used widely in ¦the manufacture of floor, ceiliny and wall coverings, as described in U.S. Pat~ 3,293,094 and 3,293,108, to ~airn, et al. Such chemical embossing techniques normally have involved coating a base material with a substantially uniform layer of a resinous material. The resinous material includes a foaming or blowing agent uniformly dispersed therein, and which is adapted, upon subsequent heating, to decompose and to liberate gaseous decompo-¦ sition products to expand and create a foamed, blown resinous ' product.
~ One aspect of such chemical embossing techniques has j comprised the printing of selected, predetermined areas of thesurface of the heat-foamable resinous material, prior to the heating, with a solvent foam-growth-controlling printing ink ; composition which is capable of affecting and changing the degree of foam-growth of those selected, predetermined areas, when the heat-foamable resinous materials are subsequently heated to the required elevated temperature.
Such solvent foam-growth-controlling printing ink compo- !
sitions have contained either: (l) agents for inhibiting or suppr~ssing the decomposition of the foaming or blowing agents to thus decrease the resulting expanding gaseous action on the foamable resinous materials and to correspondingly decrease the foam-growth in the selected, predetermined areas to which-hhey , are applied; or (2) agents for cataly7ing or accsleratiny the ¦ decomposition of the foaming ~r `blowi~g agents to thus increase ,1' 1 75~ 1 , D~-1174 , '.
the resulting gaseous action on the foamable resinous materials and to correspondingly increase the foam-growth in the selected, predetermined areas to which they are applied, ll As a consequence, the surface of the resulting, foamed ¦l or blown resinous materials have been given an embossed or relief i i pattern effect containing relatively higher areas or lands and i relatively lower areas or valleys, thus providing excellent sur- ~
face interest. `¦
¦¦ The solvent foam-growth-controlling printing ink compo-! sitions have thus contained both: ~1) the foam-growth-controlling' . agents, and (2) the pigme~ts, ink, dyes or other coloring materials, whereby the resulting embossed or relief pattern effects have been I made to coincide very accurately and very preci,sely with the ink-¦l printing pattern, thus creating excellent visual and tactile effects which are in substantially perfect alignment and registry , at all times.
A number of organic solvent-based foam-growth-controlling printing ink compositions as described in said patents, have been j used previously in such chemic~ embossing manufacturing techni-ques, and have proved to be relatively successful therein. How-ever, organic ~ -based printing inks are relatively expensive, are usually very difficult to remove or clean from printing equipment, are occasioDall~,not adaptable for use with conventionai commercial printing equipment, are often ~lammable or have relatively low flash points which are unfortunately conducive to dangerous or hazardous conditions, fre~uently cause significant waste, ecological, or pollution problems, and sometimes require ' costly and time-consuming solvent-recovery programs.
7~
li DN-1174 I~ l An improved solvent, growth-controlling printing ink composition is described in U.S.Pat. 4,083,907. These compositions employ a~ueous-alcohol as solvents and are advantageous as com-pared to organic solvent inks in that they do not pollute the latmosphere excessively. However, they require a large amount of ¦heat energy to remove the aqueous-alcoholic solvents.
l Accordingly, it would be of considerable advantage to ithe industry to provide a solventless, foam-growth controlling printing ink composition fo~ use with chemical embossing processes, which compositions are particularly adapted to require less heat ¦
energy than in the past which do not create dangerous or hazardous conditions, or cr~ate significant waste, ecological or pollution problems; and which enable the production of commercial embossed i flooring products using economical manufacturing e~uipment and processes.
SUMMA RY OF THE I NVENT I ON
~ The present invention provides a solventless, radiation i curable growth-controlling printing ink composition for chemically embossing heat foamable material, which composition includes abou.
5% to about 99% of 3 radiation curable vehicle, about 1% to about ¦ 25% of a foam-controlling chemical agent about 0.1% to about 95%
i Of a pigment, and about 0.1% to about 15% of a photo initiator~
Such an ink composition is capable of ~eing readily printed onto the foamable materia~ and cured using radiation energy to provide ~ a film surface which is non-tacky, non-crocking and non-blocking, ¦~ and which exhibits good adhesion to both the foamable material i , 4 ~ 9~7~ DN-1174 ¦~ and to the wear layer.. After blowing, effectively embossed floor-~ ing product is formed.
¦ DETAILED DE~CRIPTION OF THE
PREFERRED _MBODIMENTS _F T E INVENTION
The Foam-Growth Controllinq Aqent: ¦
. ~
The radiation curable foam-growth-controlling printing ink compositions for controlling the foam-growth of heat-foamable and expandable resinous materials upon heating lncludes a foam-growth controlling agent which is present in an amount of at least about 1% and normally up to about 25% by weight, based upon the total weight of the printing ink composltion. The amount¦
of the foam-growth controlling agent used will depend upon the ¦ degree of the embossing effect which is desired or re~uired.
