CN111978918B - Hot-melt pressure-sensitive adhesive for ultralow-temperature coated paper labeling and preparation method thereof - Google Patents
Hot-melt pressure-sensitive adhesive for ultralow-temperature coated paper labeling and preparation method thereof Download PDFInfo
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
- C09J193/04—Rosin
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/334—Applications of adhesives in processes or use of adhesives in the form of films or foils as a label
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/28—Presence of paper
- C09J2400/283—Presence of paper in the substrate
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2409/00—Presence of diene rubber
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2453/00—Presence of block copolymer
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2491/00—Presence of oils, fats or waxes
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2493/00—Presence of natural resin
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Abstract
The invention relates to a hot-melt pressure-sensitive adhesive for ultra-low temperature coated paper labeling and a preparation method thereof, wherein the hot-melt pressure-sensitive adhesive comprises the following components in parts by weight: 20-30 parts of modified rubber, 5-10 parts of tackifying resin, 5-15 parts of styrene butadiene rubber, 2-4 parts of rosin glyceride and 1-3 parts of synthetic wax, mixing the modified rubber, the styrene butadiene rubber and the synthetic wax, stirring for 1-2 hours at the temperature of 150-. The product prepared by the invention has the advantages of low temperature resistance, high peel strength and firm bonding, can keep a better adhesion state at the extremely low temperature of-25 ℃, does not harden the colloid at the low temperature, and meets the use requirement of the ultralow temperature.
Description
Technical Field
The invention relates to the technical field of synthetic adhesives, in particular to a hot-melt pressure-sensitive adhesive for ultralow-temperature coated paper labeling and a preparation method thereof.
Background
Currently, labels are needed in many industries. The early labels are mostly labeled by hands, and due to the rapid rise of labor cost and the development of industrial automation, the automatic labeling develops rapidly, and the manual labeling is replaced. Automatic labeling has been developed at a low speed to a high speed, which requires that the hot melt pressure sensitive adhesive for the label should have a good tack for quick application. However, the existing hot-melt pressure-sensitive adhesive with a large initial adhesion force for the label has a small permanent adhesion force and is not firmly adhered, while the hot-melt pressure-sensitive adhesive with a large permanent adhesion force is not easy to adhere because of a small initial adhesion force, and phenomena such as label warping and label dropping often occur during use.
Especially, to mark with hot melt pressure sensitive adhesive to art paper, take place easily in winter (like under northeast region or extreme low temperature) the use and stick up phenomenon such as mark or fall mark, this is mainly because, service environment temperature changes great, the low ambient temperature of crossing can make the hot melt pressure sensitive adhesive that uses harden crisp, the adhesion force descends, the glue film hardens, and too high ambient temperature can make the hot melt pressure sensitive adhesive melting that uses, the viscosity reduces, receive the influence of high low temperature, can produce the effect of expend with heat and contract with cold, the bonding stability has been reduced.
Therefore, how to improve the ultralow temperature use performance of the hot melt pressure sensitive adhesive for labeling art paper is a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the hot-melt pressure-sensitive adhesive for the ultralow-temperature coated paper labeling and the preparation method thereof, which have excellent ultralow-temperature bonding performance under the condition of ensuring good initial adhesion and strong permanent adhesion and can meet the use requirements under severe ultralow-temperature environment.
The purpose of the invention can be realized by the following technical scheme:
the hot-melt pressure-sensitive adhesive for the ultralow-temperature coated paper label comprises the following components in parts by weight: 20-30 parts of modified rubber, 5-10 parts of tackifying resin, 5-15 parts of styrene butadiene rubber, 2-4 parts of rosin glyceride and 1-3 parts of synthetic wax.
Preferably, the feed comprises the following components in parts by weight: 23 parts of modified rubber, 6 parts of tackifying resin, 7 parts of styrene butadiene rubber, 3 parts of rosin glyceride and 2 parts of synthetic wax.
Preferably, the modified rubber is prepared by the following method:
step 1): preparing the following components in parts by weight: 13880-90 parts of resin, 20-40 parts of toughened elastomer, 10-30 parts of compatilizer, 0.3-1 part of coupling agent and 0.5-2 parts of processing aid;
step 2): uniformly mixing the toughened elastomer, 50-60% of compatilizer, coupling agent and processing aid by weight in a hot melting way at the temperature of 120-150 ℃, preserving the heat for 15-45 minutes, then adding resin 138 while stirring, and naturally cooling to room temperature after uniform mixing to prepare premix;
step 3): heating the rest of the compatilizer until the viscosity is 500 centipoise, and uniformly mixing the compatilizer with the premix prepared in the step 2).
Preferably, the compatilizer is selected from coumarone resin, the coupling agent is selected from silane coupling agent KH550, and the processing aid is selected from any one of calcium stearate, sodium stearate or zinc stearate.
Preferably, the tackifying resin is resin KA100L, KA100L is taken as a tackifier, so that the product has cold resistance and aging resistance, good stability, compatibility and solubility, good surface resistance and good color retention, and particularly, the tackifier is matched with synthetic wax to contribute to excellent viscosity at extremely low temperature.
