CN110734719A - Modified hot-melt pressure-sensitive adhesive and preparation method thereof - Google Patents
Modified hot-melt pressure-sensitive adhesive 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
- C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09J157/02—Copolymers of mineral oil hydrocarbons
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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
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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Abstract
The invention relates to hot-melt pressure-sensitive adhesives, in particular to modified hot-melt pressure-sensitive adhesives and a preparation method thereof, wherein the modified hot-melt pressure-sensitive adhesives comprise styrene thermoplastic elastomers, petroleum resins, Fischer-Tropsch wax, pentaerythritol esters, main antioxidants, auxiliary antioxidants and softeners, wherein the styrene thermoplastic elastomers are SIS (styrene-styrene) and have a linear structure, the styrene content is 15% -21%, and the diblock content is 50% -75%, C5 petroleum resins and pentaerythritol esters are dissolved in both a rubber phase (polyisoprene phase) and a hardness (polystyrene phase) of the thermoplastic elastomers, two tackifying resins act together to improve the compatibility of the hot-melt pressure-sensitive adhesives, and the hot-melt pressure-sensitive adhesives have good fluidity, meet the use requirements of holding power and peel strength, are not increased along with time, and can be peeled cleanly from a base material.
Description
Technical Field
The invention relates to hot-melt pressure-sensitive adhesives, in particular to modified hot-melt pressure-sensitive adhesives and a preparation method thereof.
Background
The hot melt pressure sensitive adhesive is kinds of adhesive which takes thermoplastic elastomer as main material and can be bonded by adding tackifying resin, plasticizer, antioxidant and a small amount of other components and applying a small amount of external force, and because of the convenience and rapidness of the hot melt pressure sensitive adhesive, the hot melt pressure sensitive adhesive is very extensive in the application of industries such as sanitary materials, foods, labels and the like.
Compared with the traditional hot-melt pressure-sensitive adhesive, the hot-melt pressure-sensitive adhesive modified by the Fischer-Tropsch wax can be conveniently and quickly applied to various occasions, the existing hot-melt pressure-sensitive adhesive has the defects that the fluidity of the hot-melt pressure-sensitive adhesive is poor due to the addition of tackifying resin, the peeling strength of the hot-melt pressure-sensitive adhesive is increased along with the time after the hot-melt pressure-sensitive adhesive is used for periods, the hot-melt pressure-sensitive adhesive cannot be peeled cleanly from a base.
In order to overcome the defects of the existing hot-melt pressure-sensitive adhesive, many researchers modify the hot-melt pressure-sensitive adhesive, but the effect is not ideal, and the prepared hot-melt pressure-sensitive adhesive has low peeling strength and low permanent adhesion, or has high peeling strength and high permanent adhesion, or the adhesive can not be cleanly glazed from a substrate. In addition, the unstable amount and poor fluidity of the hot-melt pressure-sensitive adhesive become obstacles in the research of the hot-melt pressure-sensitive adhesive.
Chinese patent CN 106318292B discloses removable hot-melt pressure-sensitive adhesives and a preparation method thereof, wherein a triblock copolymer of styrene-isoprene-styrene, C5 petroleum resin, dioctyl terephthalate, polyethylene wax and liquid petroleum resin are added in a fixed proportion and sequence of for mixing and melting.
Chinese patent CN 109266268A discloses removable pressure sensitive adhesive compositions, which are prepared by mixing at least styrene-isoprene-styrene block copolymers, at least tackifying resins, and at least liquid plasticizers and stabilizers in proportion and sequence to fully react.
Chinese patent CN 108611034A discloses green and environment-friendly label adhesives and a preparation method thereof, wherein styrene thermoplastic elastomer, EVA, petroleum resin, rosin resin, paraffin, softener and antioxidant are mixed in in a fixed proportion and sequence.