¦ Another complete list of suitable foam-growth controlling~
agents is described in the aforementioned Nairn patents~ The preferred commercial foam-controlling agents are trimellitic an-I hydride and benzotriazole, although many others known in the art ¦ may be used as well. Such foam-growth controlling agents must be sufficiently soluble or dispersible in the printing ink compo-sitions and they must be sufficiently stable therein as not to be convertible, through reaction with the radiation curable vehi- ¦
cle, or otherwise, into other chemical forms in which they lose their foam-growth controlling properties and characteristics.
.
!
7~
.
The Radiation Curable Vehicle: `
j The radiation curable vehicle of the printing ink compo- ' I sition of the invention functions to hold the pigment component I of the ink in dispersion and, when cured, as a binder in the ' ¦ resulting film coating. Accordingly, any radiation curable resin I
¦ system which has a suitable viscosity to disperse the pigment and j which forms a flexible coating upon curing which is adharent to both the foam and wear layers may be used. Such reactive resin systems are well known in the art, and are described in such U.S.
patents as 4,100,318; 4,180,615; 3,924,023; 4,122,2~5; 4,309,452;
3,485,732; and 4,196,243~ 1 ¦ Generally the components of a preferred radiation curable¦
vehicle in the printing ink composition of the present invention includes one or more of an unsaturated resin, a re~ctive monomer, ~ ~ f and a multifunctional monomer,and, if desired, an-i~ polymer resin. The unsaturated resins are usually low molecular weight polymers or oligomers containing a functional group which partici-pates in the polymerization process. The unsaturated resins commonly employed herein are compounds which contain polar groups,¦
preferably urethanes. However, polyethers, epoxides, amides and I the like terminated by two or more photopolymerizable ethyleni-i cally unsaturated groups csn be employed.
¦ The reactive monomers preferably includes those contain-ing at least one acrylyl or methacryl group, or are lighter alkyl ! acrylamides and methacrylamides. Illustrative of which one can i mention acrylic acid, methyl acrylate, ethyl acrylate, butyl i acrylate, hexyl acrylate, 2-ethylhe~yl acrylate, butoxyethyl 7~
!. DN-1174 , . .
acrylate, dicyclopentenyl acrylate, isodecyl acrylate, 2-phenox-yethyl acrylate, glycidyl acrylate, 2-ethozyethyl acrylate,
2-methoxyethyl acrylate, 2-(N, N-diethylamino) ethyl acrylate, trimethoxyallyloxymethyl acrylate, vinyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, (methylcarbamyl) etyly acrylate and the corresponding methacrylates; and nonyl and dodecyl acrylamides and methacrylamiaes. However, other photo curable, monofunctional monomers known in the art may be used as well.
Other reactive monomers, such as vinyl pyrollidone, also may be included with the reactive monomer~to aid in dispersing the pig-ment and to improve the flexibility of the resultant film coating.
Multifunctional monomers may be added along with the reactive monomers when it is desired to increase the cross-link density of the coating while preserving the flexibility of the film. The multifunctional monomers are prefera~ly of the acrylyl type, such as neopentyl glycol diacrylate, pentacrytanitol triacrylate, 1, 6-hexane dioldiacrylate, trimethylolpropane tria~ j crylate and the like. The multifunctional monomers listed above are for illustrative purposes only. As with the reactive monomers~
~iven above, any multifunctional monomers capable of curing on exposure to radiation are suitable.
The ~Re~ resin is a polymeric material which does not contain any unsaturation, it helps in film formation, adherence ,~'7~
and to increase the viscosity of the vehicle~ Generally the ~e-~t resins are polyolefins and modified polyolefins, the vinyl poly-1 mers, the polyethers, the polyesters, the polylactones, the ¦~ polyamides, the pol~lre~hanes~ the polyureas, the polysiloxanes, I the polysulfies, ~he polysulfones, the polyformaldehydes, the phenol~formaldehyde polymers, the natural and modified natural polymers, the heterocyclic polymers, and the like.
