WO2023130609A1

WO2023130609A1 - Water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive, and preparation method therefor and use thereof

Info

Publication number: WO2023130609A1
Application number: PCT/CN2022/087174
Authority: WO
Inventors: 高洁; 吴立霞; 汪加胜; 唐舫成
Original assignee: 广州鹿山新材料股份有限公司; 广州鹿山光电材料有限公司
Priority date: 2022-01-07
Filing date: 2022-04-15
Publication date: 2023-07-13
Also published as: CN114350291A; CN114350291B

Abstract

The present disclosure relates to the technical field of pressure-sensitive adhesives, in particular to a water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive, and a preparation method therefor and the use thereof. The water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive is mainly prepared from the following components in parts by weight: 5-35 parts of a styrene block copolymer, 5-25 parts of a polyurethane elastomer, 10-30 parts of a plasticizer, 30-50 parts of a tackifying resin, 0-1 part(s) of an antioxidant, 2-30 parts of a water-absorbing high polymer, and 1-10 parts of a polyphenol biomimetic material. In the present disclosure, by means of the cooperation of all the components and the use of a certain amount of the styrene block copolymer and the polyurethane elastomer in cooperation, it is ensured that the pressure-sensitive adhesive has both an improved viscosity and improved cohesive strength and maintains excellent adhesion to skin without leaving any adhesive residue; and by introducing a certain amount of the water-absorbing high polymer and the polyphenol biomimetic material, the water resistance and sweat resistance of the hot-melt pressure-sensitive adhesive are improved, and the hot-melt pressure-sensitive adhesive is also ensured to be free from sensitization and irritation to skin.

Description

Water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive and its preparation method and application

Cross References to Related Applications

This disclosure claims the priority of the Chinese patent application with the application number "CN202210015386.8" and the title "water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive and its preparation method and application" submitted to the Chinese Patent Office on January 07, 2022. The entire contents are incorporated by reference in this disclosure.

technical field

The disclosure relates to the technical field of pressure-sensitive adhesives, in particular to a water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive and its preparation method and application.

Background technique

In the field of medical supplies, pressure-sensitive adhesives are used for the bonding of medical supplies and as a carrier for drug release and skin adhesion. Medical bandages, protective clothing composite glue, etc.

Traditional commercially available medical pressure-sensitive adhesive products mainly include natural rubber, acrylic ester, and silicone. Natural rubber pressure-sensitive adhesives are mostly solvent-based products with low safety, poor air permeability, and serious skin irritation and allergies. Acrylic pressure-sensitive adhesives are mostly solvent-based products, the preparation process is not environmentally friendly, and the presence of residual monomers will reduce their biocompatibility. Silicone rubber-based pressure-sensitive adhesives have problems such as poor adhesion to skin, low drug loading, and high cost.

Hot-melt pressure-sensitive adhesive (HMPSA) is mainly made of a mixture of thermoplastic elastomers, tackifying resins, plasticizers, antioxidants, etc., and the components and preparation process are solvent-free. Due to its environmental protection, good biocompatibility and process It is simple, efficient, and has good performance. It is currently being promoted rapidly in the medical field. However, the current commercially available products still have unstable viscosity, especially poor sweat resistance, that is, the problem that the viscosity decreases after the skin is attached to water, sweat, and interstitial fluid.

Contents of the invention

The present disclosure provides a water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive, which is mainly prepared from the following components in parts by weight:

5-35 parts of styrene block copolymer, 5-25 parts of polyurethane elastomer, 10-30 parts of plasticizer, 30-50 parts of tackifying resin, 0-1 part of antioxidant, 2-30 parts of water-absorbing polymer and 1-10 parts of polyphenol biomimetic materials.

In some embodiments of the present disclosure, the water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive is mainly prepared from the following components in parts by weight:

15-25 parts of styrene block copolymer, 10-20 parts of polyurethane elastomer, 25-30 parts of plasticizer, 35-45 parts of tackifying resin, 0.5-0.8 parts of antioxidant, 5-15 parts of water-absorbing polymer and 3 to 8 parts of polyphenol biomimetic materials.

