Patent Grant
8410212
The present invention relates to an alcohol-soluble copolymeric resin, particularly an alcohol-soluble resin used as a major raw material for preparing alcohol-soluble fine chemical products such as alcohol-soluble ink and alcohol-soluble plastic composite adhesive, and a method for preparing the same.
Resin is a kind of main raw material in producing fine chemical products such as ink, adhesive, paint, etc., and the resin is decisive to the performance and cost of these fine chemical products as well as to the kind of solvent to be used for dilution during application. At present, most of the resins for producing the above products are dissolved and diluted with benzenes and ketones. These solvents not only pollute the environment severely, but as they are extracted from petroleum, their costs are also continuously increasing with the rise of the petroleum price. Due to the pressure of both the cost and the environmental protection, there is an increasing demand for resins that are soluble in alcohols. So far, there are several mature alcohol-soluble resins that can be used to produce the above fine chemical products, including alcohol-soluble polyamide resin, alcohol-soluble polyurethane resin, and polyvinyl acetal resin. However, as a result of the high cost of raw materials, the process of production, and other factors, these kinds of resins are rather expensive, which greatly increases the cost of producing the above products. Therefore, there is an urgent demand in the market to reduce the cost of the alcohol-soluble resin.
As vinyl acetate is one of the cheapest and nontoxic monomer materials in the market, and its polymer is soluble in alcohol, the cost of the alcohol-soluble resin that is produced with vinyl acetate as a main raw material can be reduced greatly. But as the glass transition temperature of vinyl acetate homopolymer is 28° C. and the softening point is low, it will be softened and transfigured when heated. In addition, it is easy to absorb moisture, after which the performance of the resin will be greatly affected. Therefore, there is no existing report at home and abroad of using vinyl acetate as a main raw material in the synthesis of alcohol-soluble resins that are up to the requirements of the above products.
The first object of the present invention is to prepare an alcohol-soluble resin for producing fine chemical products such as ink and the like. Another object of the present invention is to provide a method for producing the said resin and use of the same.
The alcohol-soluble resin provided in the present invention is polymerized by using a raw material containing 50% to 90% w/w of vinyl acetate and azodiisobutyronitrile and/or benzoyl peroxide as initiator.
Particularly, the alcohol-soluble resin of the present invention is prepared by a raw material of the following weight ratio:
A final product will be obtained by adding an initiator of 0.1-1.1% of the total weight of the raw material and polymerizing in ester and/or alcohol solvent(s). After screening and comparing, the preferred weight ratio of the raw material is as follows:
During preparation, the alcohol-soluble resin of the present invention is obtained by adding azodiisobutyronitrile and/or benzoyl peroxide of 0.2%-0.9% of the total weight of the above raw material as initiator and polymerizing in ester and/or alcohol solvent(s).
The said reactive functional group-containing compound includes one or more selected from the group consisting of acrylic acid, methacrylic acid, butene dioic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, reaction product of unsaturated acid and diepoxide, acrylamide, methacrylamide, and hydroxymethyl acrylamide.
The method for preparing the alcohol-soluble resin provided in the present invention comprises the following steps:
a) weighing the raw material according to the following content ratio:
Constituent A:
Then add alcohol or ester solvent, its amount being 10% to 35% of the total weight of the above vinyl acetate and the acrylic ester and/or methacrylic ester;
Constituent B:
An initiator of 0.1%-0.7% of the total weight of the raw material;
Constituent C:
Initiator of 0.1%-0.4% of the total weight of the raw material, dissolved in ester and/or alcohol solvent(s) for use;
The total weight of the above initiators is 0.1%-1.1% of the total weight of the raw material;
b) adding constituent A into a reactor tank, stirring and heating the material up to the reflux temperature;
c) adding constituent B dropwise into the reactor tank in 1.5 to 4 hours, and leave it for further reaction of 1 hour;
d) adding constituent C dropwise into the reactor tank in 0.5 hour after step c, and leave it for further reaction of 2 hours while keeping the material temperature between 70 to 85° C.
e) adding alcohol and/or ester solvent(s) into the reactor tank for dilution according to the concentration requirement of the product, and stirring while cooling it down, and discharging when the temperature of the material in the tank is below 50° C. so that the alcohol-soluble resin of desired concentration is obtained
A preferable embodiment of the content ratio of the raw material in step a) is as follows:
Constituent A:
Then add alcohol or ester solvent, its amount being 10% to 35% of the total weight of the above vinyl acetate and acrylic ester and/or methacrylic ester;
Constituent B:
an initiator of 0.1-0.7% of the total weight of the raw material;
Constituent C:
initiator of 0.1%-0.4% of the total weight of the raw material, dissolved in the ester and/or alcohol solvent(s) for use.