' ~7-57~
¦I DN-1174 !l j I~lustrative of these polymers are the acrylic polymers such as po~y tacrylic acid), poly (methyl acrylate), poly-(ethyl acrylate), poly (methacrylic acid), poly (methyl methacrylate~, poly (ethyl mathacrylate); poly (vinyl chloride) poly (vinyl alcohol); poly (ethylene/propylene/5-ethylidenebicyclo (2.2.1)-hept-2--~ne); polyethylene: polypropylene; synthetic rubbers, e.g.:
butadiene/acrylonitrile copolymers and chloro-2-butadiene 1,3 polymers; the polyesters, copolyesters, polyamides and copolyamides, such as polycaproiactone, poly (caprolactone/vinyl chloride) poly tethylene glycol terephthalate), poly (hexamethylene succinate), poly (hexamethylene maleate~, poly (hexamethylene carbonate), poly (caprolactam), poly (hexamethylene adipamide), and thP like; I
the polyethers such as poly (glutaraldehyde), polyethylene oxide, ! polypropylene oxide, poly (tetrahydrofuran), polycyclohexene oxide, copolymers of ethylene oxide and propylene oxide with ' starters containing reactive hydrogen atoms such as the ~ixed i copolymers using ethylene glycol, glycerol, sucrose, etc., as the starter vinylidene polymers and copolymers, e.g., vinylidene chloride/acrylonitrile, vinylidene chloride/methacrylate and vinylidene chloride/vinyl acetate polymerss ethylene/vinyl acetat~
copolymers; the polyureas and polyurethanes, such as described in _ol irethanes ChemistrY and Technoloqy, ~olumes I and II, ~ J D ~RS
-~nae~ and Frisch, published by Interscience Publishers; the ¦ polycarbonates; polystyrenes; polyvinyl acetals, e.g., polyvinyl butyral, polyvinyl formal; the cellulose ethersO e.g., methyl cellulose, ethyl cellulose, and benzyl cellulose; the cellulose l' l' , -8-,~
,, ¦! DM-117q esters, e.g., cellulose acetate, cellulose acetate succinate and j cellulose acetate butyrate, as well as the natural and modified ¦ natural polym~rs such as gutta percha, cellulose, gelatin, starch, I silk, wool, and the like: the siloxane polymers and copolymers;
¦ the formaldehyde polymers such as polyformaldehyde; formaldehyde resins such as phenol-formaldehyde, melamine-formaldehyde, urea-formaldehyde, aniline-formaldehyde and acetone-formaldehyde ! phenolic resins and the like.
¦ In general, the amount of radiation curable vehicle used ¦
i in the ink composition of the invPntion will depend ~y~rthe amount of pigment needed for the degree of color desired, its particle size, and the viscosity of the vehicle. Usually the ink composition includes about 5% to 99% of the radiation curable vehicle and preferably about 10~90%. The unsaturated resin may comprise 0-99,' of the vehicle, the reactive and multifunctional , ,~
monomers 0-99%, and the ~n~ resin 0-30% by weight of the vehicle To assure a flexible film having good adhesion to the foam before curing, and to the wear layer after curing, it is preferable that the ink composition contain from 0.1 to less ¦ than 1 equivalent of curable vehicle, material per 500g. of the ~ ink composition.
. l PHOTOINIATORS
The curing reaction can be initiated by either W radia-tion or high energy ionizing radiation. Th~ W radiation can be ! obtained from~sunlight or special light sources which emit sig-nificant amounts of W light having a wavelength in the range of ~ 7~ ~
! DN-1174 1 1.
about 2000 to about 4000 Angstrom units. Whan W radiation is used for the curing reaction, a dose of 0.0004 to 60 wa~ts/centi- j meter is employed.
When U.V. radiation is used for curing, a photoinitiator ¦
is added to the composition to increase the photopolymerization or photocurin~ reaction rate. Various photoinitiators and co-initiators are operable and well known to those skilled in the art. Examples of photoinitiators include, but are not limited to, valerophenone, acetophenone, dibenzosuberone, 4-aminobenzophe-none, hexanophenone, a-tetralone, 9-fluorenone, thioxanthen-9-one,l 7-H-benz(de)anthracene-7-one, 4,4'-bis(dimethylamino)benzophenone,l o-methoxybenzophenone, triphenylphosphine, tri-o-tolylphosphine, benz(a)anthracene-7, 12-dione, benzoin isopropyl ether, benzoin isobutyl ether, benzoin tetrahydropyranyl ether, 2,2-diethoxy-acetophenone, 2,2-dimethoxy-2-phenylacetophenone, thixoanthrone,
Other reactive monomers, such as vinyl pyrollidone, also may be included with the reactive monomer~to aid in dispersing the pig-ment and to improve the flexibility of the resultant film coating.
Multifunctional monomers may be added along with the reactive monomers when it is desired to increase the cross-link density of the coating while preserving the flexibility of the film. The multifunctional monomers are prefera~ly of the acrylyl type, such as neopentyl glycol diacrylate, pentacrytanitol triacrylate, 1, 6-hexane dioldiacrylate, trimethylolpropane tria~ j crylate and the like. The multifunctional monomers listed above are for illustrative purposes only. As with the reactive monomers~
~iven above, any multifunctional monomers capable of curing on exposure to radiation are suitable.
The ~Re~ resin is a polymeric material which does not contain any unsaturation, it helps in film formation, adherence ,~'7~
and to increase the viscosity of the vehicle~ Generally the ~e-~t resins are polyolefins and modified polyolefins, the vinyl poly-1 mers, the polyethers, the polyesters, the polylactones, the ¦~ polyamides, the pol~lre~hanes~ the polyureas, the polysiloxanes, I the polysulfies, ~he polysulfones, the polyformaldehydes, the phenol~formaldehyde polymers, the natural and modified natural polymers, the heterocyclic polymers, and the like.
