JP2021183051A - Adhesive material - Google Patents

Abstract

To provide an adhesive material that is superior in moisture permeability and water resistance.SOLUTION: An adhesive material includes: a support having the moisture permeability of 2,000 g/(m2/day) or more; and an adhesive layer having the moisture permeability of 2, 500 g/(m2/day) or more. In the adhesive material, the adhesive layer comprises a polymer having a constitutional unit based on a monomer having a (meth) acryloyl oxy group, urethane bond and linear polyoxyalkylene chain, the polyoxyalkylene chain has a number-average molecular weight of 1,000 or more, and the content of an ethylene oxide unit is 50 mass% or less.SELECTED DRAWING: None

Description

The present invention relates to a patch.

The patch material applied to the skin is required to have excellent moisture permeability so that the moisture due to sweating from the skin evaporates to the outside of the patch material. Furthermore, it is required to have excellent water resistance so that it will not come off due to sweat or shower.

Patent Document 1, a moisture permeability of 3,000g ^/ (m 2 · day) or more supports, moisture permeability and a 5,000g ^/ (m 2 · day) or more pressure-sensitive adhesive layer adhesive preparation It has been disclosed. The pressure-sensitive adhesive layer comprises (1) an active hydrogen compound having a polyoxyalkylene structure having a number average molecular weight of 5,000 or more and an average number of functional groups of 2 or more, and (2) an average of (2) a number average molecular weight of 1,500 to 5,000. It contains a polyurethane-based pressure-sensitive adhesive obtained by reacting an active hydrogen compound having a polyoxyalkylene structure having one functional group with (3) an organic polyisocyanate. The average number of functional groups of the total active hydrogen compound used to obtain the pressure-sensitive adhesive is 2 to 2.6, and the content of ethylene oxide units of the total active hydrogen compound in the pressure-sensitive adhesive is 3 to 8% by weight. be.

Further, Patent Document 1 discloses that the moisture permeability can be improved by increasing the ratio of ethylene oxide units in the pressure-sensitive adhesive layer.

Japanese Patent No. 5457446

The moisture permeability of the patch material described in Patent Document 1 is not sufficient. Therefore, the inventors of the present application have studied to increase the ethylene oxide units in the polymer contained in the pressure-sensitive adhesive layer constituting the patch material described in Patent Document 1 for the purpose of improving the moisture permeability of the patch material. As a result, it was found that the moisture permeability of the patch was improved, but the water resistance was insufficient.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a patch material having excellent moisture permeability and water resistance.

The present invention is the following [1] to [9].
[1] moisture permeability is an adhesive material and 2,000g ^/ (m 2 · day) or more supports, the moisture permeability and a 2,500g ^/ (m 2 · day) or more of the pressure-sensitive adhesive layer, The pressure-sensitive adhesive layer contains a polymer having a structural unit based on a monomer having a (meth) acryloyloxy group, a urethane bond, and a linear polyoxyalkylene chain, and the polyoxyalkylene chain has a number average. A patch having a molecular weight of 1,000 or more and a content of ethylene oxide units of 50% by mass or less.
[2] The pressure-sensitive adhesive layer is located on at least a part of the surface of the support, and the moisture permeability of the portion where the support and the pressure-sensitive adhesive layer overlap is 2,000 g / (m ² · day) or more. , [1].
[3] The patch according to [1] or [2], wherein the pressure-sensitive adhesive layer has a thickness of 10 to 40 μm.
[4] The support is a film, a porous film, a woven fabric or a non-woven fabric, and the material of the support is selected from an ether-based urethane resin, an ester-based urethane resin, a polyester resin, a polyamide resin, and a polyolefin resin. The patch according to any one of [1] to [3], which is at least one kind.
[5] The patch according to any one of [1] to [4], which comprises a supporter in a peelable state on the opposite side of the surface of the pressure-sensitive adhesive layer to which the support is provided.
[6] The patch according to any one of [1] to [5], wherein the adhesive force to human skin is 0.1 to 1.2 N / 15 mm.
[7] The patch according to any one of [1] to [6], which is for medical use.
[8] The dressing material according to [7].
[9] The sticking material according to any one of [1] to [8], which is a sticking material directly applied to the skin.

According to the present invention, it is possible to provide a patch material having excellent moisture permeability and water resistance.

It is sectional drawing which shows one Embodiment of the pasting material which concerns on this invention.

Definitions of terms herein are as follows.
The numerical range represented by "~" means a numerical range in which the numerical values before and after ~ are the lower limit value and the upper limit value.
"Unit" means an atomic group directly formed by polymerization of a monomer.
"(Meta) acryloyloxy" means either or both of acryloyloxy and methacryloyloxy.
The “number of functional groups” means the number of (meth) acryloyloxy groups in one molecule unless otherwise specified.
Unless otherwise specified, the "average number of functional groups" means the average number of (meth) acryloyloxy groups in one molecule having a formula weight obtained based on a chemical formula or a number average molecular weight as one unit.

The number average molecular weight (hereinafter, also referred to as “Mn”) is converted to polystyrene obtained by measuring with gel permeation chromatography (GPC) using a calibration curve prepared using a standard polystyrene sample having a known molecular weight. It is a molecular weight. The molecular weight distribution is a value obtained by dividing the mass average molecular weight (hereinafter, also referred to as “Mw”; the polystyrene-equivalent molecular weight obtained by GPC in the same manner as Mn) by Mn (hereinafter, also referred to as “Mw / Mn”). When a peak of an unreacted low molecular weight component (monomer or the like) appears in the measurement of GPC, Mn is obtained by excluding the peak.
Even if it is specified by Mn, if Mw / Mn does not exist, it shall be replaced by the molecular weight represented by the formula weight obtained based on the chemical formula.

The hydroxyl value of the compound having one hydroxyl group and having a linear polyoxyalkylene chain, which will be described later, or the compound having two hydroxyl groups and having a linear polyoxyalkylene chain is JIS K1557 (2007 edition). ) Is the value obtained by the measurement.
The hydroxyl group-equivalent molecular weight is a value calculated by applying the hydroxyl value to the formula "56100 / (hydroxyl group value) × (number of hydroxyl groups of the initiator)".

Patch of the present embodiment includes moisture permeability and 2,000g ^/ (m 2 · day) or more supports, moisture permeability and 2,500g ^/ (m 2 · day) or more adhesive layers.
The pressure-sensitive adhesive layer of the present embodiment is a structural unit based on a monomer having a (meth) acryloyloxy group, a urethane bond, and a linear polyoxyalkylene chain (hereinafter referred to as "monomer x"). (Hereinafter referred to as "polymer A"). The polyoxyalkylene chain has a number average molecular weight of 1,000 or more and an ethylene oxide unit content of 50% by mass or less.

<Monomer x>
The monomer x is a monomer having a (meth) acryloyloxy group, a urethane bond, and a linear polyoxyalkylene chain.
The monomer x constituting the polymer may be two or more kinds.
The number of (meth) acryloyloxy groups in the monomer x is preferably 1 to 4, more preferably 1 to 2, and even more preferably 1 from the viewpoint of the flexibility of the obtained polymer.
The number of urethane bonds in the monomer x is preferably 1 to 4, more preferably 1 to 2, and even more preferably 1 because the curable composition containing the monomer x has a low viscosity. ..

The ratio of the (meth) acryloyloxy group to the total amount of the monomer x is 0.15 to 7.0 from the viewpoint of the curability of the curable composition containing the monomer x and the flexibility of the obtained polymer. The mass% is preferable, 0.2 to 2.3 mass% is more preferable, and 0.22 to 1.7 mass% is further preferable.
The ratio of the urethane bond to the total amount of the monomer x is preferably 0.15 to 1.6% by mass from the viewpoint of the curability of the curable composition containing the monomer x and the flexibility of the obtained polymer. , 0.18 to 2.2% by mass is more preferable, and 0.20 to 1.4% by mass is further preferable.

The ratio of urethane bonds to the total amount of monomer x is calculated as follows, assuming that all the isocyanate groups in the compound used for producing the monomer x form urethane bonds (molecular weight 59). Calculated from.
Urethane bond content (unit: mass%) = Mi x 59 / Wb x 100
Wb: Total mass of monomer x Mi: Total number of moles of isocyanate groups present in the compound used to produce the monomer x of mass Wb

The Mn of the polyoxyalkylene chain in the monomer x is 1,000 or more, preferably 1,000 to 25,000, preferably 3,000 to 25,000, from the viewpoint of the flexibility and adhesiveness of the obtained polymer. 24,000 is more preferable, and 4,000 to 24,000 is even more preferable.
The Mw / Mn of the polyoxyalkylene chain in the monomer x is preferably 1.03 to 1.2, and 1.04 to 1. 15 is more preferable, and 1.05 to 1.14 is even more preferable.

The content of the ethylene oxide unit of the polyoxyalkylene chain in the monomer x is 0 to 50% by mass, preferably 0 to 40% by mass, and more preferably 0 to 25% by mass. When the content of the ethylene oxide unit is not more than the above upper limit value, the water resistance of the patch material including the pressure-sensitive adhesive layer containing the polymer having the structural unit based on the monomer x is improved. The ethylene oxide content of the monomer x can be calculated by ^{1 H-NMR.}

The content of the propylene oxide unit of the polyoxyalkylene chain in the monomer x is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, still more preferably 75 to 100% by mass.

