JP3944614B2 - Wet adhesive composition and patch using the same - Google Patents

Description

【００４８】
表１に示すように、本発明に係る実施例１及び実施例２の貼付材にあっては、角栓の取れ方では、比較例１及び比較例２の貼付材に比べて、それぞれ約１点スコアが向上した。また、鼻への剥離残渣量では、実施例２の貼付材では比較例２の貼付材よりやや糊残りが見られたが、実施例１の貼付材では比較例１の貼付材に比べて１．６点スコアが向上した。さらに、剥離時の痛みについては、実施例１及び実施例２の貼付材とも、比較例２の貼付材よりも痛みが軽減された。
【００４９】
【発明の効果】
本発明に係る湿潤粘着性組成物にあっては、速やかに乾燥し、乾燥後の機械的強度も適度であり、剥離も良好な貼付層を形成することができる。また、当該湿潤粘着性組成物は、ピールオフタイプの化粧用パックや湿潤又は濡れた皮膚面に対する皮膚カバー材等として有用であり、特に角栓除去が効果的に行なえ、しかも剥離時の痛みが少ない角栓除去材を提供できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a wet adhesive composition and a patch using the same. Specifically, or be wetted by water or a hydrophilic medium such as methyl alcohol or ethyl alcohol, to the wet pressure-sensitive adhesive composition and adhesive material using the wet adhesive composition shows tackiness and or is get wet et al .
[0002]
[Prior art]
Skin cover materials (medical materials applied to skin such as dressings) used in hospitals and the like use natural rubber or acrylic medical adhesives in order to obtain good adhesion to the skin. It was. Since these medical adhesives are designed to show good adhesion to the skin, adhesion to wet surfaces cannot be expected. In addition, in order to increase the moisture permeability of the adhesive, a water-absorbing polymer is added to the adhesive, or fine through holes are provided in the substrate or the adhesive layer. Adhesiveness to the surface cannot be ensured sufficiently.
[0003]
In addition, there are various cosmetic packs that are used by being attached to the skin surface. Particularly, as a peel-off type cosmetic pack, a film-forming agent is applied to the skin surface and dried for a certain period of time. The type that peels from the skin after it is sufficiently formed is the mainstream, and jelly-like, paste-like and powder-like products are known as these product forms. However, these cosmetic packs have a problem in that they are left for a long time after being applied to the skin until a film is formed, that is, the time required for drying.
[0004]
On the other hand, a sheet-like cosmetic pack in which a film-forming agent is pre-formed into a sheet shape is also known. For example, the film-forming agent is brought into contact with water or a hydrophilic medium before sticking to be wet or wet, and then attached to a sticking site. There is a type that is attached or used after applying water or a hydrophilic medium in advance to the application site.
[0005]
This type of cosmetic pack generally uses a wet adhesive composition mainly composed of various water-soluble organic polymer materials, and the wet adhesive composition is water, methyl alcohol or ethyl. It becomes wet or wet with a hydrophilic medium such as alcohol and exhibits adhesiveness.
[0006]
Here, when the water-soluble organic polymer has an excessive molecular weight, there is a problem that it takes a long time to exhibit adhesiveness through water or a hydrophilic medium. On the other hand, water-soluble organic polymers with low molecular weight have the advantage of exhibiting adhesiveness quickly through water or a hydrophilic medium and exhibiting adhesiveness within a short period of time. Since the mechanical strength of the film is low, not only is it difficult to peel and remove the dried film made of the above composition, but there is also a problem that a peeling residue is generated at the time of peeling.
[0007]
Furthermore, the amount of water or hydrophilic medium on the surface to be applied varies depending on the application site and the time required for application, and is not constant. Therefore, in order to obtain a stable sticking effect under any conditions, the film thickness of the film made of the above composition is generally adjusted to a relatively thick film of 100 to 300 μm. As a result, it takes a long time to dry the coated film.
