CA2195603C - Aqueous and radiation-curable printing varnishes and printing inks with improved properties - Google Patents
Aqueous and radiation-curable printing varnishes and printing inks with improved properties Download PDFInfo
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- CA2195603C CA2195603C CA002195603A CA2195603A CA2195603C CA 2195603 C CA2195603 C CA 2195603C CA 002195603 A CA002195603 A CA 002195603A CA 2195603 A CA2195603 A CA 2195603A CA 2195603 C CA2195603 C CA 2195603C
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
Abstract
Aqueous and radiation-curable printing varnishes and printing inks, are disclosed which contain special polyoxyalkylene polysiloxane copolymers. These printing varnishes and printing inks have improved scratch resistance, a higher gliding ability and an extremely low tendency to foam, so that the production of printing inks proceeds without problems and, at the same time, an optically attractive typography can be obtained.
Description
2 ~ 95603 AQUEOUS AND RADIATION-CURABLE PRINTING VARNISHES
AND PRINTING INKS WITH IMPROVED PROPERTIES
FIELD OF INVENTION:
The invention relates to aqueous and radiation-curable printing varnishes and printing inks, which contain special polyoxyalkylene polysiloxane copolymers. These printing varnishes and printing inks have improved scratch resistance, increased sliding ability, as well as an extremely low tendency to foam, so that the production of printing inks proceeds with less problems and, at the same time, an optically attractive typography can be obtained.
BACKGROUND INFORMATION AND PRIOR ART:
A constantly increasing number of printing inks and printing varnishes are being changed over to ecologically safer, water-based and radiation-curable systems. These systems are known and described, for example, in "The Printing Ink Manual" (R. H. Leach, R. J. Pearce, London 1993) or "UV and EB Curing Formulation for Printing Inks, Coatings and Paints" (R. Holeman, P. Oldring, London 1988).
Their production and especially their processing properties are causally linked to the additives used.
Because of the binders and wetting agents used, aqueous printing inks and printing varnishes have a great tendency to foam. This becomes noticeable, not only during the production of these inks, but also especially during the application, when high amounts of air are introduced into the printing inks and printing varnishes.
Defoaming is frequently also a very critical problem for radiation-curable systems. In order to achieve a defoaming effect, a certain incompatibility is necessary. Radiation-curable systems frequently also have a very low dissolving l0 power, so that the addition of known defoaming substances (such as silicone oils) easily leads to cloudiness, flow disorders or gloss reduction particularly in the case of printing varnishes.
The use of silicone oils, particularly of dimethylpolysiloxanes of low to moderate viscosity, for defoaming aqueous and radiation-curable printing inks is known and described, for example, in the book by W. Noll, "Chemie and Technologie der Silicone" (Chemistry and Technology of the Silicones) (1968) (Verlag Chemie GMBH, 20 Weinheim/Bergstr.) or in the aforementioned literature.
The use of polyoxyalkylene polysiloxane copolymers as defoaming agents is also known. The US Patent 3,763,021 discloses a preparation for defoaming aqueous latexes, which is composed of (1) 1 to 20o by weight of a siloxane glycol copolymer of the general formula ~H3 ~H3 (CH3)3Si0 i1-0 ii-O Si(CH3)3 Y
wherein x has an average value of 6 to 420 and y an average value of 3 to 30 and G represents a group having the structure -D(OR)ZA, in which D is an alkylene group, R
represents ethylene groups and propylene groups or butylene groups in such a ratio of ethylene groups to other alkylene groups, that the ratio of carbon atoms to oxygen atoms in all OR blocks ranges from 2.3 . 1 to 2.8 . 1, z has an average value of 25 to 100 and A is a terminal group, (2) 65 to 98~ by weight of polypropylene glycol with an average molecular weight ranging from 1000 to 2000 and (3) 1 to 15$
by weight of a hydrophobic silicon oxide.
Typical methods for producing these aforementioned polyoxyalkylene polysiloxane copolymers are described in U.S. Patent No. 3,402,192, U.S. Patent No. 3,746,653, U.S.
Patent No. 3,784,479 and U.S. Patent No. 3,865,544.
These preparations, containing silicone oils or polyoxyalkylene polysiloxane copolymers, as known in the art, are suitable to a greater or lesser extent to prevent the formation of foam or destroy already existing foam in aqueous or radiation-curable printing inks or printing varnishes. However, it has turned out that printing varnishes and printing inks, to which polysiloxanes or polyoxyalkylene polysiloxane copolymers were added for defoaming, frequently have wetting defects or reduced gloss when applied on surfaces. This becomes evident particularly in highly sensitive systems and for printing on critical substrates (such as polyolefin film).
An important field of use are printing inks for paper and film. The handling of these objects for the industrial production of these printed products creates difficulties, because it is not always possible to avoid damaging the surface of the elements, which are often stacked or transported after the printing process.
Attempts have already been made to improve the ability to manipulate freshly printed objects by adding friction reducing additives, such as oils or waxes (for example, polyethylene or polytetrafluoroethyiene waxes) to the printing ink or applying these subsequently on the printed surface. This frequently also leads to a disturbing loss of gloss. Also subsequent application of wax on the printed product may not always be satisfactory, particularly since the manufacturing costs are increased by this additional processing step. Furthermore, high use concentrations are required in order to achieve an improvement in the scratch resistance.
AND PRINTING INKS WITH IMPROVED PROPERTIES
FIELD OF INVENTION:
The invention relates to aqueous and radiation-curable printing varnishes and printing inks, which contain special polyoxyalkylene polysiloxane copolymers. These printing varnishes and printing inks have improved scratch resistance, increased sliding ability, as well as an extremely low tendency to foam, so that the production of printing inks proceeds with less problems and, at the same time, an optically attractive typography can be obtained.
BACKGROUND INFORMATION AND PRIOR ART:
A constantly increasing number of printing inks and printing varnishes are being changed over to ecologically safer, water-based and radiation-curable systems. These systems are known and described, for example, in "The Printing Ink Manual" (R. H. Leach, R. J. Pearce, London 1993) or "UV and EB Curing Formulation for Printing Inks, Coatings and Paints" (R. Holeman, P. Oldring, London 1988).
Their production and especially their processing properties are causally linked to the additives used.
Because of the binders and wetting agents used, aqueous printing inks and printing varnishes have a great tendency to foam. This becomes noticeable, not only during the production of these inks, but also especially during the application, when high amounts of air are introduced into the printing inks and printing varnishes.