The Mn of the monomer x is preferably 1,000 to 35,000, more preferably 6,000 to 30,000, and even more preferably 7,000 to 25,000. When the Mn of the monomer x is in the above range, the viscosity of the curable composition containing the monomer x can be easily adjusted, and the adhesiveness of the obtained polymer tends to be good.
The Mw / Mn of the monomer x is preferably 1.01 to 1.30, more preferably 1.03 to 1.20, further preferably 1.04 to 1.15, and 1.05 to 1.14. Especially preferable.

The monomer x preferably contains one or both of the following monomers a and b.
Monomer a: A monomer having one (meth) acryloyloxy group, a urethane bond, and a linear polyoxyalkylene chain in one molecule.
Monomer b: A monomer having two (meth) acryloyloxy groups, a urethane bond, and a linear polyoxyalkylene chain in one molecule.
The ratio of the total of the monomer a and the monomer b to the total amount of the monomer x is preferably 50 to 100% by mass, more preferably 70 to 100% by mass. Within the above range, a patch material having better moisture permeability and water resistance can be obtained.
The ratio of the monomer a to the total amount of the monomer x is preferably 50 to 100% by mass, more preferably 70 to 100% by mass. Within the above range, a patch material having better moisture permeability and water resistance can be obtained.
The mass ratio of the monomer a to the monomer b in the monomer x is preferably 50/50 to 100/0, more preferably 70/30 to 100/0, as the monomer a / monomer b. Preferably, 80/20 to 99/1 is more preferable. Within the above range, a patch material having better moisture permeability and water resistance can be obtained.

<Monomer a>
The monomer a has one (meth) acryloyloxy group in one molecule, a urethane bond, and a linear polyoxyalkylene chain.
The monomer a constituting the polymer A may be two or more kinds.

The monomer a can be obtained, for example, by the following three production methods (1) to (3).
(1) The monomer a is obtained by a urethanization reaction between a compound having one hydroxyl group and a linear polyoxyalkylene chain and a compound having a (meth) acryloyloxy group and an isocyanate group.
(2) In the monomer a, a compound having one hydroxyl group and having a linear polyoxyalkylene chain and a compound having two isocyanate groups are subjected to a urethanization reaction to have an isocyanate group at the terminal. A polymer is obtained by a urethanization reaction between the isocyanate group of the prepolymer and a compound having one hydroxyl group and a (meth) acryloyloxy group.
(3) Monomer a is a urethanization of one hydroxyl group of a compound having two hydroxyl groups and a linear polyoxyalkylene chain, and a compound having a (meth) acryloyloxy group and an isocyanate group. Obtained by reaction.
The patch material of the present invention is provided with a pressure-sensitive adhesive layer containing a polymer having a structural unit based on the monomer a, and is excellent in moisture permeability even if the content of ethylene oxide units in the polymer is low.

The ratio of the (meth) acryloyloxy group to the total amount of the monomer a is 0.15 to 7.0 from the viewpoint of the curability of the curable composition containing the monomer a and the flexibility of the obtained polymer. The mass% is preferable, 0.2 to 2.3 mass% is more preferable, and 0.22 to 1.7 mass% is further preferable.
The ratio of the urethane bond to the total amount of the monomer a is preferably 0.15 to 1.6% by mass from the viewpoint of the curability of the curable composition containing the monomer a and the flexibility of the obtained polymer. , 0.18 to 2.2% by mass is more preferable, and 0.20 to 1.4% by mass is further preferable.

The Mn of the polyoxyalkylene chain in the monomer a is 1,000 or more, preferably 1,000 to 25,000, preferably 3,000 to 25,000, from the viewpoint of the flexibility and adhesiveness of the obtained polymer. 24,000 is more preferable, and 4,000 to 24,000 is even more preferable.
The Mw / Mn of the polyoxyalkylene chain in the monomer a is preferably 1.03 to 1.2, and 1.04 to 1. 15 is more preferable, and 1.05 to 1.14 is even more preferable.

The Mn and Mw / Mn of the polyoxyalkylene chain in the monomer a are compounds having one hydroxyl group and having a linear polyoxyalkylene chain, or hydroxyl groups, which are used in the above three production methods. It is obtained by measuring Mn and Mw of a compound having two and having a linear polyoxyalkylene chain.

Specifically, the urethane bond of the monomer a is hydrolyzed under alkaline conditions, and the obtained compound has one hydroxyl group and has a linear polyoxyalkylene chain, or has two hydroxyl groups. And Mn and Mw of the compound having a linear polyoxyalkylene chain are measured.

The content of the ethylene oxide unit of the polyoxyalkylene chain in the monomer a is 0 to 50% by mass, preferably 0 to 40% by mass, and more preferably 0 to 25% by mass. When the content of the ethylene oxide unit is not more than the above upper limit value, the water resistance of the patch material including the pressure-sensitive adhesive layer containing the polymer having the structural unit based on the monomer a is improved. The ethylene oxide content of the monomer a can be calculated by ^{1 1 H-NMR.}

The content of the propylene oxide unit of the polyoxyalkylene chain in the monomer a is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, still more preferably 75 to 100% by mass.

The Mn of the monomer a is preferably 5,000 to 25,000, more preferably 6,000 to 24,500, and even more preferably 7,000 to 24,000. When the Mn of the monomer a is in the above range, the viscosity of the curable composition containing the monomer a can be easily adjusted. Further, when it is at least the lower limit value in the above range, the curing shrinkage rate of the obtained polymer tends to be low, and the adhesiveness to the skin tends to be good.
When two or more kinds of monomers a are used, it is preferable that each Mn is within the above range.
The Mw / Mn of the monomer a is preferably 1.03 to 1.20, more preferably 1.04 to 1.15, and even more preferably 1.05 to 1.14.
When two or more kinds of monomers a are used, it is preferable that each Mw / Mn is within the above range.

When producing the monomer a, the water content in the raw material composition containing the compound having a linear polyoxyalkylene chain is preferably as small as possible, and is 300 mass ppm with respect to the compound having a linear polyoxyalkylene chain. The following is preferable, 250 mass ppm or less is more preferable, and 50 to 200 mass ppm is further preferable. When the water content is within the above range, the production of reaction products between the water content and the compound having an isocyanate group is small, and the stability of the obtained monomer a is improved. Further, it is easy to suppress the change in appearance of the curable composition containing the monomer a over time, and the elastic modulus of the polymer obtained from the curable composition and the adhesiveness to the skin are likely to be good.
The content of the reaction product of the water and the compound having an isocyanate group is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, based on the total amount of the monomer a.

In the step of producing the monomer a, a by-product other than the monomer a such as a reaction product between the water content and the isocyanate group-containing compound is generated in the product (hereinafter referred to as “product a”). In some cases.
The total ratio of the by-products in the product a is preferably 20% by mass or less, more preferably 15% by mass or less, and most preferably 0% by mass. When it is 20% by mass or less, the function as the monomer a is sufficiently exhibited, so that the product a can be regarded as the monomer a.

Examples of the monomer a include the monomer a-1 represented by the following formula 3, the monomer a-2 represented by the following formula 4, and the monomer a-3 described later.

The monomer a-1 has one hydroxyl group represented by the following formula 3a and has a linear polyoxyalkylene chain (hereinafter referred to as “compound 3a”), and is represented by the following formula 3b. It is obtained by a urethanization reaction with a compound having a (meth) acryloyloxy group and an isocyanate group (hereinafter, referred to as “Compound 3b”).

Since each of compound 3a and compound 3b has one group capable of urethanization reaction in one molecule, it is easy to control the urethane bond in one molecule of monomer a-1 to one. .. If the number of urethane bonds in one molecule of the monomer a-1 is small, the viscosity of the curable composition containing the monomer a tends to be low. Therefore, it is more preferable that the monomer a contains the monomer a-1 in that the curable composition has a low viscosity and a polymer having excellent flexibility and adhesiveness to the skin can be easily obtained.

Compound 3a is a known method for carrying out ring-opening addition polymerization of an alkylene oxide using a monohydric alcohol or a compound obtained by adding an alkylene oxide to a monohydric alcohol as an initiator, or a ring-opening addition polymerization of an alkylene oxide on a −OH group of a monocarboxylic acid. It is obtained by a known method. Specific examples of the alkylene oxide include propylene oxide, ethylene oxide, 1,2-butylene oxide, 2,3-butylene oxide and the like.