' ~7-57~
¦I DN-1174 !l j I~lustrative of these polymers are the acrylic polymers such as po~y tacrylic acid), poly (methyl acrylate), poly-(ethyl acrylate), poly (methacrylic acid), poly (methyl methacrylate~, poly (ethyl mathacrylate); poly (vinyl chloride) poly (vinyl alcohol); poly (ethylene/propylene/5-ethylidenebicyclo (2.2.1)-hept-2--~ne); polyethylene: polypropylene; synthetic rubbers, e.g.:
butadiene/acrylonitrile copolymers and chloro-2-butadiene 1,3 polymers; the polyesters, copolyesters, polyamides and copolyamides, such as polycaproiactone, poly (caprolactone/vinyl chloride) poly tethylene glycol terephthalate), poly (hexamethylene succinate), poly (hexamethylene maleate~, poly (hexamethylene carbonate), poly (caprolactam), poly (hexamethylene adipamide), and thP like; I
the polyethers such as poly (glutaraldehyde), polyethylene oxide, ! polypropylene oxide, poly (tetrahydrofuran), polycyclohexene oxide, copolymers of ethylene oxide and propylene oxide with ' starters containing reactive hydrogen atoms such as the ~ixed i copolymers using ethylene glycol, glycerol, sucrose, etc., as the starter vinylidene polymers and copolymers, e.g., vinylidene chloride/acrylonitrile, vinylidene chloride/methacrylate and vinylidene chloride/vinyl acetate polymerss ethylene/vinyl acetat~
copolymers; the polyureas and polyurethanes, such as described in _ol irethanes ChemistrY and Technoloqy, ~olumes I and II, ~ J D ~RS
-~nae~ and Frisch, published by Interscience Publishers; the ¦ polycarbonates; polystyrenes; polyvinyl acetals, e.g., polyvinyl butyral, polyvinyl formal; the cellulose ethersO e.g., methyl cellulose, ethyl cellulose, and benzyl cellulose; the cellulose l' l' , -8-,~
,, ¦! DM-117q esters, e.g., cellulose acetate, cellulose acetate succinate and j cellulose acetate butyrate, as well as the natural and modified ¦ natural polym~rs such as gutta percha, cellulose, gelatin, starch, I silk, wool, and the like: the siloxane polymers and copolymers;
¦ the formaldehyde polymers such as polyformaldehyde; formaldehyde resins such as phenol-formaldehyde, melamine-formaldehyde, urea-formaldehyde, aniline-formaldehyde and acetone-formaldehyde ! phenolic resins and the like.
¦ In general, the amount of radiation curable vehicle used ¦
i in the ink composition of the invPntion will depend ~y~rthe amount of pigment needed for the degree of color desired, its particle size, and the viscosity of the vehicle. Usually the ink composition includes about 5% to 99% of the radiation curable vehicle and preferably about 10~90%. The unsaturated resin may comprise 0-99,' of the vehicle, the reactive and multifunctional , ,~
monomers 0-99%, and the ~n~ resin 0-30% by weight of the vehicle To assure a flexible film having good adhesion to the foam before curing, and to the wear layer after curing, it is preferable that the ink composition contain from 0.1 to less ¦ than 1 equivalent of curable vehicle, material per 500g. of the ~ ink composition.
. l PHOTOINIATORS
The curing reaction can be initiated by either W radia-tion or high energy ionizing radiation. Th~ W radiation can be ! obtained from~sunlight or special light sources which emit sig-nificant amounts of W light having a wavelength in the range of ~ 7~ ~
! DN-1174 1 1.
about 2000 to about 4000 Angstrom units. Whan W radiation is used for the curing reaction, a dose of 0.0004 to 60 wa~ts/centi- j meter is employed.
When U.V. radiation is used for curing, a photoinitiator ¦
is added to the composition to increase the photopolymerization or photocurin~ reaction rate. Various photoinitiators and co-initiators are operable and well known to those skilled in the art. Examples of photoinitiators include, but are not limited to, valerophenone, acetophenone, dibenzosuberone, 4-aminobenzophe-none, hexanophenone, a-tetralone, 9-fluorenone, thioxanthen-9-one,l 7-H-benz(de)anthracene-7-one, 4,4'-bis(dimethylamino)benzophenone,l o-methoxybenzophenone, triphenylphosphine, tri-o-tolylphosphine, benz(a)anthracene-7, 12-dione, benzoin isopropyl ether, benzoin isobutyl ether, benzoin tetrahydropyranyl ether, 2,2-diethoxy-acetophenone, 2,2-dimethoxy-2-phenylacetophenone, thixoanthrone,
3-methoxybenzophenone, 4-methoxybenzophenone, ben~ophenone,
4,4'-dimethoxybenzophenone, 4-methoxybenzaldehyde, 4-methoxyace-tophenone, benzaldehyde,~dibenzosuberone, ethyl benzoin ether, isobutyl benzoin ether, a,a-diethoxy-a-phenylacetophenone, a-methylolbenzoinmethyl ether, a,a, a-trichloroacetophenone 3nd 2,3-butanedione and mixtures thereof, which service to give great-ly reduced exposure times and thexeby, when used in conjunction with various forms of energetic radiation, yield very rapid, commercially practical time cycles by the practice of the instant invention.
