JP2021080442A - Tacky adhesive composition and article containing adhesive layer containing the tacky adhesive composition - Google Patents

Abstract

To provide a tacky adhesive composition having excellent followability to a biological surface, and an article containing an adhesive layer containing the tacky adhesive composition.SOLUTION: A tacky adhesive composition has an acrylic triblock copolymer (I) that has two polymer blocks (A1) and (A2) composed of methacrylate units, and one polymer block (B) composed of acrylate units, and has a (A1)-(B)-(A2) block structure, the total content of the polymer blocks (A1) and (A2) being 7 mass% or more and 20 mass% or less, with a weight average molecular weight of 150,000-400,000.SELECTED DRAWING: None

Description

The present invention relates to an adhesive composition containing an acrylic block copolymer and an article containing an adhesive layer containing the adhesive composition.

Conventionally, acrylic block copolymers or compositions containing acrylic block copolymers have been studied for use as adhesives because of their excellent adhesive performance. For example, in order to obtain an adhesive with less bleeding and excellent transparency, adhesive properties, and processability, an adhesive composition obtained by combining two specific types with an acrylic triblock copolymer. It is being studied (see Patent Document 1).

Adhesives are used in a variety of applications, one example of which is a biological surface dressing (eg, a wound) that contains at least a portion of the surface in contact with the biological surface, such as skin, as an adhesive layer made of the adhesive. There is a covering material). This biological surface adhering material is required to have properties different from those of other uses, such as followability to the biological surface. For example, a viscous adhesive composition containing a specific acrylic triblock copolymer and a specific diblock copolymer, which is mainly intended to adhere to the surface of a living body, has been studied (see Patent Document 2). ).

JP-A-2018-003035 Special Table 2017-533298

However, any of the adhesive compositions described in the above patent documents has room for improvement in the ability to follow and retain the surface of the living body. An object of the present invention is an adhesive composition having excellent followability and holding power to the surface of a living body and a small amount of components transferred to the surface of the living body, and an adhesive layer containing the adhesive composition. To provide goods that include.

As a result of diligent studies by the present inventors to achieve the above object, the adhesive composition containing a specific acrylic triblock copolymer has excellent followability and holding power to the biological surface. Moreover, it was found that the amount of components transferred to the surface of the living body is small.

According to the present invention, the above object is
[1] It has two polymer blocks (A1) and (A2) composed of methacrylic acid ester units and one polymer block (B) composed of acrylic acid ester units, and (A1)-(B). -(A2) has a block structure and has a block structure
The total content of the polymer blocks (A1) and (A2) is 7% by mass or more and 20% by mass or less.
Weight average molecular weight is 150,000-400,000,
Adhesive composition containing acrylic triblock copolymer (I);
[2] It has two polymer blocks (C1) and (C2) composed of methacrylic acid ester units and one polymer block (D) composed of acrylic acid ester units, and (C1)-(D). -(C2) has a block structure and has a block structure
The total content of the polymer blocks (C1) and (C2) is 5% by mass or more and 15% by mass or less.
Weight average molecular weight is 10,000-120,000,
The adhesive composition according to [1], which further comprises an acrylic triblock copolymer (II);
[3] The adhesive composition according to [1] or [2], which further comprises a tackifier resin;
[4] The adhesive composition according to any one of [1] to [3] further containing a plasticizer;
[5] An article containing a base material and an adhesive layer composed of the adhesive composition according to any one of [1] to [4];
[6] A biological surface adhering material composed of the article according to [5];
Is achieved by providing.

According to the present invention, it is possible to obtain an adhesive composition capable of forming an adhesive layer having excellent followability and holding power to the surface of a living body and a small amount of components transferred to the surface of the living body.

Hereinafter, the present invention will be described in detail. In the present specification, "(meth) acrylic acid ester" is a general term for "methacrylic acid ester" and "acrylic acid ester", and "(meth) acrylic" is a general term for "methacrylic acid" and "acrylic". It is a generic term.

(Acrylic triblock copolymer (I))
The acrylic triblock copolymer (I) contained in the adhesive composition of the present invention is composed of two polymer blocks (A1) and (A2) composed of methacrylic acid ester units and an acrylic acid ester unit. It has one polymer block (B) and has a (A1)-(B)-(A2) block structure.
The total content of the polymer blocks (A1) and (A2) is 7% by mass or more and 20% by mass or less.
The weight average molecular weight is 150,000 to 400,000.