In the formulas 3, 3a and 3b, R ¹¹ is a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
− (OR ¹² ) _c − represents a linear polyoxyalkylene chain formed from a unit based on an alkylene oxide.
R ¹² is a linear or branched alkylene group having 2 to 4 carbon atoms, and a plurality of R ^12s present in one molecule may be the same or different from each other. When two or more types of R ¹² are present in ^{one molecule, the −OR 12} − chain may be block or random. R ¹² is preferably one or both of an ethylene group and a propylene group. As the ethylene group and the propylene group, a 1,2-ethylene group and a 1,2-propylene group are preferable.
R ¹³ represents an alkyl group having 1 to 20 carbon atoms or a carboxylic acid residue having 1 to 20 carbon atoms together with an oxygen atom bonded to ^{R 13.} The carboxylic acid residue is a monovalent group in which one hydrogen atom in the carboxy group is removed from a monocarboxylic acid having 1 to 20 carbon atoms containing a carbon atom in the carboxy group. R ¹³ is preferably an alkyl group having 1 to 20 carbon atoms and preferably an alkyl group having 2 to 8 carbon atoms because the reaction is easy.
b is an integer of 1 to 8, and an integer of 1 to 4 is preferable.
c is an integer of 20 to 600, preferably an integer of 35 to 500, and more preferably an integer of 65 to 250.

The hydroxyl value of compound 3a is preferably 2.3 mgKOH / g or more and less than 56.1 mgKOH / g, and more preferably 3 to 14 mgKOH / g. The hydroxyl group equivalent molecular weight is preferably more than 1,000 and 25,000 or less, more preferably 4,000 to 15,000.
When the hydroxyl group-equivalent molecular weight of compound 3a is in the above range, the Mn of the monomer a-1 can be adjusted to the range of 5,000 to 25,000. When the hydroxyl group-equivalent molecular weight of compound 3a is within the above range, the average number of functional groups of the produced monomer a-1 can be easily adjusted to 0.8 to 1.3. The smaller the hydroxyl group equivalent molecular weight, the easier it is to adjust the upper limit of the average number of functional groups to 1.3 or less.

In the production of compound 3a, it is not particularly necessary to remove water by degassing under reduced pressure, and the amount of water normally contained in the raw material or the like charged into the reaction system is acceptable. For example, usually, the smaller the water content of the initiator, the more preferable, 500 mass ppm or less is more preferable, and 300 mass ppm or less is further preferable. When the water content is in this range, the amount of diol produced from water is suppressed, so that the amount of by-product obtained by adding the (meth) acryloyloxy group to the diol is finally suppressed, and the amount of the by-product is suppressed. It is easy to adjust the upper limit of the average number of functional groups of the product a-1 including the product and the monomer a-1 to 1.3 or less.

As the compound 3b, a commercially available product can be used, for example, Calends-AOI (R ¹¹ = H, b = 2 in the formula 3b), Calends-MOI (R ¹¹ = CH ₃ , b = 2 in the formula 3b) (either Also, Showa Denko Corporation product name).
The reaction between the compound 3a and the compound 3b is a urethanization reaction, and can be carried out by using a known method. When these are reacted, the compounding ratio of compound 3b to compound 3a is preferably 80 to 100, more preferably 90 to 100, and most preferably 100 in terms of index (NCO / OH ratio). By setting the index in the above range, it is easy to adjust the average number of functional groups of the product a-1 to the range of 0.8 to 1.3.
Compound 3a may be a mixture of two or more. In this case, each compound 3a is preferably a compound included in the above category.

The ratio of the monomer a-1 to the total amount of the product a-1 is preferably 80% by mass or more, more preferably 85 to 100% by mass, because the function as the monomer a is sufficiently exhibited. When the product a-1 contains the monomer a-1 in the above ratio, the function of the monomer a is fully exerted, so that the product a-1 is regarded as the monomer a-1. be able to.

The Mn of the monomer a-1 is preferably 5,000 to 25,000, more preferably 6,000 to 24,500, and even more preferably 7,000 to 24,000. When the Mn of the monomer a-1 is in the above range, the viscosity of the curable composition containing the monomer a-1 can be easily adjusted. Further, when it is at least the lower limit value in the above range, the curing shrinkage rate of the obtained polymer tends to be low, and the adhesiveness to the skin tends to be good.
When two or more kinds of monomers a-1 are used, it is preferable that each Mn is within the above range.
The Mw / Mn of the monomer a-1 is preferably 1.03 to 1.20, more preferably 1.04 to 1.15, and even more preferably 1.05 to 1.14.
When two or more kinds of monomers a-1 are used, it is preferable that each Mw / Mn is within the above range.

The Mn of the product a-1 is preferably 5,000 to 25,000, more preferably 6,000 to 24,500, and even more preferably 7,000 to 24,000. When the Mn of the product a-1 is in the above range, it is easy to adjust the viscosity of the curable composition containing the product a-1. Further, when it is at least the lower limit value in the above range, the curing shrinkage rate of the obtained polymer tends to be low, and the adhesiveness to the skin tends to be good.
When two or more kinds of products a-1 are used, it is preferable that each Mn is within the above range.
The Mw / Mn of the product a-1 is preferably 1.03 to 1.20, more preferably 1.04 to 1.15, and even more preferably 1.05 to 1.14.
When two or more kinds of products a-1 are used, it is preferable that each Mw / Mn is within the above range.

When the product a-1 can be regarded as the monomer a-1, the average number of functional groups obtained from the Mn of the product a-1 and the number of functional groups is the average number of functional groups of the monomer a-1. Can be regarded. In this case, the average number of functional groups in the product a-1 is preferably 0.8 to 1.3, more preferably 0.9 to 1.2. The product a-1 within the above range tends to reduce shrinkage during curing, easily reduce the elastic modulus of the obtained polymer, and tend to have good adhesiveness to the skin.

The monomer a-1 is a compound represented by the above formula 3, and the ratio of the propylene group to the total amount of ^{R 12 present in one molecule is 50 to 100% by mass.} It is preferable to contain -1-PO.

Wherein the monomers a-1-PO, the ratio of propylene to the total amount of the ^{R 12} is more preferably 57 to 100 mass%, particularly preferably 100 mass%. ^{Of the R 12} present in one molecule, the alkylene group other than the propylene group is preferably an ethylene group. When the R ¹² contains an ethylene group, ^{the ratio of the propylene group to the total amount of the R 12} is preferably 66 to 99% by mass, more preferably 74 to 95% by mass.
Ratio of ethylene to the total amount of ^{R 12} monomeric a-1-PO is preferably 0-43 wt%, more preferably from 1 to 34 wt%, more preferably 5 to 26 wt%.

When the monomer a-1-PO is used, the ratio of the monomer a-1-PO to the total amount of the monomer a is preferably 50 to 100% by mass, more preferably 80 to 100% by mass. When the ratio of the monomer a-1-PO is equal to or higher than the lower limit of the above range, the curable composition containing the monomer a-1-PO has a lower viscosity, and the obtained polymer is more flexible. Excellent for.

The monomer a-2 has a compound having one hydroxyl group represented by the following formula 4a and having a linear polyoxyalkylene chain (hereinafter referred to as “compound 4a”), and the monomer a-2 is represented by the following formula 4b. A compound having two isocyanate groups (hereinafter referred to as "Compound 4b") is subjected to a urethanization reaction to obtain a prepolymer having an isocyanate group at the terminal (isocyanate group-terminated urethane prepolymer), and then the prepolymer. It is obtained by reacting the isocyanate group of No. 1 with a compound having one hydroxyl group represented by the following formula 4c and having a (meth) acryloyloxy group (hereinafter referred to as "Compound 4c").

Compound 4a is a known method for carrying out ring-opening addition polymerization of an alkylene oxide using a monohydric alcohol or a compound obtained by adding an alkylene oxide to a monohydric alcohol as an initiator, or a known method for carrying out ring-opening addition polymerization of an alkylene oxide on a hydroxyl group of a monocarboxylic acid. It is obtained by the method of. Specific examples of the alkylene oxide include propylene oxide, ethylene oxide, 1,2-butylene oxide, 2,3-butylene oxide and the like.

In the formulas 4 and 4c, R ²¹ is a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
− (OR ²² ) _e − represents a linear polyoxyalkylene chain formed from a unit based on an alkylene oxide.
R ²² is a linear or branched alkylene group having 2 to 4 carbon atoms, and a plurality of R ^22s present in one molecule may be the same or different from each other. When two or more types of R ²² are present in ^{one molecule, the −OR 22} − chain may be block or random. R ²² is preferably one or both of an ethylene group and a propylene group. As the ethylene group and the propylene group, a 1,2-ethylene group and a 1,2-propylene group are preferable.
R ²³ indicates an alkyl group having 1 to 20 carbon atoms or a carboxylic acid residue having 1 to 20 carbon atoms together with an oxygen atom bonded to ^{R 23.} The carboxylic acid residue is a monovalent group in which one hydrogen atom in the carboxy group is removed from a monocarboxylic acid having 1 to 20 carbon atoms containing a carbon atom in the carboxy group. R ²³ is preferably an alkyl group having 1 to 20 carbon atoms and preferably an alkyl group having 2 to 8 carbon atoms because the reaction is easy.

