Surface control additive for radiation curing system, preparation method therefor and application thereof

Abstract

The present invention is related to a surface control additive for a radiation curing system, the method for its preparation as well as its application. The surface control additive has the following structure: ##STR00001##
wherein A is ##STR00002##
wherein m is an integer from 0 to 400, n is an integer from 1 to 500, x is an integer from 0 to 800, p is an integer from 0 to 600, q is an integer from 1 to 800, R.sup.4 and R.sup.5 are H or CH.sub.3 respectively, R.sup.6 is H or a linear or a branched alkyl group containing 1-18 carbon atoms or an acyl group containing 2-5 carbon atoms. The surface control additive of the present invention is applied to radiation curing (UV/EB) paint and inks, enables the coatings to maintain non-adhesive and smooth for a long time, and minimizes transferable precipitates from a cured film. In addition, by using different combinations of EO and PO, the surface control additive of the present invention can adapt to a free selection from high-polarity aquosity to a low-polarity aliphatic hydrocarbon solvent system.

Claims

1. A surface control additive for a radiation curing system, characterized in that the surface control additive has the following formula: ##STR00013## wherein A is ##STR00014## wherein m is an integer from 0 to 400, n is an integer from 1 to 500, x is an integer from 0 to 800, p is an integer from 0 to 600, q is an integer from 1 to 800, R.sup.4 and R.sup.5 are independently H or CH.sub.3, R.sup.6 is H or a linear or a branched alkyl group containing 1-18 carbon atoms or an acyl group containing 2-5 carbon atoms.

2. The surface control additive according to claim 1, wherein R.sup.6 is methyl, ethyl, n-butyl, isobutyl or acetyl group.

3. A method to prepare a surface control additive according to claim 1, wherein the method contains the following steps: first, component A and component B are added to the reactor, and 2% hexachloroplatinic acid solution is added as a catalyst and constitutes a final concentration of 0.02-0.2 wt % of the whole mixture, and the reaction is carried out under 100-120° C. for 4-8 hours, and hydrogen addition silicide reaction occurs, wherein component B reacts with 1-90% of the silicon hydrogen groups in component A, the temperature in the reaction system is decreased to 60 to 80° C., component C and D are added and the reaction is carried out further for 2-6 hours until the characteristic IR peak of the silicon hydrogen disappears, wherein component C constitutes a concentration of 0.01-1 wt % of the whole mixture, component D reacts with 1-90% of the silicon hydrogen groups in component A, and volatile components are removed under vacuum at 70-100° C. and the surface control additive is obtained, wherein said component A is hydrogen containing polysiloxane with the following formula: ##STR00015## wherein R.sup.1 is CH.sub.3, R.sup.2 is CH.sub.3 or H and at least one R.sup.2 is H, and R.sup.3 is H, p is an integer from 1 to 600, q is an integer from 1 to 800; wherein said component B is an allyl polyether with the following formula: ##STR00016## wherein R.sup.4 and R.sup.5 are independently H or CH.sub.3, R.sup.6 is H or a linear or branched alkyl group containing 1-18 carbon atoms or an acyl group containing 2-5 carbon atoms, m is an integer from 0 to 400, n is an integer from 1 to 500, and the number average molecular weight of component B is 200 to 20000; wherein said component C is quinone, a phenol or arylamine polymerization inhibitor, and the amount of component C is 0.01-1 wt % of the whole mixture; and wherein said component D is allyl acrylate or allyl methacrylate.

4. The method according to claim 3, wherein said component A has a number average molecular weight of 500-20000, said R.sup.6 is methyl, ethyl, butyl, isobutyl or acetyl group, and component B has a number average molecular weight of 300-10000.

5. The method according to claim 4, wherein said component A has a number average molecular weight of 1000-3000, and said component B has a number average molecular weight of 400-3000.

6. The method according to claim 3, wherein said component B has an HLB value of 1-17.

7. The method according to claim 6, wherein said component C is p-methoxyphenol, hydroquinone, phenothiazine, p-tert-butylcatechol, 1-hyroxy-4-methoxy benzene or 2,6-2,6-di-tert-butyl-4-methylphenol.

