WO2020175681A1 - Layered body for skin adhesion and method for producing same - Google Patents

Abstract

One embodiment of the present invention provides: a layered body for skin adhesion, which has a first layer containing a silicone elastomer and a second layer that contacts the first layer and is adhesive, and in which the layered product of the first layer and the second layer has a tensile stress at 40% elongation of 0.8 MPa or less and a total thickness of 1 mm or less; and a method for producing the layered body for skin adhesion.

Description

\¥0 2020/175681 1 卩 (: 17 2020/008363 Clarification

Title of invention: Laminate for skin application and method for producing the same

Technical field

[0001] The present disclosure relates to a laminate for skin application and a method for producing the same.

Background technology

[0002] Examples of the skin-adhesive laminate include wound dressings and transdermal preparations, which have various uses.

生体貼付用積層 体が開示されている。 For example, in Japanese Patent Laid-Open Publication No. 20 18-0 4 395 0, a pressure-sensitive adhesive layer containing a carboxylic acid ester for sticking to a living body and one of the pressure-sensitive adhesive layers in the thickness direction is used. A base layer disposed on the side and supporting the pressure-sensitive adhesive layer, and a barrier layer interposed between the pressure-sensitive adhesive layer and the base layer, and the difference from the three values of the carboxylic acid ester. Absolute value of

A laminated body for sticking to a living body is disclosed.

[0003] In Japanese Patent Laid-Open No. 2106-10 2 2 2 23, there is described a film base material, a first adhesive layer on the bottom surface of the film base material, and a second adhesive layer on the upper surface of the film base material. And a first release liner and a second release liner attached to each of the first adhesive layer and the second adhesive layer of the protective film member. The following medical protective film material is disclosed.

Summary of the invention

Problems to be Solved by the Invention

[0004] Some of the laminates for skin application are desired to be applied to the skin for a long time. Such a skin patch laminate has excellent permeability of water vapor released from the skin, and has less discomfort due to the weight and feeling of foreign matter when it is applied, and follows the movement of the skin. Is also desired.

[0005] Therefore, an object of an embodiment of the present disclosure is to apply a skin that is applied without feeling uncomfortable, follows the movement of the skin, and has excellent permeability of water vapor released from the skin. \¥0 2020/175681 2 (:171? 2020/008363

An object of the present invention is to provide a laminated body for use and a manufacturing method thereof.

Means for solving the problem

[0006] The present disclosure includes the following embodiments.

[1] A first layer containing a silicone elastomer, and a second layer in contact with the first layer and exhibiting adhesiveness,

And the total thickness is 1 111 111 or less,

Laminate for skin application.

[0007] [2] The tensile breaking elongation of the laminate of the first layer and the second layer is 100% or more,

The laminate for skin application according to [1].

[3] The laminate for skin application according to [1] or [2], wherein the first layer contains silica particles.

[4] The laminate for skin patch according to [3], wherein the content of the silica particles is 7% by mass to 30% by mass with respect to the total mass of the first layer.

[5] The skin patch laminate according to any one of [1] to [4], wherein the silicone elastomer has a crosslinked structure by a hydrosilylation reaction.

[0008] [6] The first support member, which is in contact with the surface of the first layer opposite to the surface in contact with the second layer, and the second member, which is in contact with the surface of the second layer opposite to the surface in contact with the first layer. A laminate for skin application according to any one of [1] to [5], further comprising a support.

[7] The surface of the first support on the first layer side and the surface of the second support on the second layer side at least _ have a silicone layer or are surface-treated with silicone. [6] A laminate for skin application.

[8] The laminate for skin application according to any one of [1] to [7], which is used for a biological monitoring device, a display element, a wound dressing material, a transdermal preparation, or a cosmetic product.

[0009] [9] Step 8 of forming a first layer containing a silicone elastomer,

A step of forming a second layer having adhesiveness,

Have \¥0 2020/175681 3 卩(: 17 2020/008363

Manufacture of a laminate for skin application, in which the tensile stress at 40% elongation of the laminate of the first layer and the second layer is not more than 0.81\/18 and the total thickness is not more than 1 Method

[0010] [10] In Step 8, a coating liquid containing a silicone polymer having a crosslinkable group, a crosslinking agent, and a solvent is applied and dried on the first support to form a first layer. The method for producing the laminate for skin application according to [9], which is a step.

[11] In Step 8, a coating liquid containing a silicone polymer having a crosslinkable group, a crosslinking agent, silica particles, and a silicone solvent is applied and dried on the first support to form a first layer. The method for producing a laminate for skin application according to [9], which is a step of forming.

[12] The method for producing a skin patch laminate according to any one of [9] to [11], wherein the step S is a step of forming the second layer on the first layer.

[13] Laminate for skin application according to any one of [9] to [12], in which the first support is continuously conveyed and the process and process are performed by the mouth-to-roll method. Body manufacturing method.

[1 4] Step 1 of attaching a protective film to the surface of the first layer formed in step 8 between step 8 and step _, and the laminated protective film from the surface of the first layer The method for producing a skin patch laminate according to any one of [9] to [13], further comprising a peeling step 82.

[001 1] [15] [9] to [14], which further includes a step 8 3 of hydrophilizing the surface of the first layer formed in step 8 between step 8 and step 9. 1. The method for producing a laminate for skin application according to any one of 1.

[1 6] The surface of the first layer hydrophilically treated in step 83 has a contact angle with 1\1-methyl-2-pyrrolidone of 60° or less, and the skin according to [1 5] Method for manufacturing laminated body for sticking.

[17] The method for producing a laminate for skin patch according to any one of [9] to [16], further including a step 0 of laminating the second support on the second layer after the step Law. \\0 2020/175681 4 卩 (: 171? 2020 /008363 Effect of invention

[0012] According to an embodiment of the present disclosure, there is provided a skin-adhesive laminate which is affixed without any discomfort, follows the movement of the skin, and has excellent permeability of water vapor released from the skin, and a method for producing the same. be able to.

MODE FOR CARRYING OUT THE INVENTION

[0013] Hereinafter, examples of specific embodiments of the present disclosure will be described in detail, but the following embodiments are merely examples and are not limited to the following description, and within the scope of the object of the present invention. It can be implemented with appropriate changes.

[0014] In the present specification, the numerical range indicated by "to" indicates the range including the numerical values before and after "to" as the minimum value and the maximum value, respectively.

Further, in the present specification, the amount of each component contained in the composition means the total amount of the plurality of substances, unless otherwise specified, when the composition contains a plurality of substances corresponding to the respective components.

In the numerical ranges described stepwise in the present specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another stepwise described numerical range. .. Further, in the numerical ranges described in the present specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.

In the present specification, “(meth)acrylic” means at least one of acrylic and methacrylic.

In the present specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0015] <Layer for skin application>

以下であり、 且つ、 総厚 みが 1 01 01以下である。 \¥02020/175681 5 卩（：171? 2020 /008363 A skin patch laminate of the present disclosure (hereinafter, also referred to as “laminate of the present disclosure”) has a first layer containing a silicone elastomer, and a second layer that is in contact with the first layer and exhibits adhesiveness. .. The laminate of the first layer and the second layer of the laminate of the present disclosure has a tensile stress at 40% elongation of ◯.

The total thickness is less than or equal to 101 01. \¥02020/175681 5 卩 (: 171? 2020 /008363

以下であり、 且つ、 総厚みが 1

以下であることで、 違 和感なく貼付けられ、 皮膚の動きに追従するといった効果を奏するものと推 測される。 [0016] The laminate of the present disclosure has a tensile stress of 40% elongation of the laminate of the first layer and the second layer.

Below, and the total thickness is 1

It is presumed that the following will be applied with no discomfort and will have the effect of following the movement of the skin.

Furthermore, since the first layer is a layer containing a silicone elastomer, it is presumed that the first layer has an effect of being excellent in permeability of water vapor released from the skin due to its material.