Defoaming is frequently also a very critical problem for radiation-curable systems. In order to achieve a defoaming effect, a certain incompatibility is necessary. Radiation-curable systems frequently also have a very low dissolving l0 power, so that the addition of known defoaming substances (such as silicone oils) easily leads to cloudiness, flow disorders or gloss reduction particularly in the case of printing varnishes.
The use of silicone oils, particularly of dimethylpolysiloxanes of low to moderate viscosity, for defoaming aqueous and radiation-curable printing inks is known and described, for example, in the book by W. Noll, "Chemie and Technologie der Silicone" (Chemistry and Technology of the Silicones) (1968) (Verlag Chemie GMBH, 20 Weinheim/Bergstr.) or in the aforementioned literature.
The use of polyoxyalkylene polysiloxane copolymers as defoaming agents is also known. The US Patent 3,763,021 discloses a preparation for defoaming aqueous latexes, which is composed of (1) 1 to 20o by weight of a siloxane glycol copolymer of the general formula ~H3 ~H3 (CH3)3Si0 i1-0 ii-O Si(CH3)3 Y
wherein x has an average value of 6 to 420 and y an average value of 3 to 30 and G represents a group having the structure -D(OR)ZA, in which D is an alkylene group, R
represents ethylene groups and propylene groups or butylene groups in such a ratio of ethylene groups to other alkylene groups, that the ratio of carbon atoms to oxygen atoms in all OR blocks ranges from 2.3 . 1 to 2.8 . 1, z has an average value of 25 to 100 and A is a terminal group, (2) 65 to 98~ by weight of polypropylene glycol with an average molecular weight ranging from 1000 to 2000 and (3) 1 to 15$
by weight of a hydrophobic silicon oxide.
Typical methods for producing these aforementioned polyoxyalkylene polysiloxane copolymers are described in U.S. Patent No. 3,402,192, U.S. Patent No. 3,746,653, U.S.
Patent No. 3,784,479 and U.S. Patent No. 3,865,544.
These preparations, containing silicone oils or polyoxyalkylene polysiloxane copolymers, as known in the art, are suitable to a greater or lesser extent to prevent the formation of foam or destroy already existing foam in aqueous or radiation-curable printing inks or printing varnishes. However, it has turned out that printing varnishes and printing inks, to which polysiloxanes or polyoxyalkylene polysiloxane copolymers were added for defoaming, frequently have wetting defects or reduced gloss when applied on surfaces. This becomes evident particularly in highly sensitive systems and for printing on critical substrates (such as polyolefin film).
An important field of use are printing inks for paper and film. The handling of these objects for the industrial production of these printed products creates difficulties, because it is not always possible to avoid damaging the surface of the elements, which are often stacked or transported after the printing process.
Attempts have already been made to improve the ability to manipulate freshly printed objects by adding friction reducing additives, such as oils or waxes (for example, polyethylene or polytetrafluoroethyiene waxes) to the printing ink or applying these subsequently on the printed surface. This frequently also leads to a disturbing loss of gloss. Also subsequent application of wax on the printed product may not always be satisfactory, particularly since the manufacturing costs are increased by this additional processing step. Furthermore, high use concentrations are required in order to achieve an improvement in the scratch resistance.
2j~~603 In much the same way as in air drying or forced (temperature) drying system, silicone oils, organically modified siloxanes, such as polyoxyalkylene polysiloxane copolymers (for example, German patent 36 37 155) or also spherical silicone elastomer particles are also added for these purposes at the present time to aqueous and radiation-curable printing varnishes and printing inks.
However, the aforementioned polyoxyalkylene polysiloxane copolymers, which effectively improve scratch resistance only at very high concentrations, lead to appreciable foam stabilization. Such foam stabilization is undesirable for the production of printing inks as well as for the actual printing process, since the printing result or the typography is negatively affected. On the other hand, those skilled in the art are also aware that the use of spherical, elastomeric silicone particles can lead to a reduction in gloss and can also lead to various wetting defects.
There is therefore a practical need for modified silicone additives, which in small concentrations improve the ability to manipulate objects, particularly objects printed serially. These additives are needed to, in particular, improve the scratch resistance of fresh surfaces, increase the sliding ability of these surfaces and, at the same time, prevent the formation of foam or destroy foam already formed, without having a negative effect on the typography.
However, the aforementioned polyoxyalkylene polysiloxane copolymers, which effectively improve scratch resistance only at very high concentrations, lead to appreciable foam stabilization. Such foam stabilization is undesirable for the production of printing inks as well as for the actual printing process, since the printing result or the typography is negatively affected. On the other hand, those skilled in the art are also aware that the use of spherical, elastomeric silicone particles can lead to a reduction in gloss and can also lead to various wetting defects.
There is therefore a practical need for modified silicone additives, which in small concentrations improve the ability to manipulate objects, particularly objects printed serially. These additives are needed to, in particular, improve the scratch resistance of fresh surfaces, increase the sliding ability of these surfaces and, at the same time, prevent the formation of foam or destroy foam already formed, without having a negative effect on the typography.
' 2.95~~3 Moreover, such additives shall be universally usable that is, largely independent of the nature and composition of the printing inks and printing varnishes to which they are added in order to improve the aforementioned properties. These additive should be effective in the least possible quantities and should not adversely affect the application properties of the printing inks and the printing varnishes.
In particular, they should not have a harmful effect on the development of the surface film and the curing of the printing inks. Furthermore, they may not have a disadvantageous effect on the stability of the printing inks and the printing varnishes and should not make the running properties worse.
OBJECT OF THE INVENTION:
It is therefore an object of the invention to provide compounds which fulfill the aforementioned requirements and are effective when added in small amounts.
SUMMARY OF THE INVENTION:
Pursuant to the invention, this objective is accomplished by aqueous and radiation-curable printing varnishes and printing inks, which contain polyoxyalkylene polysiloxane copolymers of the general formula R1 CH3 Ri R3C(OC3H6-)y (OC2Hd-)x~R2- ~ ip- Si0- Si-R2- (C2Ha0) x(C3H60) y R3 i CH3 n CH3 m RZy(CZH40) x.( C3Hsp") y~R3 wherein R1 = an alkyl group with 1 to 8 carbon atoms, RZ = (CH2)p0-, wherein p = 2, 3 or 4, R3 = hydrogen, an alkyl group with 1 to 4 carbon atoms or a (meth)acryloxy group, n = 40 to 60 and m = 0 to 3, x and y being selected so that the average molecular weight (Mw) of the polyoxyalkylene blocks is 300 to 800 g/mole and the molar ratio of x . y is 0:2 to 0.7, in amounts of 0.001 to 1.5$ by weight based on the varnish formulation, for improving scratch resistance and for defoaming.