The existing hot-melt pressure-sensitive adhesive has the defects that the fluidity of the hot-melt pressure-sensitive adhesive is poor due to the addition of tackifying resin, and the peel strength of the hot-melt pressure-sensitive adhesive is increased along with the time after the hot-melt pressure-sensitive adhesive is used for periods, so that the hot-melt pressure-sensitive adhesive cannot be cleanly peeled from a base material.
Disclosure of Invention
The invention aims to provide modified hot-melt pressure-sensitive adhesives, which have good fluidity, high permanent adhesion meeting the use requirement, no increase of the peel strength along with time and can be cleanly peeled from a base material, and also provides preparation methods thereof.
The modified hot-melt pressure-sensitive adhesive comprises the following components: styrene thermoplastic elastomer, petroleum resin, Fischer-Tropsch wax, pentaerythritol ester, a main antioxidant, an auxiliary antioxidant and a softener; wherein: the styrene thermoplastic elastomer is SIS with a linear structure, the styrene content is 15-21%, and the diblock content is 50-75%.
The styrene thermoplastic elastomer adopted by the invention is SIS, the styrene content is 15-21%, the diblock content is 50-75%, if the styrene content is too much, the diblock content is too little, the adhesion force of the modified hot-melt pressure-sensitive adhesive is reduced, and the initial adhesion force is reduced; if the content of the styrene is too low, the content of the diblock copolymer is too high, the cohesive force of the adhesive is reduced, and the permanent adhesive force is reduced.
As preferred technical schemes, the modified hot melt pressure sensitive adhesive comprises, by weight, 20-30 parts of a styrene thermoplastic elastomer, 30-35 parts of petroleum resin, 3-8 parts of Fischer-Tropsch wax, 10-15 parts of pentaerythritol ester, 0.1-0.3 part of a main antioxidant, 0.1-0.3 part of an auxiliary antioxidant and 14-16 parts of a softener.
Wherein:
the petroleum resin is C5 petroleum resin, and has a softening point of 80-100 deg.C.
The Fischer-Tropsch wax adopted by the invention is a methylene polymer synthesized by a coal-based Fischer-Tropsch polymerization process, is produced by a cobalt-based catalyst, has the molecular weight of 500-1000, the freezing point of 105 ℃ and the price of the Fischer-Tropsch wax is too high if the freezing point is too high, the cost performance of the hot-melt pressure-sensitive adhesive is lower, and if the Fischer-Tropsch wax with a low freezing point is adopted, the Fischer-Tropsch wax is similar to other raw materials in the hot-melt pressure-sensitive adhesive and has poor compatibility, so that the cohesive force of the hot-melt pressure-sensitive adhesive is reduced, and the cohesive force of the hot; the Fischer-Tropsch wax adopted by the invention has higher crystallinity and fewer branched chains, is easy to permeate into a macromolecular chain with high viscosity, obviously reduces the melt viscosity of the adhesive and has small mobility. The Fischer-Tropsch wax is mainly used as an internal lubricant in the hot-melt pressure-sensitive adhesive, and the internal lubricant can be fused between polymer molecular chains in the processing process of the hot-melt pressure-sensitive adhesive, so that the internal friction force is reduced, the melt viscosity is reduced, the fluidity of the hot-melt pressure-sensitive adhesive is increased, the peel strength is reduced, and the processing performance of the hot-melt pressure-sensitive adhesive is improved. The hot-melt pressure-sensitive adhesive modified by the Fischer-Tropsch wax is a great challenge to the traditional hot-melt pressure-sensitive adhesive material and plays a crucial role in the development of the adhesive field.
The softening point of the pentaerythritol ester is 95-110 ℃, the softening point is in the range of the softening point again and is close to the softening points of other raw materials in the hot-melt pressure-sensitive adhesive, the compatibility of the hot-melt pressure-sensitive adhesive is improved, and the oil permeability is reduced.
The main antioxidant is tetra [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the auxiliary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
The softener is Clarithromane oil KN 4010.