In some embodiments of the present disclosure, the weight ratio of the styrene block copolymer to the polyurethane elastomer is 1:(0.2˜5).

In some embodiments of the present disclosure, the weight ratio of the styrene block copolymer to the polyurethane elastomer is 1:(0.2˜1.5).

In some embodiments of the present disclosure, the water-absorbing polymer is a polymer material containing any one or more of carboxyl groups, hydroxyl groups and amide groups.

In some embodiments of the present disclosure, the water-absorbing polymer includes any one or more of natural water-absorbing polymers, semi-synthetic water-absorbing polymers and synthetic water-absorbing polymers.

In some embodiments of the present disclosure, the natural water-absorbing polymer includes any one or more of cellulose, starch, chitosan, alginate and gelatin. In some embodiments of the present disclosure, the semi-synthetic water-absorbing polymer includes any one or more of carboxylated or hydroxylated starch, carboxylated or hydroxylated cellulose, and carboxylated or hydroxylated chitosan kind. In some embodiments of the present disclosure, the synthetic water-absorbing polymer includes any one or more of acrylic polymers, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, and polyvinyl methyl ether.

In some embodiments of the present disclosure, the water-absorbing polymer includes sodium carboxymethylcellulose.

In some embodiments of the present disclosure, the polyphenol biomimetic material includes any one or more of tyrosine-based biomimetic material, mussel biomimetic material and tannin biomimetic material.

In some embodiments of the present disclosure, the polyphenol biomimetic material is a mussel biomimetic material.

In some embodiments of the present disclosure, the mussel biomimetic material is dopamine hydrochloride.

In some embodiments of the present disclosure, the tackifying resin is a hydrogenated resin.

In some embodiments of the present disclosure, the tackifying resin includes rosin resin, terpene resin, terpene phenol resin, C5 petroleum resin, C9 petroleum resin, C5C9 copolymer petroleum resin and acrylate copolymer and Any one or more of the respective modified derivatives.

In some embodiments of the present disclosure, the tackifying resin is a mixture of hydrogenated C5 petroleum resin and hydrogenated rosin resin. In some embodiments of the present disclosure, the softening point of the hydrogenated C5 petroleum resin is 80-140°C. In some embodiments of the present disclosure, the softening point of the hydrogenated rosin resin is 80-120° C., and the acid value is 10-250 mg/g.

In some embodiments of the present disclosure, the styrenic block copolymer includes any one or more of SIS, SBS, SEBS, and SEPS.

In some embodiments of the present disclosure, in the styrene block copolymer, the content of styrene is 14wt%-40wt%, and the content of diblock is 0wt%-70wt%.

In some embodiments of the present disclosure, in the styrene block copolymer, the content of styrene is 14wt%-29wt%, and the content of diblock is 40wt%-60wt%.

In some embodiments of the present disclosure, the polyurethane elastomer includes polyether polyurethane elastomer and/or polyester polyurethane elastomer. In some embodiments of the present disclosure, the softening temperature of the polyurethane elastomer is 80-120°C, and the melt index at 200°C/5kg is 50-500g/min.

In some embodiments of the present disclosure, the plasticizer includes any one or more of naphthenic oil, paraffin oil and polyisobutylene oil.

In some embodiments of the present disclosure, the plasticizer is a mixture of paraffin oil and polyisobutylene oil. In some embodiments of the present disclosure, the antioxidant includes any one or more of hindered phenolic antioxidants, phosphite antioxidants, and thiodipropyl ester antioxidants.

The present disclosure also provides a method for preparing any one of the above-mentioned water-resistant and sweat-resistant hot-melt pressure-sensitive adhesives, including the following steps:

Styrene block copolymer, plasticizer, polyurethane elastomer and antioxidant are uniformly mixed at 140-170°C, sheared and melted to obtain a melted material;

Mix the obtained melted material with tackifying resin and water-absorbing polymer at 140-170°C, and vacuumize for 20-60 minutes to obtain the mixed material;

The temperature of the obtained mixed material is lowered to 100-120° C., polyphenol biomimetic material is added, and stirred with nitrogen gas for 15-20 minutes to obtain a hot-melt pressure-sensitive adhesive.