[0017] Note that Japanese Patent Laid-Open Nos. 201 8-043950 and 201 6-02222

None of the laminates described in Japanese Patent Publication No. 3 has a layer containing a silicone elastomer as a layer adjacent to the adhesive layer. Further, in the laminates described in JP-A-2010-04395-O and JP-A-2016-022223, the tensile stress in the laminate of the adhesive layer and the adjacent layer is not examined at all.

[0018] [Tensile stress at 40% elongation]

以下である。 In the laminate of the present disclosure, the tensile stress at 40% elongation of the laminate of the first layer and the second layer is 0.

It is the following.

以下が好ましく、 〇. 61\/1 3以下がより好ましく、 〇.The tensile stress at 40% elongation of the laminate is easy to follow the movement of the skin.

The following is preferred, and 〇.61\/1 3 or less is more preferred, 〇.

31\/13 or less is more preferable.

The lower limit of tensile stress at 40% elongation of the laminate is, for example, 0.001 IV! ₃ .

以下で あることが好ましく、 〇. 21\/1 3以下であることがより好ましく、 0. 1 IV! 3以下であることが更に好ましい。 [0019] Further, in the laminated body of the present disclosure, from the viewpoint of easily following the movement of the skin, the tensile stress at 10% elongation of the laminated body of the first layer and the second layer is ◯.

It is preferably not more than 0.21, more preferably not more than 0.13 and even more preferably not more than 0.1 IV! 3.

The lower limit of the tensile stress at 10% elongation of the laminate is, for example, 0.001 IV! ₃ .

[0020] [Tensile breaking elongation] \\02020/175681 6 卩 (: 171? 2020 /008363

In the laminate of the present disclosure, from the viewpoint of easily following the movement of the skin, the tensile elongation at break of the laminate of the first layer and the second layer is preferably 100% or more, and 150% or more. Is more preferable and 200% or more is further preferable.

The upper limit of the tensile elongation at break of the laminate is, for example, 900%.

[0021] In order to bring the tensile stress and the tensile elongation at break of the laminate into the above ranges, the method for adjusting the tensile stress and the tensile elongation at break of the first layer, the tensile stress and the tensile elongation at break of the second layer are adjusted. And a method of adjusting the film thickness ratio between the first layer and the second layer.

When making the second layer, which is adhesive to the skin, thinner than the first layer, the tensile stress and tensile elongation at break of the laminate should be adjusted by adjusting the tensile stress and tensile elongation at break of the first layer in the laminate. It is preferable to control by a method.

[0022] (Measurement)

Here, the tensile stress at 40% elongation and the tensile elongation at break in the laminate are measured as follows.

First, prepare three test pieces with a width of 20 and a chuck-to-chuck distance of 40 from the measurement object. Using a tensile tester (for example, Autograph 803-X manufactured by Shimadzu Corporation), stretch each of the three test pieces at a pulling speed of 50/〇! 丨. Then, the tensile stress is calculated using the following equation (1), and the tensile fracture elongation is calculated using the following equation (2). The tensile stress and tensile elongation at break in the laminate are obtained by averaging the tensile stress and tensile elongation at break obtained from each of the three test pieces.

The test piece shall be extended in an environment of 25 ± 2 ^° .

= /八 Formula (1) Tensile stress

= / Eight

In the formula (1), represents the load (1\!) when the test piece is stretched by 40%, and 8 is the cross-sectional area of the test piece before extension (○! ² , specifically, 20○1111). \111111, X represents the thickness of the test piece).

Formula (2) Tensile breaking elongation (%) = (02-01) /01 X 100 \¥0 2020/175681 7 卩 (: 171? 2020 /008363

チャック間距離 （ ） を表し、 0 2は、 破断時の チャック間距離 （01 111） を表す。 In formula (2),

The chuck-to-chuck distance () is represented, and 0 2 is the chuck-to-chuck distance (01 111) at break.

The tensile stress at 10% elongation is the tensile stress at 10% elongation except that the load (1\○) when the test piece is expanded by 10% is added to the above formula (1). It is calculated in the same way as.

[0023] [Total thickness]

In the laminate of the present disclosure, the total thickness of the laminate of the first layer and the second layer is 1101 or less.

以下であることで、 皮膚への貼付け時に、 重さ、 異物感等 を感じにくくなり、 違和感なく貼付けられる。 Total thickness is 1

The following items make it less likely to feel weight and foreign matter when applied to the skin, so that the product can be applied comfortably.

7 が好ましく、 0 . 0 1 01 01〜〇. 5 01 01がより好ましく、 〇.

が更に好ま しく、 〇. 0 2〇1 111 ~〇. 1 01 111が特に好ましい。 The thinner the total thickness of the laminate, the more comfortable the attachment. Specifically, the total thickness of the laminate is:

7 is preferable, 0.0 1 01 01 to ○ 0.5 01 01 is more preferable, and ○.

Is more preferable, and 0.02 ○ 1 111 to ○ 0.11 111 is particularly preferable.

Further, the lower limit of the total thickness of the laminated body is, for example, from the viewpoint of manufacturing suitability, 0.00 0.001 01.

[0024] (Measurement)

Here, the total thickness of the laminate of the first layer and the second layer is measured as follows.

To measure the thickness, use a constant pressure thickness gauge (stand type digital thickness gauge, 〇-20", manufactured by Teclock Co.).

For the measurement, a laminate composed of the first support/first layer/second layer/second support was applied, and the thickness of the first support and the second support was calculated from the total thickness of this stack. The total thickness of the first and second layers is obtained by subtracting the thickness. Therefore, the thickness of each of the first support and the second support should be measured beforehand with the above-mentioned constant pressure thickness gauge.

The test pieces of the laminate used for the measurement have the same shape as the test pieces used for the measurement of the tensile stress and the tensile elongation at break, and three pieces are prepared. \¥0 2020/175681 8 卩 (: 171? 2020 /008363

The center of the test piece is measured 3 times with the above-mentioned constant pressure thickness gauge, and the average value of 3 times is taken as the thickness of the test piece. The same measurement is performed on three test pieces, and the average value of the thickness of the three test pieces is taken as the total thickness of the laminate of the first layer and the second layer.

[0025] When measuring the thickness of only the first layer, the first support/first layer is used for the measurement.

A laminate composed of one layer/protective film may be applied. The thickness of the first layer can be determined by subtracting the thickness of the first support and the protective film from the total thickness of this laminate. Therefore, in addition to the first support, measure the thickness of the protective film alone with the above-mentioned constant pressure thickness measuring device.

The laminate composed of the first support/first layer/protective film is, for example, the first support/first layer/protection obtained through step 1 in the method for producing a skin patch laminate described later. A laminate composed of a film may be mentioned.

The thickness of the second layer can also be calculated by subtracting the thickness of only the first layer from the total thickness of the first layer and the second layer obtained by the above method.

[0026] Hereinafter, the first layer and the second layer of the laminate of the present disclosure will be described.

[0027] [First layer]

The laminate of the present disclosure has a first layer that includes a silicone elastomer. The first layer may contain silica particles in addition to the silicone elastomer. The first layer may have a single-layer structure or a multi-layer structure. When the first layer has a multi-layer structure, at least one of the layers may contain a silicone elastomer.

When the first layer has a multi-layer structure, the respective layers may have different cross-linking densities of the silicone elastomer. When the first layer has a multilayer structure, the presence or absence of addition of silica particles may be changed in each layer, or the content of silica particles may be different.

[0028] (Silicone elastomer)

The silicone elastomer refers to a crosslinked product of a silicone polymer, and is preferably a three-dimensional crosslinked product of a silicone polymer. \\02020/175681

More specifically, the three-dimensional crosslinked product of the silicone polymer is more preferably a reaction product of a silicone polymer having a crosslinkable group and a crosslinking agent.

[0029] Examples of the silicone polymer having a crosslinkable group include polydimethylsiloxane, polymethylphenylsiloxane, polymethyldiphenylsiloxane, and the like, which have two or more crosslinkable groups in the molecule. From the viewpoint of actual use and the ease of obtaining a three-dimensional crosslinked product, polydimethylsiloxane having two or more crosslinkable groups in the molecule is preferable, and polydimethylsiloxane having crosslinkable groups at both main chain terminals is particularly preferable. Is preferred.