The numerical values of the subscripts n and m are of vital importance for the properties of the compounds, n indicating the number of methylalkylsiloxy units and determining the chain length. For the compounds, which are to be used pursuant to the invention, n has a numerical value of 40 to 60. It is well known to those skilled in the art that the compounds are present in the form of a mixture with a distribution determined essentially by the laws of 2~956~3 statistics. The value of n therefore represents the average value of the number of methylalkylsiloxy units.
The value of m is 0 to 3 and preferably 0 to 1. If m =
0, the compounds are linear siloxanes, which have terminal polyoxyalkylene units. The polyoxyalkylene blocks consist of oxyethylene and oxypropylene units, the molecular weight of the polyoxyalkylene blocks being 300 to 800 g/mole. The molar ratio of oxyethylene units to oxypropylene units, expressed by the ratio of x . Y, is 0.2 to 0.7. it has l0 turned out that these structures of the block copolymers are of decisive importance for the advantages achieved pursuant to the invention.
For formulating radiation-curable systems in the printing ink industry, it is constantly becoming more important to increase the proportion of cross-linkable components in the formulation. The use of acrylated or methacrylated and thus cross-linkable additives minimizes their tendency to migrate and the proportion of substances extractable from the film.
Their use in radiation-curable printing varnishes and 20 printing inks is therefore particularly preferred.
Examples of polyoxyalkyiene polysiloxane copolymers, which can be used pursuant to the invention and are particularly suitable are ~~95603 H3 ~ H3 Hj~3H6-) 7 ~CC2H4' ) 3,C ~CH2) g- S10- S1-(CH2) 3'~~C2H4C) 3 ~C3H6C) 7 JH
CH3 5o CH3 i H3 ~3 r H3C L(OC3H6-) 7 (~2H4-) 3~ ~ (CHZ) 3- ~ Si ~ l~ Si-(CH2 ) 3 ~ ~(C2HI~) s tC3~) ~ CH3 H3 47 ~~2 ) g ~ H3 ~~C2H4d) 3 tC3H6C) 7~ CH3 Hg CH3 H i~3Hs') 11 i~2H4-) 3 0 iCH2) ~ ~i "i-iCH2) ~0 LiC2H40) 3 iC~sO) y H
L ~ I 1 CH~i-C- i0C3H&')si0C2H4-)4 OiQiz-) Si0- Sl iCHz-)3 iG~~40)4 iC~)s ~C-~'i2 ~3 40 ~3 These polyoxyalkylene polysiloxane copolymers are synthesized by the addition reaction between polyoxyalkylene glycols or polyoxyalkylene ethers of olefinically unsaturated alcohols, such as allyl polyoxyalkylene ethers, and appropriate hydrogensiloxanes. This reaction is ~~95b03 catalyzed by platinum compounds and described, for example, in the German patent 11 65 028.
Any free polyoxyalkylene glycols or their monoethers or monoesters which, due to the synthesis procedure, are contained in the copolymers to be used pursuant to the invention, can be tolerated and do not have to be removed from the product.
By reacting hydroxy-functional poiyoxyalkyiene-polysiloxane copolymers with acrylic acid or methacrylic acid or their esters, the corresponding acryloxy-functional or methacryloxy-functional polyoxyalkylene polysiloxane copolymers can be obtained by esterification and transesterification reactions known in the art.
The polyoxyalkylene polysiioxane copolymers can be used as such or in the form of aqueous emulsions.
The compounds, which are to be used pursuant to the invention, are added to aqueous, radiation-curable printing varnishes and printing inks in amounts of 0.001 to 1.5~ by weight, based on the formulation of the paint or varnish.
The polyoxyaikylene polysiloxane copolymers which are to be tested, correspond to the general formula I, in which the Rl, R2 and R3 groups as well as the subscripts n, m, x and y have the meanings or values given in the table below.
~~ 956t~3 Table Compound n m x y x/y R1 R2 R3 1 50 0 3 7 0.43 methyl propoxy H
2 47 3 3 7 0.43 methyl propoxy methyl 3 40 0 3 11 0.28 methyl propoxy H
4 40 0 4 6 0.66 methyl propoxy acryl 50 8 3 7 0.43 methyl propoxy H
6 20 0 3 7 0.43 methyl propoxy H
7 50 0 9 21 0.43 methyl propoxy H
8 47 3 7 7 1 methyl propoxy H
9 47 3 7 7 1 methyl propoxy acryl 10 40 0 0 10 0 methyl propoxy methyl The application properties of various compounds 1 to 4, which are to be used pursuant to the invention, as well as of the compounds of the comparison examples 5 to 10 are shown in the following.
For checking the application properties, the following formulations of aqueous and radiation-curable printing varnishes and printing inks were selected. The numerical data is given in ~ by weight.
