KR101956445B1 - Manufacturing Method Of Adhesive Having Semi IPN Structure For Skin, And Adhesive Manufactured Thereby - Google Patents

Abstract

A method for manufacturing a hydrogel-type adhesive for skin attachment having a semi-Iphene structure and a pressure-sensitive adhesive prepared therefrom are disclosed. A method for manufacturing a hydrogel-type adhesive for skin attachment according to an embodiment of the present invention is a method for producing a hydrogel-type adhesive for skin adhesion by polymerizing a sticky hydrogel having a semi-IPN structure, comprising the steps of: a) A step of producing a crosslinked hydrogel structure in which an ethylenically unsaturated group is formed in a monomer to form a polymer compound; b) preparing a non-crosslinked hydrogel structure for imparting a carboxyl functional group to a monomer containing a hydroxyl group in the structure to produce a sticky polymer; c) mixing the polymer compound produced from the step of preparing the crosslinked hydrogel structure with the adhesive polymer produced through the step of preparing the non-crosslinked hydrogel structure; And d) curing the mixed mixture through a mixing step to produce a hydrogel-type pressure-sensitive adhesive having a semi-IPN structure by free radical curing.
According to the present invention, it is possible to provide a cosmetic composition which is not excessively sticky according to a desired situation and has a low rejection, maintains high adhesion and adhesion to skin even after repeated use, does not show irritation and toxicity to the skin, It is possible to manufacture a hydrogel-type pressure-sensitive adhesive for skin attachment which can be removed, and in which the pressure-sensitive adhesive sheet is not detached even in a severe body movement.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogel-type pressure-sensitive adhesive for skin attachment having a semi-

TECHNICAL FIELD The present invention relates to a method for manufacturing a hydrogel-type pressure-sensitive adhesive for skin attachment and a pressure-sensitive adhesive prepared thereby. More particularly, the present invention relates to a method for manufacturing a hydrogel-type adhesive for skin attachment having a semi-IPN structure, will be.

Hydrogel polymer manufacturing technology has basically been continuously studied as a method that is directly applied to the inside or outside of the human body.

It is being developed for various medical products.

Particularly, the adhesive hydrogel is produced in a sheet form and plays a very important role as a part of a measuring device for human stimulation such as electrocardiogram.

However, when a hydrogel-type adhesive for medical use is produced, a high cohesive force is required because it is required to have high adhesion and adhesion to the skin, which is a biological tissue, and it is very important to balance the adhesive strength in order to ensure good adhesion.

However, in the case of most adhesive sheets for skin, there is a problem in that repetitive detachment of adhesive force is decreased due to deterioration of adhesiveness due to pollution factors such as keratin and sweat when repetitive detachment is performed.

Therefore, there is a need for a technique that can solve the problems of the conventional method for producing a pressure sensitive adhesive sheet for skin.

Korean Registered Patent No. 10-1017882 (registered on February 21, 2011)

It is an object of the present invention to provide a cosmetic composition which is not excessively sticky according to a desired situation and has a low rejection, maintains high adhesion and adhesion to skin even after repeated use, does not show irritation and toxicity to the skin, The present invention provides a method for manufacturing a hydrogel-type pressure-sensitive adhesive for skin attachment and a pressure-sensitive adhesive prepared by the method.

According to an aspect of the present invention, there is provided a method for preparing a hydrogel-type pressure-sensitive adhesive for skin attachment by polymerizing a pressure-sensitive adhesive having a semi-IPN structure, a) a step of producing a crosslinked hydrogel structure in which an ethylenically unsaturated group is formed in a monomer containing a hydroxyl group in the structure to produce a polymer compound; b) preparing a non-crosslinked hydrogel structure for imparting a carboxyl functional group to a monomer containing a hydroxyl group in the structure to produce a sticky polymer; c) mixing the polymer compound produced from the step of preparing the crosslinked hydrogel structure with the adhesive polymer produced through the step of preparing the non-crosslinked hydrogel structure; And d) a curing step of subjecting the mixed mixture to a free radical curing through a mixing step to produce a hydrogel-type pressure-sensitive adhesive of a semi-IPN structure.