The crosslinkable group contained in the silicone polymer may be a functional group used in reactions such as hydrosilylation, reaction with organic peroxide, deacetic acid, dehydration, dealcoholization, etc., which is known as a crosslinking reaction of silicone polymers. Good. Among them, as the crosslinking reaction of the silicone polymer, hydrosilylation that does not generate a reaction by-product is preferable, and as the crosslinking group, a vinyl group is particularly preferable.

That is, as the silicone polymer having a crosslinkable group, polydimethylsiloxane having vinyl groups at both main chain terminals is particularly preferable.

The weight average molecular weight of the silicone polymer having a crosslinkable group is not particularly limited, but examples thereof include 800 to 50,000, and preferably 10,000 to 300,000.

The silicone polymer having a crosslinkable group may be used alone or in combination of two or more.

The weight average molecular weight of the silicone polymer having a crosslinkable group can be measured by gel permeation chromatography (XX). Specifically, 1 ^~ 11_ 〇 81 81 〇 〇, 30-8020 (Tosoh Corporation) was used, and the column was D3 3 <96 1, 3 Li 6 “1 ^~ 11\/1— 1 ^~ 1 (Tosoh Corporation, 6.

It can be measured by using two (1500!) and tetrahydrofuran (D1 ^to 1) as the eluent. As conditions, sample concentration is 0.5 mass% and flow rate is 0.9.

、 サンプル注入量を 1 0 丨 （マイクロリツ トル） 、 測定温 度を 40 ^°〇とし、 示差屈折計 （[¾ 丨） 検出器を用いて行なうことができる。 \¥02020/175681 10 卩（：171?2020/008363 6

The sample injection amount can be set to 10 (microliter), the measurement temperature can be set to 40 ^° , and a differential refractometer ([¾]) detector can be used. \¥02020/175681 10 ((171?2020/008363

㊀標準試料丁 3

The calibration curve is based on Tosoh Corporation “○I

㊀ Standard sample knife 3

34: "8-500", "-1", "-10", "-80", "-380", "eight-2,500", "-4", "-40", "-1" It is possible to use those made from 10 samples of "28" and "-700".

[0032] The cross-linking agent is not particularly limited as long as it has a functional group that reacts with the cross-linking group of the silicone polymer having a cross-linking group, but from the viewpoint of easy control of the cross-linking density, a siloxane compound is used. Preferably.

As the cross-linking agent, specifically, a siloxane compound having two or more hydrosilyl groups in the molecule is preferable. Specifically, polymethylhydrosiloxane, a copolymer of methylhydrosiloxane and dimethylsiloxane, polymethylphenyl is preferable. Examples thereof include copolymers of siloxane or polymethyldiphenylsiloxane and polymethylhydrosiloxane.

As the cross-linking agent, a copolymer of methylhydrosiloxane and dimethylsiloxane is particularly preferable.

[0033] The weight average molecular weight of the siloxane compound that is preferable as the crosslinking agent is not particularly limited, but examples thereof include 500 to 30,000, and preferably 10,000 to 25,000.

The weight average molecular weight of the siloxane compound is measured by the same method as the weight average molecular weight of the silicone polymer having a crosslinkable group.

The crosslinking agents may be used alone or in combination of two or more.

[0034] The amount ratio of the silicone polymer having a crosslinkable group and the crosslinking agent may be determined according to the tensile stress and the tensile elongation at break required for the first layer.

The amount ratio of the cross-linkable group-containing silicone polymer and the cross-linking agent is, for example, in terms of mass ratio, the cross-linkable group-containing silicone polymer:crosslinking agent=7:3 to 9:1 is preferable, and 3:1 to 19 :1 is preferable, 4:1 to 19:1 is more preferable, and 17:3 to 9:1 is further preferable.

[0035] As described above, the silicone elastomer contained in the first layer is \\0 2020/175681 1 1 卩 (: 171? 2020 /008363

Those having a cross-linking structure due to the sulfation reaction are preferable.

The presence of the crosslinked structure due to the hydrosilylation reaction can be estimated by confirming the presence or absence of a vinyl group and the presence or absence of a metal catalyst (preferably both) in the first layer.

In the silicone elastomer having a crosslinked structure by the hydrosilylation reaction, unreacted vinyl groups usually remain. Therefore, by confirming the presence or absence of a vinyl group remaining in the first layer, the existence of a crosslinked structure due to the hydrosilylation reaction in the silicone elastomer is estimated.

Further, a metal catalyst may be used in the hydrosilylation reaction as described later. Therefore, by confirming the presence or absence of the metal catalyst in the first layer, the existence of a crosslinked structure due to the hydrosilylation reaction in the silicone elastomer is estimated.

6 0 0が用いられる。 [0036] The presence or absence of the vinyl group can be confirmed by using the nuclear magnetic resonance spectroscopy or the like for the vinyl group remaining in the first layer. Nuclear magnetic resonance spectroscopy can be performed, for example, by Bruker 888 1\100 Ⅲ

600 is used.

The presence or absence of a metal catalyst can be confirmed by analyzing metal elements (platinum, titanium, etc.) by X-ray fluorescence analysis. For the fluorescent X-ray analysis method, for example, “R011 type 311 manufactured by Rigaku Corporation” is used.

[0037] When the first layer does not contain silica particles described below, the content of the silicone elastomer (that is, a cross-linked product of the silicone polymer) is 70% by mass to 10% with respect to the total mass of the first layer. 0 mass% is preferable, 75 mass% to 100 mass% is more preferable, and 80 mass% to 100 mass% is further preferable.

When the first layer contains silica particles described below, the content of silicone elastomer _ (that is, a cross-linked product of silicone polymer) is 70% by mass to 93% by mass with respect to the total mass of the first layer. 75% by mass to 93% by mass is more preferable, and 80% by mass to 90% by mass is further preferable.

[0038] (silica particles)

The first layer preferably contains silica particles. \¥0 2020/175681 12 卩 (: 171? 2020 /008363

The inclusion of silica particles makes it easier to control the tensile stress and tensile fracture elongation of the first layer. Here, it is confirmed that the first layer contains silica particles as follows.

That is, the presence or absence of silica particles can be directly confirmed by dissolving the first layer and observing the dissolved solution with a transmission electron microscope (Chomi!\/1). As a transmission electron microscope, for example, is a JEOL Ltd.'s "1\/1-1 2 0 0 跳跂跳-Cho 1\/1", and the acceleration voltage at the time of measurement is 1 2 0 1 < The solution for the first layer can be prepared by immersing the first layer in a mixed solution of methyl orthoformate, methanolic hydrochloric acid, and toluene, and stirring the solution.

[0039] The silica particles are not particularly limited, and may be any of fumed silica and colloidal silica, and may be crystalline or amorphous.

In particular, fumed silica is preferable from the viewpoints of dispersibility in a silicone solvent, dispersibility in a crosslinked product of a silicone polymer, and stability of coating solution viscosity. The shape of silica particles is not particularly limited. However, a spherical shape, a plate shape, a needle shape, a bead shape, or a shape in which two or more kinds of these are combined is included.

[0040] The silica particles have an average primary particle size of 3 n from the viewpoint of dispersibility in the first layer.

It is more preferably 71^111 to 4001.

The average primary particle size of the silica particles is measured by observing the first layer with a transmission electron microscope (Cho IV!). More specifically, the average primary particle diameter of the silica particles is, when the shape of the silica particles is spherical or substantially spherical with an elliptical cross section, the silica particles dispersed in the first layer are observed by a transmission electron microscope, From the obtained observation photograph, the projected area of 300 or more particles is measured, the equivalent circle diameter is determined from the projected area, and the obtained equivalent circle diameter is taken as the average primary particle diameter of silica particles. If the shape of silica particles is not spherical or nearly spherical, use another method. \\0 2020/175681 13 卩 (: 171? 2020 /008363

, For example, using a dynamic light scattering method, the average primary particle diameter of silica particles is determined.