1. Aqueous Test Systems Printing Varnish 1 TM
Neocryl BT 21 Solution. *) 39.0 TM
Neocryl BT 44 48.5 styrene modified acrylate . emulsion / Zeneca Isopropanol 3.8 Propylene glycol 1.9 TM
Aquacare 531 1.9 wax emulsion / W. Priem GmbH & Co. KG
Water, demineralized 4.7 Additive 0.2 100.0 TM
*) Neocryl BT 21 62.5 anionic acrylate emulsion /
Zeneca Ammonia, 25~ 3.3 Isopropanol 4.0 Water, demineralized 30.2 100.0 Printing Varnish 2 TM
Joncryl 74 50.5 Acrylate dispersion /
Johnson Polymer TM
Joncryl 680 solution *) 23.9 TM
Jonwax 35 7.2 polyethylene wax emulsion /
Johnson Polymer . Water, demineralized 12.4 Isopropanol 2.9 Zinc solution 2.9 Additive 0.2 TM
*) Joncryl 680 45.0 acylate resin / Johnson Polymer Ammonia, 25~ 11.2 Isopropanol 10.0 Water, demineralized 33.8 100.0 Printinct Varnish 3 TM
Joncryl 90 51.4 Styrol acrylate dispersion / Johnson Polymer TM
Joncryl 682 solution *) 25.7 TM
Dowanol DPM 1.8 TM
Jonwax 35 4.6 polyethylene wax emulsion /
Johnson Polymer Isopropanol 3.7 Water, demineralized 8.9 Dioctyl sulfosuccinate 3.7 solution 50~
Additive 0.2 100.0 TM
*) Joncryl 682 47.3 Acrylate resin / Johnson Polymer Ammonia, 250 15.8 Isopropanol 5.3 Water, demineralized 31.6 100.0 Printing Ink 1 Material to be milled:
TM
Joncryl 61 18.7 Acrylate resin solution /
Johnson Polymer Tego Foamex 810TM 0.1 Defoamer / Tego Chemie Service Water, demineralized 7.5 Heliogenblau D7080 11.2 Phthalocyanine blue / BASF
Dispersed for one hour (equipment: Scandex) Lacquer deposit:
TM
Joncryl 8051 46.2 Acrylate despersion /
Johnson Polymer TM
Jonwax 35 4.7 Polyethylene wax emulsion /
Johnson Polymer Additive 0.1 Water, demineralized 6.8 Isopropanol 4.7 Dispersed for 5 minutes (equipment: Scandex) 100.0 2. Radiation-Curable Systems Printina Varnish A
TM
Ebecryl 608 40.0 Epoxy acrylate oligomer / UCB
TPGDA 19.0 Difunctional acrylate monomer / UCB
TM
Ebecryl P 115 5.0 Tertiary amine / UCB
OTA 480 20.0 Trifunctional acrylate oligomer / UCB
Benzophenone 3.0 Photoinitiator / UCB
TM
Irgacure 651 2.0 Photoinitiator / UCB
Additive 1.0 100.0 Printing Varnish B
TM
Ebecryl 204 41.5 PU acrylate / UCB
TPGDA 41.0 Difunctional acrylate monomer / UCB
TM
Darocure 1173 4.0 Photoinitiator / Ciba-Geigy , TM
Ebecryl P 115 8.0 Tertiary amine / UCB
. Additive 1.0 100.0 The aqueous and radiation-curable printing inks are formulated in the usual manner in accordance with the formulations above. In each case, the additives are added as the last component and are incorporated by means of a TM
Perlmill disk for 3 minutes at 1500 rpm. The printing ink TM
is produced with the formulation above, using a Scandex for the dispersing, and the additives are the last components to be added to the lacquer deposit.
The radiation-curable printing varnishes are applied with a spiral doctor blade (12 mm) on wet Lenetta film, which has been pretreated with a corona discharge, and the printing inks are applied with a doctor blade on transparent PVC film. Curing is accomplished by two passages through 120 watt/cm ultraviolet light at a speed of 20 m/min.
Scratch resistance is the ability of a surface to resist visible, linear damage by hard objects moving in contact with the surface. Specially converted film-drawing equipment, which is driven by an electric motor, is used for the measurement of so-called scratch values. Instead of the film-drawing doctor blade, a plate is mounted on the moving ?195603 doctor blade holder; at the other end of the equipment the plate lies on rollers. The plate, on which the substrate (with the film coated with the printing ink) is fastened, can be moved with the help of the doctor blade holder. In order to simulate scratch stresses, a block with three points is placed on the printing ink film and loaded down with 500 g. The test film on the plate is pulled at a speed of 12 mm/sec under the weight. The vertical force required for this is measured and referred to as the scratch value.
Scratch values are determined 24 hours after the film is cured.
If the points are replaced by hemispheres and the procedure above is followed, the so-called sliding value is measured as a frictional force.
Foaming Test The aqueous printing varnish or printing ink (50 g) is weighed into a 150 mL beaker and sheared for 1 minute at 250 rpm with a Dissolver disk (3 cm diameter). Subsequently, 45 g are weighed into a measuring cylinder and the foam height is given in mm.
~~95603 Deaeration Test The radiation-curable printing varnish (30 g) is weighed into a 50 mL screw-top jar and sheared for 5 minutes at 3000 rpm with a Dissolver disk (2 cm diameter). The foam height is measured in mm and the decay height of the foam is measured in hours.
Wetting Behavior The films, produced as described previously, are examined visually for wetting disorders and evaluated on a scale from 1 to 4, 1 being a defect-free film and 4 being a film with many wetting defects.
z ~ ~~~o~
Results in Printing Varnish 1 Compound Concentration Foam Scratch Sliding Wetting Value Value Value Behavior mL/45g mN/m mN/m (Scale of 1-4) Blank 0 110 234 230 1 1 0.2 48 108 78 1 2 0.2 50 92 74 1 3 0.2 47 125 92 1 4 0.2 52 83 67 1 5 0.2 53 170 134 1 6 0.2 57 155 128 1 7 0.2 72 136 100 2 8 0.2 75 98 79 1 9 0.2 73 104 79 1 10 0.2 52 180 134 3 Results in Printing Varnish 2 Compound Concentration Foam Scratch Sliding Wetting Value Value Value Behavior m1,/45g mN/m mN/m (Scale of 1-4) Blank 0 69 185 107 1 1 0.2 46 100 62 1 2 0.2 48 90 58 1 3 0.2 46 102 66 1 4 0.2 47 85 63 1 5 0.2 51 152 95 1 6 0.2 53 155 92 1 7 0.2 65 118 70 2 8 0.2 63 98 64 1 9 0.2 60 104 61 i 10 0.2 48 123 70 4 ~1956~3 Results in Printing Varnish 3 Compound Concentration Foam Scratch Sliding Wetting Value Value Value Behavior mL/45g mN/m mN/m (Scale of 1-4) Blank 0 103 182 142 1 1 0.2 47 108 90 1 2 0.2 48 90 82 1 3 0.2 46 100 88 1 4 0.2 48 89 79 1 5 0.2 51 140 123 1 6 0.2 52 138 127 1 7 0.2 72 106 76 2 8 0.2 70 110 76 l 9 0.2 68 104 90 1 10 0.2 47 140 118 3 Results in Printing Ink 1 Compound Concentration Foam Scratch Sliding Wetting Value Value Value Behavior mL/45g mN/m mN/m (Scale of 1-4) Blank 0 62 159 120 1 1 0.2 45 106 70 1 2 0.2 47 90 68 1 3 0.2 46 99 72 1 4 0.2 47 89 66 1 5 0.2 49 128 99 2 6 0.2 52 138 106 1 7 0.2 58 103 73 2 8 0.2 57 108 75 2 9 0.2 57 104 74 2 10 0.2 46 140 108 4 2~9~~~
Results in Printing Varnish A
Com- Concen- Foam Foam Scratch Sliding Wetting pound tration Height Decay Value Value Behavior mm Time min mN/m mN/m (Scale of 1-4) Blank 0 10 180 230 198 3 %19~6~3 (Results in Printing Varnish B
',Comp- Concen- Foam Foam Scratch Sliding Wetting pound tration Height Decay Value Value Behavior mm Time min mN/m mN/m (Scale of 1-4) Blank 0 8 150 210 168 2 As can be seen from the preceding Tables, the compounds, which are to be used persuant to the invention, are distinguished by their universal applicability.