(Polymer blocks (A1) and (A2))
The acrylic triblock copolymer (I) has a polymer block composed of two methacrylic acid ester units (A1) and (A2).

Examples of the methacrylic acid ester that is a constituent unit of the polymer blocks (A1) and (A2) include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, and methacrylic acid. Isobutyl, sec-butyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, methacrylic acid Non-functional methacrylic acid esters such as isobornyl, phenyl methacrylate, benzyl methacrylate; methoxyethyl methacrylate, ethoxyethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, 2-aminoethyl methacrylate , Methacrylic acid esters having functional groups such as glycidyl methacrylate and tetrahydrofurfuryl methacrylate.

Among these, methacrylic acid ester having no functional group is preferable from the viewpoint of improving the heat resistance and durability of the obtained polymer, and methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, etc. Isobornyl methacrylate and phenyl methacrylate are more preferable, and methyl methacrylate is further preferable because the phase separation between the polymer blocks (A1) and (A2) and the polymer block (B) becomes clearer and the cohesive force becomes higher. .. The polymer blocks (A1) and (A2) may be composed of one kind of these methacrylic acid esters, or may be composed of two or more kinds. Further, the acrylic triblock copolymer (I) has two polymer blocks (A1) and (A2) as polymer blocks composed of methacrylic acid ester units, and these polymer blocks (A1) and The methacrylic acid esters constituting (A2) may be the same or different. The proportion of the methacrylic acid ester unit contained in the polymer blocks (A1) and (A2) is preferably 60% by mass or more in each of the polymer blocks (A1) and (A2), and is 80%. By mass% or more is more preferable, 90% by mass or more is further preferable, and 95% by mass or more is further preferable. Further, the ratio of the methacrylic acid ester units of the polymer blocks (A1) and (A2) may be 100% by mass.

The stereoregularity of the methacrylic acid ester units contained in the polymer blocks (A1) and (A2) composed of the methacrylic acid ester units may be the same or different from each other.

In the acrylic triblock copolymer (I), the total content of the polymer blocks (A1) and (A2) is 20% by mass or less, preferably 19% by mass or less, and preferably 18% by mass or less. More preferably, it is more preferably 17% by mass or less. The total content of the polymer blocks (A1) and (A2) is 7% by mass or more, more preferably 8% by mass or more. When the total content of the polymer blocks (A1) and (A2) is within the above range, excellent adhesion is achieved when the acrylic triblock copolymer (I) is contained in the adhesive composition. It is possible to produce an adhesive layer that not only has adhesion characteristics but also has excellent followability to the surface of a living body. Further, the contents of the polymer blocks (A1) and (A2) contained in the acrylic triblock copolymer (I) may be the same or different.

In the acrylic triblock copolymer (I), the weight average molecular weights of the polymer blocks (A1) and (A2) are preferably 3,000 or more, and more preferably 5,000 or more. The weight average molecular weight of each of the polymer blocks (A1) and (A2) is preferably 30,000 or less, more preferably 25,000 or less.
When the weight average molecular weights of the polymer blocks (A1) and (A2) are within the above ranges, when the acrylic triblock copolymer (I) is contained in the adhesive composition, it is produced at the time of production. While maintaining excellent handleability, it exhibits excellent cohesive force and improves holding power. In addition, the tack and adhesive strength are further improved. In addition, the holding power of the adhesive composition tends to be more excellent. Further, the weight average molecular weights of the polymer blocks (A1) and (A2) contained in the acrylic triblock copolymer (I) may be the same or different.

The glass transition temperature of each of the polymer blocks (A1) and (A2) is preferably 60 to 140 ° C, more preferably 70 to 130 ° C, and even more preferably 80 to 130 ° C. When the glass transition temperature is in this range, the polymer blocks (A1) and (A2) act as physical pseudo-crosslink points at the normal operating temperature of the adhesive, so that cohesive force is developed and the adhesive becomes viscous. When contained in an adhesive composition, it has excellent adhesive properties, durability, heat resistance, and the like. The glass transition temperature in the present specification is the extrapolation start temperature of the curve obtained by DSC measurement.

The glass transition temperatures of the polymer blocks (A1) and (A2) may be the same or different. Even when the glass transition temperatures of the polymer blocks (A1) and (A2) are different, it is preferable that the glass transition temperatures of both polymer blocks are in the above range.