The present disclosure also provides the application of any one of the above-mentioned water-resistant and sweat-resistant hot-melt pressure-sensitive adhesives in medical pressure-sensitive adhesives.

In some embodiments of the present disclosure, the preparation of the medical pressure-sensitive adhesive includes: coating the hot-melt pressure-sensitive adhesive on the surface of the substrate, and then covering the glue-coated surface with a release layer or directly winding it.

In some embodiments of the present disclosure, the substrate includes a non-woven fabric; the release layer includes a release paper or a release film.

Detailed ways

The technical solution of the present disclosure will be clearly and completely described below in conjunction with some embodiments, but those skilled in the art will understand that the embodiments described below are some of the embodiments of the present disclosure, rather than all embodiments, and are only used for illustrate the present disclosure and should not be considered as limiting the scope of the present disclosure. Based on the embodiments in the present disclosure, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present disclosure. Those who do not indicate the specific conditions in the examples are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used were not indicated by the manufacturer, and they were all conventional products that could be purchased from the market.

Definition of Terms

As used herein, the term "peel strength" refers to the load per unit width that can be borne by a bonded sample when it is separated under specified peeling conditions, which reflects the bond strength of the material.

As used herein, the term "stick holding power" refers to the ability of an adhesive product (such as a pressure-sensitive adhesive) to withstand a static force applied on the same plane as the backing material, which can be expressed as the time of continuous adhesion, usually adhesive products Generally speaking, the stronger the sticking force, the better the product's ability to adhere and the strength of the colloid, and it will not fall off easily.

Some embodiments of the present disclosure provide a water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive, which is mainly prepared from the following components in parts by weight:

The water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive of the present disclosure can improve the stickiness and conformability of the pressure-sensitive adhesive to the skin through the coordination of various components, and on the basis of improving the viscosity and cohesive strength at the same time, it can achieve no residue on the skin. The effect of glue; by introducing a certain amount of water-absorbing polymers, the water absorption rate can be increased, so that the pressure-sensitive adhesive has the property of absorbing the liquid at the bonding interface, keeping the bonding interface with less liquid or even no liquid, and reducing the adhesive force of the liquid on the bonding interface The impact of polyphenol bionic materials is added, on the one hand, it can improve the adhesion with the bonding surface in a wet environment, on the other hand, it can improve the compatibility of pressure-sensitive adhesives, and ensure that it is non-sensitizing and irritating to the skin.

As in different embodiments, the dosage of each component of the water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive can be as follows:

The amount of the styrene block copolymer can be, for example, 5 to 30 parts, 10 to 35 parts or 10 to 30 parts, such as 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, etc.;

The amount of polyurethane elastomer can be, for example, 6-25 parts, 5-20 parts or 10-25 parts, such as 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, etc.;

The amount of plasticizer can be, for example, 15-30 parts, 10-25 parts or 12-28 parts, such as 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, etc.;

The amount of tackifying resin can be, for example, 34-50 parts, 30-45 parts or 40-50 parts, such as 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, etc.;

The amount of antioxidant can be, for example, 0-0.5 parts, 0.1-1 parts or 0.1-0.9 parts, such as 0 parts, 0.2 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts, 1 part, etc.;

The amount of water-absorbing polymer can be, for example, 5-30 parts, 2-25 parts or 10-28 parts, such as 2 parts, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, etc.;

The amount of polyphenol biomimetic material can be, for example, 1-5 parts, 2-10 parts or 3-8 parts, such as 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 copies, 10 copies, etc.

In some embodiments of the present disclosure, the weight ratio of the styrene block copolymer to the polyurethane elastomer is 1:(0.2-5), such as 1:(0.5-4), 1:(1-4 ) or 1: (1.5～3.5), such as 1:0.5, 1:1.1, 1:1.6, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5 .

In some embodiments of the present disclosure, the weight ratio of the styrene block copolymer to the polyurethane elastomer is 1:(0.2˜1.5). For example, it can be 1:(0.2~1.0), 1:(0.4~1.5) or 1:(0.5~1.4), such as 1:0.2, 1:0.4, 1:0.6, 1:0.8, 1:1, 1: 1.2, 1:1.4, 1:1.5, etc.