8. The surface control additive according to claim 1, wherein said surface control additive is applied to radiation curing (UV/EB) dopes and inks.

9. The surface control additive according to claim 2, wherein said surface control additive is applied to radiation curing (MEE) dopes and inks.

10. The method according to claim 3, wherein R.sup.6 is methyl, ethyl, n-butyl, isobutyl or acetyl group.

11. The method accordingly to claim 3, wherein R.sup.2 is H.

Description

DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is the IR spectrum of product in example 1.

DESCRIPTION OF THE PREFERRED EMBODIMENT

(2) The current invention is further illustrated by the following examples, which do not limit the protection scope of the current invention.

(3) First the preparation method of component A is as follows:

(4) Hydrogen containing polysiloxane A1 (Mw=2052, SiH content is 0.39%):

(5) Under the protection of nitrogen, 7.92 weight portions of hexamethyldisiloxane, 26.0 weight portions of hydrogen containing silicone oil 202 (SiH content is 1.5%, domestic) and 66.08 weight portions of octamethylcyclotetrasiloxane are added, the temperature is increased to 50-60° C., 0.88 weight portions of 10% trifluoromethane sulfonic acid butyl acetate solution is added, the temperature is maintained for 8 hours, and 0.1 weight portion of triethylamine is added, after 1 hour of neutralization, the mixture is let sit for 12 hours, filtered and self-made polysiloxane A1 is obtained. The average structure of the products is as follows:

(6) ##STR00007##

(7) Hydrogen containing polysiloxane A2 (Mw=1680, SiH content is 0.48%):

(8) Under the protection of nitrogen, 8.0 weight portions of hexamethyldisiloxane, 24.0 weight portions of hydrogen containing silicone oil 202 (SiH content is 1.5%, domestic) and 68.0 weight portions of octamethylcyclotetrasiloxane are added, the temperature is increased to 50-60° C., 0.88 weight portions of 10% trifluoromethane sulfonic acid butyl acetate solution is added, the temperature is maintained for 8 hours, and 0.1 weight portion of triethylamine is added, after 1 hour of neutralization, the mixture is let sit for 12 hours, filtered and self-made polysiloxane A2 is obtained. The average structure of the products is as follows:

(9) ##STR00008##

(10) Hydrogen containing polysiloxane A3 (Mw=2000, SiH content is 0.3%):

(11) Under the protection of nitrogen, 8.12 weight portions of hexamethyldisiloxane, 20.0 weight portions of hydrogen containing silicone oil 202 (SiH content is 1.5%, domestic) and 71.88 weight portions of octamethylcyclotetrasiloxane are added, the temperature is increased to 50-60° C., 0.88 weight portions of 10% trifluoromethane sulfonic acid butyl acetate solution is added, the temperature is maintained for 8 hours, and 0.1 weight portion of triethylamine is added, after 1 hour of neutralization, the mixture is let sit for 12 hours, filtered and self-made polysiloxane A3 is obtained. The average structure of the products is as follows:

(12) ##STR00009##

Example 1 (Solvent Type for UV)

(13) In the four-mouth bottle, 41.37 weight portions of hydrogen containing polysiloxane A1 and 0.06 weight portions of 2% hexachloroplatinic acid solution are added. The temperature is increased to 100° C. After 2 hours of stirring, 48.46 weight portions of allyl polyether (Mw=600, PO:EO=3:1, the end is OCH.sub.3), the temperature is kept at 100-120° C. for 6 hours until the characteristic peak of SiH does not have any significant change, and the temperature is then decreased to 60-80° C. 0.04 weight portion of hydroquinone is added, and the mixture is stirred for 15 minutes. A pre-mixture of 15 weight portion of allyl methacrylate and 0.06 portion of hydroquinone is dropwise added within 3 hours. The temperature is maintained until the characteristic IR peak of SiH disappears. The mixture is vacuumized at 80° C. until the weight portion of solids is more than 98% (120° C.), and yellow low viscosity liquid is obtained, which is the target product of the current invention. FIG. 1 is the IR spectrum of the product. The average formula is as follows:

(14) ##STR00010##

(15) wherein B is the residues of the silicide hydrogen addition reaction of allyl polyether.