(Polymer block (B))
The acrylic triblock copolymer (I) has one polymer block (B) composed of acrylic acid ester units.

Examples of the acrylic acid ester serving as a constituent unit of the polymer block (B) include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, and acrylate. sec-butyl, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, isobornyl acrylate, acrylate Acrylic acid esters without functional groups such as lauryl, octadecyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate; methoxyethyl acrylate, ethoxyethyl acrylate, 2-hydroxyethyl acrylate, 2 acrylate -Acrylic acid esters having a functional group such as aminoethyl, glycidyl acrylate, tetrahydrofurfuryl acrylate, diethylaminoethyl acrylate, and phenoxyethyl acrylate can be mentioned.

Among these, from the viewpoint of transparency and flexibility when prepared as an adhesive composition, the general formula CH ₂ = CH-COOR ¹ (in the formula, R ¹ represents an organic group having 1 to 10 carbon atoms). The acrylic acid ester represented by is more preferable, and the phase separation between the polymer blocks (A1) and (A2) and the polymer block (B) becomes clear, and the adhesive composition exhibits high cohesiveness. Methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, acrylate Non-functional acrylic acids such as n-hexyl, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, isobornyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate. Esters are even more preferred. Methyl acrylate, n-butyl acrylate, acrylic from the viewpoint that the adhesive composition has appropriate adhesiveness at room temperature and exhibits stable adhesive force under a wide temperature range and a wide peeling speed condition. At least one selected from 2-ethylhexyl acrylate, n-octyl acrylate and isooctyl acrylate is even more preferred, and n-butyl acrylate, 2-ethylhexyl acrylate are particularly preferred.

The polymer block (B) may be composed of one kind of these acrylic acid esters, or may be composed of two or more kinds. The proportion of the acrylic acid ester unit contained in the polymer block (B) is preferably 60% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, still more preferably 95% by mass or more. Moreover, the ratio of the acrylic acid ester unit of the polymer block (B) may be 100% by mass.

In the acrylic triblock copolymer (I), the content of the polymer block (B) is usually 80% by mass or more, preferably 81% by mass or more, and more preferably 82% by mass or more. It is preferably 83% by mass or more, and more preferably 83% by mass or more. The content of the polymer block (B) is usually 93% by mass or less, preferably 92% by mass or less. When the content of the polymer block (B) is within the above range, not only the adhesive performance is excellent when the acrylic triblock copolymer (I) is used in the adhesive composition, but also the adhesive performance is excellent. An adhesive layer having excellent followability to the surface of a living body can be obtained.

The glass transition temperature of the polymer block (B) is preferably −100 to 30 ° C., more preferably −80 to 10 ° C., and even more preferably −70 to 0 ° C. When the glass transition temperature is in this range, excellent tack and adhesive strength can be exhibited when used in an adhesive composition.

The polymer blocks (A1) and (A2) and the polymer block (B) may contain each other's monomer components as long as the effects of the present invention are not impaired. For example, it may have a tapered structure at the boundary between the polymer block (A1) or (A2) and the polymer block (B). Further, the polymer block (A1) or (A2) and the polymer block (B) may not contain each other's monomer components.

Further, the polymer blocks (A1) and (A2) and the polymer block (B) may contain other monomer units, if necessary. Examples of such other monomers include vinyl-based monomers having a carboxyl group such as (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, and fumaric acid; (meth) acrylamide, (meth) acrylonitrile, and the like. Vinyl-based monomers having functional groups such as vinyl acetate, vinyl chloride, vinylidene chloride; aromatic vinyl-based monomers such as styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene; butadiene, isoprene, etc. Conjugate diene-based monomers; olefin-based monomers such as ethylene, propylene, isobutene, and octene; lactone-based monomers such as ε-caprolactone and valerolactone. When each polymer block contains these other monomers, the content thereof is preferably 20% by mass or less, more preferably 10% by mass, based on the total mass of the monomers constituting each polymer block. % Or less, more preferably 5% by mass or less.

The acrylic triblock copolymer (I) has a (A1)-(B)-(A2) block structure in which the polymer block (A1), the polymer block (B), and the polymer block (A2) are bonded in this order. Has. When the acrylic triblock copolymer (I) having such a structure is contained in the adhesive composition, the adhesive strength, holding power, and cohesive power tend to be excellent.