[0008]
In order to solve the above problems, the present inventors have found that a wet pressure-sensitive adhesive composition comprising polyvinylpyrrolidone and a vinylpyrrolidone / vinyl acetate copolymer polymer can exhibit excellent effects, and has filed a patent application. (Japanese Patent Application No. 8-213835).
[0009]
However, when this wet pressure-sensitive adhesive composition is mainly composed of a single polymer having an appropriate molecular weight (molecular weight: 20,000 to 1,200,000), particularly when used as a plug removal material, There has been a problem in that removal of horn plugs on the skin cannot be performed effectively. In addition, there is a problem in use such that the pain at the time of peeling from the applied site, particularly the nose, is too strong. Therefore, the present inventors have further studied and, as a result of intensive efforts, have come to solve the above problems.
[0010]
The present invention has been made in view of the drawbacks of the conventional examples described above. The object of the present invention is to exhibit adhesiveness with water or a hydrophilic medium, and to adhere well to the application site and to dry quickly. Another object of the present invention is to provide a wet pressure-sensitive adhesive composition and a patch that are high in mechanical strength after drying and easy to peel off, and are suitable for removing horn plugs .
[0011]
[Means for Solving the Problems]
The wet pressure-sensitive adhesive composition of the present invention contains polyvinyl pyrrolidone or / and vinyl pyrrolidone / vinyl acetate copolymer as the A component, a liquid plasticizer compatible with the A component as the B component, and a filler as the C component. In the wet adhesive composition, the component A is a mixture of a high molecular weight polymer having a molecular weight of 1,000,000 to 5,000,000 and a low molecular weight polymer having a molecular weight of 5,000 to 300,000 . Here, the molecular weight in the present invention means a weight average molecular weight.
[0012]
In the wet-adhesive composition of the conventional example, a polymer having an average molecular weight of almost unity is used. When such a polymer is used, there are the following drawbacks. That is, when the polymer to be used has a high molecular weight, specifically a molecular weight of 700,000 or more, the adhesive layer obtained from the wet adhesive composition having the composition as described above is It has the advantage of high mechanical strength and less so-called adhesive residue (exfoliation residue), but on the other hand, when wet with water, it takes time for the polymer on the surface of the adhesive layer as a sheet-like cosmetic pack to dissolve. Rather than require or dissolve, it cannot swell enough to reach the part of the horn plug that swells and penetrates deep into the pores of the skin. As a result, there arises a problem that square plugs cannot be sufficiently removed.
[0013]
On the other hand, when the polymer used has a low molecular weight, that is, a molecular weight of less than 700,000, it is effective in that the polymer on the surface of the adhesive layer immediately dissolves and easily reaches the horn plug portion. However, there is a disadvantage that it takes time until the surface of the adhesive layer containing water or a hydrophilic medium used is sufficiently dried. Moreover, even if it is in a sufficiently dried state, moisture and the like remain in the adhesive layer, so that a part of the polymer is close to a dry dissolved state and the mechanical strength is low. For this reason, it is easy to produce adhesive residue at the time of peeling, and as a result, there arises a problem that the square plug cannot be sufficiently removed. Also, if you try to evaporate moisture etc. sufficiently to prevent adhesive residue, it must be applied for a long time, and it is very painful to remain attached until it is fully dry. is there. Incidentally, the general waiting time is about 5 to 30 minutes, and if it exceeds 30 minutes, it becomes unbearable.
[0014]
Therefore, by using the high molecular weight polymer having a molecular weight of 700,000 or more, preferably 1,000,000 to 5,000,000 and the low molecular weight polymer having a molecular weight of less than 700,000, preferably 5,000 to 300,000, the characteristics of both are utilized. A wet adhesive composition can be provided.
[0015]
The polymer used in the present invention is not limited to any one of polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymer, but may be used by appropriately mixing both. In this case, from the viewpoint of increasing the mechanical strength after drying, a high molecular weight vinyl pyrrolidone / vinyl acetate copolymer is mixed in low molecular weight polyvinyl pyrrolidone, or high molecular weight polyvinyl pyrrolidone and low molecular weight polyvinyl pyrrolidone are mixed. It is desirable to mix in the mixture.