R ²⁴ is a divalent group obtained by removing the isocyanate group from compound 4b. Examples of the compound 4b include compounds having two isocyanate groups, and examples thereof include non-yellowing aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and various modified products of these dipolyisocyanates (two isocyanate groups). Denatured substances having). Two or more kinds of diisocyanates can be used in combination.
As the diisocyanate, an aliphatic diisocyanate and an alicyclic diisocyanate are preferable because they are excellent in light resistance, weather resistance and heat resistance and can maintain transparency.
Examples of the non-yellowing aromatic diisocyanate include xylylene diisocyanate and tetramethylxylylene diisocyanate. Examples of the aliphatic diisocyanate include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. Examples of the alicyclic diisocyanate include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,5-norbornane diisocyanate, and 2,6-norbornane diisocyanate.
As the compound 4b, isophorone diisocyanate and 1,6-hexamethylene diisocyanate are preferable.
d is an integer of 1 to 8, and an integer of 1 to 4 is preferable. e is an integer of 20 to 600, preferably an integer of 35 to 500, and more preferably an integer of 65 to 250.

The hydroxyl value of compound 4a is preferably 2.3 mgKOH / g or more and less than 56.1 mgKOH / g, and more preferably 3 to 14 mgKOH / g. The hydroxyl group equivalent molecular weight is preferably more than 1,000 and 25,000 or less, more preferably 4,000 to 15,000.
By setting the hydroxyl group-equivalent molecular weight of compound 4a in the above range, the Mn of the monomer a-2 can be adjusted in the range of 5,000 to 25,000.
Compound 4a may be a mixture of two or more. In this case, each compound 4a is preferably a compound included in the above category.

The water content and molecular weight at the time of producing the compound 4a are the same as those of the compound 3a. Also in the production of compound 4a, as in the case of compound 3a, a product containing a by-product in which a (meth) acryloyloxy group is added to a diol produced from water contained in a raw material and a monomer a-2 ( Hereinafter, "product a-2") may be obtained.

The reaction of reacting the compound 4a with the compound 4b to obtain a prepolymer having an isocyanate group at the terminal (isocyanate group-terminated urethane prepolymer) is a urethanization reaction, and can be carried out by using a known method. When these are reacted, the compounding ratio of the compound 4b to the compound 4a is preferably 100 to 200 in terms of index (NCO / OH ratio), more preferably 180 to 200, and most preferably 200.

The reaction between the obtained isocyanate group-terminated urethane prepolymer and the compound 4c is a urethanization reaction, and can be carried out by using a known method.

When these are reacted, the compounding ratio of the prepolymer to the compound 4c is such that the molar ratio of the isocyanate group in the prepolymer: the hydroxyl group in the compound 4c is 1: 1.0 to 1: 1.1. Preferably, 1: 1.0 to 1: 1.05 is more preferable. Within the above range, the average number of functional groups of the product a-2 can be easily adjusted to the range of 0.8 to 1.2.
The ratio of the monomer a-2 to the total mass of the product a-2 is preferably 80% by mass or more, more preferably 85 to 100% by mass, because the function as the monomer a is sufficiently exhibited. When the product a-2 contains the monomer a-2 in the above ratio, the function of the monomer a is fully exerted, so that the product a-2 is regarded as the monomer a-2. be able to.

The Mn of the monomer a-2 is preferably 5,000 to 25,000, more preferably 6,000 to 24,500, and even more preferably 7,000 to 24,000. When the Mn of the monomer a-2 is in the above range, the viscosity of the curable composition containing the monomer a-2 can be easily adjusted. Further, when it is at least the lower limit value in the above range, the curing shrinkage rate of the obtained polymer tends to be low, and the adhesiveness to the skin tends to be good.
When two or more kinds of monomers a-2 are used, it is preferable that each Mn is within the above range.
The Mw / Mn of the monomer a-2 is preferably 1.03 to 1.20, more preferably 1.04 to 1.15, and even more preferably 1.05 to 1.14.
When two or more kinds of monomers a-2 are used, it is preferable that each Mw / Mn is within the above range.

The Mn of the product a-2 is preferably 5,000 to 25,000, more preferably 6,000 to 24,500, and even more preferably 7,000 to 24,000. When the Mn of the product a-2 is in the above range, it is easy to adjust the viscosity of the curable composition containing the product a-2. Further, when it is at least the lower limit value in the above range, the curing shrinkage rate of the obtained polymer tends to be low, and the adhesiveness to the skin tends to be good.
When two or more kinds of products a-2 are used, it is preferable that each Mn is within the above range.
The Mw / Mn of the product a-2 is preferably 1.03 to 1.20, more preferably 1.04 to 1.15, and even more preferably 1.05 to 1.14.
When two or more kinds of products a-2 are used, it is preferable that each Mw / Mn is within the above range.

When the product a-2 can be regarded as the monomer a-2, the average number of functional groups obtained from the Mn of the product a-2 and the number of functional groups is the average number of functional groups of the monomer a-2. Can be regarded. In this case, the average number of functional groups in the product a-2 is preferably 0.8 to 1.3, more preferably 0.9 to 1.2. The product a-2 within the above range tends to reduce shrinkage during curing, easily reduce the elastic modulus of the obtained polymer, and tend to have good adhesiveness to the skin.

The monomer a-2 is a compound represented by the above formula 4, and the ratio of the propylene group to the total amount of ^{R 22 present in one molecule is 50 to 100% by mass.} -Preferably contains PO.

In the monomer a-2-PO, ^{the ratio of the propylene group to the total amount of R 22} is more preferably 57 to 100% by mass, and particularly preferably 100% by mass. ^{Of the R 22} present in one molecule, the alkylene group other than the propylene group is preferably an ethylene group. When R ²² contains ethylene groups, ^{the ratio of propylene groups to the total amount of R 22} is preferably 66 to 99% by mass, more preferably 74 to 95% by mass.
^{The ratio of ethylene groups to the total amount of R 22} of the monomer a-2-PO is preferably 0 to 43% by mass, more preferably 1 to 34% by mass, still more preferably 5 to 26% by mass.

When the monomer a-2-PO is used, the ratio of the monomer a-2-PO to the total amount of the monomer a is preferably 50 to 100% by mass, more preferably 80 to 100% by mass. When the ratio of the monomer a-2-PO is equal to or higher than the lower limit of the above range, the curable composition containing the monomer a-2-PO has a lower viscosity, and the obtained polymer becomes more flexible. Excellent.

The monomer a-3 is obtained by a urethanization reaction between a compound having two hydroxyl groups and a linear polyoxyalkylene chain (hereinafter referred to as “compound 5a”) and the compound 3b. It is a monomer having 1 functional group.

Compound 5a is a polyoxyalkylene diol obtained by ring-opening addition polymerization of an alkylene oxide using a dihydric alcohol or a compound obtained by adding an alkylene oxide to a dihydric alcohol as an initiator. Compound 5a has an initiator residue, a polyoxyalkylene chain, and a hydroxyl group corresponding to the number of alcoholic hydroxyl groups of the initiator. Ring-opening addition polymerization of divalent alcohol and alkylene oxide and ring-opening addition polymerization of initiator and alkylene oxide are conventionally known in the presence of an alkaline catalyst such as KOH or a catalyst such as a composite metal cyanide complex catalyst. The method can be used.
The divalent alcohol preferably has 1 to 12 carbon atoms, more preferably 2 to 8 carbon atoms. Specific examples of the dihydric alcohol include ethylene glycol, propylene glycol, polypropylene glycol such as dipropylene glycol, 1,4-butanediol and the like.

The number of carbon atoms of the alkylene oxide unit present in the compound 5a is preferably 2 to 4. Specific examples thereof include propylene oxide, ethylene oxide, 1,2-butylene oxide and 2,3-butylene oxide. Multiple alkylene oxide units present in one molecule may be the same or different from each other. When a chain of two or more kinds of alkylene oxide units is present in one molecule, it may be a block chain or a random chain.
The alkylene oxide unit is preferably one or both of an ethylene oxide unit and a propylene oxide unit. The ratio of the propylene oxide unit to the total amount of the alkylene oxide unit is preferably 57 to 100% by mass, more preferably 100% by mass. Of the alkylene oxide units present in one molecule, the alkylene oxide unit other than the propylene oxide unit is preferably an ethylene oxide unit. When the alkylene oxide unit contains an ethylene group, the ratio of the propylene group to the total amount of the alkylene oxide unit is preferably 66 to 99% by mass, more preferably 74 to 95% by mass.
The ratio of ethylene groups to the total amount of the alkylene oxide unit is preferably 0 to 43% by mass, more preferably 1 to 34% by mass, still more preferably 5 to 26% by mass.

The hydroxyl value of compound 5a is preferably 1.6 to 56.1 mgKOH / g, more preferably 3.7 to 14 mgKOH / g. The hydroxyl group equivalent molecular weight is preferably more than 1,000 and 25,000 or less, more preferably 4,000 to 15,000.
When the hydroxyl group-equivalent molecular weight of the compound 5a is in the above range, the Mn of the monomer a-3 can be adjusted to the range of 5,000 to 25,000. When the hydroxyl group-equivalent molecular weight of compound 5a is within the above range, the average number of functional groups of the produced monomer a-3 can be easily adjusted to 0.8 to 1.3. The smaller the hydroxyl group equivalent molecular weight, the easier it is to adjust the upper limit of the average number of functional groups to 1.3 or less.
Compound 5a may be a mixture of two or more polyoxyalkylene diols. In this case, it is preferable that each polyoxyalkylene diol is a compound included in the above category.