[0041] As the specific surface area of the silica particles by the Mitsumi method, from the viewpoint of dispersibility in the first layer, the viewpoint of reducing the in-plane distribution of the mechanical properties of the first layer, and the viewpoint of manufacturing stability, 5 0 ² /9 to 600 0 ² /9 is preferable, 2 00 0! ² / to 40

It is more preferably 0 01 ² /9.

[0042] When the first layer contains silica particles, the content of the silica particles is such that the bow I tensile stress and the tensile elongation at break of the first layer can be easily controlled with respect to the total mass of the first layer. , 7 mass% to 30 mass% is preferable, 7 mass% to 25 mass% is more preferable, and 10 mass% to 20 mass% is further preferable.

[0043] (Other ingredients)

The first layer may contain other components in addition to the above-mentioned silicone elastomer (that is, a crosslinked product of silicone polymer) and silica particles. Other components include a silicone elastomer (that is, a silicone polymer). (A crosslinked product of mer), and a reaction catalyst and the like used. As other components, a coloring agent such as a pigment may be used.

The reaction catalyst used when obtaining the silicone elastomer may be any catalyst that contributes to the promotion of the reaction for obtaining the three-dimensional crosslinked product of the silicone polymer. In particular, the reaction catalyst is preferably a catalyst for promoting the hydrosilylation reaction.

Specific examples of the reaction catalyst include metal catalysts, and in particular, platinum, titanium, gold, silver and the like are mentioned from the viewpoint of low irritation to the skin.

Among them, titanium and platinum are preferable as the catalyst from the viewpoint of high reaction promoting efficiency and low skin irritation.

As the platinum catalyst, a known platinum catalyst (preferably platinum complex) that contributes to reaction promotion for obtaining a three-dimensional crosslinked product of a silicone polymer can be applied.

[0045] The thickness of the first layer is from the viewpoint of suppressing a feeling of discomfort such as a feeling of weight during attachment, and \¥0 2020/175681 14 卩 (: 171? 2020 /008363

以下が好まし く、 〇.

以下がより好ましく、 〇. 1

以下が更に好ましい。 And from the standpoint of preventing peeling of clothing and other items against external disturbances.

The following are preferred:

The following are more preferable:

The following is more preferable.

[0046] [Second layer]

The laminate of the present disclosure has a second layer that is in contact with the above-mentioned first layer and exhibits tackiness.

Since the second layer corresponds to the layer attached to the skin, it may be any layer that is adhesive to the skin.

Here, the term "adhesiveness" refers to a property of stickiness, which is used for temporary adhesion and can be peeled off later.

[0047] (Adhesive)

The second layer is preferably a layer containing an adhesive.

The pressure-sensitive adhesive is not particularly limited, and known pressure-sensitive adhesives can be used. Specific examples of the pressure sensitive adhesive include silicone pressure sensitive adhesive, acrylic pressure sensitive adhesive, rubber pressure sensitive adhesive and urethane pressure sensitive adhesive.

Above all, a silicone-based pressure-sensitive adhesive is preferable from the viewpoint of low irritation to the skin and from the viewpoint of adhesion to the first layer.

[0048] Silicone adhesive

The silicone-based pressure-sensitive adhesive in the present disclosure means a pressure-sensitive adhesive that uses a silicone polymer as a base polymer (a main component among polymer components, that is, a component that accounts for 50% by mass or more of the entire polymer component).

The silicone adhesive is not particularly limited, and known silicone adhesives can be used.

Specific examples of the silicone-based pressure-sensitive adhesive include an addition reaction-type silicone-based pressure-sensitive adhesive, a peroxide-curable silicone-based pressure-sensitive adhesive, and a condensation-type silicone-based pressure-sensitive adhesive. Above all, an addition reaction type silicone-based pressure-sensitive adhesive by hydrosilylation is preferable from the viewpoint that reaction by-products are not generated.

[0049] In particular, from the viewpoints of adhesion to the first layer and production suitability, an addition reaction type silicone containing the same silicone polymer having a crosslinkable group and the crosslinking agent as the first layer. \¥0 2020/175681 15 卩 (: 171? 2020 /008363

It is preferably a corn adhesive.

That is, the silicone-based pressure-sensitive adhesive preferably contains, for example, polydimethylsiloxane having vinyl groups at both ends of the main chain, and a copolymer of methylhydrosiloxane and dimethylsiloxan.

Further, the silicone-based pressure-sensitive adhesive may contain a reaction catalyst.

Furthermore, the silicone-based pressure-sensitive adhesive may optionally contain various additives contained in known silicone-based pressure-sensitive adhesives.

[0050] Acrylic adhesive

The acrylic pressure-sensitive adhesive in the present disclosure means a pressure-sensitive adhesive using an acrylic polymer as a base polymer.

The acrylic pressure-sensitive adhesive is not particularly limited, and known acrylic pressure-sensitive adhesives can be used.

Specific examples of the acrylic polymer contained in the acrylic pressure-sensitive adhesive include a homopolymer of an acrylic acid ester compound or a copolymer of an acrylic acid ester compound and another monomer.

Examples of acrylic acid ester compounds include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethyl. Aminoethyl methacrylate, glycidyl methacrylate and the like can be mentioned. Examples of other monomers include vinyl acetate, (meth)acrylonitrile, (meth)acrylic amide, styrene, methacrylic acid, acrylic acid, itaconic acid, methylol acrylic amide, maleic anhydride and the like.

The acrylic polymer may have a crosslinked structure.

[0051] The acrylic pressure-sensitive adhesive may contain a tackifier in addition to the acrylic polymer from the viewpoint of enhancing the tackiness.

Examples of tackifiers include rosin-based tackifier resins, terpene-based tackifier resins, hydrocarbon-based tackifier resins, epoxy-based tackifier resins, and polyamides. \¥0 2020/175681 16 卩 (: 171? 2020 /008363

Examples of the tackifying resin include an elastomer-based tackifying resin, an elastomer-based tackifying resin, a phenol-based tackifying resin, and a ketone-based tackifying resin.

The acrylate-based pressure-sensitive adhesive may contain, in addition to the acrylate polymer and the tackifier, various additives contained in known acrylic-based pressure-sensitive adhesives, if necessary.

[0052]-Rubber adhesive

The rubber-based pressure-sensitive adhesive in the present disclosure means a pressure-sensitive adhesive having rubber as a base polymer.

The rubber is not particularly limited, and may be natural rubber (including modified natural rubber) or synthetic rubber.

As the synthetic rubber, a type or a type block copolymer (is a thermoplastic block, and a type is a rubber block. Styrene-isoprene styrene copolymer (3 1 3), styrene-butadiene Examples thereof include styrene copolymers (363) and the like. The rubber may be a combination of natural rubber and synthetic rubber.

[0053] The rubber-based pressure-sensitive adhesive may contain a tackifier in addition to the rubber from the viewpoint of enhancing the tackiness.

Examples of the tackifier include various tackifier resins used for acrylate-based tackifiers.

The rubber-based pressure-sensitive adhesive may contain, in addition to the rubber and the tackifier, various additives contained in known rubber-based pressure-sensitive adhesives, if necessary.

[0054] (Other ingredients)

The second layer may contain other components in addition to the adhesive. Other components may be appropriately determined depending on the use of the skin patch laminate.

For example, when the skin patch laminate is used as a transdermal preparation, the second layer preferably contains a drug and an additive for retaining and releasing the drug. \¥0 2020/175681 17 卩(: 17 2020/008363

As the drug, a known drug applicable to transdermal preparations is used. In addition, as an additive for holding and releasing the drug, from the viewpoint of actual use, for example, lactic acid, glycolic acid, stearic acid, oleic acid, isopropyl myristate,! _ _Menthol, ethanol, propylene glycol, etc.

[0055] The thickness of the second layer is 5 to 3 from the viewpoint of exhibiting adhesion to the skin.

0!! is preferred, 50!! to 1500! is more preferred, and 50! to 1000 or less is even more preferred.