This solution adopts the combination of styrene block copolymer and polyurethane elastomer to increase the polarity of the material and increase the peel strength; at the same time, the ratio of the two is controlled within the above range to avoid poor compatibility of the system caused by excessive use of polyurethane elastomer , leading to a significant drop in peeling force after soaking, and it is easy to fall off.

In some embodiments of the present disclosure, the water-absorbing polymer is a polymer material containing any one or more of carboxyl, hydroxyl and amide groups. In some embodiments, the water-absorbing polymer includes any one or more of natural water-absorbing polymers, semi-synthetic water-absorbing polymers, and synthetic water-absorbing polymers. In some embodiments, the natural water-absorbing polymer includes any one or more of cellulose, starch, chitosan, alginate, and gelatin. In some embodiments, the semi-synthetic water-absorbing polymer includes any one or more of carboxylated or hydroxylated starch, carboxylated or hydroxylated cellulose, and carboxylated or hydroxylated chitosan. In some embodiments, the synthetic water-absorbing polymer includes any one or more of acrylic polymers, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, and polyvinyl methyl ether.

In some embodiments of the present disclosure, the water-absorbing polymer includes sodium carboxymethylcellulose. In some embodiments, the particle size of the water-absorbing polymer is <10 μm. The use of water-absorbing polymers with the aforementioned particle size is beneficial to subsequent coating processing and the like.

In some embodiments, sodium carboxymethylcellulose is used in the hot-melt pressure-sensitive adhesive system to cooperate with other components to further improve the water absorption capacity of the hot-melt pressure-sensitive adhesive system, and carboxymethylcellulose Sodium can be uniformly dispersed in the hot melt pressure sensitive adhesive system. It should be noted that carboxymethyl cellulose is only a choice of water-absorbing polymer in the present disclosure, and the choice of water-absorbing polymer in the present disclosure includes but not limited to carboxymethyl cellulose.

In some embodiments of the present disclosure, the polyphenol biomimetic material includes any one or more of tyrosine-based biomimetic material, mussel biomimetic material and tannin biomimetic material. It is not believed to be bound by theory that tyrosine-based biomimetic materials refer to biomimetic materials containing monophenolic hydroxyl groups, mussel biomimetic materials refer to biomimetic materials containing catechol, and tannin-based biomimetic materials refer to biomimetic materials containing pyrogallol biomimetic materials.

In some embodiments of the present disclosure, the polyphenolic biomimetic material is a mussel biomimetic material. In some embodiments, the mussel biomimetic material is dopamine hydrochloride.

In some embodiments, the mussel biomimetic material is dopamine hydrochloride, which can be combined with the carboxyl group of the hydrogenated rosin resin in the tackifying resin by using dopamine hydrochloride, which helps to stabilize in the system, and is not easy to get out of the glue when it encounters water or tissue fluid. Separation and lose the role of bonding, etc.

In some embodiments of the present disclosure, the tackifying resin is a hydrogenated resin. In some embodiments, the tackifying resin includes rosin resin, terpene resin, terpene phenol resin, C5 petroleum resin, C9 petroleum resin, C5C9 copolymerized petroleum resin and acrylate copolymer and modified derivatives thereof any one or more of them.

In some embodiments of the present disclosure, the tackifying resin is a mixture of hydrogenated C-penta petroleum resin and hydrogenated rosin resin. In some embodiments, the softening point of the hydrogenated C5 petroleum resin is 80-140°C, for example, it may be 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C. In some embodiments, the softening point of the hydrogenated rosin resin is 80-120°C, for example, 80°C, 90°C, 100°C, 110°C, 120°C; the acid value of the hydrogenated rosin resin is 10-250 mg/g. In some embodiments, the mass proportion of the hydrogenated rosin resin in the tackifying resin may be 20%-70%.

As in different embodiments, in the tackifying resin, the mass proportion of hydrogenated rosin resin can be, for example, 25% to 70%, 25% to 65%, or 30% to 60%, such as 20%, 30%, 40%, 50%, 60%, 70% and so on.