, ,~
', -10-~, I
. I
7~3~ , DN~1174 ~ -THE PIGr~NT
sy the term "piqment" as used herein is ~eant those colored organic and inorganic compounds which are normally used in the art to impart color as well as organic dyes which are used ¦
for the same purpose. There is no restriction as to pigments or dyes except ~hat they be nonreactive to the components of the ink.
Illustrative of the various inorganic pigments are titanium dioxide, carbon black, metallic flakès, powders and dusts such as aluminum powder, bronze powder, and the like. Organic pigments and dyes which can be used include Phthalocyanine green, Phthalo-cyanine blue, Permanent red 2B, Lithol red, Lithol rubine, Toluidine red, Hansa yellow, Toluidine yellow, oil soluble dyes, and the like.
There is no particular criticality in respect to the amount of coloring material to be used. However, sufficient colorant should be used to provide good covering properties with the proper density of color. While economic factors generally determine the maximum amount of pigment to be used, it aoes with-out saying that pigments should not be used in such amounts as to cause the ink to chalk on drying, or to make the viscosity of the ink unreasonably high. ~aturally the specific amount of pigment used is dependent upon the coloring properties of the pigm~nt, the properties of the inks and so forth.
Most any commercia1 ~ment can be used with this ink system. Among them are rhodamines, rubines, lithols, red lake C~ ¦
2-B reds, phthalo blues and greens, carbon blacks, alkali blues, methyl violets, moly orange=, benzidine rellows, chrome ~ellows I
, : I
~s79~ j li carbazole violets, etc. Pigments that do not inhibit the poly-merization of the reactive monomers are preferred.
In addition to the essential components of the curable i, I composition of the invention set forth above, additional materials ¦ may be added in order to obtain the necessary properties for a ¦ legend ink. These are listed in the Table below in their respec-tive proportions by weight.
TABLE
Broadly Preferably Component % bv Wt. % by Wt.
Inhibitors .01-1 .05-0.2 Fillers 30-70 45~55 Thixotropic Agent 0-4.0 0-2.0 Levelling Agent 0.05-2.0 ~0,1-1 Coinitiators 0.05-1.5 0.05-0.2 The choice of the materials and the amounts used may be readily determined by those skilled in the art.
PROPERTIES OF FIL~ OF GROWTH-CONTROLLING
RADI~TION CURABL~ PRINTING INK COMPOSITION
ON FOAMABLE RESINOUS LAYER
In general, to form a non-tacky, non-crocking and non~ ¦
blocking film coating, it is preferable that at least 50% of the i radiation curable vehicle be cured, and within a reasonable time. i j Any liquid remaininy after r~diation curing will be absorbed into ¦ the pigment and will cure thermally during su~se~uent operations.
¦ The inks of the invention can be printed by any con-ventional method, including rotogravure and screen printing.
Usually for rotogravure printing a lower viscosity ink is used l il .1 1 , I
i Ii D~-1174 . . .
¦I while for screen prin~ing a higher viscosity or even a paste ink I may be used.
I In commercial applications, these inks can be cured at speeds ranging from 260 to 500 fpm, The speed of cure depends larse~y on the number of lamps being used and the color of the ink being photopolymerized. FOI instance, an ultra violet curable, yellow colored metal decorating ink of this invention can be cured, at speeds up to 400 fpm using two 200 watt per linear inch lamps , while a black ink of the same invention would require five 200 ¦ watt per linear inch lamps to cure at the same sp~ed, Preferably j I the inXs are cured in an air atmosphere in which the adhesion ¦ of the ink film to the wear layer is improved.
1 The invention will be illustrated with reference to the ¦
¦~ following examples:
` EXAMPLES
! x mple 1 ,' Component of Ink Composition Parts by Wto Radiation Curable Vehicle Dicyclop~ntenyloxyethyl methacrylate 31,17 Vinyl pyrrolidone 44.01 Vinyl chloride-Vinylacetate copolymer ~.41 I Foam-Growth Controllinq Aqent i Trim llitic anhydride 9.09 Photoinitiator Benzophe~one 2.68 Sandoray 1000 2,68 Piqment ~ j Microlith 1095-K60 3.96 The components are mixed, 40 drops of FC170C surfactant l~
, are added, and the ink composition is printed on selected, pr~- i `~ e ~/,~
i l l .