The preparation method of the modified hot-melt pressure-sensitive adhesive comprises the following steps: the method comprises the following steps:
(1) weighing the following raw materials in parts by weight: 20-30 parts of styrene thermoplastic elastomer, 30-35 parts of petroleum resin, 3-8 parts of Fischer-Tropsch wax, 10-15 parts of pentaerythritol ester, 0.1-0.3 part of main antioxidant, 0.1-0.3 part of auxiliary antioxidant and 14-16 parts of softener;
(2) adding a softening agent into a reaction container, heating and stirring;
(3) putting petroleum resin, Fischer-Tropsch wax, pentaerythritol ester, a main antioxidant and an auxiliary antioxidant into a reaction container, vacuumizing, and continuously heating;
(4) heating to constant temperature, adding styrene thermoplastic elastomer in several times, stirring uniformly and reacting;
(5) stopping stirring after the reaction is finished, discharging after the reaction substance is stable, and cooling.
Wherein:
the heating temperature of the step (2) is 130-140 ℃, and the stirring speed is 100 r/min.
In the step (2), the reaction vessel is preferably a 100ml three-necked flask, and when washing, it is preferably washed with ethanol.
The continuous temperature rise in the step (3) is as follows: heating to 170 deg.C, stirring at constant speed, and continuously heating for 20-30 min.
The stirring speed in the step (4) is 155r/min, otherwise, the stirring is easy to be uneven.
The step (4) is as follows: heating to 180 ℃ at a heating rate of 5 ℃/min, adding a styrene thermoplastic elastomer accounting for 50 percent of the total weight of the styrene thermoplastic elastomer after all the components are melted uniformly, stirring uniformly, and continuously heating for 30-40 min for reaction; after the added raw materials are completely and uniformly mixed, adding the rest styrene thermoplastic elastomer, vacuumizing, removing white bubbles, uniformly stirring, keeping the temperature, and continuously heating for 40-60 min until the system is uniform. The styrene thermoplastic elastomer is added in two times, so that the raw materials are mixed more uniformly, and the phenomena of high polymer agglomeration and pole climbing are avoided, and the adhesive property of the adhesive is not influenced.
In the step (5), the temperature of the discharge hole is maintained at 155-160 ℃, otherwise, the solidification is easily caused, and the product is wasted.
Compared with the prior art, the invention has the following advantages:
(1) the invention relates to the permanent adhesive force of hot melt pressure sensitive adhesive, which relates to the adhesive force, cohesive force and the like, pentaerythritol ester is taken as of tackifying resin, which is dissolved in a soft phase (polyisoprene phase) of a thermoplastic elastomer and a hard end (polystyrene phase) of the thermoplastic elastomer, in the manufacturing process of the hot melt pressure sensitive adhesive, the pentaerythritol ester generates swelling action on the thermoplastic elastomer, enhances the cohesive force of the hot melt pressure sensitive adhesive, reduces the glue remaining amount when the hot melt pressure sensitive adhesive is stripped, improves the permanent adhesive force of the hot melt pressure sensitive adhesive, and ensures that the hot melt pressure sensitive adhesive keeps high permanent adhesive force under the condition of low stripping strength.
(2) The Fischer-Tropsch wax adopted by the invention is methylene polymers, is a refined alkane product synthesized by a coal-based Fischer-Tropsch polymerization process, is produced by a cobalt-based catalyst, has the molecular weight of 500-1000, has higher crystallinity and fewer branched chains, is easy to permeate into high-viscosity macromolecular chains, obviously reduces the melt viscosity of the adhesive, and has small mobility.