It is believed, without being bound by theory, that hydrogenated C-penta petroleum resins and hydrogenated rosin resins have excellent anti-aging properties, are good in biocompatibility, and are non-sensitizing and irritating to the skin. And as mentioned above, in some embodiments, the polyphenol biomimetic material dopamine hydrochloride can be combined with the carboxyl group of hydrogenated rosin resin, which helps to stabilize in the system and is not easy to separate from the glue when it encounters water or interstitial fluid Losing the role of bonding can further improve the biocompatibility and water and sweat resistance of the hot-melt pressure-sensitive adhesive.

In some embodiments of the present disclosure, the styrenic block copolymer includes any one or more of SIS, SBS, SEBS, and SEPS. In some embodiments, in the styrene block copolymer, the content of styrene is 14wt%-40wt%, the content of diblock is 0wt%-70wt%, and the melt index at 200°C/5kg is 1-35g /min.

In some embodiments of the present disclosure, in the styrene block copolymer, the content of styrene is 14wt%-29wt%, and the content of diblock is 40wt%-60wt%. In some embodiments of the present disclosure, in the styrene block copolymer, the content of styrene can be 14wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, and the content of the diblock is 0wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%.

The use of the above-mentioned styrene block copolymer helps to improve the wettability of the pressure-sensitive adhesive, thereby improving the peeling force, the peeling force after soaking, and the adhesion to the skin. When the styrene block copolymer used has a high styrene content and a low diblock content, it will affect the wettability of the pressure-sensitive adhesive system of the present disclosure, resulting in a decrease in peeling force and adhesion.

In some embodiments of the present disclosure, the polyurethane elastomer includes polyether polyurethane elastomer and/or polyester polyurethane elastomer. In some embodiments, the softening temperature of the polyurethane elastomer is 80-120°C, such as 90-120°C, 80-110°C or 80-100°C; the melt index at 200°C/5kg is 50-500g/min , for example, 100-500 g/min, 50-400 g/min or 150-500 g/min.

In some embodiments of the present disclosure, the plasticizer includes any one or more of naphthenic oils, paraffinic oils, and polyisobutylene oils. In some embodiments, the plasticizer is a mixture of paraffin oil and polyisobutylene oil. In some embodiments, the paraffin oil has a dynamic viscosity of 10-120 mm/s at 40°C and a flash point of >200°C; the polyisobutylene oil has a viscosity-average molecular weight of 500-5000.

In some embodiments of the present disclosure, in the plasticizer, the weight ratio of paraffin oil and polyisobutylene oil is 1:(0.8˜1.5). In some embodiments, the weight ratio of paraffin oil to polyisobutylene oil can be, for example, 1:0.8, 1:0.9, 1:1.0, 1:1.1, 1:1.2, 1:1.3, 1:1.4, or 1:1.5 .

It is believed, without being bound by theory, that paraffin oil has excellent low-temperature resistance, moderate peel force when used in the preparation of medical pressure-sensitive adhesives, and can help adhere to the skin without pain and residue; polyisobutylene oil and The combination of various components can further increase the wettability and sweat resistance of the medical pressure-sensitive adhesive.

In some embodiments of the present disclosure, the antioxidant includes any one or more of hindered phenolic antioxidants, phosphite antioxidants, and thiodipropyl ester antioxidants.

In actual operation, the types of antioxidants can be routinely adjusted according to actual conditions.

(a) mixing styrene block copolymer, plasticizer, polyurethane elastomer and antioxidant at 140-170° C., shearing and melting to obtain a melted material;

(b) Mix the melted material obtained in step (a) with the tackifying resin and the water-absorbing polymer at 140-170° C., and vacuumize for 20-60 minutes to obtain the mixed material;

(c) Cool down the mixed material obtained in step (b) to 100-120° C., add polyphenol biomimetic materials, and stir with nitrogen gas for 15-20 minutes to obtain a hot-melt pressure-sensitive adhesive.