In one embodiment of the present invention, the step of preparing the crosslinked hydrogel structure comprises the steps of reacting a monofunctional oligomer-type polyethylene co-polypropylene random copolymer having a hydroxyl group at the terminal thereof with a monofunctional monomer to form a hydroxyl group It can be made into an ethylenic unsaturated group.

In this case, the monofunctional monomer may be an anhydride monomer.

In one embodiment of the present invention, the polyethylene copolypropylene oligomer in which the hydroxyl group is substituted with an ethylenically unsaturated group is prepared by allowing the oligomer-type precursor to have a number average molecular weight within the range of 11,000 to 15,000, Can be crosslinked through the acrylic monomer.

In this case, the acrylic monomer may have three or four functional groups.

In one embodiment of the present invention, the step of preparing the non-crosslinked hydrogel structure comprises the steps of: using a random copolymer of polyethylene copolypropylene in the form of a bifunctional oligomer having a terminal hydroxyl group, It can be made into a functional group.

In this case, the monofunctional monomer may be an anhydride monomer.

In one embodiment of the present invention, the carboxyl functional group substituted from the hydroxyl group may be prepared by allowing the oligomer-type precursor to have a number average molecular weight in the range of 11,000 to 15,000 and then crosslinking through a bifunctional or trifunctional amine- Lt; / RTI > to have an amide group in the structure.

In one embodiment of the present invention, the curing step may be performed by sequentially irradiating ultraviolet light and heat to proceed free radical curing to the mixed mixture.

The present invention can also provide a pressure-sensitive adhesive prepared by the above method for manufacturing a hydrogel-type pressure-sensitive adhesive for skin attachment.

INDUSTRIAL APPLICABILITY As described above, according to the method for manufacturing a hydrogel-type pressure-sensitive adhesive for skin attachment of the present invention, by including the step of preparing a crosslinked hydrogel structure having a specific constitution, the step of preparing a non-crosslinked hydrogel structure, The hydrogel-type pressure-sensitive adhesive for skin attachment can be effectively produced.

In addition, according to the method for producing a hydrogel-type adhesive for skin attachment of the present invention, it is possible to provide a skin-sticking hydrogel-type pressure-sensitive adhesive composition which is less sticky and less resistant to a desired situation, maintains high adhesion and adhesion to skin even after repeated use, It is possible to produce a hydrogel-type adhesive for skin attachment which can be removed without leaving any residue even upon desorption.

According to the method for manufacturing a hydrogel-type pressure-sensitive adhesive for skin attachment of the present invention, it is possible to provide a hydrogel-type hydrogel-type adhesive for skin, which maintains high adhesion and adhesive force to skin, A pressure-sensitive adhesive can be produced.

1 is a flowchart illustrating a method of manufacturing a hydrogel-type pressure-sensitive adhesive for skin attachment according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. Prior to the description, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and should be construed in accordance with the technical concept of the present invention.

FIG. 1 is a flow chart illustrating a method of manufacturing a hydrogel-type pressure-sensitive adhesive for skin attachment according to an embodiment of the present invention.

Referring to FIG. 1, a method (S100) for producing a hydrogel-type adhesive for skin attachment according to this embodiment is a method for producing a hydrogel-type adhesive for skin attachment by polymerizing a sticky hydrogel having a semi-IPN structure (S110), a non-crosslinked hydrogel structure preparation step (S120), a mixing step (S130), and a curing step (S140).

Accordingly, the method (S100) for producing a hydrogel-type pressure-sensitive adhesive for skin attachment according to this embodiment can effectively produce a hydrogel-type pressure-sensitive adhesive for skin attachment having a semi- ipene structure.

Hereinafter, each step constituting the hydrogel-type adhesive for skin attachment (S100) according to the present embodiment will be described in detail.

The step (S110) of producing a crosslinked hydrogel structure is a step of producing an ethylenically unsaturated group in a monomer containing a hydroxyl group in the structure to produce a polymer compound.

At this time, it is possible to make the hydroxyl group into an ethylenic unsaturated group by reacting with a monofunctional monomer by using a random copolymer of polyethylene copolymer having a hydroxyl group at the terminal and having the form of a bifunctional oligomer.

The monofunctional monomer used herein is preferably an anhydride monomer such as methacrylic anhydride. In the case of this monomer, it may contain a monomer capable of reacting with the hydroxyl group of the crosslinked hydrogel structure to provide an ethylenically unsaturated group.