[0056] [First support and second support]

The laminate of the present disclosure includes a first support member that contacts the surface of the first layer opposite to the surface that contacts the second layer, and a first support member that contacts the surface of the second layer opposite to the surface that contacts the first layer. Two supports may be included.

The first support and the second support are temporary supports that are peeled off when attached to the skin.

[0057] The first support and the second support are not particularly limited, and a resin film is preferably used.

Further, the first support and the second support may be the same or different.

Examples of the resin film include resin films such as polyester (for example, polyethylene terephthalate (polyester), polyethylene naphthalate, polypropylene terephthalate, etc.), polyurethane, silicone, polyolefin (for example, polyethylene, polypropylene, etc.), polystyrene, etc. To be Among them, as the resin film, polyethylene terephthalate (Mending) is preferable from the viewpoint of excellent handling properties when applied to the mouth tow roll method and from the viewpoint of thermal stability.

[0058] The thickness of the first support and the second support is not particularly limited, but from the viewpoint of excellent handleability when applied to the mouth-to-roll method and the ease of peeling, 100 !~100 is preferred, 2011~100 is more preferred \¥0 2020/175681 18 卩 (: 171? 2020 /008363

However, 500!~100100 is more preferable.

[0059] As described above, the first support and the second support are peeled off at the time of application to the skin, and therefore, between the first support and the first layer, and between the second support and the second layer. It is preferable to have a peeling property between them.

Therefore, it is preferable that at least one of the first support side of the first support and the second support side of the second support has a silicone layer or is surface-treated with silicone, if necessary. ..

The silicone layer may be a layer containing a silicone polymer, and is preferably a layer containing a fluorosilicone polymer having a substituent containing a fluorine atom or a fluorine atom in the molecule (hereinafter, also referred to as a fluorosilicone layer). .. By adjusting the amount of fluorine atoms in the fluorosilicone polymer, the peelability from the first layer and the second layer can be controlled.

The surface treatment with silicone includes, for example, surface treatment using liquid phase film formation using a solution coating/drying method.

As a method of imparting releasability to the first support and the second support, surface treatment with a fluorine-containing compound may be used, for example. Specifically, for the surface treatment with a fluorine-containing compound, surface treatment using vapor phase film formation such as sputtering or vapor deposition is applied.

As the first support and the second support, commercially available products may be used. Examples of commercially available products include a release film (for example, a fluorosilicone release film, etc.) having a silicone layer manufactured by Fujiko Co., Ltd. on one side or both sides.

<Method for producing laminate for skin application>

The skin patch laminate of the present disclosure is preferably produced by the following method (that is, the method for producing the skin patch laminate of the present disclosure).

以下である、 皮膚貼付け用積層 体の製造方法 （以下、 積層体の製造方法ともいう） である。 That is, the method for producing a skin patch laminate of the present disclosure includes a step 8 of forming a first layer containing a silicone elastomer, and a step of forming a second layer having adhesiveness. The tensile stress at 40% elongation of the laminate of the first layer and the second layer is ◯. \\02020/175681 19

The following is a method for producing a laminate for skin application (hereinafter, also referred to as a method for producing a laminate).

[0061] [Step 8]

In step 8, a first layer containing a silicone elastomer is formed. The method for forming the first layer is not limited, but the following steps are preferable.

That is, in the step 8, a coating liquid (hereinafter, also referred to as coating liquid!-1) containing a silicone polymer having a crosslinkable group, a crosslinking agent, and a solvent is applied onto the first support and dried to form a first coating. The eighth step of forming a layer is preferable.

Step 8 is to coat and dry a coating solution (hereinafter also referred to as coating solution 1-2) containing a silicone polymer having a crosslinkable group, a crosslinking agent, silica particles, and a silicone solvent on the first support. Then, the step of forming the first layer is preferable.

That is, it is preferable that the step is formed by applying and drying the coating liquid !_ 1 or !_ 2 on the first support.

In addition, in the method for manufacturing a laminated body of the present disclosure, it is preferable that the first support that is continuously conveyed is used and that the steps and the steps described below are performed by a mouth-to-roll method.

[0062] (Coating liquids !_ 1 and !_ 2)

Coating liquid! Examples of the silicone polymer having a crosslinkable group, the crosslinker, and the silica particles contained in 1 and 1_2 include the components described in the section of the first layer, and the preferred embodiments are also the same. ..

Coating liquid! -The solvent contained in 1 and !_ 2 is preferably a good solvent for a silicone polymer having a crosslinkable group. Examples of the good solvent for the silicone polymer having a crosslinkable group include silicone solvents, ethyl acetate, heptane, tetrahydrofuran, methyl ethyl ketone, and the like. The solvents contained in the coating liquids 1_1 and 1-2 may be used alone or in combination of two or more. Above all, a silicone-based solvent is preferable as the solvent contained in the coating liquids !_ 1 and !_ 2. \¥0 2020/175681 20 卩 (: 171? 2020 /008363

Coating liquid! -1 and the silicone solvent contained in the coating liquid 1_2 are preferably cyclic siloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclotetrasiloxane (also referred to as cyclopentasiloxane).

Coating liquid !_ 1 and coating liquid !_ 2 may each contain the other components described in the section of the first layer.

Furthermore, the coating liquid 1-1 and the coating liquid !_2 may contain a reaction retarder, a reaction inhibitor, etc. used in the reaction for obtaining the silicone elastomer.

The reaction retarder or reaction inhibitor is preferably a component that does not easily remain in the first layer, and is preferably a volatile (for example, boiling point is 100 ^° C. or less) compound. It is more preferable that the compound has a boiling point lower than that of the solvent (eg, silicone-based solvent such as cyclic siloxane) contained in _ 1 and the coating liquid !_ 2. Specific examples of the reaction retarder or reaction inhibitor include, for example, acetylene alcohols (eg, 2-methyl-3-butyne-2-yl), cyclic siloxanes (eg, tetravinyltetramethylcyclotetrasiloxane), etc. Is mentioned.

[0063] The solid content (total amount of components excluding the solvent) in the coating liquid !_ 1 and the coating liquid !_ 2 depends on the ease of applying the coating liquid, the ease of feeding and filtering the coating liquid, and the like. It may be determined according to the conditions, preferably 10% by mass to 70% by mass, more preferably 15% by mass to 65% by mass, further preferably 20% by mass to 50% by mass.

[0064] (First support)

Examples of the first support used in step 8 include the above-mentioned first support, and the preferred embodiments are also the same.

That is, the first support used in step 8 preferably has a silicone layer on the surface on the first layer side from the viewpoint of enhancing the releasability from the first layer.

(Coating and drying)

Coating liquid !_ 1 or coating liquid! As the coating method of -2, a known coating method can be applied. \¥0 2020/175681 21 卩 (: 171? 2020 /008363

Specific coating methods include force-ten coating method, dip coating method, spin coating method, print coating method, spray coating method, slot coating method, mouth coating method, slide coating method, blade coating method. Method, gravure coating method, wire bar method and the like.

Above all, the slot coating method is preferable as the coating method when the step 8 is performed by the mouth toe roll method using the first support which is continuously conveyed.

[0066] As the drying method used in Step 8, a known drying method can be applied.

Specific examples of the drying method include a method using an oven, a warm air blower, an infrared ray (see [¾] heater), and the like. In drying with a warm air blower, warm air may be applied from the surface of the first support opposite to the surface coated with the coating liquid.

The drying conditions, e.g., in the range of 7 0 ^° 〇 ~ 1 1 0 ^° 〇, between 1 0 minutes to 3 0 minutes is preferred.

If necessary, the first layer after drying may be heated to remove the reaction delay agent, reaction inhibitor, etc. contained in the coating liquid !_ 1 and the coating liquid !_2. .. Heating conditions during this heating may, for example, in the range of 7 0 ^° 〇 ~ 1 5 0 ^° 〇, preferably 3 0 minutes to 9 0 minutes.

[0067] [Processing method]

In the process step, the second layer having adhesiveness is formed.

The process step may be, for example, a step of forming the second layer on the second support described later, or a step of forming the second layer on the first layer formed in step 8. Good.