Example 2 (Solvent Type for UV)

(16) In the four-mouth bottle, 37.56 weight portions of hydrogen containing polysiloxane A1 and 0.06 weight portions of 2% hexachloroplatinic acid solution are added. The temperature is increased to 100° C. After 2 hours of stirring, 51.13 weight portions of allyl polyether (Mw=570, PO:EO=1:3, the end is O(CH.sub.2).sub.3CH.sub.3), the temperature is kept at 100-120° C. for 6 hours until the characteristic peak of SiH does not have any significant change, and the temperature is then decreased to 60-80° C. 0.04 weight portion of hydroquinone is added, and the mixture is stirred for 15 minutes. A pre-mixture of 15 weight portion of allyl methacrylate and 0.06 portion of hydroquinone is dropwise added within 3 hours. The temperature is maintained until the characteristic IR peak of SiH disappears. The mixture is vacuumized at 80° C. until the weight portion of solids is more than 98% (120° C.), and yellow low viscosity liquid is obtained, which is the target product of the current invention. FIG. 1 is the IR spectrum of the product. The average formula is as follows:

(17) ##STR00011##

(18) wherein C is the residues of the silicide hydrogen addition reaction of allyl polyether.

Example 3 (Aqueous for UV)

(19) In the four-mouth bottle, 39.24 weight portions of hydrogen containing polysiloxane A3 and 0.06 weight portions of 2% hexachloroplatinic acid solution are added. The temperature is increased to 100° C. After 2 hours of stirring, 52.29 weight portions of allyl polyether (Mw=800, EO, the end is OCH.sub.3), the temperature is kept at 100-120° C. for 6 hours until the characteristic peak of SiH does not have any significant change, and the temperature is then decreased to 60-80° C. 0.04 weight portion of hydroquinone is added, and the mixture is stirred for 1.5 minutes. A pre-mixture of 10 weight portion of allyl methacrylate and 0.06 portion of hydroquinone is dropwise added within 3 hours. The temperature is maintained until the characteristic IR peak of SiH disappears. The mixture is vacuumized at 80° C. until the weight portion of solids is more than 96% (120° C.), and yellow low viscosity liquid is obtained, which is the target product of the current invention. FIG. 1 is the IR spectrum of the product. The average formula is as follows:

(20) ##STR00012##

(21) wherein D is the residues of the silicide hydrogen addition reaction of allyl polyether.

(22) The data of application of the products of the examples of the current invention:

(23) In order to evaluate the characteristics of the surface control additive of the current invention, certain amount of the surface control additive is added into the UV paint, and the paint is then sprayed onto tinplate or onto plastic base material. These are then placed into a UV solidifier to be solidify, and the levelling, smoothness and the durability of the coating smoothness are tested.

(24) As a control, two normal organosilicon leveling agents which do not contain acryloyl group, AFCONA 3231 and AFCONA 3522 (for aqueous system), and a surface control additive L on the market (a polysiloxane containing unsaturated functional groups) are used. The UV curing machine is Xlite 7250 P from OPAS UV Curing Corporation, Taiwan.

(25) The three testing recipes of table 1 are used to evaluate the surface control additives of the current invention.

(26) TABLE-US-00001 TABLE 1 Test Recipes Recipes for Mass the Test Raw Material fraction Chemical structures Source Recipe I Desmolux VP 50 Aliphatic urethane BAYER (solvent LS 2265 portions acrylates type UV) TPGDA 35 Tripropylene glycol domestic portions diacrylante PEG(400)DA 10 polyethylene glycol domestic portions (400) acrylate Darocur 1173 4 α-hydroxy Ciba portions ketone Surface control 1 additive portion Recipe II Laromer LR 60 aliphatic epoxy BASF (Solvent 8765 portions acrylates type UV) TPGDA 20 Tripropylene glycol domestic portions diacrylante TMPTA 15 Trimethylolpropane domestic portions triacrylate Darocur 1173 3 α-hydroxyl Ciba portions ketone Surface control 1 additive portion Recipe III Bayhydrol UV 76.3 water-based BAYER (aquesous 2282 portions polyurethane UV) acrylates Tert-butyl 15.9 domestic alcohol portions Tinuvin 292 2.5 sebacic acid esters, Ciba portions light stabilizer Darocur 1173 3.5 α-hydroxyl Ciba portions ketone Surface control 1.8 additive portions