The weight average molecular weight of the acrylic triblock copolymer (I) is 150,000 to 400,000. From the viewpoint of adhesive performance, particularly high holding power, it is preferably 170,000 to 380,000, more preferably 180,000 to 360,000, and 190,000 to 340,000. Is even more preferable. If the weight average molecular weight of the acrylic triblock copolymer (I) is less than 150,000, the adhesive performance, particularly the holding power, may be inferior. Further, if the weight average molecular weight exceeds 400,000, the handleability at the time of manufacturing may be inferior.

The molecular weight distribution (Mw / Mn) of the acrylic triblock copolymer (I) is preferably 1.0 to 1.5, and 1.0 to 1.4 is a component transferred to the biological surface. It is more preferable from the viewpoint that the amount can be easily reduced. The weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present specification are the standard polystyrene-equivalent weight average molecular weight and the number average molecular weight obtained by gel permeation chromatography (GPC) measurement.

(Acrylic triblock copolymer (II))
In the adhesive composition of the present invention, in addition to the acrylic triblock copolymer (I), at least two polymer blocks (C1) and (C2) composed of methacrylic acid ester units and acrylic acid It has at least one polymer block (D) composed of ester units, and has a (C1)-(D)-(C2) block structure.
The total content of the polymer blocks (C1) and (C2) is 5% by mass or more and 15% by mass or less.
Weight average molecular weight is 10,000-120,000,
Acrylic triblock copolymer (II) may be contained.

(Polymer blocks (C1) and (C2))
The acrylic triblock copolymer (II) has a polymer block composed of two methacrylic acid ester units (C1) and (C2).

Specific examples of the methacrylic acid ester that is the constituent unit of the polymer blocks (C1) and (C2) are the constituent units of the polymer blocks (A1) and (A2) of the acrylic triblock copolymer (I). Similar to methacrylic acid ester.

Among these, methacrylic acid ester having no functional group is preferable from the viewpoint of improving the heat resistance and durability of the obtained polymer, and methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, etc. Isobornyl methacrylate and phenyl methacrylate are more preferable, and methyl methacrylate is further preferable because the phase separation between the polymer blocks (C1) and (C2) and the polymer block (D) becomes clearer and the cohesive force becomes higher. .. The polymer blocks (C1) and (C2) may be composed of one kind of these methacrylic acid esters, or may be composed of two or more kinds. The proportion of the methacrylic acid ester unit contained in the polymer blocks (C1) and (C2) is preferably 60% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and 95% by mass or more. Even more preferable. Further, the ratio of the methacrylic acid ester units of the polymer blocks (C1) and (C2) may be 100% by mass.

In the acrylic triblock copolymer (II), the total content of the polymer blocks (C1) and (C2) is 15% by mass or less, preferably 12% by mass or less, and 10% by mass or less. Is more preferable. The content of the polymer blocks (C1) and (C2) is 5% by mass or more, preferably 6% by mass or more. When the total content of the polymer blocks (C1) and (C2) is within the above range, the holding power is impaired when the acrylic triblock copolymer (II) is contained in the adhesive composition. Instead, it tends to have better tackiness and workability, and better followability to the surface of the living body.

The glass transition temperature of the polymer blocks (C1) and (C2) is preferably 60 to 140 ° C, more preferably 70 to 130 ° C, and even more preferably 80 to 130 ° C. When the glass transition temperature is in this range, the polymer blocks (C1) and (C2) act as physical pseudo-crosslink points at the normal operating temperature of the adhesive, so that cohesive force is developed and the adhesive becomes viscous. When contained in an adhesive composition, it has excellent adhesive properties, durability, heat resistance, and the like.

Further, it is preferable that the acrylic triblock copolymer (II) has polymer blocks (C1) and (C2) having different weight average molecular weights. In this case, the weight average molecular weight of at least one of the polymer blocks (C1) and (C2) is 300 or more and less than 3,000. Further, it is preferably 500 or more and less than 3,000. When the weight average molecular weight of at least one of the polymer blocks (C1) and (C2) is 300 or more, the obtained acrylic triblock copolymer (II) tends to have excellent cohesive power. Further, when the weight average molecular weight of at least one of the polymer blocks (C1) and (C2) is less than 3,000, the melt viscosity of the obtained acrylic triblock copolymer (II) becomes low, and the melt viscosity becomes low. It tends to be excellent in productivity when producing a viscous adhesive composition.