The polyethylene copolypropylene oligomer in which the hydroxyl group is replaced with an ethylenically unsaturated group may be crosslinked through a trifunctional or tetrafunctional acrylic monomer after the oligomeric precursor has a number average molecular weight in the range of 11,000 to 15,000 .

The acrylic monomer used here preferably has three or four functional groups. In some cases, single use or more than one may be used to control cohesion and cohesion.

In the non-crosslinked hydrogel structure production step (S120), a carboxyl functional group is added to a monomer containing a hydroxyl group in the structure to produce a sticky polymer.

At this time, the functional group can be made into a carboxyl functional group by reaction with a monofunctional monomer by using a bifunctional oligomer-type polyethylene copolymer having a terminal hydroxyl group.

The monofunctional monomer used herein is preferably an anhydride monomer such as maleic anhydride. In the case of this monomer, it may contain a monomer capable of reacting with the hydroxyl group of the non-crosslinked hydrogel structure to provide a carboxyl functional group.

Further, the carboxyl functional group substituted from the hydroxyl group may be obtained by allowing the oligomer-type precursor to have a number average molecular weight within the range of 11,000 to 15,000 and then crosslinking through a bifunctional or trifunctional amine-based crosslinking agent to induce a structure amide group .

The carboxyl functional group substituted from the hydroxyl group by the above method is preferably crosslinked through a bifunctional or trifunctional amine type crosslinking agent.

The bifunctional or trifunctional amine-based crosslinking agent used here serves to help a part of the hydrogel-type pressure-sensitive adhesive to be cured into a crosslinked structure through thermal crosslinking, such as bis (hexamethylene) triamine. In the case of such a selected crosslinking agent It should be chosen that it is not reactive with the ethylenic unsaturation in its structure.

The mixing step (S130) is a step of mixing the polymeric compound produced from the crosslinking type hydrogel structure producing step (S110) and the adhesive polymer produced through the non-crosslinking hydrogel structure producing step (S120).

Meanwhile, the curing step (S140) is a step of promoting free radical curing on the mixed mixture through a mixing step to produce a hydrogel type adhesive having a semi-IPN structure.

Specifically, in the curing step (S140), ultraviolet irradiation and heat irradiation may be sequentially performed to promote free radical curing in the mixed mixture.

The present invention can also provide a pressure-sensitive adhesive prepared by the above method (S100) for hydrogel adhesive for skin attachment.

That is, the crosslinked hydrogel structure and the non-crosslinked hydrogel structure produced through the series of steps (S100) are mixed with each other, followed by free radical curing using both ultraviolet irradiation and heat irradiation in that order, A hydrogel-type pressure-sensitive adhesive having a semi-IPN structure can be produced. The ratio of the crosslinked hydrogel structure to the non-crosslinked hydrogel structure may be varied depending on the physical properties of the finally produced pressure sensitive adhesive. At this time, the hydrogel type pressure-sensitive adhesive for skin attachment can be finally prepared through both the ultraviolet irradiation and the heat irradiation, which are the curing methods used.

The final adhesive property was confirmed by a 180 ㅀ peel strength tester, and as a result, the pure glass was washed with acetone and then dried in a high temperature oven for drying.

<Examples>

The contents of monomers and additives for all examples are based on parts by weight.

The adhesion referred to in all the examples also means the result of the 180 peel strength test.

The test was conducted according to the standard KS A 1108, and the thickness of the coated adhesive was about 800 μm except for the base film.

The adhesive strength of the adhesive was measured 30 minutes after the sample was adhered to the adherend using an automatic adhesion roller which reciprocates at a speed of 300 mm / min.

&Lt; Example 1-1 >

The hydroxyl groups at both terminals are substituted with methacrylic anhydride using a polyethylene glycol propylene glycol random copolymer having a molecular weight of 6,000 (number average) g / mol. In this process, 200 g of polyethylene glycol propylene glycol was placed in a round-bottom flask-type reaction tank, heated at 100 ° C using a heating mantle, added with 0.1 g of 2,6-di- tert -butyl-4-methylphenol as a catalyst , 5.632 g of methacrylic anhydride was added, and the stirring was continued at 150 rpm. Through this process, the hydroxyl groups at both ends are replaced by methacrylic anhydride.