(27) Test of Solvent type UV: add different kinds of surface control additives to the above pre-prepared UV paint (recipe I and II). The mixture is placed into a shaker and is shaked for 5 minutes. The foam inhibition and antifoam effects are observed. After the foam disappears completely, the paint is sprayed onto a tinplate, and the tinplate is then placed into a solidifier to be solidified completely. The coating is 30 μm thick. The levelling, cavity shrinkage cavity situation, smoothness and the smoothness after 100 times cleaning with acetic ether are tested.

(28) Test of aqueous UV: add different kinds of surface control additives to the above pre-prepared UV paint (recipe III). The mixture is placed into a shaker and is shaked for 5 minutes. The foam inhibition and antifoam effects are observed. After the foam disappears completely, the paint is sprayed onto plastics base material, and the material is then placed into an oven and is baked at 60° C. for some time in order to remove water and other volatile components. It is then placed into a solidifier to be solidified completely. The coating is 30 μm thick. The levelling, cavity shrinkage cavity situation, smoothness and the smoothness after 100 times cleaning with acetic ether are tested.

(29) The test results are shown in Table 2:

(30) TABLE-US-00002 TABLE 2 Application test groups and Test results Test Recipe Groups Foam Antifoam Surface Inhibition Effects Smoothness Paint Control in the in the Leveling Cavity (after Project Recipe Additives Bottle Bottle property Shrinkage Smoothness cleaning) 1 Test Product in 2 2 1 none 1 1- Recipe example 1 I 2 Test Product in 3 3 1 none 1 1- Recipe Example 2 I 3 Test Product L on 2 1 1 With 1 1- Recipe the market cavity I shrinkage 4 Test AFCONA3231 3 2 1 none 1 4  Recipe I 5 Test Product in 3 2 1 none 1 1- Recipe example 1 II 6 Test Product in 4 3 1 none 1 1- Recipe Example 2 II 7 Test Product L on 2 1 1 With 1 1- Recipe the market cavity II shrinkage 8 Test AFCONA3231 3 3 1 none 1 4  Recipe II 9 Test Product in 3 3 1 none 1 1- Recipe example 3 III 10 Test AFCONA3522 3 2 1 none 1 4  Recipe III * foam inhibition test: eyeballing, 1 means no foam, 2 means with few foam, 3 means with moderate amount of foam, 4 means with a considerable amount of foam, 5 means foam is all over. Anti-foam test: eyeballing, 1 means anti-foam effect is extremely fast, 2 means anti-foam effect is fast, 3 means anti-foam effect is OK, 4 means anti-foam effect is relatively slow, 5 means anti-foam effect is slow; Levelling test: eyeballing, 1 means coating is continuous and smooth, 2 means coating is relatively continuous but with careful observation it is a little uneven, 3 means coating is not very smooth and is with stripes, 4 means coating has orange skin, orange stripes, 5 means coating has cavity shrinkage. Smoothness test: hand feel, 1 means very smooth, without impedance, 2 means with certain impedance, 3 means smooth but hand feel is poor, 4 means coating is not smooth, with poor hand feel, 5 means hand feel with great impedance, not smooth.

(31) From projects 1-4 and 5-6, it can be derived that, although the smoothness of product L does not change after cleaning, which is the same as the test results of the products of example 1 and 2, however, since the product L does not contain polyether modified chain segments, it does not possess good compatibility of the system, and the coating has obvious cavity shrinkage phenomenon. Since AFCONA3231 contains polyether modified chain segments, no shrinkage phenomenon occurs. However, since AFCONA3231 lacks reactive functional groups which can be solidified, the smoothness is lost significantly during cleaning with acetic ether. The products of example 1 and 2 have adjustable and compatible polyether segments, and also contain acryloyl group which can be solidified with paint coating, they can keep the coating levelling, and cavity shrinkage resistant, as well as a good smoothness for a long time. The test results of 9-10 further demonstrate that the surface control additives of the current invention have great system compatibility and can maintain the characteristics of the UV paint coating for a long time.