(3) By adopting the antioxidant combination, the styrene thermoplastic elastomer in the modified hot-melt pressure-sensitive adhesive contains unsaturated bonds, and can be aged under the action of environmental factors such as oxygen, light, heat and the like, and the tackifying resin is stirred at high temperature and has lower stability. The primary antioxidant is pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] ester, the hydrogen atom on the phenolic hydroxyl group of which is detached from its molecule and reacts with peroxide radicals, thereby breaking or preventing the branching stage of the chain and simultaneously generating a stable product in a lower energy state. The auxiliary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite, a d-orbit participating in bonding is arranged in a phosphorus atom of the antioxidant, the antioxidant can be overlapped with a P-orbit of an adjacent atom to form a P pi-d pi bond, and the stability of the adhesive is improved under the combined action of the main antioxidant and the auxiliary antioxidant.
(4) The naphthenic oil KN4010 is a good plasticizer, has good compatibility with a rubber phase (polyisoprene phase) of a thermoplastic elastomer and petroleum resin, facilitates mixing and processing of the hot-melt pressure-sensitive adhesive, reduces oil permeability of the hot-melt pressure-sensitive adhesive, and reduces hardness and glass transition temperature of the hot-melt pressure-sensitive adhesive.
(5) The styrene thermoplastic elastomer SIS has no adhesiveness, and must be matched with proper tackifying resin to improve the wettability, the cohesive force, the peel strength, the shear strength, the initial adhesion force and the permanent adhesion strength, reduce the melt viscosity of the hot melt pressure sensitive adhesive and improve the operation performance. The C5 petroleum resin and pentaerythritol ester are dissolved in the rubber phase (polyisoprene phase) and the hardness (polystyrene phase) of the thermoplastic elastomer, and the two tackifying resins act together to improve the compatibility of the hot-melt pressure-sensitive adhesive.
(6) According to the invention, Fischer-Tropsch wax is used as a filler to modify the hot-melt pressure-sensitive adhesive, and the raw materials are mutually cooperated to obtain hot-melt pressure-sensitive adhesives which have good fluidity, meet the use requirement of permanent adhesion, have no increase of peel strength with time and can be cleanly peeled from a base material.
Detailed Description
The invention is further illustrated with reference to the following examples.
Example 1
kinds of modified hot melt pressure sensitive adhesive comprises the following components in parts by weight:
wherein: the styrene thermoplastic elastomer is SIS, has a linear structure, the styrene content is 15 percent, and the diblock content is 50 percent.
The petroleum resin is C5 petroleum resin, and the softening point is 80 ℃.
The softening point of pentaerythritol ester is 95 ℃.
The Fischer-Tropsch wax is a methylene polymer synthesized by a coal-based Fischer-Tropsch polymerization process, is produced by a cobalt-based catalyst, has the molecular mass of about 800 and the freezing point of 105 ℃.
The preparation method of the hot-melt pressure-sensitive adhesive comprises the following steps:
(1) according to example 1, styrenic thermoplastic elastomer, petroleum resin, Fischer-Tropsch wax, pentaerythritol ester, primary antioxidant, secondary antioxidant, and softener were weighed.
(2) A100 ml three-neck flask was washed, dried, and charged with a stirring rod, a thermometer, and Clarithrome oil KN4010, and the heating temperature was 130 ℃ and the stirring rate was 100 r/min.
(3) And (2) continuously heating the reaction container in the step (1) to 170 ℃, keeping the stirring speed unchanged, heating for 20min, adding petroleum resin, Fischer-Tropsch wax, pentaerythritol ester and main and auxiliary antioxidants into the reaction container, vacuumizing, and continuously heating.
(4) And (3) heating to 180 ℃ at the heating rate of 5 ℃/min, adding the thermoplastic elastomer accounting for 50 percent of the total weight of the SIS thermoplastic elastomer into the reaction vessel in the step (2) after all the components are melted uniformly, and continuously heating for 30 min. The stirring speed was 155r/min, which otherwise easily caused uneven stirring. And after the added raw materials are completely and uniformly mixed, adding the rest raw materials, vacuumizing, removing white bubbles, and continuously heating for 50min at constant temperature until the system is uniform.
(5) Stopping stirring after the reaction is finished, maintaining the temperature of the discharge port at 155 ℃, discharging after the reaction substances are stable, and cooling.