When the process step is a process of forming the second layer on the second support, the first layer is formed on the formed second layer in step 8, and the laminated body of the present disclosure is manufactured. Good. In addition, when the process step is a process of forming the second layer on the second support, the second layer formed and the first layer formed on the first support in step 8 are attached. match \¥0 2020/175681 22 卩 (: 171? 2020 /008363

Thus, the laminated body of the present disclosure may be manufactured.

In the method for manufacturing a laminated body of the present disclosure, from the viewpoint of manufacturing suitability, it is preferable that the process step is a step of forming the second layer on the first layer formed in step 8.

More specifically, the process step is preferably a process of forming a second layer by applying a coating liquid containing an adhesive (hereinafter, also referred to as coating liquid 1-3) on the first layer and drying the coating liquid. ..

[0068] (Coating liquid 1_3)

Examples of the adhesive contained in the coating liquids 1_3 include the adhesives described in the section of the second layer, and the preferred embodiments are also the same.

The coating liquids 1_3 preferably contain a solvent together with the adhesive.

The solvent contained in the coating liquids 1_3 is preferably a good solvent for the base polymer in the adhesive. For example, when the adhesive contained in 1_3 is a silicone-based adhesive, it is preferable to use a silicone-based solvent as the solvent. Examples of silicone-based solvents include the silicone-based solvents contained in coating liquid !-1 and coating liquid !_2.

[0069] The solid content (total amount of components excluding the solvent) in the coating liquid 1-3 is determined according to the ease of applying the coating liquid, the ease with which the coating liquid is delivered and filtered. Of course, 10 mass% to 65 mass% is preferable, 15 mass% to 60 mass% is more preferable, and 25 mass% to 55 mass% is further preferable.

[0070] (Coating and drying)

Examples of the coating method and the drying method used in the process step include the coating method and the drying method in the step, and preferred embodiments are also the same.

[0071] [Step 1 and Step 8 2]

From the viewpoint of production efficiency and the like, in the method for producing a layered product of the present disclosure, it is preferable that the first support to be conveyed be used to carry out the steps and steps in a mouth-to-roll method.

Therefore, in order to protect the first layer, the following steps should be performed between step 8 and step \¥0 2020/175681 23 卩 (: 171? 2020 /008363

It is preferable to carry out step 81 and step 82.

For example, in the case where the process is carried out by the mouth-to-roll method using the continuously transported first support, the first support having the first layer may be wound after the process 8 but before the process. is there. When the first layer contacts the back surface of the first support (that is, the surface opposite to the surface on which the first layer is formed) by this winding, the first layer may be damaged. Therefore, it is preferable to protect the surface of the first layer by performing the following steps 81 and 82 between step 8 and step.

[0072] (Process eight 1)

In step 81, a protective film is attached to the surface of the first layer formed in step 8.

As the protective film, it is preferable that at least the surface in contact with the first layer has releasability from the first layer.

Specific examples of the protective film include a Mitsuhachi (ethylene-vinyl acetate copolymer resin) film (commercially available products include, for example, 803 series of Sanae Kaken Co., Ltd. 80 series), polyolefin film ( Examples of commercially available products include surface protective films of Toray Industries, Inc., Tretec (registered trademark) series, and the like.

As a method for laminating the protective film, a known film laminating method such as a mouth laminating method can be applied.

(Step 8 2)

In step 82, the protective film attached in step 81 is peeled from the surface of the first layer.

As a method for peeling the protective film, a known method for peeling or removing the film can be applied.

[0074] [Step 8 3]

In order to enhance the adhesion between the first layer and the second layer, it is preferable to perform step 3 of hydrophilicizing the surface of the first layer formed in step 8 between step 8 and step. .. \¥0 2020/175681 24 卩 (: 171? 2020 /008363

Examples of the hydrophilic treatment for the surface of the first layer performed in step 83 include corona treatment and plasma treatment. Particularly, from the viewpoint of productivity and the viewpoint of equipment maintenance, corona treatment is preferable.

社製等の口ールトゥロール方式で処理可能なコロ ナ処理装置の他、 春日電機 （株） の丁巳（3 _ 4 乂が挙げられる。 The corona treatment device used for corona treatment is not particularly limited, for example, vetaphone,

In addition to the corona treatment equipment that can be processed by the mouth-to-roll method such as manufactured by the company, there is a Tatsumi (3 _ 4) manufactured by Kasuga Electric Co., Ltd.

The conditions for the hydrophilization treatment may be appropriately determined, for example, so that the contact angle is as shown below.

ともいう） との接触角が 6 0度以下であることが好まし く、 5 0度以下であることがより好ましい。 [0075] The surface of the first layer hydrophilized in step 83 was 1\1-methyl-2-pyrrolidone (hereinafter,

Also referred to as a contact angle) is preferably 60 degrees or less, and more preferably 50 degrees or less.

To measure the contact angle between the surface of the first layer and 1\/1?, a contact angle meter (for example, mouth 1\/1○_7101 of Kyowa Surface Science Co., Ltd.) is used. The contact angle shall be measured at 25°°.

[0076] [Process 〇]

In order to protect the second layer, it is preferable to have a step <3 of laminating the second support on the second layer after the second layer is formed in the step.

As a method for laminating the second support, a known film laminating method can be applied.

[0077] (Second support)

Examples of the second support used in the step ◯ include the above-mentioned second support, and the preferred embodiments are also the same.

That is, it is preferable that the second support used in the step ◯ has a silicone layer on the surface on the second layer side from the viewpoint of enhancing the releasability from the second layer.

The laminate of the present disclosure can be manufactured as described above.

[0079] <Use of laminated body>

The application of the laminate of the present disclosure is not particularly limited as long as it is applied to the skin of the application target person. \¥0 2020/175681 25 卩 (: 171? 2020 /008363

In particular, since the laminate of the present disclosure is applied without feeling uncomfortable, follows the movement of the skin, and has excellent permeability of water vapor released from the skin, it is a use for a long time of application of the present disclosure. The effect of the laminated body is easily exhibited.

Specifically, the laminate of the present disclosure is preferably used for a living body monitoring device, a display element, a wound dressing material, a transdermal preparation, or a cosmetic product.

As a biological monitoring device, it can be attached to the skin of the target person to obtain biological information of the target person (for example, skin temperature, blood pressure, blood oxygen concentration, heart rate, pulse rate, UV dose, activity level, heart rate, heart rate). Examples include electric monitors, wearable devices that measure sweat (○!·!, etc.). The layered product of the present disclosure can be applied to a part to be attached to the skin that is a part of the biological monitoring device.

The display element has, for example, a display function (for example, an organic semiconductor 1_display, etc.), and by sticking it on the skin of the person to whom it is applied, by sticking it on the skin of the person to whom it is applied, Examples include wearable devices that display information (the same as above) and other information (for example, mobile terminal information). The laminated body of the present disclosure can be applied to a part to be attached to the skin which is a part of the display element.

Wound dressings, also called dressings, are laminates that are used to cover skin wounds, burns, etc. by applying them to the skin of the person to whom they are applied. The laminate of the present disclosure may be used as a wound dressing itself, may be applied to the joining portion to the skin is a ^_ part of the wound dressing.

The transdermal preparation is a laminate used for percutaneously absorbing the drug contained in the transdermal preparation by applying it to the skin of the application subject. The layered product of the present disclosure preferably contains a drug in the second layer and is used as a transdermal preparation itself. The layered product of the present disclosure is applied to the skin of an application target, for example, as a cosmetic to beautify the skin. You may use. Specifically, the laminate of the present disclosure may be used as a cosmetic for the purpose of concealing wounds, spots, tattoos, etc. on the skin, or as a cosmetic for the purpose of filling or extending wrinkles on the skin. Good. <How to use the laminate>

The layered product of the present disclosure is used by being attached to the skin of the person to whom it is applied, but the place of attachment is not particularly limited. In addition, the laminate of the present disclosure may be attached, for example, a nail or the like, or may be attached across both the skin and the nail, as long as the adhesiveness can be exhibited.