The present invention also provides the use of the alcohol-soluble resin in preparing ink, plastic composite adhesive, glazing lacquer for woodware, lustering oil for printing paper and superficial decorating coatings for plastic material, safeguard coatings for metal surface, and hair colorant.
The present invention further provides the ink and plastic composite adhesive prepared with the above alcohol-soluble resin.
Further details of the present invention will be set forth through embodiments as follows. However, the description of those embodiments should not be understood as the limitation to the scope of the present invention. All of the modifications, variations or adaptations of the invention, made within the principles of the invention and based on known or customary practice in the art, shall fall within the limits of the invention.
Equipments: a reactor tank equipped with a stirrer, a reflux condenser, a stainless steel dropper, and a device for heating and temperature controlling are required in accordance with the present invention.
The process of example 1 comprises:
Step 1: Add into the reactor tank constituent A comprising 40 kg of vinyl acetate, 2 kg of ethyl acrylate, 1 kg of methyl acrylate and 3 kg of methyl methacrylate, in addition with solvent of 10 kg of isopropyl alcohol and 5 kg of ethyl acetate for dilution, and heat up the material while stirring;
Step 2: Prepare in the dropper constituent B comprising 40 kg of vinyl acetate, 3 kg of ethyl acrylate, 1 kg of methyl acrylate, 3 kg of methyl methacrylate, 4 kg of acrylic acid, 3 kg of hydroxypropyl acrylate and 0.5 kg of azodiisobutyronitrile, add the same dropwise into the reactor tank in 2 hours after the material in the tank is heated up to the reflux temperature, and then leave it reacting for 1 hour;
Step 3: Dissolve 0.2 kg of azodiisobutyronitrile in 2.5 kg of isopropyl alcohol and 2.5 kg of ethyl acetate, and add dropwise into the reactor tank in 0.5 hour;
Step 4: Add 20 kg of ethyl acetate and 60 kg of industrial alcohol into the reactor tank after a continuously reaction for 2 hours under a constant temperature in the tank, and then cool down and discharge to obtain 200.7 kg of resin with 50% of solid content.
The resin prepared according to the formula of example 1 is most suitable for producing plastic gravure surface printing ink.
Weigh the raw materials according to the following content ratio:
Constituent A:
With another 15 kg of isopropyl alcohol as diluent;
Constituent B:
Constituent C:
0.2 kg of azodiisobutyronitrile dissolved in 2.5 kg of isopropyl alcohol and 2.5 kg of ethyl acetate.
With 20 kg of ethyl acetate and 60 kg of industrial alcohol as diluent and prepared according to the same method as that of Example 1, 200.7 kg of resin with 50% of solid content will be obtained.
The resin prepared according to the formula of example 2 is most suitable for producing heat and steam endurance plastic gravure composite ink.
Weigh the raw materials according to the following content ratio:
Constituent A:
With another 15 kg of absolute alcohol as diluent;
Constituent B:
Constituent C:
0.2 kg of azodiisobutyronitrile dissolved in 5 kg of solvent of ethyl acetate.
With 20 kg of ethyl acetate and 60 kg of industrial alcohol as diluent, and prepared according to the same method as that of Example 1, 200.7 kg of resin with 50% of solid content will be obtained.
The resin prepared according to the formula of example 3 is most suitable for producing ordinary plastic gravure composite ink.
Weigh the raw materials according to the following content ratio:
Constituent A:
With another 15 kg of isopropyl alcohol as diluent;
Constituent B:
Constituent C:
0.2 kg of azodiisobutyronitrile dissolved in 2.5 kg of isopropyl alcohol and 2.5 kg of ethyl acetate.
With 40 kg of ethyl acetate and 40 kg of industrial alcohol as diluent, and prepared according to the same method as that of Example 1, 200.9 kg of resin with 50% of solid content will be obtained.
The resin prepared according to the formula of example 4 is a plastic composite adhesive with 50% of solid content.
Formula for producing the alcohol-soluble ink by use of the resin of the present invention is as follows (weight ratio):
Process for producing the alcohol-soluble ink by use of the resin of the present invention is as follows:
Add the above raw materials into a vessel, stir at high speed for 20 minutes for the materials to blend fully and disperse uniformly, and mill in a sand mill with the material's temperature not higher than 40° C. When the fineness is less than 15 micron, the final product is finished.
Weigh the raw materials according to the following content ratio:
Constituent A:
With another 10 kg of isopropyl alcohol as diluent;
Constituent B:
Constituent C:
0.3 kg of benzoyl peroxide dissolved in 5 kg of ethyl acetate;
With 20 kg of ethyl acetate and 60 kg of industrial alcohol as diluent, and prepared according to the same method as that of Example 1, 200.8 kg of resin with 50% of solid content will be obtained.