Example 2
kinds of modified hot melt pressure sensitive adhesive comprises the following components in parts by weight:
wherein: the styrene thermoplastic elastomer is SIS, has a linear structure, the styrene content is 18 percent, and the diblock content is 60 percent.
The petroleum resin is C5 petroleum resin, and the softening point is 89 ℃.
The softening point of the pentaerythritol ester is 100 ℃.
The Fischer-Tropsch wax is a methylene polymer synthesized by a coal-based Fischer-Tropsch polymerization process, is produced by a cobalt-based catalyst, has the molecular mass of about 700, and has the freezing point of 105 ℃.
The preparation method of the hot-melt pressure-sensitive adhesive comprises the following steps:
(1) according to example 2, styrenic thermoplastic elastomer, petroleum resin, Fischer-Tropsch wax, pentaerythritol ester, primary antioxidant, secondary antioxidant, and softener were weighed.
(2) A100 ml three-neck flask was washed, dried, and charged with a stirring rod, a thermometer, and Clarithrome oil KN4010, and the heating temperature was 130 ℃ and the stirring rate was 100 r/min.
(3) And (2) continuously heating the reaction container in the step (1) to 170 ℃, keeping the stirring speed unchanged, keeping the heating time at 25min, adding petroleum resin, Fischer-Tropsch wax, pentaerythritol ester and main and auxiliary antioxidants into the reaction container, vacuumizing, and continuously heating.
(4) And (3) heating to 180 ℃ at the heating rate of 5 ℃/min, adding the thermoplastic elastomer accounting for 50 percent of the total weight of the SIS thermoplastic elastomer into the reaction vessel in the step (2) after all the components are melted uniformly, and continuously heating for 35 min. The stirring speed was 155r/min, which otherwise easily caused uneven stirring. And after the added raw materials are completely and uniformly mixed, adding the rest raw materials, vacuumizing, removing white bubbles, and continuously heating for 45min at constant temperature until the system is uniform.
(5) Stopping stirring after the reaction is finished, maintaining the temperature of the discharge port at 155 ℃, discharging after the reaction substances are stable, and cooling.
Example 3
kinds of modified hot melt pressure sensitive adhesive comprises the following components in parts by weight:
wherein: the styrene thermoplastic elastomer is SIS, has a linear structure, the styrene content is 20 percent, and the diblock content is 60 percent.
The petroleum resin is C5 petroleum resin, and the softening point is 92 ℃.
The softening point of pentaerythritol ester is 105 ℃.
The Fischer-Tropsch wax is a methylene polymer synthesized by a coal-based Fischer-Tropsch polymerization process, is produced by a cobalt-based catalyst, has the molecular mass of about 800 and the freezing point of 105 ℃.
The preparation method of the hot-melt pressure-sensitive adhesive comprises the following steps:
(1) according to example 3, styrenic thermoplastic elastomer, petroleum resin, Fischer-Tropsch wax, pentaerythritol ester, primary antioxidant, secondary antioxidant, and softener were weighed.
(2) A100 ml three-neck flask was washed, dried, and charged with a stirring rod, a thermometer, and Clarithrome oil KN4010, and the heating temperature was 130 ℃ and the stirring rate was 100 r/min.
(3) And (2) continuously heating the reaction container in the step (1) to 170 ℃, keeping the stirring speed unchanged, keeping the heating time at 27min, adding petroleum resin, Fischer-Tropsch wax, pentaerythritol ester and main and auxiliary antioxidants into the reaction container, vacuumizing, and continuously heating.
(4) And (3) heating to 180 ℃ at the heating rate of 5 ℃/min, adding the thermoplastic elastomer accounting for 50 percent of the total weight of the SIS thermoplastic elastomer into the reaction vessel in the step (2) after all the components are melted uniformly, and continuously heating for 35 min. The stirring speed was 155r/min, which otherwise easily caused uneven stirring. And after the added raw materials are completely and uniformly mixed, adding the rest raw materials, vacuumizing, removing white bubbles, and continuously heating at constant temperature for 55min until the system is uniform.