As is evident from the Comparison Examples, the subscripts n and m and, the values of x and y as well as their ratio to one another are responsible for the fact that the polyoxyalkylene polysiloxane copolymers, which are to be used pursuant to the invention, are excellent defoamers and, at the same time, increase the scratch resistance of the printing inks as well as their sliding ability, without causing wetting defects during the printing process.
In particular, they should not have a harmful effect on the development of the surface film and the curing of the printing inks. Furthermore, they may not have a disadvantageous effect on the stability of the printing inks and the printing varnishes and should not make the running properties worse.
OBJECT OF THE INVENTION:
It is therefore an object of the invention to provide compounds which fulfill the aforementioned requirements and are effective when added in small amounts.
SUMMARY OF THE INVENTION:
Pursuant to the invention, this objective is accomplished by aqueous and radiation-curable printing varnishes and printing inks, which contain polyoxyalkylene polysiloxane copolymers of the general formula R1 CH3 Ri R3C(OC3H6-)y (OC2Hd-)x~R2- ~ ip- Si0- Si-R2- (C2Ha0) x(C3H60) y R3 i CH3 n CH3 m RZy(CZH40) x.( C3Hsp") y~R3 wherein R1 = an alkyl group with 1 to 8 carbon atoms, RZ = (CH2)p0-, wherein p = 2, 3 or 4, R3 = hydrogen, an alkyl group with 1 to 4 carbon atoms or a (meth)acryloxy group, n = 40 to 60 and m = 0 to 3, x and y being selected so that the average molecular weight (Mw) of the polyoxyalkylene blocks is 300 to 800 g/mole and the molar ratio of x . y is 0:2 to 0.7, in amounts of 0.001 to 1.5$ by weight based on the varnish formulation, for improving scratch resistance and for defoaming.
The numerical values of the subscripts n and m are of vital importance for the properties of the compounds, n indicating the number of methylalkylsiloxy units and determining the chain length. For the compounds, which are to be used pursuant to the invention, n has a numerical value of 40 to 60. It is well known to those skilled in the art that the compounds are present in the form of a mixture with a distribution determined essentially by the laws of 2~956~3 statistics. The value of n therefore represents the average value of the number of methylalkylsiloxy units.
The value of m is 0 to 3 and preferably 0 to 1. If m =
0, the compounds are linear siloxanes, which have terminal polyoxyalkylene units. The polyoxyalkylene blocks consist of oxyethylene and oxypropylene units, the molecular weight of the polyoxyalkylene blocks being 300 to 800 g/mole. The molar ratio of oxyethylene units to oxypropylene units, expressed by the ratio of x . Y, is 0.2 to 0.7. it has l0 turned out that these structures of the block copolymers are of decisive importance for the advantages achieved pursuant to the invention.
For formulating radiation-curable systems in the printing ink industry, it is constantly becoming more important to increase the proportion of cross-linkable components in the formulation. The use of acrylated or methacrylated and thus cross-linkable additives minimizes their tendency to migrate and the proportion of substances extractable from the film.
Their use in radiation-curable printing varnishes and 20 printing inks is therefore particularly preferred.
Examples of polyoxyalkyiene polysiloxane copolymers, which can be used pursuant to the invention and are particularly suitable are ~~95603 H3 ~ H3 Hj~3H6-) 7 ~CC2H4' ) 3,C ~CH2) g- S10- S1-(CH2) 3'~~C2H4C) 3 ~C3H6C) 7 JH
CH3 5o CH3 i H3 ~3 r H3C L(OC3H6-) 7 (~2H4-) 3~ ~ (CHZ) 3- ~ Si ~ l~ Si-(CH2 ) 3 ~ ~(C2HI~) s tC3~) ~ CH3 H3 47 ~~2 ) g ~ H3 ~~C2H4d) 3 tC3H6C) 7~ CH3 Hg CH3 H i~3Hs') 11 i~2H4-) 3 0 iCH2) ~ ~i "i-iCH2) ~0 LiC2H40) 3 iC~sO) y H
L ~ I 1 CH~i-C- i0C3H&')si0C2H4-)4 OiQiz-) Si0- Sl iCHz-)3 iG~~40)4 iC~)s ~C-~'i2 ~3 40 ~3 These polyoxyalkylene polysiloxane copolymers are synthesized by the addition reaction between polyoxyalkylene glycols or polyoxyalkylene ethers of olefinically unsaturated alcohols, such as allyl polyoxyalkylene ethers, and appropriate hydrogensiloxanes. This reaction is ~~95b03 catalyzed by platinum compounds and described, for example, in the German patent 11 65 028.
Any free polyoxyalkylene glycols or their monoethers or monoesters which, due to the synthesis procedure, are contained in the copolymers to be used pursuant to the invention, can be tolerated and do not have to be removed from the product.
By reacting hydroxy-functional poiyoxyalkyiene-polysiloxane copolymers with acrylic acid or methacrylic acid or their esters, the corresponding acryloxy-functional or methacryloxy-functional polyoxyalkylene polysiloxane copolymers can be obtained by esterification and transesterification reactions known in the art.
The polyoxyalkylene polysiioxane copolymers can be used as such or in the form of aqueous emulsions.
The compounds, which are to be used pursuant to the invention, are added to aqueous, radiation-curable printing varnishes and printing inks in amounts of 0.001 to 1.5~ by weight, based on the formulation of the paint or varnish.
The polyoxyaikylene polysiloxane copolymers which are to be tested, correspond to the general formula I, in which the Rl, R2 and R3 groups as well as the subscripts n, m, x and y have the meanings or values given in the table below.
~~ 956t~3 Table Compound n m x y x/y R1 R2 R3 1 50 0 3 7 0.43 methyl propoxy H
2 47 3 3 7 0.43 methyl propoxy methyl 3 40 0 3 11 0.28 methyl propoxy H
4 40 0 4 6 0.66 methyl propoxy acryl 50 8 3 7 0.43 methyl propoxy H
6 20 0 3 7 0.43 methyl propoxy H
7 50 0 9 21 0.43 methyl propoxy H
8 47 3 7 7 1 methyl propoxy H
9 47 3 7 7 1 methyl propoxy acryl 10 40 0 0 10 0 methyl propoxy methyl The application properties of various compounds 1 to 4, which are to be used pursuant to the invention, as well as of the compounds of the comparison examples 5 to 10 are shown in the following.