In particular, the laminate of the present disclosure can be applied to a joint site such as a knee, an elbow, or a finger, since it can be applied without a feeling of strangeness and follows the movement of the skin.

Since the laminate of the present disclosure is excellent in the permeability of water vapor released from the skin, the application time may be, for example, 48 hours or more.

Example

[0081] Hereinafter, the laminate for skin application will be described in detail with reference to Examples. However, the present invention is not limited to the following examples.

[Examples 1 to 13 and Comparative Examples 3 to 4]

(Formation of the first layer)

_Preparation of coating liquid_

The vial silica particles (Alfa Corp., Si I icon (IV) oxide , amorphous fume d, surface treated, the specific surface area by the B ET ^{method: 205 m 2 / g~ 245 m} 2 / g, CAS 7631-86-9 ), cyclopentasiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., K F-995) loxane), vinyl terminated, weight average molecular weight ~ 25,000, viscosity 850-1 ,150 c St) and stir until the powder of silica particles dissolves.

After visually confirming the solubility of the silica particle powder, a metal catalyst (abbreviated as Pt catalyst, platinum (○) — 1,3-divinyl-1,1,1,3,3-tetramethyldisiloxane complex solution ( Aldrich))) is added in an amount of 500 ppm with respect to the total mass of the coating solution, and the mixture is stirred for 30 minutes.

Next, a copolymer of methylhydrosiloxane and dimethylsiloxane (abbreviated as H — PDMS, manufactured by Aldrich, Polv (dimethylsi loxane-co-methy [hydros i loxane), tr imethy isiily terminated, number average molecular weight ~ 13,000, methy Ihydrosi loxane 3 ~ 4mol%) was added and stirred to obtain a coating solution for forming the first layer.

The contents of silica particles, V-P DMS, and H-P DMS in the coating liquid for forming the first layer are summarized in Tables 1 and 2 below.

The coating liquid for forming the first layer was diluted with cyclopentasiloxane so that the solid content of silica particles, V-P DMS, and H-P D MS was 65% by mass.

[0083] One application and drying of the coating solution

As the first support, a release film having a fluorosilicone layer on the surface of the PET film (manufactured by Fujiko, model number K1, thickness 50 Mm) was prepared.

The coating liquid for forming the first layer was applied onto the fluorosilicone layer of the first support by adjusting the thickness so that the coating amount was appropriate to obtain a desired film thickness. The coating solution was applied 2 minutes after the copolymer of methylhydrosiloxane and dimethylsiloxane was added.

After application, the cyclopentasiloxane was removed by performing a drying treatment for 1 hour in a blast dryer at 90°C to form a first layer.

[0084] (Hydrophilic treatment of the first layer)

Then, the surface of the first layer was subjected to corona treatment to make the surface hydrophilic. As the corona treatment device, TEC-4AX manufactured by Kasuga Electric Co., Ltd. was used. Corona treatment conditions were 0.74 J/cm ² .

The contact angle between the surface of the first layer and NMP after corona treatment was 60 degrees or less in all cases. The contact angle between the surface of the first layer after corona treatment and NMP was measured by the method described above.

(Formation of Second Layer: Formation of Second Layer with Silicone Adhesive)

A silicone adhesive (Bio PSA 7 -4202, manufactured by Dow Corning) was diluted with ethyl acetate to prepare a coating solution for forming the second layer.

The content of each component in the coating liquid for forming the second layer is shown in Tables 1 and 2 below. \\0 2020/175681 28 卩 (: 171? 2020 /008363

Summarized.

Apply the coating liquid for forming the second layer on the first layer, adjusting the thickness so that the coating amount is appropriate to obtain the desired film thickness, and then drying with blowing air at 90 ° 〇. A second layer was formed by removing ethyl acetate by drying in a machine for 1 hour.

[0086] (Lamination of the second support)

On the second layer, a release film having a fluorosilicone layer on the surface of the Mending film (manufactured by Fujico, model number [< 1, thickness 50) was attached to obtain a laminate.

[0087] [Example 14]

A laminated body of Example 14 was obtained in the same manner as in Examples 1 to 13 except that the formation of the second layer was changed as follows.

(Formation of Second Layer: Formation of Second Layer with Rubber Adhesive)

（株） の 3 I 3 5 0 0 2 （商品名） ） 5 0質量部、 及び、 粘 着性付与剤として脂環族飽和炭化水素樹脂であるアルコン （登録商標）

Styrene-isoprene-styrene block copolymer, a thermoplastic elastomer

3 I 3500 2 (trade name)) 50 parts by mass, and Alcon (registered trademark) which is an alicyclic saturated hydrocarbon resin as an adhesiveness-imparting agent.

100 (manufactured by Arakawa Chemical Industry Co., Ltd.) 50 parts by mass was placed in a container, and a mixed solvent of cyclohexane (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and ethyl acetate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) (50% by mass/50% by mass) to prepare a coating liquid for forming the second layer using a rubber-based adhesive.

When preparing the rubber-based pressure-sensitive adhesive, the total amount of the thermoplastic elastomer and the tackiness-imparting agent is 15% by mass with respect to the total mass of the rubber-based pressure-sensitive adhesive, and is dissolved in the above mixed solvent. , Sufficiently stirred.

The coating liquid for forming the second layer is applied on the first layer by adjusting the thickness so as to obtain an appropriate coating amount to obtain a desired film thickness, and then applied by a blast dryer at 90° 〇. The above mixed solvent was removed by drying for 1 hour to form the second layer.

[0089] [Example 15]

Same as Examples 1 to 13 except that the formation of the second layer was changed as follows. \¥02020/175681 29 卩 (: 171? 2020 /008363

Thus, a laminate of Example 15 was obtained.

(Formation of Second Layer: Formation of Second Layer with Acrylic Adhesive)

87 -428 7 : アクリル酸 2 -エチルヘキシル ·酢酸ビニル · アクリル酸 2 -ヒドロキ シエチルコポリマー （架橋剤を含まず、 水酸基を有し、 且つカルボキシル基 を有さないアクリル系粘着剤） を、 粘着剤固形分の濃度が 20質量％になる ように酢酸エチル （富士フィルム和光純薬 （株） 製） に溶解し、 充分に撹拌 を行い、 第 2層形成用の塗布液を調製した。 As an acrylic adhesive, Henkel's mouth II 0-11-8

87 -428 7: 2-Ethylhexyl Acrylate-Vinyl Acetate-2-Hydroxyethyl Acrylate Copolymer (Acrylic adhesive that does not contain cross-linking agent, has hydroxyl group and does not have carboxyl group) It was dissolved in ethyl acetate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) so that the concentration of the solid content was 20% by mass, and sufficiently stirred to prepare a coating solution for forming the second layer.

The coating liquid for forming the second layer is applied on the first layer by adjusting the thickness so as to obtain an appropriate coating amount to obtain a desired film thickness, and then in a 90 ^° blast dryer. Ethyl acetate was removed by drying for 1 hour to form a second layer.

[0091] [Comparative example! ~ 2]

As Comparative Example 1, Tegaderm (registered trademark, 3M Japan KK, 1621, 1 0001X 1 20111) was used.

製品番号 66250704） を用いた。 As Comparative Example 2, 〇丨 0801808 [¾mi (registered trademark, Smith & Nephew,

The product number 66250704) was used.

In Table 2, the numerical value shown in the column of “total thickness of the first layer and the second layer” is the thickness after peeling the release film from Tegaderm in Comparative Example 1, and in Comparative Example 2, It is the thickness of I 808.

[0092]

[¾1]

[0093] \¥02020/175681 31 卩(: 171? 2020/008363

[Table 2]

[0094] [Measurement of Tensile Stress at 10% Elongation, Tensile Stress at 40% Elongation, and Tensile Rupture Elongation]

Tensile tension at 10% elongation of the laminate consisting of the first and second layers in each example \¥0 2020/175681 32 卩 (: 171? 2020 /008363

The stress, the tensile stress at 40% elongation, and the tensile elongation at break were measured by the methods described above.