Preferably, the rosin glyceride is stearic acid modified rosin glyceride, and the stearic acid modified rosin glyceride effectively improves the minimum use temperature of the pressure-sensitive adhesive and helps to reduce the glass transition temperature of the pressure-sensitive adhesive.
Preferably, the stearic acid modified rosin glyceride is prepared by mixing rosin glyceride powder with stearic acid, and keeping the temperature at 240 ℃ for 6 h.
Preferably, the hot-melt pressure-sensitive adhesive for labeling the ultralow-temperature coated paper can be added with auxiliary materials according to needs, wherein the auxiliary materials comprise one or more of matting powder, yellow powder, zinc oxide, black paste and titanium dioxide R518.
A preparation method of a hot-melt pressure-sensitive adhesive for labeling ultra-low temperature coated paper comprises the following steps:
(1) preparing materials according to the following formula: 20-30 parts of modified rubber, 5-10 parts of tackifying resin, 5-15 parts of styrene butadiene rubber, 2-4 parts of rosin glyceride and 1-3 parts of synthetic wax;
(2) mixing the modified rubber, the styrene-butadiene rubber and the synthetic wax, stirring for 1-2 hours at the temperature of 150-160 ℃, adding the tackifying resin and the rosin glyceride, and continuously stirring until the mixture is in a transparent colloid state to obtain the product.
Compared with the prior art, the invention has the following beneficial effects:
the invention selects the modified rubber as the base material to be compounded with the thermoplastic styrene-butadiene rubber and the tackifying resin, so that the produced pressure-sensitive adhesive product has excellent adhesive force to the surface of the base material under the low temperature condition, improves the tackifying effect, and then adds the rosin glyceride and the synthetic wax, so that the vitrification temperature of the adhesive can be reduced, the low temperature resistance of the adhesive is enhanced, and the temperature resistance and the oil permeability of the adhesive are improved.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Examples 1 to 5 and comparative examples 1 to 4
The raw materials used are all commercially available, wherein:
the tackifying resin is resin KA100L, and is prepared by Guangdong Ke Maolin production chemical industry Co., Ltd;
the styrene-butadiene rubber adopts 1502 products of Shenzhen Xin synthetic rubber trade company Limited;
the synthetic wax is made from the product of the Anyang Wanwei chemical Co., Ltd;
the rosin glyceride is stearic acid modified rosin glyceride, the rosin glyceride is a limited chemical product of Zhengzhou Guangjie province, the stearic acid is a product of a Haian petrochemical plant of Jiangsu province, and the modified rosin glyceride is prepared by mixing rosin glyceride powder with stearic acid, and preserving heat at 240 ℃ for 6 hours, wherein the usage amount of the stearic acid is 16% of the weight of the rosin glyceride powder.
The preparation method of the modified rubber comprises the following steps:
step 1): preparing materials according to the table 1;
step 2): uniformly mixing the toughened elastomer, 55% of compatilizer, coupling agent and processing aid by weight in a hot melting way at 130 ℃, preserving the heat for 30 minutes, then adding resin 138 while stirring, and naturally cooling to room temperature after uniform mixing to prepare a premix;
step 3): heating the rest of the compatilizer until the viscosity is 500 centipoise, and uniformly mixing the compatilizer with the premix prepared in the step 2).
Table 1 weight ratio of modified rubber raw materials
Modified rubber 1 | Resin 13880 | SBS791 20 | Coumarone resin 10 | Silane coupling agent KH 5500.3 | Calcium stearate 0.5 |
Modified rubber 2 | Resin 13885 | SBS792 30 | Coumarone resin 20 | Silane coupling agent KH 5500.5 | Zinc stearate 1 |
Modified rubber 3 | Resin 13890 | SBS796 40 | Coumarone resin 30 | Silane coupling agent KH 5501 | Sodium stearate 2 |
The preparation method of the hot melt pressure sensitive adhesive in the examples 1 to 5 and the comparative examples 1 to 4 is as follows:
(1) preparing materials according to the formula in the table 2, wherein the component proportion is shown in the table 2;
(2) mixing the modified rubber, the styrene-butadiene rubber and the synthetic wax, stirring for 2 hours at 155 ℃, adding the tackifying resin and the rosin glyceride, and continuously stirring until the mixture is in a transparent colloid state to obtain the product.
TABLE 2 weight parts ratios of examples 1-5 and comparative examples 1-4 of hot melt pressure sensitive adhesive
Components | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
Modified rubber 1 | 23 | -- | -- | -- | -- | ||||
Modified rubber 2 | -- | -- | 23 | 20 | 30 | 23 | 23 | 23 | 23 |
Modified rubber 3 | -- | 23 | -- | -- | -- | ||||
Styrene butadiene rubber | 8 | 10 | 7 | 5 | 15 | —— | 7 | 7 | 7 |
Synthetic wax | 2 | 2.5 | 2 | 1 | 3 | 2 | —— | 2 | 2 |
Rosin glyceride | 3 | 2 | 3 | 2 | 4 | 3 | 3 | —— | 3 |
Resin KA100L | 7 | 9 | 6 | 5 | 10 | 6 | 6 | 6 | —— |
The pressure-sensitive adhesives obtained in examples 1 to 5 and comparative examples 1 to 4 were melt-coated and tested for properties.