The reaction between the compound 5a and the compound 3b is a urethanization reaction, and can be carried out by using a known method.
In such a reaction, since the hydroxyl groups at both ends of the compound 5a can react with the compound 3b, a product containing a monomer having a functional group number of 2 as a by-product in addition to the monomer having a functional group number of 1 (a product containing a monomer having a functional group number of 2). Hereinafter, "product a-3") can be produced.
The average number of functional groups of the product a-3 is preferably 0.8 to 1.3, more preferably 0.9 to 1.2.

In such a reaction, the compounding ratio of compound 3b to compound 5a is preferably 30 to 50, more preferably 40 to 50, and most preferably 50 in terms of index (NCO / OH ratio). When the index is within the above range, it is easy to obtain a compound in which one molecule of compound 3b reacts with one molecule of compound 5a, and the average number of functional groups of the product a-3 is in the range of 0.8 to 1.3. Easy to adjust.

The ratio of the monomer a-3 to the total amount of the product a-3 is preferably 80% by mass or more, more preferably 85 to 100% by mass, because the function as the monomer a is sufficiently exhibited. When the product a-3 contains the monomer a-3 in a ratio within the above range, the function of the monomer a is fully exerted, so that the product a-3 is converted into the monomer a-3. It can be regarded as 3.

When the product a-3 can be regarded as the monomer a-3, the average number of functional groups obtained from the Mn of the product a-3 and the number of functional groups is the average number of functional groups of the monomer a-3. Can be regarded. In this case, the average number of functional groups in the product a-3 is preferably 0.8 to 1.3, more preferably 0.9 to 1.2. The product a-3 within the above range tends to reduce shrinkage during curing, easily reduce the elastic modulus of the obtained polymer, and tend to have good adhesiveness to the skin.

The Mn of the monomer a-3 is preferably 5,000 to 25,000, more preferably 6,000 to 24,500, and even more preferably 7,000 to 24,000. When the Mn of the monomer a-3 is in the above range, the viscosity of the curable composition containing the monomer a-3 can be easily adjusted. Further, when it is at least the lower limit value in the above range, the curing shrinkage rate of the obtained polymer tends to be low, and the adhesiveness to the skin tends to be good.
When two or more kinds of monomers a-3 are used, it is preferable that each Mn is within the above range.
The Mw / Mn of the monomer a-3 is preferably 1.03 to 1.20, more preferably 1.04 to 1.15, and even more preferably 1.05 to 1.14.
When two or more kinds of monomers a-3 are used, it is preferable that each Mw / Mn is within the above range.

The Mn of the product a-3 is preferably 5,000 to 25,000, more preferably 6,000 to 24,500, and even more preferably 7,000 to 24,000. When the Mn of the product a-3 is in the above range, it is easy to adjust the viscosity of the curable composition containing the product a-3. Further, when it is at least the lower limit value in the above range, the curing shrinkage rate of the obtained polymer tends to be low, and the adhesiveness to the skin tends to be good.
When two or more kinds of products a-3 are used, it is preferable that each Mn is within the above range.
The Mw / Mn of the product a-3 is preferably 1.03 to 1.20, more preferably 1.04 to 1.15, and even more preferably 1.05 to 1.14.
When two or more kinds of products a-3 are used, it is preferable that each Mw / Mn is within the above range.

The ratio of the monomer a-1 to the total amount of the monomer a is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, still more preferably 80 to 100% by mass.
The ratio of the monomer a-2 to the total amount of the monomer a is preferably 0 to 50% by mass, more preferably 0 to 25% by mass, still more preferably 0 to 20% by mass.
The ratio of the monomer a-3 to the total amount of the monomer a is preferably 0 to 50% by mass, more preferably 0 to 25% by mass, still more preferably 0 to 20% by mass.

It is particularly preferable that the monomer a contains at least one selected from the group consisting of the monomers a-1 and the monomers a-2.
The total ratio of the monomer a-1 and the monomer a-2 to the total amount of the monomer a is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 100% by mass. preferable.
When the total ratio of the monomer a-1 and the monomer a-2 is equal to or higher than the lower limit of the above range, the effect of reducing the curing shrinkage rate is excellent, the flexibility of the obtained polymer tends to be high, and the skin Adhesion to is likely to be good. The mass ratio of the monomer a-1 to the monomer a-2 (a-1): (a-2) is preferably 1: 0 to 1: 1.

<Monomer b>
The monomer b has two (meth) acryloyloxy groups in one molecule, a urethane bond, and a linear polyoxyalkylene chain.
From the viewpoint of curing rate, it is preferable that the monomer b has an acryloyloxy group.
The monomer b constituting the polymer A may be two or more kinds.

The monomer b can be obtained, for example, by the following two production methods (i) and (ii).
(I) Monomer b is a urethanization of two hydroxyl groups of a compound having two hydroxyl groups and a linear polyoxyalkylene chain, and a compound having a (meth) acryloyloxy group and an isocyanate group. Obtained by reaction.
(Ii) The monomer b has an isocyanate group at both ends by subjecting a compound having two hydroxyl groups and having a linear polyoxyalkylene chain and a compound having two isocyanate groups to a urethanization reaction. A prepolymer is obtained by a urethanization reaction between the isocyanate group of the prepolymer and a compound having one hydroxyl group and a (meth) acryloyloxy group.

In the production methods (i) and (ii), the compound 5a can be used as the compound having two hydroxyl groups and having a linear polyoxyalkylene chain.
In the production method (i), the compound 3b can be used as the compound having (meth) acryloyloxy group and isocyanate group.
In the production method (ii), the compound 4b can be used as the compound having two isocyanate groups.
In the production method (ii), the compound 4c can be used as the compound having one hydroxyl group and having a (meth) acryloyloxy group.
The patch material of the present invention is provided with a pressure-sensitive adhesive layer containing a polymer having a structural unit based on the monomer b, and is excellent in moisture permeability even if the content of ethylene oxide units in the polymer is low.

The number of urethane bonds in one molecule of the monomer b is one or more.
The urethane bond content is preferably 3.90 to 6.00% by mass, more preferably 3.92 to 5.70% by mass, and 3.95 to 5.50% by mass with respect to the total amount of the monomer b. Is even more preferable. With such a high concentration (presence ratio) of urethane bonds, the adhesiveness of the obtained polymer can be improved.
The urethane bond content with respect to the total amount of the monomer b is calculated in the same manner as the urethane bond content with respect to the total amount of the monomer a.

The Mn of the polyoxyalkylene chain in the monomer b is 1,000 or more, preferably 1,000 to 35,000, preferably 5,000 to 35,000, from the viewpoint of flexibility and low viscosity of the obtained polymer. 30,000 is more preferable, and 8,000 to 25,000 is even more preferable.
The Mw / Mn of the polyoxyalkylene chain in the monomer b is preferably 1.01 to 1.30, preferably 1.03 to 1.30, because the curable composition containing the monomer b tends to have a lower viscosity. .20 is more preferable, and 1.02 to 1.10 is even more preferable.

The Mn and Mw / Mn of the polyoxyalkylene chain in the monomer b are the Mn and Mw of the compound having two hydroxyl groups and having a linear polyoxyalkylene chain used in the above two production methods. Obtained by measurement.
Specifically, it can be measured by the same method as Mn and Mw / Mn of the polyoxyalkylene chain in the monomer a.

The Mn of the monomer b is preferably 1,000 to 35,000, more preferably 6,000 to 30,000, and even more preferably 9,000 to 25,000. When the Mn of the monomer b is in the above range, the viscosity of the curable composition can be easily adjusted, and the adhesiveness of the obtained polymer tends to be good.
When the curable composition contains two or more types of monomer b, it is preferable that the Mn of each monomer b is within the above range.
The Mw / Mn of the monomer b is preferably 1.01 to 1.30, more preferably 1.03 to 1.20.
When the curable composition contains two or more types of monomer b, it is preferable that each Mw / Mn is within the above range.

In the manufacturing process of the monomer b, a by-product other than the monomer b may be generated in the product (hereinafter referred to as “product b”).
The content of the by-product in the product b is preferably 20% by mass or less, more preferably 15% by mass or less, preferably 10% by mass or less, and most preferably zero. When the content is 20% by mass or less, the function as the monomer b is sufficiently exhibited, so that the product b can be regarded as the monomer b.

The Mn of the product b is preferably 1,000 to 35,000, more preferably 6,000 to 30,000, and even more preferably 9,000 to 25,000. When the Mn of the product b is in the above range, it is easy to adjust the viscosity of the curable composition containing the product b. Further, when it is at least the lower limit value in the above range, the curing shrinkage rate of the obtained polymer tends to be low, and the adhesiveness to the skin tends to be good.
When two or more kinds of product b are used, it is preferable that each Mn is within the above range.
The Mw / Mn of the product b is preferably 1.01 to 1.30, more preferably 1.03 to 1.20.
When two or more kinds of product b are used, it is preferable that each Mw / Mn is within the above range.