The material polymerized by this method is a crosslinked polymer that is crosslinked through the use of additive additives and is called resin-N1.

&Lt; Example 1-2 >

A hydroxyl group at both terminals is substituted with methacrylic anhydride by using a polyethylene glycol propylene glycol random copolymer having a molecular weight of 12,000 (number average) g / mol. In this process, 200 g of polyethylene glycol propylene glycol was placed in a round-bottom flask-type reaction tank, heated at 100 ° C. using a heating mantle, and 0.1 g of 2,6-di-tert- , 5.632 g of methacrylic anhydride was added, and the stirrer was set at 150 rpm and continuously stirred. Through this process, the hydroxyl groups at both ends are replaced by methacrylic anhydride.

The material polymerized by this method is a crosslinked polymer that is crosslinked through the use of additive additives and is called resin-N2.

&Lt; Example 1-3 >

3 g of Resin-N1, 2 polymerized according to Examples 1-1 and 2 were dispensed into different beakers, and 5 g of distilled water was administered, followed by dissolving using a magnet rod. Then, 0.6 g of trimethylolpropane tri (methyl) acrylate as a crosslinking agent and 0.07 g of Irgacure 2959 as a photocuring initiator were added. Both formulations with all additives added were cured through a UV curing device.

As a result, the adhesion of Resin-N1, 2 was measured as follows.

<Table 1>

As shown in Example 1-3, in the case of Example 1-1 of the polymers of Examples 1-1 and 1-2, the adhesive force was very low and the adhesive was very easily peeled off from the substrate. It looked. In both cases, however, it was confirmed that they had similar water content.

The resulting figures are given in Table 1.

From the results of Example 3, it was judged that the polyethylene glycol propylene glycol random copolymer having a molecular weight of about 6,000 used in Example 1-1 had a rather high crosslinking density and was not suitable for use in the post-test process, Resin-N2 polymerized with a 12,000 (number average) g / mol polyethyleneglycol propylene glycol random copolymer was selected as the base material of the net type polymer.

&Lt; Example 1-4 >

From the results of Examples 1-3, experiments were conducted to obtain a net-like polymer by obtaining Resin-N2 through Examples 1-2 and to include a linear polymer structure in the inside thereof to expect an increase in adhesion. A maleic anhydride is substituted for the hydroxyl groups at both ends by using a polyethylene glycol propylene glycol random copolymer having a molecular weight of 12,000 (number average) g / mol. In this process, 200 g of polyethylene glycol propylene glycol was placed in a round-bottom flask-type reaction tank, heated at 100 ° C. using a heating mantle, and 0.1 g of 2,6-di-tert- And 5.632 g of maleic anhydride was added, and the stirrer was continuously stirred at 150 rpm. Through this process, the hydroxyl groups at both ends are replaced by maleic anhydride.

The material polymerized by this method is an adhesive polymer that is crosslinked or increased in molecular weight through the use of additive additives. This polymer is called resin-S1.

&Lt; Example 1-5 >

Resin-N2 polymerized by Example 1-2 and Resin-S1 polymerized by Example 4 were changed to one beaker so that the total weight was 5 g, and 5 g of distilled water was administered. Then, using a magnet rod Dissolve. 0.85 g of trimethylolpropane tri (methyl) acrylate as a crosslinking agent and 0.1 g of Irgacure 2959 (a water-soluble photoinitiator, Sigma Aldrich) as a photocuring initiator were added. The two additives with all additives were cured by UV curing with a total energy of 545 mJ / cm ³ , and the adhesion was measured to confirm the change of adhesion according to the mixing ratio of Resin-N2 and Resin-S1.

<Table 2>

The results are shown in Table 2. As the ratio of resin-S1 increased, the adhesion increased slightly.

However, as the mixing ratio of resin-N2 and resin-S1 is 6: 4 to 4: 6, it is confirmed that the contamination of the applied agent is increased, so that the ratio is 7: 3 or 6: 4 Could.

&Lt; Example 1-6 >

Through Examples 1-5, a change in adhesion occurred in the process of repeated attachment and detachment of pure glass using a hydrogel adhesive having a ratio of 7: 3.