The resin prepared according to the formula of example 6 is suitable for producing glazing lacquer for woodware, lustering oil for printing paper, and superficial decorating coatings for plastic materials.
Formula for producing the glazing lacquer for woodware by use of the resin of the present invention is as follows (weight ratio):
Process for producing the glazing lacquer for woodware of the present invention is as follows:
Put the above raw materials into a vessel, stir for 10 minutes for them to blend fully and disperse uniformly, and the final product will be obtained after filtering.
Formula for producing the lustering oil for printing paper of this example is as follows (weight ratio):
The process of this example is as follows:
Put the above raw materials into a vessel, stir at high speed for 30 minutes for them to blend fully and disperse uniformly, and the final product will be obtained after filtering.
Formula for producing the superficial decorating coatings for plastic materials by use of resin of the present invention is as follows (weight ratio):
The process for producing the superficial decorating coatings for plastic materials by use of resin of the present invention is as follows:
Put the above raw materials into a vessel, stir at high speed for 10 minutes for them to blend fully and disperse uniformly, and the final product will be obtained after milling in a sand mill to make the fineness less than 15 micron.
Weigh the raw materials according to the following content ratio:
Constituent A:
addition with 10 kg of isopropyl alcohol as diluent;
Constituent B:
Constituent C:
0.2 kg of azodiisobutyronitrile dissolved in solvent of 5 kg of ethyl acetate;
With 20 kg of ethyl acetate and 65 kg of industrial alcohol as diluent, and prepared according to the same method as that of Example 1, 200.8 kg of resin with 50% of solid content will be obtained.
The resin prepared according to the formula of example 10 is suitable for producing safeguard coatings of metal surface.
Formula for producing the rotproof coatings for metal by use of the resin of the present invention is as follows (weight ratio):
Process for producing rotproof coatings for metal by use of resin of the present invention is as follows:
Put the above raw materials into a vessel, stir at high speed for 10 minutes for them to blend fully and disperse uniformly, and the final product will be obtained after milling in a sand mill to make the fineness less than 15 micron.
Weigh the raw materials according to the following content ratio:
Constituent A:
With 10 kg of isopropyl alcohol as diluent;
Constituent B:
Constituent C:
0.2 kg of azodiisobutyronitrile dissolved in 5 kg of solvent of ethyl acetate;
With 20 kg of ethyl acetate and 65 kg of industrial alcohol as diluent, and prepared according to the same method as that of Example 1, 200.8 kg of resin with 50% of solid content will be obtained.
Formula for producing alcohol-soluble hair colorant by use of the resin of the present invention is as follows (weight ratio):
Process for producing the alcohol-soluble hair colorant by use of the resin of the present invention is as follows:
Put the above raw materials into a vessel, stir at high speed for 10 minutes for them to blend fully and disperse uniformly, and the final product will be obtained.
The alcohol-soluble ink prepared in Example 5 is tested according to the ink standard of QB/T2024-94, and the result is shown in table 1.
It can be seen in the table that the ink prepared by the resin provided in accordance with the present invention advantageously has a good adhesive strength which is much higher than 85%. It is also of low amount of residual solvent and leaves no odour. The ink prepared has been tried by many printing plants, and the results show that when printed on BOPP, PE, PA, PET films, the ink prepared by the resin of the present invention reveals excellent printing adaptability, i.e., steady printing effect in different seasons, at different temperatures and humidities, with different devices and on different printing films, and good compatibility of overprint and adhesion with the existing polyamide surface printing ink system, chlorinated polypropylene composite ink system, and polyurethane steam ink system.
In conclusion, by polymerizing the main raw material vinyl acetate together with various monomers, the present invention advantageously provides a resin of good performance and low cost. Furthermore, the range of solvent for this resin is broad, including solvents of alcohols as well as, if necessary, solvents of benzenes, esters, or ketones. Therefore, a new type of resin of good performance is provided for a variety of fine chemical products such as ink, adhesive and coatings, etc.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2005 1 0021271 | Jul 2005 | CN | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/CN2006/000025 | 1/9/2006 | WO | 00 | 9/5/2008 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2007/009325 | 1/25/2007 | WO | A |
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| 3634329 | Chujo et al. | Jan 1972 | A |
| 4937303 | Wolf et al. | Jun 1990 | A |
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| 85100687 | Apr 1985 | CN |
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| Number | Date | Country | |
|---|---|---|---|
| 20090149615 A1 | Jun 2009 | US |