(5) Stopping stirring after the reaction is finished, maintaining the temperature of the discharge hole at 160 ℃, discharging after the reaction substances are stable, and cooling.
Example 4
kinds of modified hot melt pressure sensitive adhesive comprises the following components in parts by weight:
wherein: the styrene thermoplastic elastomer is SIS, has a linear structure, the styrene content is 21 percent, and the diblock content is 70 percent.
The petroleum resin is C5 petroleum resin, and the softening point is 100 ℃.
The softening point of pentaerythritol ester is 105 ℃.
The Fischer-Tropsch wax is a methylene polymer synthesized by a coal-based Fischer-Tropsch polymerization process, is produced by a cobalt-based catalyst, has the molecular mass of about 800 and the freezing point of 105 ℃.
The preparation method of the hot-melt pressure-sensitive adhesive comprises the following steps:
(1) according to example 4, styrenic thermoplastic elastomer, petroleum resin, Fischer-Tropsch wax, pentaerythritol ester, primary antioxidant, secondary antioxidant, softener were weighed.
(2) A100 ml three-neck flask was washed, dried, and charged with a stirring rod, a thermometer, and Clarithrome oil KN4010, and the heating temperature was 130 ℃ and the stirring rate was 100 r/min.
(3) And (2) continuously heating the reaction container in the step (1) to 170 ℃, keeping the stirring speed unchanged, keeping the heating time at 28min, adding petroleum resin, Fischer-Tropsch wax, pentaerythritol ester and main and auxiliary antioxidants into the reaction container, vacuumizing, and continuously heating.
(4) And (3) heating to 180 ℃ at the heating rate of 5 ℃/min, adding the thermoplastic elastomer accounting for 50 percent of the total weight of the SIS thermoplastic elastomer into the reaction vessel in the step (2) after all the components are melted uniformly, and continuously heating for 40 min. The stirring speed was 155r/min, which otherwise easily caused uneven stirring. And after the added raw materials are completely and uniformly mixed, adding the rest raw materials, vacuumizing, removing white bubbles, and continuously heating for 50min at constant temperature until the system is uniform.
(5) Stopping stirring after the reaction is finished, maintaining the temperature of the discharge hole at 160 ℃, discharging after the reaction substances are stable, and cooling.
Comparative example 1
modified hot melt pressure sensitive adhesives were prepared using the same ingredients and procedure as in example 1, except that differs from the reaction materials in that no Fischer-Tropsch wax was added.
Comparative example 2
kinds of modified hot melt pressure sensitive adhesive has the same components and preparation process as example 1 except that is different from the reaction material without adding pentaerythritol ester.
Comparative example 3
kinds of modified hot melt pressure sensitive adhesive comprises the following components in parts by weight:
the comparative example used styrenic thermoplastic elastomer, petroleum resin, pentaerythritol ester, Fischer-Tropsch wax, antioxidant, and naphthenic oil, all similar to those of example 1.
The preparation method comprises the following steps: weighing styrene thermoplastic elastomer, petroleum resin, Fischer-Tropsch wax, pentaerythritol ester, antioxidant (antioxidant 1010 and antioxidant 168 are mixed according to the mass ratio of 2: 1) and softener. The reaction vessel was washed, dried, charged with a stirring rod, a thermometer, and naphthenic oil, and heated. Continuously heating to 160 ℃, adding petroleum resin, Fischer-Tropsch wax, pentaerythritol ester and main and auxiliary antioxidants into the reaction vessel, vacuumizing, and continuously heating. The temperature was raised to 180 ℃ and 50% by weight of the thermoplastic elastomer based on the total weight of the SIS thermoplastic elastomer was charged into the reaction vessel for 40 min. Stopping stirring after the reaction is finished, discharging after the reaction substance is stable, and cooling.