For checking the application properties, the following formulations of aqueous and radiation-curable printing varnishes and printing inks were selected. The numerical data is given in ~ by weight.
1. Aqueous Test Systems Printing Varnish 1 TM
Neocryl BT 21 Solution. *) 39.0 TM
Neocryl BT 44 48.5 styrene modified acrylate . emulsion / Zeneca Isopropanol 3.8 Propylene glycol 1.9 TM
Aquacare 531 1.9 wax emulsion / W. Priem GmbH & Co. KG
Water, demineralized 4.7 Additive 0.2 100.0 TM
*) Neocryl BT 21 62.5 anionic acrylate emulsion /
Zeneca Ammonia, 25~ 3.3 Isopropanol 4.0 Water, demineralized 30.2 100.0 Printing Varnish 2 TM
Joncryl 74 50.5 Acrylate dispersion /
Johnson Polymer TM
Joncryl 680 solution *) 23.9 TM
Jonwax 35 7.2 polyethylene wax emulsion /
Johnson Polymer . Water, demineralized 12.4 Isopropanol 2.9 Zinc solution 2.9 Additive 0.2 TM
*) Joncryl 680 45.0 acylate resin / Johnson Polymer Ammonia, 25~ 11.2 Isopropanol 10.0 Water, demineralized 33.8 100.0 Printinct Varnish 3 TM
Joncryl 90 51.4 Styrol acrylate dispersion / Johnson Polymer TM
Joncryl 682 solution *) 25.7 TM
Dowanol DPM 1.8 TM
Jonwax 35 4.6 polyethylene wax emulsion /
Johnson Polymer Isopropanol 3.7 Water, demineralized 8.9 Dioctyl sulfosuccinate 3.7 solution 50~
Additive 0.2 100.0 TM
*) Joncryl 682 47.3 Acrylate resin / Johnson Polymer Ammonia, 250 15.8 Isopropanol 5.3 Water, demineralized 31.6 100.0 Printing Ink 1 Material to be milled:
TM
Joncryl 61 18.7 Acrylate resin solution /
Johnson Polymer Tego Foamex 810TM 0.1 Defoamer / Tego Chemie Service Water, demineralized 7.5 Heliogenblau D7080 11.2 Phthalocyanine blue / BASF
Dispersed for one hour (equipment: Scandex) Lacquer deposit:
TM
Joncryl 8051 46.2 Acrylate despersion /
Johnson Polymer TM
Jonwax 35 4.7 Polyethylene wax emulsion /
Johnson Polymer Additive 0.1 Water, demineralized 6.8 Isopropanol 4.7 Dispersed for 5 minutes (equipment: Scandex) 100.0 2. Radiation-Curable Systems Printina Varnish A
TM
Ebecryl 608 40.0 Epoxy acrylate oligomer / UCB
TPGDA 19.0 Difunctional acrylate monomer / UCB
TM
Ebecryl P 115 5.0 Tertiary amine / UCB
OTA 480 20.0 Trifunctional acrylate oligomer / UCB
Benzophenone 3.0 Photoinitiator / UCB
TM
Irgacure 651 2.0 Photoinitiator / UCB
Additive 1.0 100.0 Printing Varnish B
TM
Ebecryl 204 41.5 PU acrylate / UCB
TPGDA 41.0 Difunctional acrylate monomer / UCB
TM
Darocure 1173 4.0 Photoinitiator / Ciba-Geigy , TM
Ebecryl P 115 8.0 Tertiary amine / UCB
. Additive 1.0 100.0 The aqueous and radiation-curable printing inks are formulated in the usual manner in accordance with the formulations above. In each case, the additives are added as the last component and are incorporated by means of a TM
Perlmill disk for 3 minutes at 1500 rpm. The printing ink TM
is produced with the formulation above, using a Scandex for the dispersing, and the additives are the last components to be added to the lacquer deposit.
The radiation-curable printing varnishes are applied with a spiral doctor blade (12 mm) on wet Lenetta film, which has been pretreated with a corona discharge, and the printing inks are applied with a doctor blade on transparent PVC film. Curing is accomplished by two passages through 120 watt/cm ultraviolet light at a speed of 20 m/min.
Scratch resistance is the ability of a surface to resist visible, linear damage by hard objects moving in contact with the surface. Specially converted film-drawing equipment, which is driven by an electric motor, is used for the measurement of so-called scratch values. Instead of the film-drawing doctor blade, a plate is mounted on the moving ?195603 doctor blade holder; at the other end of the equipment the plate lies on rollers. The plate, on which the substrate (with the film coated with the printing ink) is fastened, can be moved with the help of the doctor blade holder. In order to simulate scratch stresses, a block with three points is placed on the printing ink film and loaded down with 500 g. The test film on the plate is pulled at a speed of 12 mm/sec under the weight. The vertical force required for this is measured and referred to as the scratch value.
Scratch values are determined 24 hours after the film is cured.
If the points are replaced by hemispheres and the procedure above is followed, the so-called sliding value is measured as a frictional force.
Foaming Test The aqueous printing varnish or printing ink (50 g) is weighed into a 150 mL beaker and sheared for 1 minute at 250 rpm with a Dissolver disk (3 cm diameter). Subsequently, 45 g are weighed into a measuring cylinder and the foam height is given in mm.
~~95603 Deaeration Test The radiation-curable printing varnish (30 g) is weighed into a 50 mL screw-top jar and sheared for 5 minutes at 3000 rpm with a Dissolver disk (2 cm diameter). The foam height is measured in mm and the decay height of the foam is measured in hours.
Wetting Behavior The films, produced as described previously, are examined visually for wetting disorders and evaluated on a scale from 1 to 4, 1 being a defect-free film and 4 being a film with many wetting defects.