The water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive of the present disclosure solves the problem of poor sweat resistance in the prior art pressure-sensitive adhesives for traditional Chinese medicine, that is, the problem that the viscosity decreases after the skin is attached to water, sweat, and tissue fluid, and avoids pressure-sensitive adhesives. The residual problem on the skin after the sensitive glue is torn off, and solves the problems of irritation and sensitization to the skin at the same time.

In actual operation, a hot melt coating machine is used to coat the hot melt pressure sensitive adhesive on the surface of the substrate at 140-180°C.

In some embodiments of the present disclosure, the grammage of the coating is 20-1000 gsm. The grammage of the coating is adjusted and selected according to the actual application scenario.

The disclosure provides a water- and sweat-resistant hot-melt pressure-sensitive adhesive, which solves technical problems such as poor water and sweat resistance in the prior art.

Compared with the prior art, the beneficial effects of the present disclosure are:

(1) The water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive of the present disclosure adopts a certain amount of styrene block copolymer and polyurethane elastomer to cooperate with each component, so as to ensure the improvement of viscosity and cohesive strength, so that the pressure-sensitive The glue maintains excellent adhesion to the skin, and there is no glue residue;

(2) This disclosure introduces a certain amount of water-absorbing polymers, which can keep the bonding interface relatively dry and improve the water and sweat resistance of hot-melt pressure-sensitive adhesives; and further introduce polyphenol bionic materials, which not only improve the peeling force before soaking, It also reduces the degree of peeling force drop after soaking to ensure that it will not fall off, and can improve the compatibility of pressure-sensitive adhesives to ensure that it is non-sensitizing and irritating to the skin;

(3) The water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive of the present disclosure has excellent adhesiveness and conformability to the skin, does not leave adhesive residue, and is non-sensitizing and irritating to the skin, and can be widely used in medical hot-melt pressure-sensitive adhesives. In pressure sensitive adhesive.

Examples 1-7

This embodiment provides a water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive and a preparation method thereof, the preparation method comprising the following steps:

(a) styrene block copolymer, plasticizer, polyurethane elastomer and antioxidant are uniformly mixed at 160-170°C, sheared and melted to obtain a melted material;

(b) Mix the melted material obtained in step (a) with the tackifying resin and the water-absorbing polymer at 160-170° C., and vacuumize for 30 minutes to obtain the mixed material;

Wherein, the information of each component of each embodiment is shown in Table 1.

Each component information of table 1 different embodiment 1-7

Among them, the styrene block copolymer 1# of Examples 1-3 and Examples 5-7 is SIS, the content of styrene is 16wt%, and the content of diblock is 50wt%; the styrene block copolymer of Example 4 Material 2# is SIS, the content of styrene is 29wt%, and the content of diblock is 0wt%;

The polyurethane elastomers of Examples 1-7 are polyester polyurethane elastomers, the softening temperature is 100°C, and the melt index under the condition of 200°C/5kg is 80g/10min;

The viscosity-average molecular weight of the polyisobutylene oil of Examples 1-7 is 2000; the dynamic viscosity of paraffin oil is 90mm/s at 40°C, and the flash point is 230°C;

The softening point of the hydrogenated C5 petroleum resin of Examples 1 to 7 is 105°C; the softening point of the hydrogenated rosin resin is 95°C, and the acid value is 160mg/g;

The antioxidant in Examples 1-7 is hindered phenolic antioxidant 1010.

Comparative example 1-5

Comparative Example Refer to the preparation method of Example 1, the difference lies in: the types and/or amounts of each component are different. The information of each component of Comparative Examples 1-5 is shown in Table 2.

Table 2 The information of each component of different comparative examples

Wherein, the styrene block copolymer involved in comparative examples 1 to 5, polyurethane elastomer, polyisobutylene oil, paraffin oil, hydrogenated carbon five petroleum resin, hydrogenated rosin resin, sodium carboxymethyl cellulose are the same as embodiment 1; The softening point of the non-hydrogenated petroleum resin in Comparative Example 2 is 100° C.; the sodium polyacrylate in Comparative Example 3 is white fine particles with a particle diameter of about 100 μm.