When the product b can be regarded as the monomer b, the average number of functional groups obtained from the Mn of the product b and the number of functional groups can be regarded as the average number of functional groups of the monomer b. In this case, the average number of functional groups in the product b is preferably 1.6 to 2.0, more preferably 1.7 to 2.0, and even more preferably 1.8 to 1.96. The product b within the above range tends to have good adhesiveness of the obtained polymer.

The monomer b-PO has an oxypropylene group content of 57 to 100% by mass and an oxyethylene group content of 0 to 43% by mass with respect to the total oxyalkylene group. Is preferably contained.
When the monomer b-PO is used, the content of the monomer b-PO with respect to the monomer b is preferably 50 to 100% by mass, more preferably 80 to 100% by mass. When the content of the monomer b-PO is within the above range, flexibility in the obtained polymer can be easily obtained.

In particular, the monomer b-PO has an oxypropylene group content of 80 to 100% by mass, an oxyethylene group content of 0 to 20% by mass, and an average number of hydroxyl groups of 2 to 3 with respect to all oxyalkylene groups. It is preferably a reaction product of a polyoxyalkylene diol having a number average molecular weight of 1,000 to 35,000, a non-yellowing diisocyanate, and a hydroxyalkyl acrylate.
As the non-yellowing diisocyanate, a diisocyanate selected from the group consisting of an aliphatic diisocyanate, an alicyclic diisocyanate and a yellowing-free aromatic diisocyanate is preferable. Specific examples thereof include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and xylylene diisocyanate.
As the hydroxyalkyl acrylate, the following compound 2 is preferable.
CH ₂ = CH-C (= O) OR'... (2)
R'represents a group in which one hydrogen atom of an alkyl group having 1 to 6 carbon atoms is substituted with a hydroxyl group.
Specific examples of the compound 2 include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.

<Adhesive layer>
The pressure-sensitive adhesive layer of this embodiment contains the polymer A. The polymer A has a structural unit based on the monomer x. The polymer of this embodiment is obtained by a polymerization reaction of the monomer x. The polymerization can be carried out by a known method using a curable composition containing the monomer x, a thermal polymerization initiator as required, a photopolymerization initiator, and other components.

The polymer A may have a unit based on other monomers in addition to the unit based on the monomer x. The other monomer may be copolymerizable with the monomer x. Examples of other monomers include hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylates and 4-hydroxybutyl (meth) acrylates, and aliphatic (meth) acrylates such as butyl (meth) acrylates and lauryl (meth) acrylates. Examples thereof include acrylamides such as meth) acrylates, dimethylacrylamides, isopropylacrylamides and acryloylmorpholins, and (meth) acrylates having a cyclic skeleton such as isoborone (meth) acrylates, tetrahydroxyfuran (meth) acrylates and cyclohexyl (meth) acrylates.

The ratio of the unit based on the monomer x to the total constituent units of the polymer A is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass. When it is at least the lower limit of the above range, the moisture permeability and water resistance of the patch material provided with the pressure-sensitive adhesive layer containing the polymer A are improved.

The polymer A is obtained by polymerizing a curable composition containing the monomer x.
The curable composition of the present embodiment may be a photocurable resin composition or a thermosetting resin composition.
When the curable composition is a thermosetting resin composition, it preferably contains a thermopolymerization initiator. When the curable composition is a photocurable resin composition, it preferably contains a photopolymerization initiator. A photocurable resin composition is preferable because it can be polymerized at a low temperature and the polymerization rate is high. If it is a photocurable resin composition, a polymer can be obtained in a shorter time, and the productivity of the patch is excellent.

(Photopolymerization initiator)
As the photopolymerization initiator, a photopolymerization initiator that is sensitive to ultraviolet rays having a wavelength of 380 nm or less is preferable from the viewpoint of ease of control of the polymerization reaction.
Examples of the photopolymerization initiator include the photopolymerization initiators described in International Publication No. 2018/173896 [0147] to [0151].
As the photopolymerization initiator, a hydrogen abstraction type photopolymerization initiator in which a photoexcited initiator and a hydrogen donor in the system form an excitation complex and transfer hydrogen of the hydrogen donor is preferable. Specific examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3-dimethyl-4-methoxybenzophenone, 4- (meth). ) Acryloyloxybenzophenone, 4- [2-((meth) acryloyloxy) ethoxy] benzophenone, 4- (meth) acryloyloxy-4'-methoxybenzophenone, 2-benzoyl methyl benzoate, methyl benzoyl formate.
Two or more kinds of photopolymerization initiators may be used in combination.

The amount of the photopolymerization initiator used is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the monomer x. When the amount of the photopolymerization initiator used is within the above range, it is easy to obtain an appropriate reaction sensitivity to active energy rays.

(Thermal polymerization initiator)
As the thermal polymerization initiator, an azo-based initiator and a peroxide-based initiator are preferable from the viewpoint of reactivity.
Examples of the thermal polymerization initiator include the thermal polymerization initiators described in JP-A-2020-35551 and JP-A-2020-8877.
Two or more kinds of thermal polymerization initiators may be used in combination.

The amount of the thermal polymerization initiator used is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the monomer x. When the amount of the thermal polymerization initiator used is within the above range, it is easy to obtain an appropriate reaction sensitivity during heat curing.

(Other ingredients)
The curable composition of the present embodiment may contain conventionally known components as other components other than the monomer x, the photopolymerization initiator, and the thermal polymerization initiator.
Other components include, for example, silane coupling agents, tackifier resins, antioxidants, light stabilizers, metal inactivating agents, rust inhibitors, antiaging agents, hygroscopic agents, antioxidants, antistatic agents, etc. Examples include antifoaming agents and inorganic particles.
If necessary, a reaction catalyst (tertiary amine compound, quaternary ammonium compound, tin laurate compound, etc.) may be contained.
If necessary, polyfunctional isocyanate (modified isophorone diisocyanate, modified hexamethylene diisocyanate, modified tolylene diisocyanate, etc.) may be contained.
If necessary, a solvent may be contained.

The mixing order of each component is not particularly limited. Further, the polymerization of the monomer x may be carried out by irradiating with ultraviolet rays after mixing each component, or by heat treatment.
Each component constituting the curable composition may be mixed in advance or may be mixed immediately before polymerization. For example, a photopolymerization initiator may be added immediately before polymerization to a premixture in which components other than the photopolymerization initiator are mixed in advance.
The curable composition of the present embodiment can be used without containing a solvent. A solvent may be contained if necessary. The solvent used is preferably removed during or after the polymerization.

The polymer A can be obtained, for example, by molding a curable composition into a desired shape and irradiating it with ultraviolet rays to polymerize the monomer x.
Examples of the molding method of the curable composition include a method of applying the curable composition on a support described later, a method of extrusion molding, and a method of injecting into a mold.
The dose of ultraviolet rays is preferably from 0.1~5J / cm ^2, more preferably 0.3~4J / cm ^2, more preferably 0.5 to 3 J / cm ^2. When the irradiation amount is at least the lower limit of the above range, the strength of the obtained pressure-sensitive adhesive layer becomes better, and when it is at least the upper limit, coloring is difficult.

The ratio of the monomer x to the total amount of the curable composition is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass.

The ratio of the polymer A to the total amount of the pressure-sensitive adhesive layer is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass. The pressure-sensitive adhesive layer of the present embodiment may contain (other components) described in the curable composition as components other than the polymer A.

The moisture permeability of the pressure-sensitive adhesive layer is 2,500 g / (m ² · day) or more, ^{preferably 3,000 g / (m 2} · day) or more, and more preferably 3,500 g / (m ² · day) or more. ..

Moisture permeability is determined as the amount of water vapor passing through the test piece ^{per 1 m 2 per day.}
The measurement of moisture permeability is performed for 24 hours (1 day) when the relative humidity of the space on one side separated by the test piece is 90% in an atmosphere of 40 ° C. and the space on the other side is kept dry by a hygroscopic agent. The mass (g) of water vapor passing through the test piece is measured and converted into ^{1 m 2 of the test material.} The measurement was performed according to the JIS Z 0208: 1976 moisture permeability test method (cup method) for the moisture-proof packaging material, and a circular test piece having a diameter about 10 mm larger than the inner diameter of the cup was placed on a cup containing about 50 g of calcium chloride hygroscopic agent. Furthermore, cover the test piece with rubber packing and ring so that the test piece does not shift, and screw it in. After measuring the total mass of this test piece, it is placed in a constant temperature and humidity chamber at 40 ° C. and a 90% RH atmosphere, the mass change at regular time intervals is measured, and the moisture permeability is determined according to the following formula.
Moisture permeability (g / (m ² · day)) = W × 240000 / S
However, S represents a moisture permeation area (cm ² ), and W represents a mass increase (g / hr) per hour.