z ~ ~~~o~
Results in Printing Varnish 1 Compound Concentration Foam Scratch Sliding Wetting Value Value Value Behavior mL/45g mN/m mN/m (Scale of 1-4) Blank 0 110 234 230 1 1 0.2 48 108 78 1 2 0.2 50 92 74 1 3 0.2 47 125 92 1 4 0.2 52 83 67 1 5 0.2 53 170 134 1 6 0.2 57 155 128 1 7 0.2 72 136 100 2 8 0.2 75 98 79 1 9 0.2 73 104 79 1 10 0.2 52 180 134 3 Results in Printing Varnish 2 Compound Concentration Foam Scratch Sliding Wetting Value Value Value Behavior m1,/45g mN/m mN/m (Scale of 1-4) Blank 0 69 185 107 1 1 0.2 46 100 62 1 2 0.2 48 90 58 1 3 0.2 46 102 66 1 4 0.2 47 85 63 1 5 0.2 51 152 95 1 6 0.2 53 155 92 1 7 0.2 65 118 70 2 8 0.2 63 98 64 1 9 0.2 60 104 61 i 10 0.2 48 123 70 4 ~1956~3 Results in Printing Varnish 3 Compound Concentration Foam Scratch Sliding Wetting Value Value Value Behavior mL/45g mN/m mN/m (Scale of 1-4) Blank 0 103 182 142 1 1 0.2 47 108 90 1 2 0.2 48 90 82 1 3 0.2 46 100 88 1 4 0.2 48 89 79 1 5 0.2 51 140 123 1 6 0.2 52 138 127 1 7 0.2 72 106 76 2 8 0.2 70 110 76 l 9 0.2 68 104 90 1 10 0.2 47 140 118 3 Results in Printing Ink 1 Compound Concentration Foam Scratch Sliding Wetting Value Value Value Behavior mL/45g mN/m mN/m (Scale of 1-4) Blank 0 62 159 120 1 1 0.2 45 106 70 1 2 0.2 47 90 68 1 3 0.2 46 99 72 1 4 0.2 47 89 66 1 5 0.2 49 128 99 2 6 0.2 52 138 106 1 7 0.2 58 103 73 2 8 0.2 57 108 75 2 9 0.2 57 104 74 2 10 0.2 46 140 108 4 2~9~~~
Results in Printing Varnish A
Com- Concen- Foam Foam Scratch Sliding Wetting pound tration Height Decay Value Value Behavior mm Time min mN/m mN/m (Scale of 1-4) Blank 0 10 180 230 198 3 %19~6~3 (Results in Printing Varnish B
',Comp- Concen- Foam Foam Scratch Sliding Wetting pound tration Height Decay Value Value Behavior mm Time min mN/m mN/m (Scale of 1-4) Blank 0 8 150 210 168 2 As can be seen from the preceding Tables, the compounds, which are to be used persuant to the invention, are distinguished by their universal applicability.
As is evident from the Comparison Examples, the subscripts n and m and, the values of x and y as well as their ratio to one another are responsible for the fact that the polyoxyalkylene polysiloxane copolymers, which are to be used pursuant to the invention, are excellent defoamers and, at the same time, increase the scratch resistance of the printing inks as well as their sliding ability, without causing wetting defects during the printing process.
Claims (4)
1. Aqueous and radiation-curable printing varnishes and printing inks, which contain polyoxyalkylene polysiloxane copolymers of the general formula wherein R1 = an alkyl group with 1 to 8 carbon atoms, R2 = (CH2)pO-, wherein p = 2, 3 or 4, R3 = hydrogen, an alkyl group with 1 to 4 carbon atoms or a (meth)acryloxy group, n = 40 to 60 and m = 0 to 3, x and y being selected so that the average molecular weight (Mw) of the polyoxyalkylene blocks is 300 to 800 g/mole and the molar ratio of x . y is 0.2 to 0.7, in amounts of 0.001 to 1.5% by weight based on the varnish formulation.
2. The aqueous and radiation-curable (UV) printing varnishes and printing inks of claim 1, wherein m = 0 or 1.
3. The radiation-curable (UV) printing varnishes and printing inks of claim 1, wherein the R3 group is methacryloxy or acryloxy.
4. The aqueous printing varnishes and printing inks of claim 1, wherein the R3 group is hydrogen or a methyl group.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19602097A DE19602097A1 (en) | 1996-01-22 | 1996-01-22 | Aqueous and radiation-curing printing varnishes and printing inks with improved properties |
| DE19602097.2 | 1996-01-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2195603A1 CA2195603A1 (en) | 1997-07-23 |
| CA2195603C true CA2195603C (en) | 2003-06-10 |
Family
ID=7783321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002195603A Expired - Fee Related CA2195603C (en) | 1996-01-22 | 1997-01-21 | Aqueous and radiation-curable printing varnishes and printing inks with improved properties |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US5733971A (en) |
| EP (1) | EP0785240B1 (en) |
| JP (1) | JP3569406B2 (en) |
| AT (1) | ATE194373T1 (en) |
| AU (1) | AU709188B2 (en) |
| CA (1) | CA2195603C (en) |
| DE (2) | DE19602097A1 (en) |
| DK (1) | DK0785240T3 (en) |
| ES (1) | ES2150154T3 (en) |
| GR (1) | GR3034471T3 (en) |
| PT (1) | PT785240E (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100338136B1 (en) * | 1998-03-03 | 2002-05-24 | 울프 크라스텐센, 스트라쎄 로텐베르그 | New(meth) acrylate esters of organosiloxane polyols, process for their prepartion and their use as radiation-curable coating materials |
| US6207782B1 (en) | 1998-05-28 | 2001-03-27 | Cromption Corporation | Hydrophilic siloxane latex emulsions |
| DE19836260A1 (en) | 1998-08-11 | 2000-02-24 | Wacker Chemie Gmbh | Linear polyether-polysiloxane copolymers useful as foam stabilisers or defoaming agents in aqueous emulsions and compositions |
| US6576155B1 (en) * | 1998-11-10 | 2003-06-10 | Biocrystal, Ltd. | Fluorescent ink compositions comprising functionalized fluorescent nanocrystals |
| DE50008471D1 (en) * | 1999-05-14 | 2004-12-09 | Goldschmidt Ag Th | Use of water-insoluble polyoxyarylene-polysiloxane block copolymers for defoaming aqueous media |
| US6613815B2 (en) * | 2001-02-02 | 2003-09-02 | Xerox Corporation | Inks comprising linear ABSCS′B′A′or BASCS′A′B′alkylene oxide/siloxane block copolymers |
| US7291658B2 (en) * | 2003-10-14 | 2007-11-06 | Ashland Licensing And Intellectual Property Llc | Radiation-curable inks for flexographic and screen-printing applications from multifunctional acrylate oligomers |
| US20080188673A1 (en) * | 2005-03-24 | 2008-08-07 | Goldschmidt Gmbh | Ether Alcohol-Based Surfactants Having a Reduced Surface Tension and Use Thereof |