7~ , I ~, Il determined areas of a gelled, foamable plastisol formulated by ¦, mixing the following ngredients on a Cowles mixer:
Il .
l l _ rts_ _ Polyvinyl chloride, dispersion grade, specific 50 I viscosity 0.6 ¦ Polyvinyl chloride, dispersion grade, specific 50 I viscosity 0.4 I Butyl benzyl phthalate plasticizer 25 I Di-(2-ethyl hexyl) phthalate plasticizer 45 ¦ Titanium dioxide pigment (55% solids) 7 ¦ A~odicarbonamide blowing agent 3 I V. M. & P. naphtha (boiling range 190-275F.)5 I
Heating at 375F. decomposes the azodicarbonamide blow- I
ing agent to create the desired blowing and foaming function. An ¦
~ I
embossing depth of about 26 mils is obtained at about 59 mils foam a Wear layer of about 10 mils is used. The foam-growth controllin~
properties and characteristics of the printing ink composition arei well demonstrated in this Example.
The film then is cured under two W lamps 200/200 watts in a nitrogen atmosphere containing 80 ppm oxygen, the infrared temperature being 160 F.
.
j ADDITIONAL EXAMPLES
, Example 2 j Dicyclopentenyloxyetaye methacrylate 45.53 Diacrylate of bis-phenol diglycylether 9.54 , Vinyl pyrrolidone 34.76 ~ Trimellitic anhydride (8g) 17.68 t~ Benzophe~one 2.86 f~ 1 Sandoray~1000 2.86 I Pigment BR-K 4.22 I Tergetol~4 1.94 ¦ The curing was carried out in an air atmosphere and the ¦
adhesion was excellent.
Q
, -14-, .
~ 1~
, I
.~ I
~ 957~ DM-1174 . . .
j,ExamPle 3 j Acrylated urethane 10.00 , Vinyl pyrrolidone 90~00 Trimellitic anhydride 10.00 I Benzophenone O.SO
~L ! S a~dc~ray~lQoo Pigment 10.00 ` Example 4 j Dicyclopentenyloxyethyl rethacrylate 27.44 ¦ Vinyl pyrrolidone 38.74 , Vinyl chloride-vinyl acetate copolymer 6.41 Tolyltriazole 19.97 Photoinitiator 4.72 P~gment 3.48 ' 1~
Although several specific Examples of the inventive I concept have been described, the same should not be construed as , limiting the broader aspects of the present invention which in-clude other equivalent fe~tures and materials, as set forth and defined in the appended claims.
!~ i 1 !
I' .
~ 15-I' 1.
, ,~
', -10-~, I
. I
7~3~ , DN~1174 ~ -THE PIGr~NT
sy the term "piqment" as used herein is ~eant those colored organic and inorganic compounds which are normally used in the art to impart color as well as organic dyes which are used ¦
for the same purpose. There is no restriction as to pigments or dyes except ~hat they be nonreactive to the components of the ink.
Illustrative of the various inorganic pigments are titanium dioxide, carbon black, metallic flakès, powders and dusts such as aluminum powder, bronze powder, and the like. Organic pigments and dyes which can be used include Phthalocyanine green, Phthalo-cyanine blue, Permanent red 2B, Lithol red, Lithol rubine, Toluidine red, Hansa yellow, Toluidine yellow, oil soluble dyes, and the like.
There is no particular criticality in respect to the amount of coloring material to be used. However, sufficient colorant should be used to provide good covering properties with the proper density of color. While economic factors generally determine the maximum amount of pigment to be used, it aoes with-out saying that pigments should not be used in such amounts as to cause the ink to chalk on drying, or to make the viscosity of the ink unreasonably high. ~aturally the specific amount of pigment used is dependent upon the coloring properties of the pigm~nt, the properties of the inks and so forth.
Most any commercia1 ~ment can be used with this ink system. Among them are rhodamines, rubines, lithols, red lake C~ ¦
2-B reds, phthalo blues and greens, carbon blacks, alkali blues, methyl violets, moly orange=, benzidine rellows, chrome ~ellows I
, : I
~s79~ j li carbazole violets, etc. Pigments that do not inhibit the poly-merization of the reactive monomers are preferred.
In addition to the essential components of the curable i, I composition of the invention set forth above, additional materials ¦ may be added in order to obtain the necessary properties for a ¦ legend ink. These are listed in the Table below in their respec-tive proportions by weight.
TABLE
Broadly Preferably Component % bv Wt. % by Wt.
Inhibitors .01-1 .05-0.2 Fillers 30-70 45~55 Thixotropic Agent 0-4.0 0-2.0 Levelling Agent 0.05-2.0 ~0,1-1 Coinitiators 0.05-1.5 0.05-0.2 The choice of the materials and the amounts used may be readily determined by those skilled in the art.