The moisture permeability of the pressure-sensitive adhesive layer can be obtained from the moisture permeability of the adhesive material to which the support and the pressure-sensitive adhesive layer are bonded and the moisture permeability of the support by the following formula.
(1 / Moisture permeability of adhesive layer) = (1 / Moisture permeability of patch)-(1 / Moisture permeability of support)

The thickness of the pressure-sensitive adhesive layer is preferably 10 to 40 μm, more preferably 12 to 35 μm, still more preferably 15 to 30 μm. When the thickness of the pressure-sensitive adhesive layer is within the above range, the adhesion of the pressure-sensitive adhesive layer to the skin surface becomes better.

<Attachment material>
FIG. 1 is a cross-sectional view showing an embodiment of a patch material according to the present invention. The patch 1 includes a support 11 and an adhesive layer 12 provided on the surface of the support.
Examples of the material of the support include urethane resins such as ether-based urethane resin and polyester-based urethane resin, polyamide resins such as polyether polyamide block polymer, acrylic resins such as polyacrylate, polyethylene, polypropylene and ethylene / vinyl acetate co-weight. Examples thereof include a polyolefin resin such as a coalescence and a polyester resin such as polyether polyester. As the material of the support, urethane resin, polyester resin, polyamide resin, or polyolefin resin is preferable, urethane resin or amide resin is preferable, and ether-based urethane resin, polyester-based urethane resin or amide resin is more preferable from the viewpoint of moisture permeability. preferable. As the material of the support, one kind may be used alone, or two or more kinds may be used in combination.
The form of the support is preferably a film, a porous film, a woven fabric or a non-woven fabric. The form of the support may be a laminated film in which base films manufactured from different materials are laminated. The base film can be laminated with a fabric such as a woven fabric, a non-woven fabric, a knitted fabric or a net.
The thickness of the support is not particularly limited, but when a film is used as the support, the thickness is preferably 1 to 9 μm, more preferably 3 to 9 μm. When the thickness of the support is within this range, the moisture permeability of the support is excellent, the moisture permeability of the portion where the support and the adhesive layer overlap is excellent, and the adhesive material is not easily broken, so that the adhesive material reaches the skin surface. It is easy to secure the followability of. When a breathable cloth or film such as a non-woven fabric, a woven cloth, or a porous film is used as the support, the thickness is preferably 10 to 250 μm, more preferably 20 to 150 μm. When the thickness of the support is within this range, the moisture permeability of the support is excellent, the moisture permeability of the portion where the support and the adhesive layer overlap is excellent, and the adhesive material is not easily broken, so that the adhesive material reaches the skin surface. It is easy to secure the followability of.

Moisture permeability of the support is at 2,000g ^/ (m 2 · day) or more, preferably 3,500g ^/ (m 2 · day) or ^{more, 4,500g / (m 2 · day} ) or more is more preferable.

Moisture permeability of the portion the support and the adhesive layer of the patch overlap, preferably 2,000g ^/ (m 2 · day) or ^{more, 2,800g / (m 2 · day} ) or more preferably, 3,000 g / (M ² · day) or more is more preferable.

In the patch 1 of the present embodiment, as shown in FIG. 1, the carrier 13 can be detachably laminated on the surface of the pressure-sensitive adhesive layer 12 opposite to the surface on which the support 11 is formed. The material of the carrier is not particularly limited, but is limited to a polypropylene film, a polyethylene film, a plastic film such as a silicone film that has been subjected to a silicone mold release treatment or a fluorine mold release treatment, and a high-quality paper or a glassin paper that has been subjected to a silicone mold release treatment or a fluorine mold release treatment. Paper substrate is preferable.

The adhesive strength of the patch to human skin is preferably 0.1 to 1.2 N / 15 mm, more preferably 0.2 to 0.8 N / 15 mm.
The adhesive strength of the patch to human skin is 15 mm wide on human skin under a 25 ° C atmosphere according to the test method described in "10 Adhesive Strength" of the adhesive tape / adhesive sheet test method of JIS Z 0237: 2009. The adhesive strength is obtained by attaching a test piece, crimping it back and forth once with a 2 kg rubber roll at a speed of 300 mm / min, leaving it for 20 minutes, and then measuring a peeling angle of 90 degrees and a peeling speed of 300 mm / min.

Examples of the use of the patch include a wound dressing, and a medical dressing material directly applied to the skin, a film material for fixing a medical material such as gauze, and a bandage patch are suitable.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following description.

<Measurement method / evaluation method>
[Measurement of molecular weight]
The number average molecular weight (Mn) was measured by gel permeation chromatography (GPC) under the following conditions.
-Analyzer: HLC-8120GPC Tosoh product name-Column: G7000HXL + GMHXL + GMHXL Tosoh product name-Column size: 7.8 mmφ x 30 cm each, 90 cm in total
-Column temperature: 40 ° C
・ Flow rate: 0.8 mL / min
・ Injection amount: 100 μL
-Eluent: Tetrahydrofuran-Detector: Differential refractometer (RI)
・ Standard sample: Polystyrene

[Characteristic evaluation of pasting material]
The patch material was evaluated for moisture permeability, adhesive strength to human skin, and water resistance.

[Humidity permeability]
The moisture permeation was determined as the mass per day of water vapor passing through the patch material ^{per 1 m 2.}
The moisture permeability was tested for 24 hours (1 day) when the relative humidity of the space on one side separated by the patch was set to 90% in an atmosphere of 40 ° C and the space on the other side was kept dry by a hygroscopic agent. The mass (g) of water vapor passing through the piece was measured and converted into ^{1 m 2 of affixed material.} The moisture permeability was measured according to the moisture permeability test method (cup method) of the moisture-proof packaging material of JIS Z 0208: 1976. Specifically, first, a circular patch having a diameter about 10 mm larger than the inner diameter of the cup is put on a cup containing about 50 g of calcium chloride hygroscopic agent, and then a rubber packing and a ring are put on the stick so that the sticker does not shift. I screwed it. Next, after measuring the total mass of this patch, it was placed in a constant temperature and humidity chamber at 40 ° C. and a 90% RH atmosphere, the mass change was measured at regular time intervals, and the moisture permeability was determined according to the following formula. ..
Moisture permeability (g / m ² · day) = W × 240000 / S
In the formula, S represents the moisture permeation area (cm ² ), and W represents the mass increase per hour (g / hr).
Moisture permeability was evaluated according to the following criteria.
A ... 2,500 g / (m ² · day) or more D ... less than 2,500 g / (m ² · day)

[Adhesive strength to human skin]
The adhesive strength to human skin was measured according to the test method described in "10 Adhesive Strength" of the adhesive tape / adhesive sheet test method of JIS Z 0237: 2009. Specifically, a pressure-sensitive adhesive layer having a width of 15 mm is attached to human skin in an atmosphere of 25 ° C., one reciprocating pressure is applied with a 2 kg rubber roll at a speed of 300 mm / min, and after leaving for 20 minutes, a peeling angle of 90 The peeling force was measured at a peeling speed of 300 mm / min. Human skin was degreased with isopropyl alcohol and then air-dried before use.
The adhesive strength to human skin was evaluated according to the following evaluation criteria.
A ... 0.2-1.2N / 15mm
D: Less than 0.2N / 15mm or more than 1.2N / 15mm

[water resistant]
To evaluate the water resistance, first, a test piece having a width of 15 mm was attached to a bakelite plate with respect to the pressure-sensitive adhesive layer of the adhesive material, and the test piece was pressure-bonded once with a 2 kg rubber roll at a speed of 300 mm / min and left for 20 minutes. Then, it was left in water for 20 minutes, and it was confirmed whether or not the adhesive layer was peeled off from the bakelite plate.
Water resistance was evaluated according to the following evaluation criteria.
A ... No peeling.
D ... There is peeling.

(Production Example 1-1: Production of compound P1)
A slurry containing a zinc hexacyanocobaltate-tert-butyl alcohol complex catalyst (hereinafter referred to as "TBA-DMC catalyst") in a pressure resistant reaction vessel equipped with a stirrer and a nitrogen introduction tube, and 1-butanol as an initiator. 30 g was charged and used as a reaction solution. The amount of the slurry added was such that the metal concentration of the TBA-DMC catalyst in the reaction solution was 46 ppm.
Next, after replacing the inside of the pressure-resistant reaction vessel with nitrogen, the reaction solution is heated with stirring, the heating is stopped when the temperature reaches 135 ° C., and 3970 g of propylene oxide (hereinafter, also referred to as “PO”) is added while continuing stirring. It was supplied into a pressure-resistant reaction vessel and reacted. Then, after confirming that the temperature rise of the reaction solution had stopped, the mixture was cooled to 135 ° C. After confirming that the change in the internal pressure had disappeared and the reaction was completed, the catalyst was neutralized and removed using a synthetic adsorbent (Kyowad 600S, manufactured by Kyowa Chemical Industry Co., Ltd.).
Table 1 shows the number of hydroxyl groups per molecule of the obtained compound P1, the ratio of Mn (Mn of polyoxyalkylene chain) and ethylene oxide (hereinafter, also referred to as “EO”) units (hereinafter, similarly shown).

(Production Example 1-2: Production of Compound P2)
Compound P2 was produced in the same manner as in Production Example 1-1, except that 3758 g of PO and 970 g of EO were supplied instead of 3970 g of PO in Production Example 1-1.