Among the block structures (C1)-(D)-(C2), the weight average molecular weight of the polymer block (C2) is preferably 300 or more and less than 3,000, and more preferably 500 or more and 2,000 or less. preferable. Further, the weight average molecular weight of the polymer block (C1) is preferably 3,000 or more and 10,000 or less, and more preferably 3,000 or more and 7,000 or less. Within the above range, not only the viscosity, cohesive force and handleability at the time of manufacture are excellent, but also the amount of components transferred to the surface of the living body tends to be easily reduced.

The stereoregularity of the methacrylic acid ester units contained in the polymer blocks (C1) and (C2) may be the same or different from each other.

(Polymer block (D))
The acrylic triblock copolymer (II) has one polymer block (D) composed of acrylic acid ester units.

Specific examples of the acrylic acid ester that is the constituent unit of the polymer block (D) are the same as those of the acrylic acid ester that is the constituent unit of the polymer block (B) of the acrylic triblock copolymer (I).

Among these, from the viewpoint of transparency and flexibility when prepared as an adhesive composition, the general formula CH ₂ = CH-COOR ¹ (in the formula, R ¹ represents an organic group having 1 to 10 carbon atoms). The acrylic acid ester represented by is more preferable, and the acrylic acid is acrylic because the phase separation between the polymer blocks (C1) and (C2) and the polymer block (D) becomes clear and the adhesive composition exhibits high cohesiveness. Methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n acrylate -Hexyl, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, isobornyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, etc. Is even more preferable. Methyl acrylate, n-butyl acrylate, acrylic from the viewpoint that the adhesive composition has appropriate adhesiveness at room temperature and exhibits stable adhesive force under a wide temperature range and a wide peeling speed condition. At least one selected from 2-ethylhexyl acid acid, n-octyl acrylate and isooctyl acrylate is even more preferable, and n-butyl acrylate is particularly preferable.

The polymer block (D) may be composed of one kind of these acrylic acid esters, or may be composed of two or more kinds. The proportion of the acrylic acid ester unit contained in the polymer block (D) is preferably 60% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, still more preferably 95% by mass or more. Moreover, the ratio of the acrylic acid ester unit of the polymer block (D) may be 100% by mass.

In the acrylic triblock copolymer (II), the content of the polymer block (D) is usually 85% by mass or more, preferably 88% by mass or more, and more preferably 90% by mass or more. preferable. The content of the polymer block (D) is usually 95% by mass or less, preferably 94% by mass or less. When the content of the polymer block (D) is within the above range, when the acrylic triblock copolymer (II) is contained in the adhesive composition, the tacking force is not impaired without impairing the holding power. A viscous adhesive layer having improved workability and excellent followability to the surface of a living body can be obtained.

The glass transition temperature of the polymer block (D) is preferably −100 to 30 ° C., more preferably −80 to 10 ° C., and even more preferably −70 to 0 ° C. When the glass transition temperature is in this range, excellent tack and adhesive strength can be exhibited when used in an adhesive composition.

The polymer blocks (C1) and (C2) and the polymer block (D) may contain each other's monomer components as long as the effects of the present invention are not impaired. For example, it may have a tapered structure at the boundary between the polymer block (C1) or (C2) and the polymer block (D). Further, the polymer block (C1) or (C2) and the polymer block (D) may not contain each other's monomer components.

Further, the polymer blocks (C1) and (C2) and the polymer block (D) may contain other monomer units, if necessary. Specific examples of such other monomers include other simples contained in the polymer blocks (A1) and (A2) of the acrylic triblock copolymer (I) and the polymer block (B) as necessary. Similar to other monomers exemplified as used for polymer units. When each polymer block contains these other monomers, the content thereof is preferably 20% by mass or less, more preferably 10% by mass, based on the total mass of the monomers constituting each polymer block. % Or less, more preferably 5% by mass or less.

The acrylic triblock copolymer (II) has a (C1)-(D)-(C2) block structure in which the polymer block (C1), the polymer block (D), and the polymer block (C2) are bonded in this order. Has. When the acrylic triblock copolymer (II) having such a structure is contained in the adhesive composition, the tackiness and processability tend to be further improved, and the ability to follow the surface of the living body is more excellent.