PROPERTIES OF FIL~ OF GROWTH-CONTROLLING
RADI~TION CURABL~ PRINTING INK COMPOSITION
ON FOAMABLE RESINOUS LAYER
In general, to form a non-tacky, non-crocking and non~ ¦
blocking film coating, it is preferable that at least 50% of the i radiation curable vehicle be cured, and within a reasonable time. i j Any liquid remaininy after r~diation curing will be absorbed into ¦ the pigment and will cure thermally during su~se~uent operations.
¦ The inks of the invention can be printed by any con-ventional method, including rotogravure and screen printing.
Usually for rotogravure printing a lower viscosity ink is used l il .1 1 , I
i Ii D~-1174 . . .
¦I while for screen prin~ing a higher viscosity or even a paste ink I may be used.
I In commercial applications, these inks can be cured at speeds ranging from 260 to 500 fpm, The speed of cure depends larse~y on the number of lamps being used and the color of the ink being photopolymerized. FOI instance, an ultra violet curable, yellow colored metal decorating ink of this invention can be cured, at speeds up to 400 fpm using two 200 watt per linear inch lamps , while a black ink of the same invention would require five 200 ¦ watt per linear inch lamps to cure at the same sp~ed, Preferably j I the inXs are cured in an air atmosphere in which the adhesion ¦ of the ink film to the wear layer is improved.
1 The invention will be illustrated with reference to the ¦
¦~ following examples:
` EXAMPLES
! x mple 1 ,' Component of Ink Composition Parts by Wto Radiation Curable Vehicle Dicyclop~ntenyloxyethyl methacrylate 31,17 Vinyl pyrrolidone 44.01 Vinyl chloride-Vinylacetate copolymer ~.41 I Foam-Growth Controllinq Aqent i Trim llitic anhydride 9.09 Photoinitiator Benzophe~one 2.68 Sandoray 1000 2,68 Piqment ~ j Microlith 1095-K60 3.96 The components are mixed, 40 drops of FC170C surfactant l~
, are added, and the ink composition is printed on selected, pr~- i `~ e ~/,~
i l l .
7~ , I ~, Il determined areas of a gelled, foamable plastisol formulated by ¦, mixing the following ngredients on a Cowles mixer:
Il .
l l _ rts_ _ Polyvinyl chloride, dispersion grade, specific 50 I viscosity 0.6 ¦ Polyvinyl chloride, dispersion grade, specific 50 I viscosity 0.4 I Butyl benzyl phthalate plasticizer 25 I Di-(2-ethyl hexyl) phthalate plasticizer 45 ¦ Titanium dioxide pigment (55% solids) 7 ¦ A~odicarbonamide blowing agent 3 I V. M. & P. naphtha (boiling range 190-275F.)5 I
Heating at 375F. decomposes the azodicarbonamide blow- I
ing agent to create the desired blowing and foaming function. An ¦
~ I
embossing depth of about 26 mils is obtained at about 59 mils foam a Wear layer of about 10 mils is used. The foam-growth controllin~
properties and characteristics of the printing ink composition arei well demonstrated in this Example.
The film then is cured under two W lamps 200/200 watts in a nitrogen atmosphere containing 80 ppm oxygen, the infrared temperature being 160 F.
.
j ADDITIONAL EXAMPLES
, Example 2 j Dicyclopentenyloxyetaye methacrylate 45.53 Diacrylate of bis-phenol diglycylether 9.54 , Vinyl pyrrolidone 34.76 ~ Trimellitic anhydride (8g) 17.68 t~ Benzophe~one 2.86 f~ 1 Sandoray~1000 2.86 I Pigment BR-K 4.22 I Tergetol~4 1.94 ¦ The curing was carried out in an air atmosphere and the ¦
adhesion was excellent.
Q
, -14-, .
~ 1~
, I
.~ I
~ 957~ DM-1174 . . .
j,ExamPle 3 j Acrylated urethane 10.00 , Vinyl pyrrolidone 90~00 Trimellitic anhydride 10.00 I Benzophenone O.SO
~L ! S a~dc~ray~lQoo Pigment 10.00 ` Example 4 j Dicyclopentenyloxyethyl rethacrylate 27.44 ¦ Vinyl pyrrolidone 38.74 , Vinyl chloride-vinyl acetate copolymer 6.41 Tolyltriazole 19.97 Photoinitiator 4.72 P~gment 3.48 ' 1~
Although several specific Examples of the inventive I concept have been described, the same should not be construed as , limiting the broader aspects of the present invention which in-clude other equivalent fe~tures and materials, as set forth and defined in the appended claims.
!~ i 1 !
I' .
~ 15-I' 1.
Claims (12)
- What is Claimed Is:
l. A radiation curable growth-controlling printing ink com-position for chemically embossing heat-foamable material which composition is capable of being applied selectively to said foam-able material and cured by radiation to provide a film which is non-tacky, non-crocking and non-blocking comprising:
a radiation curable vehicle;
a foam-controlling chemical agent therein which is non-reactive with said vehicle and diffusable into said foamable material upon curing said vehicle;
a pigment, and a photoinitiator. - 2. A radiation curable growth-controlling printing ink composition according to Claim 1 in which said radiation curable vehicle has unsaturated compounds with at least 0.1 to less than 1 equivalents of unsaturated bonds per 500g of said ink composi-tion.