[0016]
Furthermore, the mixing ratio of the high molecular weight polymer and the low molecular weight polymer varies depending on the molecular weight of the polymer used and the purpose of use, but the ratio of the high molecular weight polymer to the low molecular weight polymer is approximately 5:95 to 5 by weight. It can be used at a ratio of 95: 5, preferably 20:80 to 70:30, and more preferably, from the viewpoint of removal efficiency of horn plugs and pain when peeling off, mixing is performed so that the blending ratio of the low molecular weight polymer is increased. Is preferred.
[0017]
Moreover, as B component used for this invention, the material which has compatibility with A component, melt | dissolves A component, and shows the plasticizing effect is used. For example, ethylene glycol, diethylene glycol, triethylene glycol, hexamethylene glycol, other polyethylene glycols, propylene glycol, dipropylene glycol, other polypropylene glycols, glycerol, diglycerol, other polyglycerols, 1,3-butylene Examples include butylene glycols such as glycol and 1,4-butylene glycol, sugar alcohols such as sorbitol and mannitol, and glycerides such as lanolin, lecithin, and olive oil. Moreover, 1 type, or 2 or more types of these can be used together as B component.
[0018]
As the component C, various inorganic or organic fillers that are hardly soluble or insoluble in the mixture of the component A and the component B are used. Examples of inorganic fillers include inorganic oxides and composite oxides such as silica, alumina, zinc oxide, titanium oxide, talc, clay, kaolin, glass, barium sulfate, calcium carbonate, hydroxyapatite, ceramics, carbon, etc. Other inorganic compounds, metals such as metals and alloys of various metals, and the like are exemplified. Examples of the inorganic filler include fiber-forming polymers such as cellulose, silk, polyester, and polyolefin, polyacrylic acid ester, polymethacrylic acid ester, polystyrene, and other organic polymers. These fillers are usually preferably used in a powder state, and the shape is not particularly limited, but is preferably spherical from the viewpoint of uniform dispersibility, and the average particle size is 0.01 to 50 μm, The thing of 0.1-10 micrometers is especially preferable. Moreover, these 1 type (s) or 2 or more types can be used together as C component.
[0019]
As the composition ratio, if the amount of component B used is excessive with respect to the amount of component A, the mechanical strength after applying and drying the adhesive layer obtained from the wet pressure-sensitive adhesive composition of the present invention becomes poor, On the other hand, if it is too small, the adhesive layer obtained from the wet pressure-sensitive adhesive composition of the present invention has poor flexibility, and it is difficult to fit it well at the application site. For this reason, as usage-amount of B component, Preferably it is 1-75 weight part with respect to 100 weight part of A component, More preferably, it is 5-50 weight part.
[0020]
On the other hand, if the amount of component C used is excessive with respect to the amount of component A, the adhesive layer obtained from the wet pressure-sensitive adhesive composition of the present invention is not flexible enough to fit well at the site of application. If it is too small, the effect of improving the mechanical strength after applying and drying the adhesive layer obtained from the wet adhesive composition of the present invention is poor, and the time required for drying after application becomes long. For this reason, the amount of component C used is preferably 10 to 200 parts by weight, more preferably 25 to 100 parts by weight per 100 parts by weight of component A.
[0021]
The patch of the present invention is characterized by having at least a patch layer containing the wet adhesive composition according to the present invention. This patch can be prepared as a sheet-like material consisting only of a patch layer, but generally it is not only easy to handle, but also improves the mechanical strength of the patch and peels off from the patch site. It is preferable to form a holding layer on one side in terms of further improving the properties.