<Example 1-7>

In order to confirm the possibility of repeated attachment and detachment of the adhesive proposed in the present invention through Examples 1-6, an experiment was conducted to verify the properties of the adhesive by comparing it with a prototype product.

The comparative product was manufactured by S company of Japan. In this experiment, the experiment was carried out using bakelite instead of pure glass as an adherend, and the results are shown in Table 3.

For the comparison of the results, the thickness of the coated adhesive except for the base film was adjusted to about 800 ㎛ for both products.

The results of this experiment are the average of the values obtained from the measured results of the same 5 specimens.

<Table 3> (Unit: g _f / 25 mm)

In the foregoing detailed description of the present invention, only specific embodiments thereof have been described. It is to be understood, however, that the invention is not to be limited to the specific forms thereof, which are to be considered as being limited to the specific embodiments, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims. .

That is, the present invention is not limited to the above-described specific embodiment and description, and various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. And such variations are within the scope of protection of the present invention.

S100: Method for manufacturing a hydrogel-type pressure-sensitive adhesive for skin attachment
S110: Step of preparing cross-linked hydrogel structure
S120: Step of preparing non-crosslinked hydrogel structure
S130: Mixing step
S140: Curing step

Claims (10)

A method (S100) for producing a hydrogel-type pressure-sensitive adhesive for skin attachment by polymerizing a viscous hydrogel having a semi-IPN structure,
a) preparing a crosslinked hydrogel structure (S110) for producing an ethylenically unsaturated group in a monomer containing a hydroxyl group in the structure to produce a polymer compound;
b) preparing a non-crosslinked hydrogel structure (S120) for imparting a carboxyl functional group to a monomer containing a hydroxyl group in the structure to produce a sticky polymer;
(c) a mixing step (S130) of mixing the polymeric compound produced from the crosslinked hydrogel structure manufacturing step with the adhesive polymer produced through the non-crosslinked hydrogel structure manufacturing step; And
d) a curing step (S140) of advancing free radical curing to the mixed mixture through a mixing step to produce a hydrogel type pressure-sensitive adhesive of semi-IPN structure;
The method of manufacturing a hydrogel-type pressure-sensitive adhesive for skin attachment according to claim 1,
The method according to claim 1,
In the step (S110) of preparing the cross-linked hydrogel structure,
A process for preparing a hydrogel-type pressure-sensitive adhesive for skin attachment, comprising the steps of reacting a random copolymer of polyethylene with a monofunctional oligomer having a hydroxyl group at the terminal thereof with a monofunctional monomer to form a hydroxyl group as an ethylenically unsaturated group.
3. The method of claim 2,
Wherein the monofunctional monomer is an anhydride monomer.
3. The method of claim 2,
The polyethylene copolypropylene oligomer in which the hydroxyl group is substituted with an ethylenically unsaturated group is characterized in that the oligomer-type precursor has a number average molecular weight in the range of 11,000 to 15,000 and then crosslinked through a trifunctional or tetrafunctional acrylic monomer Wherein the hydrogel-type pressure-sensitive adhesive is applied to the skin.
5. The method of claim 4,
Wherein the acrylic monomer has 3 or 4 functional groups. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
The method according to claim 1,
The non-crosslinked hydrogel structure production step (S120)
A process for preparing a hydrogel-type pressure-sensitive adhesive for skin attachment, which comprises reacting a polyfunctional oligomer-type polyethylene co-polypropylene random copolymer having a hydroxyl group at a terminal thereof with a monofunctional monomer to form a carboxyl functional group.
The method according to claim 6,
Wherein the monofunctional monomer is an anhydride monomer.
The method according to claim 6,
The carboxyl functional group substituted from the hydroxyl group can be obtained by allowing the oligomer type precursor to have a number average molecular weight within a range of 11,000 to 15,000 and then crosslinking through a bifunctional or trifunctional amine based crosslinking agent to induce a structure amide group Wherein the hydrogel-type pressure-sensitive adhesive is applied to the skin.
The method according to claim 1,
Wherein the curing step (S140) comprises sequentially performing ultraviolet irradiation and heat irradiation to progress free radical curing to the mixed mixture.
A pressure-sensitive adhesive prepared by the method (S100) for producing a hydrogel-type pressure-sensitive adhesive for skin attachment according to any one of claims 1 to 9.

Images