Experimental example 1

In order to compare and illustrate the properties of different pressure-sensitive adhesives, the hot-melt pressure-sensitive adhesives prepared in Examples 1-7 and Comparative Examples 1-5 were tested as follows, and the test results are shown in Table 3.

Test sample preparation: use a hot-melt coater to coat the pressure-sensitive adhesives prepared in each example and comparative example on a non-woven fabric at 140-180°C, the coating weight is 40gsm, and the glued surface covers the non-woven fabric. Type paper or film, to be tested.

Peel force test standard refers to YY/T0148, test before and after soaking;

Sticking force test standard refers to YY/T0148, test before and after soaking;

Among them, the components of the soaking solution refer to the test solution A in Part 1 of YY/T 0471.1, and the temperature of the soaking solution is 37±2°C;

Human body skin test, test: (1) Whether it comes off after 48 hours, whether it remains after tearing off, whether the skin is red and allergic, refer to GB/T 16886; (2) Run 5KM after fitting, whether it falls off, whether it remains after tearing off , Whether the skin is red and allergic.

Table 3 Test results of different test samples

From the above test results, it can be seen that the present disclosure adopts a certain amount of polyurethane elastomer and styrene block copolymer, and the peeling force of the obtained hot-melt pressure-sensitive adhesive is increased by about 25%, and the holding force reaches <2.5mm; at the same time, The combination of specific tackifying resin and polyphenol bionic materials can further improve the adhesion to human skin and is non-sensitizing and irritating; adding specific water-absorbing polymer sodium carboxymethyl cellulose to the system, It can significantly reduce the degree of decline in the peeling force after soaking, and improve the water and sweat resistance.

For embodiment 3, it has increased the content of sodium carboxymethyl cellulose compared with embodiment 1, because the consumption of sodium carboxymethyl cellulose increases, the volume that meets water can expand greatly, has changed colloid and interfacial state, presses Sensitive glue turns into a gel state, the initial peeling and stickiness will be reduced, but the human skin test does not fall off, and can be used as a gel for medical dressings.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present disclosure, not to limit them; although the present disclosure has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: It is still possible to modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the various embodiments of the present disclosure. scope.

Industrial Applicability

The water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive provided by the present disclosure can ensure the improvement of viscosity and cohesive strength, so that the pressure-sensitive adhesive can maintain excellent adhesion to the skin without residual glue; at the same time, it can keep the bonding interface relatively dry and improve The water and sweat resistance of the hot-melt pressure-sensitive adhesive; at the same time, it improves the peeling force before soaking, and also reduces the decline of the peeling force after soaking, ensuring that it will not fall off, and can improve the compatibility of the pressure-sensitive adhesive to ensure no skin sensitization Sex and irritation, while the preparation method of the present disclosure is simple and convenient, and the product has a wide range of uses. The water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive provided in the present disclosure and the preparation method thereof can be widely used in medical hot-melt pressure-sensitive adhesives, and have excellent application value and broad application prospects.

Claims

The water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive is characterized in that it is mainly prepared from the following components in parts by weight:

5-35 parts of styrene block copolymer, 5-25 parts of polyurethane elastomer, 10-30 parts of plasticizer, 30-50 parts of tackifying resin, 0-1 part of antioxidant, 2-30 parts of water-absorbing polymer and 1-10 parts of polyphenol biomimetic materials.
The water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive according to claim 1, characterized in that it is mainly made of the following components in parts by weight:

15-25 parts of styrene block copolymer, 10-20 parts of polyurethane elastomer, 25-30 parts of plasticizer, 35-45 parts of tackifying resin, 0.5-0.8 parts of antioxidant, 5-15 parts of water-absorbing polymer and 3 to 8 parts of polyphenol biomimetic materials.
The water- and sweat-resistant hot-melt pressure-sensitive adhesive according to claim 1 or 2, characterized in that the weight ratio of the styrene block copolymer to the polyurethane elastomer is 1:(0.2-5).
The water- and sweat-resistant hot-melt pressure-sensitive adhesive according to claim 1 or 2, characterized in that the weight ratio of the styrene block copolymer to the polyurethane elastomer is 1:(0.2-1.5).
The water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive according to any one of claims 1-4, wherein the water-absorbing polymer is a polymer containing any one or more of carboxyl, hydroxyl and amide groups Material;