[0022]
The holding layer is not particularly limited as long as it can contribute to improvement of mechanical strength without impairing the drying rate of the adhesive layer after application or flexibility before and after application, and is made of various materials. Various structures can be used. Examples of the structure include sheet-like materials such as aggregates of fibers such as woven fabric, nonwoven fabric, knitted fabric, and paper, and films such as porous film and air permeable film. Among these, those having an appropriate stretchability that is easily adapted to the curved surface of the part to be pasted are particularly preferable. Examples of materials include synthetic or natural organic polymers such as nylon, polyester, polyethylene, polypropylene, polyurethane, and cellulose.
[0023]
The air permeability of the holding layer used in the present invention is preferably 10 seconds or less as measured according to the method of JIS P-8117. When the air permeability of the holding layer is insufficient, drying of the sticking layer after sticking is delayed, and a peeling residue may be generated at the sticking site at the time of peeling. At this time, if a holding layer longer than 10 seconds is used, the drying time becomes longer and a peeling residue is generated, which may not be practically endurable. In addition, the thickness is not particularly limited as long as this air permeability can be secured, but the thickness is preferably about 5 to 500 μm, more preferably about 10 to 200 μm in consideration of the flexibility of the patch.
[0024]
In addition, the holding layer is a state in which the adhesive layer is simply laminated and placed on one side of the holding layer, a state in which a part of the composition of the adhesive layer is impregnated from one side of the holding layer, and further, the adhesive layer holds Any of a state in which a part of the layer protrudes from one side may be used.
[0025]
The adhesive layer contains the wet adhesive composition described above, and a coating liquid comprising the wet adhesive composition and water / or a hydrophilic medium such as ethyl alcohol or methyl alcohol is used as the holding layer. In the case where it has a release layer, or when it has a release layer, it is applied on the release sheet and then dried.
[0026]
The adhesive material according to the present invention absorbs water or a hydrophilic medium applied to the application site or absorbs water or the like previously applied to the adhesive layer and exhibits adhesiveness. It is preferable to set the content of the functional medium in advance. At this time, the content of the water or the hydrophilic medium in the adhesive layer, that is, the ratio of the water or the hydrophilic medium to the adhesive layer containing water or the hydrophilic medium is 25% by weight in that good adhesiveness can be exhibited. In the following, it is particularly desirable that the content be 7 to 20% by weight or less. If it exceeds 25% by weight, the absorbability of water or hydrophilic medium applied during use tends to be inferior, the adhesive effect may not be fully exhibited, the sticking material itself may become sticky, and may adhere to the hand. It becomes difficult. Moreover, when the content rate of water or a hydrophilic medium will be 7 weight% or less, it cannot adapt to a sticking site | part.
[0027]
The adhesive layer improves the mechanical strength and peelability from the application site by mixing two kinds of polymers having different molecular weights. Depending on the physical properties, the mechanical strength in the dry state after sticking may become excessively low or excessively large. What is necessary is just to determine a ratio.
[0028]
Furthermore, the amount of water or hydrophilic medium applied in advance to the adhesive layer, and the amount of water or hydrophilic medium applied in advance to the application site are different for each use. Accordingly, the thickness of the adhesive layer is preferably set so as to absorb as much of these water and hydrophilic media as possible, specifically about 10 to 500 μm, particularly about 50 to 250 μm.
[0029]
Further, in the adhesive material of the present invention, a release layer is further laminated on the adhesive layer from the point that the adhesive layer can be stored hygienically and the adhesive material can be stacked or stored in a roll shape. Is preferred. Examples of the release layer include polyester, polyethylene, polypropylene, paper whose surface is polymer-treated, and other films and sheets.
[0030]
When the patch of the present invention has a holding layer and a release layer, it can be produced, for example, by the following method. After adding B component and C component to A component and stirring uniformly, water or a hydrophilic medium is added so that it may become 20 to 70 weight% for viscosity and density | concentration adjustment, and it is set as a liquid substance. Next, this liquid material is applied onto the release layer so that the thickness after drying is within a desired range, and is dried as necessary to form an adhesive layer. Next, a holding layer can be laminated thereon and dried to obtain a patch. The drying conditions at this time are preferably set so that the content of water or hydrophilic medium in the obtained adhesive layer is 25% by weight or less.