Comparative example 3 the amount of each raw material added was different from that of example, and no vacuum-pumping step was performed.
The hot melt pressure sensitive adhesives prepared in examples 1 to 4 and comparative examples 1 to 3 were subjected to a performance test:
(1) the detection method comprises the following steps: the peel strength test method is based on GB/T2792-.
(2) In table 1, the greater the 180 ° peel force value, the higher the peel strength; the larger the holding viscosity value is, the better the holding viscosity is; a higher softening point indicates a softer mass at ambient temperature.
TABLE 1 modified Hot melt pressure sensitive adhesive Performance test results
Claims (10)
1, modified hot melt pressure sensitive adhesives are characterized by comprising styrene thermoplastic elastomers, petroleum resin, Fischer-Tropsch wax, pentaerythritol ester, a main antioxidant, an auxiliary antioxidant and a softener, wherein the styrene thermoplastic elastomers are SIS, have a linear structure, have a styrene content of 15% -21% and have a diblock content of 50% -75%.
2. The modified hot melt pressure sensitive adhesive of claim 1, wherein: the paint comprises the following components in parts by weight: 20-30 parts of styrene thermoplastic elastomer, 30-35 parts of petroleum resin, 3-8 parts of Fischer-Tropsch wax, 10-15 parts of pentaerythritol ester, 0.1-0.3 part of main antioxidant, 0.1-0.3 part of auxiliary antioxidant and 14-16 parts of softener.
3. The modified hot melt pressure sensitive adhesive of claim 1, wherein: the petroleum resin is C5 petroleum resin, and the softening point is 80-100 ℃; the softening point of the pentaerythritol ester is 95-110 ℃.
4. The modified hot melt pressure sensitive adhesive of claim 1, wherein: the Fischer-Tropsch wax is a methylene polymer synthesized by a coal-based Fischer-Tropsch polymerization process, is produced by a cobalt-based catalyst, has the molecular mass of 500-1000 and the freezing point of 105 ℃.
5. The modified hot melt pressure sensitive adhesive of claim 1, wherein: the main antioxidant is tetra [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the auxiliary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite; the softener is Clarithromane oil KN 4010.
6, A method for preparing the modified hot melt pressure sensitive adhesive of any one of claims 1-5 to , comprising the steps of:
(1) weighing the following raw materials in parts by weight: 20-30 parts of styrene thermoplastic elastomer, 30-35 parts of petroleum resin, 3-8 parts of Fischer-Tropsch wax, 10-15 parts of pentaerythritol ester, 0.1-0.3 part of main antioxidant, 0.1-0.3 part of auxiliary antioxidant and 14-16 parts of softener;
(2) adding a softening agent into a reaction container, heating and stirring;
(3) putting petroleum resin, Fischer-Tropsch wax, pentaerythritol ester, a main antioxidant and an auxiliary antioxidant into a reaction container, vacuumizing, and continuously heating;
(4) heating to constant temperature, adding styrene thermoplastic elastomer in several times, stirring uniformly and reacting;
(5) stopping stirring after the reaction is finished, discharging after the reaction substance is stable, and cooling.
7. The preparation method of the modified hot melt pressure sensitive adhesive according to claim 6, wherein: the heating temperature of the step (2) is 130-140 ℃, and the stirring speed is 100 r/min.
8. The preparation method of the modified hot melt pressure sensitive adhesive according to claim 6, wherein: the continuous temperature rise in the step (3) is as follows: heating to 170 deg.C, stirring at constant speed, and continuously heating for 20-30 min.
9. The preparation method of the modified hot melt pressure sensitive adhesive according to claim 6, wherein:
in the step (4), the stirring speed is 155 r/min;
the step (4) is as follows: heating to 180 ℃ at a heating rate of 5 ℃/min, adding a styrene thermoplastic elastomer accounting for 50 percent of the total weight of the styrene thermoplastic elastomer after all the components are melted uniformly, stirring uniformly, and continuously heating for 30-40 min for reaction; after the added raw materials are completely and uniformly mixed, adding the rest styrene thermoplastic elastomer, vacuumizing, removing white bubbles, uniformly stirring, keeping the temperature, and continuously heating for 40-60 min until the system is uniform.