(Production Example 1-3: Production of Compound P3)
Compound P3 was prepared in the same manner as in Production Example 1-1, except that the initiator was changed from 1-butanol to 38 g of glycerin and 804 g of PO and 3217 g of EO were supplied instead of 3970 g of PO. Manufactured.

(Production Example 1-4: Production of Compound P4)
Compound P4 was produced in the same manner as in Production Example 1-2 except that the initiator was changed from 1-butanol to propylene glycol.

In addition, as commercially available compounds, PREMINOL 7012 (hereinafter referred to as "Compound P5"), PREMINOL S4011 (hereinafter referred to as "Compound P6") and PREMINOL S1004 (hereinafter referred to as "Compound P7") manufactured by AGC Inc. are used. Using. Table 1 shows the number of hydroxyl groups per molecule of compounds P4 to P7, Mn (Mn of polyoxyalkylene chain), and the ratio of EO units.

(Production Example 2-1: Production of Monomer a1)
In a reaction vessel equipped with a stirrer and a nitrogen introduction tube, 100 parts by mass of the compound P1 obtained in Production Example 1-1 and 2-acryloyloxyethyl isocyanate (Karenzu AOI, manufactured by Showa Denko KK, hereinafter referred to as "AOI") are also used. 1.39 parts by mass of 2-ethylhexaneate bismuth (hereinafter referred to as "catalyst 1") is added, and the mixture is reacted at 70 ° C. for 3 hours to obtain monomer a1. rice field.
Table 2 shows the ratio of NCO groups of 2-acryloyloxyethyl isocyanate to OH groups of monomer a1 (index (number of NCO groups / number of OH groups)), ratio of EO units to monomer a1, and Mn. (The same applies hereinafter.).

(Production Example 2-2: Production of Monomer a2)
In Production Example 2-1 in the same manner except that 50 parts by mass of compound P1, 50 parts by mass of compound P2, and 1.32 parts by mass of AOI were used instead of 100 parts by mass of compound P1. Obtained body a2.

(Production Example 2-3: Production of Monomer b1)
To a reactor equipped with a thermometer, a stirrer and a cooling tube, 44 parts by mass of compound P5, 22 parts by mass of compound P6 and 34 parts by mass of compound P7 are added and mixed at 40 ° C., and then diisocyanate (diisocyanate) ( Add 6.78 parts by mass of D201 (isocyanate group-terminated urethane prepolymer, also referred to as "D201") and 0.02 parts by mass of dibutyltin dilaurate (hereinafter referred to as "catalyst 2"). , The reaction was started at 80 ° C. The isocyanate index was 90. The reaction caused heat generation, the internal temperature became about 80 ° C., and the viscosity also increased with time. Ethyl acetate was added at appropriate times and the mixture was kept at 80 ° C. for 7 hours while diluting to obtain a monomer b1 having an average number of hydroxyl groups of 1.68 as a uniform transparent liquid.
The average number of hydroxyl groups fn in the polymer b1 was calculated from the following formula (I).
fn = Σ (fi × Wi / Mni) / Σ (Wi / Mni) ... (I)
However, fi is the number of active hydrogens per molecule of the initiator used as the raw materials of the compounds P5, P6 and P7, Wi is the mass portion of each of the compounds P5, P6 and P7, and Mni is the respective oxyalkylene polymer. Represents Mn in.

(Production Example 2-4: Production of Monomer b2)
To a reactor equipped with a thermometer, agitator and a cooling tube, 30 parts by mass of compound P3, 40 parts by mass of compound P4 and 30 parts by mass of compound P2 are added, mixed at 40 ° C., and then D201. 4.77 parts by mass and 0.02 part by mass of dibutyltin dilaurate were added, and the reaction was started at 80 ° C. The isocyanate index was 90. The reaction caused heat generation, the internal temperature became about 80 ° C., and the viscosity also increased with time. Ethyl acetate was added at appropriate times and the mixture was kept at 80 ° C. for 7 hours while diluting to obtain a monomer b2 having an average hydroxyl group number of 1.84 as a uniform transparent liquid. The average number of hydroxyl groups of the monomer b2 was calculated in the same manner as that of the monomer b1.

[Example 1]
As shown in Table 3, 100 parts by mass of the monomer a1 and 0.3 parts by mass of the photoradical polymerization initiator (Irgacure819, manufactured by BASF, hereinafter referred to as “photoinitiator 1”) were mixed and then defoamed. The obtained preparation liquid was applied as a peelable carrier on a polyester film (peeled body, thickness 50 μm) so as to have a dry film thickness of 25 μm using a knife coater, and then an illuminance of 100 mW / cm was applied with an HgXe lamp. ^{2. The} monomer a1 was temporarily cured by irradiating with light having an integrated light amount of 250 mJ / m ^2. Subsequently, a nylon woven fabric having a thickness of 70 μm and a water permeability of 6,580 g / (m ² · day) was superposed on the obtained temporarily cured product as a support, and the illuminance was 100 mW / cm ^{2 with} an HgXe lamp from the polyester film side. It was cured by irradiating it with light having an integrated light amount of 2,750 mJ / m ² , and a patch material with a carrier was produced. Moisture permeability, adhesive strength to human skin and water resistance were evaluated for the patch from which the carrier was peeled off.
Table 3 shows the moisture permeability of the obtained patch and the pressure-sensitive adhesive layer, the adhesive strength to human skin, the evaluation result of water resistance, and the ratio of the EO unit of the pressure-sensitive adhesive layer (hereinafter, the same applies).
The moisture permeability of the pressure-sensitive adhesive layer is a calculated value obtained from the moisture permeability of the adhesive and the moisture permeability of the support by the following formula.
(1 / Moisture permeability of adhesive layer) = (1 / Moisture permeability of patch)-(1 / Moisture permeability of support)

[Example 2]
As shown in Table 3, in the same manner as in Example 1, except that 50 parts by mass of the monomer a1 and 50 parts by mass of the monomer a2 were used instead of 100 parts by mass of the monomer a1. A patch was prepared.

[Example 3]
As shown in Table 3, 100 parts by mass of the monomer b1 and 2 parts by mass of a curing agent (Coronate L, Tosoh's product name, hereinafter referred to as "hardener 1") are uniformly mixed, then defoamed and peeled off. As a possible carrier, it was applied on a peeling-treated polyester film (peeling body, thickness 50 μm) using a knife coater so as to have a dry film thickness of 25 μm, and then cured and dried at 120 ° C. for 3 minutes.
Subsequently, a nylon woven fabric having a thickness of 70 μm and a moisture permeability of 6,580 g / (m ²・ day) was layered on the cured product as a support, and then stored in a hot air dryer in an atmosphere of 50 ° C. for 3 days. The cross-linking reaction of the pressure-sensitive adhesive layer was completed to prepare a patch.

[Example 4]
As shown in Table 3, a patch was prepared in the same manner as in Example 3 except that 100 parts by mass of the monomer b2 was used instead of 100 parts by mass of the monomer b1.

Examples 1 and 2 are examples, and examples 3 and 4 are comparative examples.

The patches of Examples 1 and 2 were evaluated as "A" in both moisture permeability and water resistance, and had high moisture permeability regardless of the ethylene oxide content. The pressure-sensitive adhesive layer of Example 3 had a moisture permeability rating of "D" and was considered to be due to a low ethylene oxide content. The pressure-sensitive adhesive layer of Example 4 had a water resistance rating of "D", which was considered to be due to the high ethylene oxide content.

1 ... patch, 11 ... support, 12 ... adhesive layer, 13 ... carrier

Claims (9)

And moisture permeability 2,000g ^/ (m 2 · day) or more supports, a patch of moisture permeability and a 2,500g ^/ (m 2 · day) or more of the pressure-sensitive adhesive layer,
The pressure-sensitive adhesive layer contains a polymer having a structural unit based on a monomer having a (meth) acryloyloxy group, a urethane bond, and a linear polyoxyalkylene chain, and the polyoxyalkylene chain has a number average. A patch having a molecular weight of 1,000 or more and a content of ethylene oxide units of 50% by mass or less. The claim that the pressure-sensitive adhesive layer is located on at least a part of the surface of the support, and the moisture permeability of the portion where the support and the pressure-sensitive adhesive layer overlap is 2,000 g / (m ² · day) or more. The sticking material according to 1. The patch according to claim 1 or 2, wherein the pressure-sensitive adhesive layer has a thickness of 10 to 40 μm. The support is a film, a porous film, a woven cloth or a non-woven fabric, and the material of the support is at least one selected from ether-based urethane resin, ester-based urethane resin, polyester resin, polyamide resin, and polyolefin resin. The patch according to any one of claims 1 to 3. The patch according to any one of claims 1 to 4, wherein a carrier is provided in a peelable state on the opposite side of the surface of the pressure-sensitive adhesive layer where the support is provided. The patch according to any one of claims 1 to 5, wherein the adhesive force to human skin is 0.1 to 1.2 N / 15 mm. The patch according to any one of claims 1 to 6, which is for medical use. The patching material according to claim 7, which is a dressing material. The patch according to any one of claims 1 to 8, which is a patch that is directly applied to the skin.

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