[0031]
In addition, it is possible to add normal amounts of chemicals and additives usually used in cosmetics, fragrances, preservatives, colorants, alcohol, UV absorbers, or other adhesives to the above liquids as necessary. it can.
[0032]
The patch material thus obtained is cut into an arbitrary shape, and is used by peeling off the release layer immediately before use. In addition, in order to prevent the content of water or hydrophilic medium in the adhesive layer from being reduced by drying during storage, it is stored under moderate humidity conditions by means such as hermetic packaging.
[0033]
And when using the above-mentioned patch, after peeling off the release layer before sticking and applying the water or hydrophilic medium to the sticking layer to make it wet or wet, stick it on the sticking site, or After applying water or a hydrophilic medium in advance to the application site, the application material is applied to the application site.
[0034]
Such a patch is effectively used as a peel-off type cosmetic pack, a square plug remover that can satisfactorily remove square plugs formed in pores, or a skin cover material for wet or wet skin surfaces. it can.
[0035]
【Example】
Next, patch materials of various examples and comparative examples were prepared, and the effects of the present invention as a plug removal material were confirmed. Hereinafter, the amount of each component indicates parts by weight.
[0036]
[Evaluation items and methods]
1. Moisture content of adhesive layer The adhesive layer having a predetermined size was peeled off from the prepared adhesive materials of various examples and comparative examples, and the weight (Wo) of the peeled adhesive layer was measured. After drying this with a dryer at 75 ° C. for 30 minutes, the weight (Wt) after drying was immediately measured, and the water content was determined by the following formula.
Water content (%) = (Wo−Wt) / Wo × 100
2. The thickness of the adhesive layer was measured using a dial gauge.
3. Air permeability of holding layer Measured according to JIS P-8117.
4). Practical performance of the patch material 20 female panelists were compared with the remaining one nose part on the left or right nose after face washing or without makeup on the left or right nose An example patch was applied and evaluated for usability. Each patch was cut into a size of 3 cm × 4 cm and used after the nasal patch was wetted with plenty of water. After leaving in this state for 15 minutes, the patch is peeled off, and an evaluation score is obtained on the basis of the following evaluation criteria for the degree of removal of the horn plug, the amount of peeling residue to the nose and the pain at the time of peeling. Asked. Moreover, the test was done about Example 1 and Comparative Example 1, and it carried out again about Example 2 and Comparative Example 2 at a later date.
[0037]
〔Evaluation criteria〕
(How to remove the square plug)
-Very well: 5 points-Well taken: 4 points-Cannot say well taken: 3 points-Not enough to take: 2 points-Not taken at all: 1 point (peeling to the nose) Residue amount)
・ No points left: 5 points ・ Slightly left: 4 points ・ 1/3 area left: 3 points ・ 1/3 to 1/2 area left: 2 points ・ 1/2 or more left : 1 point (pain when peeling)
・ Peeled without pain: 4 points ・ Slightly painful but without problems: 3 points ・ Slightly painful: 2 points ・ Some painful: 1 point 【0038】
Example 1
Polyvinylpyrrolidone (weight average molecular weight: 160,000) 6 parts Polyvinylpyrrolidone (weight average molecular weight: 1,200,000) 4 parts Water 16 parts Glycerin 1.2 parts Titanium oxide 0.31 parts Silicon dioxide 6 parts
Each of the above components was weighed so as to have a predetermined amount, and mixed by stirring to obtain a liquid material. This liquid material was uniformly applied onto a 50 μm thick polyester film serving as a release layer, and a polyester nonwoven fabric having a basis weight of 25 g / m 2 and a permeability of 1.5 seconds was laminated thereon. Next, the sheet-like patch of Example 1 having a three-layer structure having a holding layer and a release layer was produced by drying. Note that the thickness and moisture content of the adhesive layer were 150 μm and 15%, respectively.