10. The preparation method of the modified hot melt pressure sensitive adhesive according to claim 6, wherein: in the step (5), the temperature of the discharge hole is maintained at 155-160 ℃.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111423833A (en) * | 2020-06-01 | 2020-07-17 | 浙江辉柯纸塑制品有限公司 | Low-temperature hot-melt pressure-sensitive adhesive and preparation method thereof |
| CN112280506A (en) * | 2020-10-30 | 2021-01-29 | 中山市太力家庭用品制造有限公司 | Substrate-free removable rubber pressure-sensitive adhesive |
| CN113249066A (en) * | 2021-06-30 | 2021-08-13 | 佛山南宝高盛高新材料有限公司 | High-temperature removable label hot melt adhesive and preparation method thereof |
| CN113480955A (en) * | 2021-07-30 | 2021-10-08 | 厦门祺星新材料有限公司 | Removable hot-melt pressure-sensitive adhesive and preparation method thereof |
| CN114032055A (en) * | 2021-11-19 | 2022-02-11 | 雨中情防水技术集团股份有限公司 | Low-viscosity hot-melt pressure-sensitive adhesive capable of being coated at low temperature and preparation method thereof |
| CN114752190A (en) * | 2022-04-19 | 2022-07-15 | 东莞鸿冠新材料科技有限公司 | PET heat-sealing auxiliary agent, PET heat-sealing sheet and preparation method thereof |
| CN114933888A (en) * | 2022-04-28 | 2022-08-23 | 浙江冠豪新材料有限公司 | Hot-melt pressure-sensitive adhesive capable of being coated at high speed and preparation method thereof |
| CN114940872A (en) * | 2022-04-28 | 2022-08-26 | 浙江冠豪新材料有限公司 | Adhesive label and preparation method thereof |
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| CN111423833A (en) * | 2020-06-01 | 2020-07-17 | 浙江辉柯纸塑制品有限公司 | Low-temperature hot-melt pressure-sensitive adhesive and preparation method thereof |
| CN112280506A (en) * | 2020-10-30 | 2021-01-29 | 中山市太力家庭用品制造有限公司 | Substrate-free removable rubber pressure-sensitive adhesive |
| CN113249066A (en) * | 2021-06-30 | 2021-08-13 | 佛山南宝高盛高新材料有限公司 | High-temperature removable label hot melt adhesive and preparation method thereof |
| CN113249066B (en) * | 2021-06-30 | 2022-09-06 | 佛山南宝高盛高新材料有限公司 | High-temperature removable label hot melt adhesive and preparation method thereof |
| CN113480955A (en) * | 2021-07-30 | 2021-10-08 | 厦门祺星新材料有限公司 | Removable hot-melt pressure-sensitive adhesive and preparation method thereof |
| CN114032055A (en) * | 2021-11-19 | 2022-02-11 | 雨中情防水技术集团股份有限公司 | Low-viscosity hot-melt pressure-sensitive adhesive capable of being coated at low temperature and preparation method thereof |
| CN114752190A (en) * | 2022-04-19 | 2022-07-15 | 东莞鸿冠新材料科技有限公司 | PET heat-sealing auxiliary agent, PET heat-sealing sheet and preparation method thereof |
| CN114933888A (en) * | 2022-04-28 | 2022-08-23 | 浙江冠豪新材料有限公司 | Hot-melt pressure-sensitive adhesive capable of being coated at high speed and preparation method thereof |
| CN114940872A (en) * | 2022-04-28 | 2022-08-26 | 浙江冠豪新材料有限公司 | Adhesive label and preparation method thereof |
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