チャック間距離 4

になるように試験片を切り出 して、 また、 比較例

In Comparative Example 1, for Tegaderm, the peeling film attached to the adhesive layer was removed and the width was 2

Distance between chucks 4

The test piece was cut out so that

The test piece was cut out so that the distance between them was 40, and the tensile stress at 40% elongation and the tensile elongation at break were measured by the method described above.

The measurement results are shown in Tables 1 and 2.

[0095] [Evaluation of followability]

に切り出して 、 3人のテスターの右手の手の甲に貼付けた。 また、 比較例 2は〇 丨 〇八_

り出して、 3人のテスターの右手 の手の甲に貼付けた。 Cut the laminated body in each example into 2 0 01 01 X 4 00! On the back of the right hand of 3 testers, then peel off the 1st support and the 2nd support, and the 1st layer and the 2nd layer. Was laminated. In Comparative Example 1, with regard to Tegaderm, the release film attached to the adhesive layer was removed to obtain 2 0 ^1 01 X 4

It was cut into pieces and attached to the backs of the right hands of the three testers. In addition, Comparative Example 2 is 〇丨 〇8_

It sticked out and stuck to the back of the right hand of the three testers.

We asked three testers to move the location where the laminate was applied, and evaluated the tension on the skin according to the following three grades. The evaluation points of the three testers were averaged, and this was taken as the evaluation result of the followability.

— Tension feeling evaluation index and evaluation score

I feel a strong tension: 1 point

Feel a slight tension: 3 points

I don't feel any tension: 5 points

[0096] [Evaluation of discomfort]

に切り出して \¥0 2020/175681 33 卩（：171? 2020 /008363 Cut the laminated body in each example into 2 0 01 01 X 4 00! On the back of the right hand of 3 testers, then peel off the 1st support and the 2nd support, and the 1st layer and the 2nd layer. Was laminated. In Comparative Example 1, with regard to Tegaderm, the release film attached to the adhesive layer was removed to obtain 2 0 ^1 01 X 4

Cut out into \\0 2020/175681 33 卩 (: 171? 2020 /008363

り出して、 3人のテスターの右手 の手の甲に貼付けた。 , Affixed to the back of the right hand of three testers. In addition, Comparative Example 2 is 〇丨 〇8_

It sticked out and stuck to the back of the right hand of the three testers.

Three testers evaluated the weight and the feeling of foreign matter (immediately, the feeling of foreign matter on the skin) at the location where the laminate was applied, according to the following three grades. The evaluation points of the three testers were averaged, and this was taken as the evaluation result of the feeling of foreign matter.

Evaluation index and evaluation score of weight and foreign body feeling

Strongly feel at least one of weight and foreign body feeling: 1 point

At least one of the weight and the feeling of foreign matter is slightly felt: 3 points

At least one of the weight and the feeling of foreign matter is not felt at all: 5 points

[Evaluation of Water Vapor Permeability]

に切り出して 、 3人のテスターの上腕の内側部に貼付けた。 また、 比較例 2は〇 丨 〇八一

り出して、 3人のテスターの上腕 の内側部に貼付けた。 The laminated body in each example was cut into 2 0 01 01 X 400 !!! on the inner side of the upper arms of the three testers, and then the first support and the second support were peeled off, and the first layer and the second support were separated. A laminate of layers was applied. In Comparative Example 1, with regard to Tegaderm, the release film attached to the adhesive layer was removed to obtain 2 0 ^1 01 X 4

It was cut out and attached to the inside of the upper arms of the three testers. In addition, Comparative Example 2 is 〇丨 〇81

It sticked out and stuck to the inside of the upper arms of the three testers.

We asked three testers to evaluate the degree of stuffiness on the part where the laminate was applied for 24 hours, using the following three grades. The evaluation points of the three testers were averaged and used as the evaluation results of water vapor permeability.

-Evaluation index and evaluation score of stuffiness

Feeling stuffy: 1 point

Slight stuffiness: 3 points

No stuffiness: 5 points

[0098] From the results of Tables 1 and 2, it can be seen that the laminates of Examples all have excellent conformability, no discomfort when attached to the skin, and also excellent water vapor permeability. It was \¥02020/175681 34 卩 (: 171? 2020 /008363

[0099] The disclosure of Japanese Patent Application No. 201 9-036430 filed on Feb. 28, 2010 is incorporated herein by reference in its entirety.

All references, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference. , Incorporated herein by reference.

Claims

\¥0 2020/175681 35 卩(: 17 2020/008363 Claims [Claim 1] has a first layer containing a silicone elastomer, and a second layer in contact with the first layer and exhibiting adhesiveness, The laminate of the first layer and the second layer has a tensile stress at 40% elongation of 0.8 !\/18 or less and a total thickness of 11 11 111 or less, and is a laminate for skin application. body. [Claim 2] The laminate for skin application according to claim 1, wherein the tensile breaking elongation of the laminate of the first layer and the second layer is 100% or more. [Claim 3] The laminate for skin application according to claim 1 or 2, wherein the first layer contains silica particles. [Claim 4] The content of silica particles is 7% by mass to 30% by mass with respect to the total mass of the first layer. % Of the laminated body for skin application according to claim 3. [Claim 5] The laminate for skin application according to any one of claims 1 to 4, wherein the silicone elastomer has a crosslinked structure by a hydrosilylation reaction. [Claim 6] The first support contacting the surface of the first layer opposite to the surface in contact with the second layer, and the second support contacting the surface of the second layer opposite to the surface in contact with the first layer. A laminate for skin application according to any one of claims 1 to 5, further comprising: a body. [Claim 7] At least one of the first layer side surface of the first support and the second layer side surface of the second support has a silicone layer or is surface-treated with silicone. The laminated body for skin application as described above. [Claim 8] The laminate for skin application according to any one of claims 1 to 7, which is used for a biological monitoring device, a display element, a wound dressing, a transdermal preparation, or a cosmetic. [Claim 9] Step 8 of forming a first layer containing a silicone elastomer, A step of forming a second layer having adhesiveness, Have \¥0 2020/175681 36 卩 (: 171? 2020 /008363 The tensile stress at 40% elongation of the first layer and second layer laminate is less than 0.81\/13 and the total thickness is 1

The following is a method for producing a laminate for skin application. [Claim 10] Step 8 is a step of forming a first layer by coating and drying a coating liquid containing a silicone polymer having a crosslinkable group, a crosslinking agent, and a solvent on the first support. A method for manufacturing the laminate for skin application according to claim 9. [Claim 11] In Step 8, a coating liquid containing a silicone polymer having a crosslinkable group, a crosslinking agent, silica particles, and a silicone-based solvent is applied and dried on the first support to form a first layer. The method for producing a laminate for skin application according to claim 9, which is a step of forming a skin. [Claim 12] The method for producing a skin patch laminate according to any one of claims 9 to 11, wherein the step A is a step of forming a second layer on the first layer. [Claim 13] For skin sticking according to any one of claims 9 to 12, wherein step 8 and step 9 are performed by a mouth-to-roll method using a continuously transported first support. Method for manufacturing laminated body. [Claim 14] Between step 8 and step The method according to claim 9, further comprising the step of adhering a protective film to the surface of the first layer formed in step 8, 1 and the step of peeling the adhered protective film from the surface of the first layer. ~ A method for manufacturing the laminate for skin application according to any one of claims 13 to 13. [Claim 15] The method according to any one of claims 9 to 14, further comprising a step 3 of performing a hydrophilization treatment on the surface of the first layer formed in the step 8, between the step 8 and the step. The method for producing a laminate for skin application according to item 1. [Claim 16] The surface of the first layer hydrophilized in step 83 has a contact angle with 1\1-methyl-2-pyrrolidone of 60° or less, according to claim 15 A method for producing a laminate for skin application. [Claim 17] The method further comprises a step 0 of laminating the second support on the second layer after the step. \0 2020/175681 37 (: 17 2020/008363) The method for producing a skin patch laminate according to any one of claims 9 to 16.