| JP5475212B2 (en) * | 2006-03-30 | 2014-04-16 | 関西ペイント株式会社 | Water-based paint composition for cans |
| JP5279283B2 (en) * | 2007-02-09 | 2013-09-04 | キヤノン株式会社 | Liquid composition, image forming method, cartridge, recording unit, and ink jet recording apparatus |
| US7918928B2 (en) | 2007-02-09 | 2011-04-05 | Canon Kabushiki Kaisha | Pigment ink, ink jet recording method, ink cartridge, recording unit and ink jet recording apparatus |
| US8013051B2 (en) * | 2007-02-09 | 2011-09-06 | Canon Kabushiki Kaisha | Liquid composition, image forming method, cartridge, recording unit and ink jet recording apparatus |
| JP5435876B2 (en) * | 2007-02-09 | 2014-03-05 | キヤノン株式会社 | Pigment ink, ink jet recording method, ink cartridge, recording unit, and ink jet recording apparatus |
| JP5995396B2 (en) * | 2008-08-08 | 2016-09-21 | キヤノン株式会社 | Ink set, ink jet recording method, and ink jet recording apparatus |
| JP5663899B2 (en) * | 2010-03-03 | 2015-02-04 | 株式会社リコー | Photocurable liquid ink, method for producing photocurable liquid ink, developing device, and image forming apparatus |
| US8735524B2 (en) | 2011-09-09 | 2014-05-27 | Air Products And Chemicals, Inc. | Silicone containing compositions and uses thereof |
| CN108348955A (en) * | 2015-11-02 | 2018-07-31 | 施密德吕纳股份公司 | For generating the method for surface effect especially in UV curable layer, for the device of its manufacture and according to the article of the invention obtained |
| EP3524651A1 (en) | 2018-02-08 | 2019-08-14 | Evonik Degussa GmbH | Aqueous polyorganosiloxane hybrid resin dispersion |
| US10996491B2 (en) * | 2018-03-23 | 2021-05-04 | Johnson & Johnson Vision Care, Inc. | Ink composition for cosmetic contact lenses |
| US20220073765A1 (en) | 2018-12-20 | 2022-03-10 | Evonik Operations Gmbh | Universal slip and flow control additives with recoatable quality |
| US11891526B2 (en) | 2019-09-12 | 2024-02-06 | Johnson & Johnson Vision Care, Inc. | Ink composition for cosmetic contact lenses |
| EP3954740A1 (en) | 2020-08-14 | 2022-02-16 | Evonik Operations GmbH | Defoamer composition based on polysiloxanes with organofunctionally modified polysiloxanes |
| CN112778825A (en) * | 2020-12-31 | 2021-05-11 | 惠州乐印水性科技有限公司 | Ink for gravure printing and preparation method thereof |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA695633A (en) * | 1961-07-31 | 1964-10-06 | A. Haluska Loren | Siloxane glycol branch copolymers |
| DE1165028B (en) * | 1962-11-14 | 1964-03-12 | Goldschmidt Ag Th | Process for the production of silicon-containing hydrocarbons by the addition of hydrogen silanes to unsaturated hydrocarbons |
| US3427271A (en) * | 1966-11-04 | 1969-02-11 | Dow Corning | Novel organosilicon compositions |
| US3763021A (en) * | 1971-05-17 | 1973-10-02 | Dow Corning | Distillation process of monomers with the addition of an antifoam composition |
| US3784479A (en) * | 1972-05-15 | 1974-01-08 | Dow Corning | Foam control composition |
| BE788249A (en) * | 1972-05-15 | 1973-02-28 | Dow Corning | SILICONE COMPOSITIONS TO COMBAT FOAMING IN JET DYING PROCESSES |
| US4348431A (en) * | 1981-02-19 | 1982-09-07 | General Electric Company | Process for coating plastic films |
| GB8512483D0 (en) * | 1985-05-17 | 1985-06-19 | Dow Corning Ltd | Polish compositions |
| DE3637155C1 (en) * | 1986-10-31 | 1987-09-10 | Goldschmidt Ag Th | Use of polyoxyalkylene-polysiloxane block copolymers as a means of improving the scratch resistance and increasing the slidability of paint surfaces |
| DE4009889C1 (en) * | 1990-03-28 | 1991-06-13 | Th. Goldschmidt Ag, 4300 Essen, De | |
| US5262087A (en) * | 1991-05-01 | 1993-11-16 | Kose Corporation | Water-in-oil type emulsified composition |
| JP2999334B2 (en) * | 1992-09-14 | 2000-01-17 | 早川ゴム株式会社 | Ink composition, method for printing the same, and method for releasing printed matter |
| DE4331608A1 (en) * | 1993-09-17 | 1995-03-23 | Goldschmidt Ag Th | Organopolysiloxanes modified with acrylate groups |
| JP2790021B2 (en) * | 1993-09-30 | 1998-08-27 | 日本油脂株式会社 | Paint composition |
-
1996
- 1996-01-22 DE DE19602097A patent/DE19602097A1/en not_active Withdrawn
-
1997
- 1997-01-07 US US08/779,636 patent/US5733971A/en not_active Expired - Lifetime
- 1997-01-09 DE DE59701958T patent/DE59701958D1/en not_active Expired - Lifetime
- 1997-01-09 PT PT97100217T patent/PT785240E/en unknown
- 1997-01-09 DK DK97100217T patent/DK0785240T3/en active
- 1997-01-09 ES ES97100217T patent/ES2150154T3/en not_active Expired - Lifetime
- 1997-01-09 EP EP97100217A patent/EP0785240B1/en not_active Expired - Lifetime
- 1997-01-09 AT AT97100217T patent/ATE194373T1/en not_active IP Right Cessation
- 1997-01-20 JP JP00744197A patent/JP3569406B2/en not_active Expired - Fee Related
- 1997-01-21 CA CA002195603A patent/CA2195603C/en not_active Expired - Fee Related
- 1997-01-21 AU AU12271/97A patent/AU709188B2/en not_active Ceased
-
2000
- 2000-09-21 GR GR20000402160T patent/GR3034471T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0785240B1 (en) | 2000-07-05 |
| ES2150154T3 (en) | 2000-11-16 |
| US5733971A (en) | 1998-03-31 |
| PT785240E (en) | 2000-10-31 |
| EP0785240A2 (en) | 1997-07-23 |
| DE59701958D1 (en) | 2000-08-10 |
| ATE194373T1 (en) | 2000-07-15 |
| AU1227197A (en) | 1997-07-31 |
| DE19602097A1 (en) | 1997-07-24 |
| CA2195603A1 (en) | 1997-07-23 |
| DK0785240T3 (en) | 2000-09-18 |
| JPH09194782A (en) | 1997-07-29 |
| EP0785240A3 (en) | 1998-04-15 |
| GR3034471T3 (en) | 2000-12-29 |
| AU709188B2 (en) | 1999-08-26 |
| JP3569406B2 (en) | 2004-09-22 |
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