Coating the prepared product on a coated paper label, and testing the annular initial adhesion according to the GB/T31125-2014 initial adhesion test method at-25 ℃; the 180 DEG peel strength test was performed according to the GB2792-81 standard and the results are shown in Table 3.
TABLE 3 test results
Performance of | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
Initial adhesion (N) of ring shape | 24.15 | 23.11 | 27.82 | 25.51 | 26.35 | 15.48 | 17.65 | 13.48 | 14.49 |
180 degree peel strength (kN/m) | 0.95 | 0.88 | 1.01 | 0.81 | 0.75 | 0.34 | 0.65 | 0.24 | 0.42 |
The data in Table 3 show that the pressure-sensitive adhesive prepared by the method has excellent initial adhesion and 180-degree peel strength at the low temperature of-25 ℃ and can meet the use requirement at the low temperature.
In the test data of table 3, the best effect is that in example 3, compared with example 3, in comparative example 1, styrene-butadiene rubber is not used, in comparative example 2, synthetic wax is not used, in comparative example 3, rosin glycerin is not used, and in comparative example 4, resin KA100L is not used, the initial adhesion and 180 ° peel strength of the product are greatly reduced, the better performance of the inventive example is not achieved, and the stricter use requirement is not met.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (8)
1. The hot-melt pressure-sensitive adhesive for the ultralow-temperature coated paper label is characterized by comprising the following components in parts by weight: 20-30 parts of modified rubber, 5-10 parts of tackifying resin, 5-15 parts of styrene butadiene rubber, 2-4 parts of rosin glyceride and 1-3 parts of synthetic wax; the preparation method of the modified rubber comprises the following steps:
step 1): preparing the following components in parts by weight: 13880-90 parts of resin, 20-40 parts of toughened elastomer, 10-30 parts of compatilizer, 0.3-1 part of coupling agent and 0.5-2 parts of processing aid;
step 2): uniformly mixing the toughened elastomer, 50-60% of compatilizer, coupling agent and processing aid by weight in a hot melting way at the temperature of 120-150 ℃, preserving the heat for 15-45 minutes, then adding resin 138 while stirring, and naturally cooling to room temperature after uniform mixing to prepare premix;
step 3): heating the rest of the compatilizer until the viscosity is 500 centipoise, and uniformly mixing the compatilizer with the premix prepared in the step 2);
the processing aid is selected from any one of calcium stearate, sodium stearate or zinc stearate.
2. The hot-melt pressure-sensitive adhesive for the ultra-low temperature coated paper labeling according to claim 1, which is characterized by comprising the following components in parts by weight: 23 parts of modified rubber, 6 parts of tackifying resin, 7 parts of styrene butadiene rubber, 3 parts of rosin glyceride and 2 parts of synthetic wax.
3. The hot melt pressure sensitive adhesive for ultra-low temperature coated paper labeling according to claim 1, wherein the toughening elastomer is one or two selected from styrene-butadiene-styrene block copolymer or styrene-isoprene-styrene block copolymer.
4. The hot melt pressure sensitive adhesive for ultra-low temperature coated paper labeling according to claim 1, wherein the compatilizer is selected from coumarone resin, and the coupling agent is selected from silane coupling agent KH 550.
5. The hot melt pressure sensitive adhesive for ultra-low temperature art paper labeling according to claim 1 or 2, wherein the tackifying resin is resin KA 100L.
6. The hot melt pressure sensitive adhesive for ultra-low temperature art paper labeling according to claim 1 or 2, wherein the rosin glyceride is stearic acid modified rosin glyceride.
7. The hot melt pressure sensitive adhesive for ultra-low temperature art paper labeling according to claim 1, wherein the stearic acid modified rosin glyceride is prepared by mixing rosin glyceride powder with stearic acid, and keeping the temperature at 240 ℃ for 6 hours.
8. The preparation method of the hot-melt pressure-sensitive adhesive for the ultralow-temperature coated paper labeling according to claim 1, which is characterized by comprising the following steps:
(1) preparing materials according to the following formula: 20-30 parts of modified rubber, 5-10 parts of tackifying resin, 5-15 parts of styrene butadiene rubber, 2-4 parts of rosin glyceride and 1-3 parts of synthetic wax;
(2) mixing the modified rubber, the styrene-butadiene rubber and the synthetic wax, stirring for 1-2 hours at the temperature of 150-160 ℃, adding the tackifying resin and the rosin glyceride, and continuously stirring until the mixture is in a transparent colloid state to obtain the product.
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