Preferably, the water-absorbing polymer includes any one or more of natural water-absorbing polymers, semi-synthetic water-absorbing polymers and synthetic water-absorbing polymers;

Preferably, the water-absorbing polymer includes sodium carboxymethylcellulose;

Preferably, the natural water-absorbing polymer includes any one or more of cellulose, starch, chitosan, alginate and gelatin;

Preferably, the semi-synthetic water-absorbing polymer includes any one or more of carboxylated or hydroxylated starch, carboxylated or hydroxylated cellulose, and carboxylated or hydroxylated chitosan;

Preferably, the synthetic water-absorbing polymer includes any one or more of acrylic polymers, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol and polyvinyl methyl ether.
The water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive according to any one of claims 1-5, wherein the polyphenol biomimetic materials include tyrosine-based biomimetic materials, mussel biomimetic materials and tannin biomimetic materials. any one or more of

Preferably, the polyphenol biomimetic material is a mussel biomimetic material;

Preferably, the mussel biomimetic material is dopamine hydrochloride.
The water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive according to any one of claims 1-6, wherein the tackifying resin is a hydrogenated resin;

Preferably, the tackifying resin includes rosin resin, terpene resin, terpene phenol resin, carbon five petroleum resin, carbon nine petroleum resin, carbon five carbon nine copolymerized petroleum resin and acrylate copolymer and respective modified derivatives any one or more of

Preferably, the tackifying resin is a mixture of hydrogenated C5 petroleum resin and hydrogenated rosin resin;

Preferably, the softening point of the hydrogenated C5 petroleum resin is 80-140°C;

Preferably, the hydrogenated rosin resin has a softening point of 80-120° C. and an acid value of 10-250 mg/g.
The water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive according to any one of claims 1-7, wherein the styrene block copolymer comprises any one or more of SIS, SBS, SEBS and SEPS;

And/or, the polyurethane elastomer includes polyether polyurethane elastomer and/or polyester polyurethane elastomer;

Preferably, in the styrene block copolymer, the content of styrene is 14wt%-40wt%, and the content of diblock is 0wt%-70wt%;

More preferably, in the styrene block copolymer, the content of styrene is 14wt%-29wt%, and the content of diblock is 40wt%-60wt%;

Preferably, the softening temperature of the polyurethane elastomer is 80-120° C., and the melt index at 200° C./5 kg is 50-500 g/min.
The water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive according to any one of claims 1-8, wherein the plasticizer includes any one or more of naphthenic oil, paraffin oil and polyisobutylene oil;

Preferably, the plasticizer is a mixture of paraffin oil and polyisobutylene oil.
The water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive according to any one of claims 1-9, wherein the antioxidants include hindered phenolic antioxidants, phosphite antioxidants and thiodipropylene Any one or more of ester antioxidants.
The preparation method of the water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive described in any one of claims 1-10, is characterized in that, comprises the steps:

Styrene block copolymer, plasticizer, polyurethane elastomer and antioxidant are uniformly mixed at 140-170°C, sheared and melted to obtain a melted material;

Mix the obtained melted material with tackifying resin and water-absorbing polymer at 140-170°C, and vacuumize for 20-60 minutes to obtain the mixed material;

The temperature of the obtained mixed material is lowered to 100-120° C., polyphenol biomimetic material is added, and stirred with nitrogen gas for 15-20 minutes to obtain a hot-melt pressure-sensitive adhesive.
The application of the water-resistant and sweat-resistant hot-melt pressure-sensitive adhesive described in any one of claims 1-10 in medical pressure-sensitive adhesives;

Preferably, the preparation of the medical pressure-sensitive adhesive includes: coating the hot-melt pressure-sensitive adhesive on the surface of the substrate, and then covering the glue-coated surface with a release layer or winding it up directly.
The application according to claim 12, characterized in that, the base material comprises a non-woven fabric; and the release layer comprises a release paper or a release film.