- 3. A solventless radiation curable growth controlling print-ing ink composition according to Claim l comprising about 5% to about 99% of said radiation curable vehicle, about 1% to about 25% of said foam-controlling chemical agent, about 0.1% to about 95% of said pigment, and about 0.1% to about 15% of said photo-initiator, by weight of said composition.
- 4. A radiation curable printing ink composition according to Claim 1 in which said radiation curable vehicle includes one or more components selected from an unsaturated resin, a reactive monomer, and a multifunctional monomer and, optionally, an inert polymeric resin.
- 5. A radiation curable printing ink composition according to Claim 1 includes 10-90% of said radiation curable vehicle.
- 6. A radiation curable printing ink composition according to Claim 1 in which such foam-controlling chemical agent acts as an inhibitor for any blowing agent present in the heat foamable material.
- 7. A flooring article of manufacture com-prising:
a foamable gel, and a radiation curable ink of Claim 1 coated on said gel. - 8. A flooring product comprising:
a foamable gel, a radiation cured growth-controlling printing ink of the composition of Claim 1 coated on said gel, and a wear layer on said gel, said coating exhibiting good adhesion with the gel and the wear layer. - 9. A method of making a chemically embossed flooring product comprising:
providing a heat foamable material, applying a radiation curable growth-controlling printing ink composition as defined in Claim 1, selectively on said material, curing said composition by radiation to form a film thereon, and foaming said material in the presence of said growth controlling chemical agent. - 10. A method according to Claim 9 including the additional step of applying a wear layer on said foamable material.
- 11. A method according to Claim 9 in which at least 50% of the radiation curable material in said composition is cured.
- 12. A method according to Claim 9 in which said film exhibits good adhesion between both foam material and said wear layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US41700882A | 1982-09-13 | 1982-09-13 | |
| US417,008 | 1982-09-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1195791A true CA1195791A (en) | 1985-10-22 |
Family
ID=23652220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000423882A Expired CA1195791A (en) | 1982-09-13 | 1983-03-17 | Radiation curable growth controlling printing ink compositions for chemically embossing heat-foamable material |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1195791A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6353037B1 (en) | 2000-07-12 | 2002-03-05 | 3M Innovative Properties Company | Foams containing functionalized metal oxide nanoparticles and methods of making same |
| US6573305B1 (en) | 1999-09-17 | 2003-06-03 | 3M Innovative Properties Company | Foams made by photopolymerization of emulsions |
| US7138436B2 (en) | 2001-06-13 | 2006-11-21 | 3M Innovative Properties Company | Uncrosslinked foams made from emulsions |
| WO2018015357A1 (en) * | 2016-07-18 | 2018-01-25 | Beaulieu International Group Nv | Multi-layered sheets suitable as floor of wall covering exhibiting a three-dimensional relief and a decorative image |
-
1983
- 1983-03-17 CA CA000423882A patent/CA1195791A/en not_active Expired
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6573305B1 (en) | 1999-09-17 | 2003-06-03 | 3M Innovative Properties Company | Foams made by photopolymerization of emulsions |
| US6759080B2 (en) | 1999-09-17 | 2004-07-06 | 3M Innovative Properties Company | Process for making foams by photopolymerization of emulsions |
| US6353037B1 (en) | 2000-07-12 | 2002-03-05 | 3M Innovative Properties Company | Foams containing functionalized metal oxide nanoparticles and methods of making same |
| US6462100B1 (en) | 2000-07-12 | 2002-10-08 | 3M Innovative Properties Company | Foams containing functionalized metal oxide nanoparticles and methods of making same |
| US7138436B2 (en) | 2001-06-13 | 2006-11-21 | 3M Innovative Properties Company | Uncrosslinked foams made from emulsions |
| WO2018015357A1 (en) * | 2016-07-18 | 2018-01-25 | Beaulieu International Group Nv | Multi-layered sheets suitable as floor of wall covering exhibiting a three-dimensional relief and a decorative image |
| CN109789661A (en) * | 2016-07-18 | 2019-05-21 | 博优国际集团公众有限公司 | Show the multi-layer sheet for being suitable as floor or wall covering of three-dimensional embossment and decorative picture |
| RU2748351C2 (en) * | 2016-07-18 | 2021-05-24 | БОЛЬЁ ИНТЕРНЕШЕНЛ ГРУП ЭнВи | Multi-layer sheet, suitable for use as floor or wall covering, characterized by three-dimensional relief and decorative pattern |
| US11345116B2 (en) | 2016-07-18 | 2022-05-31 | Beaulieu International Group Nv | Multi-layered sheet suitable as floor or wall covering exhibiting a three-dimensional relief and a decorative image |
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