[0040]
(Example 2)
Polyvinylpyrrolidone (weight average molecular weight: 40,000) 7 parts Polyvinylpyrrolidone (weight average molecular weight: 1,500,000) 3 parts Water 16 parts Glycerin 1.2 parts Titanium oxide 0.31 part Silicon dioxide 6 parts
Each of the above components was measured so as to have a predetermined amount, and in the same manner as in Example 1, a sheet-like patch of Example 2 having a three-layer structure having a holding layer and a release layer was produced. Note that the thickness and moisture content of the adhesive layer were 150 μm and 15%, respectively.
[0042]
(Comparative Example 1)
Polyvinylpyrrolidone (weight average molecular weight: 160,000) 10 parts Water 16 parts Glycerin 1.2 parts Titanium oxide 0.31 parts Silicon dioxide 6 parts
Each of the above components was measured so as to have a predetermined amount, and a sheet-like patch of Comparative Example 1 having a three-layer structure having a holding layer and a release layer was produced in the same manner as in Example 1. The thickness and moisture content of the adhesive layer were 150 μm and 10%, respectively.
[0044]
(Comparative Example 2)
Polyvinylpyrrolidone (weight average molecular weight: 1,200,000) 10 parts Water 30 parts Glycerin 1.2 parts Titanium oxide 0.31 parts Silicon dioxide 6 parts
Each of the above components was measured so as to have a predetermined amount, and a sheet-like patch of Comparative Example 2 having a three-layer structure having a holding layer and a release layer was produced in the same manner as in Example 1. Note that the thickness and moisture content of the adhesive layer were 150 μm and 15%, respectively.
[0046]
[Practical performance evaluation results]
Table 1 shows the practical performance of each of the above examples and comparative examples.
[0047]
[Table 1]

[0048]
As shown in Table 1, in the patch materials of Examples 1 and 2 according to the present invention, in terms of how to remove the square plugs, each of the patch materials was about 1 in comparison with the patch materials of Comparative Example 1 and Comparative Example 2. Point score improved. In addition, in the amount of the residue peeled on the nose, the adhesive patch of Example 2 showed a slight adhesive residue compared to the adhesive patch of Comparative Example 2, but the adhesive patch of Example 1 was 1 in comparison with the adhesive patch of Comparative Example 1. .6 point score improved. Furthermore, regarding the pain at the time of peeling, the adhesive material of Example 1 and Example 2 was alleviated more than the adhesive material of Comparative Example 2.
[0049]
【The invention's effect】
In the wet pressure-sensitive adhesive composition according to the present invention, it is possible to form an adhesive layer which is quickly dried, has a moderate mechanical strength after drying, and has good peeling. The wet-adhesive composition is useful as a peel-off type cosmetic pack or a skin cover material for wet or wet skin, and can effectively remove horn plugs and has less pain at the time of peeling. A plug removal material can be provided.

Claims (6)

A wet adhesive composition containing polyvinylpyrrolidone or / and vinylpyrrolidone / vinyl acetate copolymer as component A, a liquid plasticizer compatible with component A as component B, and a filler as component C,
The wet adhesive composition, wherein the component A is a mixture of a high molecular weight polymer having a molecular weight of 1,000,000 to 5,000,000 and a low molecular weight polymer having a molecular weight of 5,000 to 300,000 .   An adhesive patch comprising at least an adhesive layer containing the wet adhesive composition according to claim 1.   The patch according to claim 2, further comprising a holding layer.   The patch according to claim 2 or 3, wherein the patch layer further contains water or a hydrophilic medium in a proportion of 25% by weight or less.   The patch according to claim 3 or 4, wherein the air permeability of the holding layer measured according to the method of JIS P-8117 is 10 seconds or less.   The adhesive material according to claim 2, further comprising a release layer on the adhesive layer.