The weight average molecular weight of the acrylic triblock copolymer (II) is 10,000 to 120,000. From the viewpoint of cohesive force and handleability at the time of manufacture, it is preferably 20,000 to 110,000, more preferably 25,000 to 100,000, and 30,000 to 90,000. Is even more preferable. When contained in the adhesive composition, if the weight average molecular weight of the acrylic triblock copolymer (II) is less than 10,000, the cohesive force may be inferior. Further, if the weight average molecular weight exceeds 120,000, the handleability at the time of production and the followability to the surface of the living body may be impaired.

The molecular weight distribution of the acrylic triblock copolymer (II) is preferably 1.0 to 1.5, and 1.0 to 1.4 tends to reduce the amount of components transferred to the biological surface. From the point of view, it is more preferable.

The acrylic triblock copolymer (II) preferably has a melt viscosity at 100 ° C. of 100,000 mPa · s or less as measured by a B-type viscometer. The melt viscosity is preferably 1,000 mPa · s or more and 100,000 mPa · s or less, and more preferably 5,000 mPa · s or more and 100,000 mPa · s or less. By having such a melt viscosity, the acrylic triblock copolymer (II) has a property of having low fluidity rather than a solid state at room temperature (about 25 ° C.), and when added to the adhesive composition. It tends to be excellent in workability.

When the adhesive composition of the present invention contains an acrylic triblock copolymer (II), the mass ratio of the acrylic triblock copolymer (I) to the acrylic triblock copolymer (II). Is not particularly limited, but in order to have a good balance of adhesive strength, cohesive strength, and adhesive properties, acrylic triblock copolymer (I): acrylic triblock copolymer (II) = 100 :. It is preferably 1 to 100: 300, more preferably 100: 2 to 100: 200, and even more preferably 100: 3 to 100: 100.

The method for producing the acrylic triblock copolymer (I) and the acrylic triblock copolymer (II) is not particularly limited as long as a polymer satisfying the conditions of the present invention regarding the chemical structure can be obtained. , A method according to a known method can be adopted. Generally, as a method of obtaining a block copolymer having a narrow molecular weight distribution, a method of living-polymerizing a monomer as a constituent unit is adopted. Examples of such a living polymerization method include a method of living polymerization using an organic rare earth metal complex as a polymerization initiator (see JP-A-06-93060), and an alkali metal or alkaline soil using an organic alkali metal compound as a polymerization initiator. A method of living anion polymerization in the presence of a mineral acid such as a salt of a similar metal (see Japanese Patent Application Laid-Open No. 05-507737), living anion polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organic aluminum compound. (Refer to JP-A-11-335432), Atom Transfer Radical Polymerization Method (ATRP) (Macromolecular Chemistry and Physics, 2000, Vol. 201, p. 1108 to 1114) and the like. The molecular weight distribution of the copolymer obtained by living-aon polymerization tends to have a sharper peak than the molecular weight distribution of the polymer obtained by free radical polymerization, and it tends to be easy to complete the polymerization of all the monomers to the end. Therefore, it is difficult for unreacted monomer raw materials to remain in the block copolymer of acrylic monomer.

Among the above production methods, the method of living anionic polymerization using an organoalkali metal compound as a polymerization initiator in the presence of an organoaluminum compound results in high transparency of the obtained block copolymer, a small amount of residual monomers, and an odor. It is preferable because it can suppress the generation of air bubbles after bonding when it is used as an adhesive composition. Further, it is preferable from the viewpoint that the amount of the component transferred to the surface of the living body can be easily reduced. Furthermore, the molecular structure of the methacrylic acid ester polymer block becomes highly syndiotactic, which has the effect of increasing the heat resistance of the adhesive composition, and can be industrially polymerized in the living room under relatively mild temperature conditions. It is also preferable in that the environmental load (mainly the power required for the refrigerator for controlling the polymerization temperature) is small in the case of production.

Examples of the organoaluminum compound include the following general formula (1).
AlR ² R ³ R ⁴ (1)
(In the formula (1), R ² , R ³ and R ⁴ each have an alkyl group which may independently have a substituent, a cycloalkyl group which may have a substituent, and a substituent. Table represents an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, or an N, N-disubstituted amino group. Or, R ² is one of the groups described above, and R ³ and R ⁴ together form an allylene oxy group which may have a substituent.) Examples include aluminum compounds.

The organoaluminum compound represented by the general formula (1) is isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) from the viewpoint of high living property of polymerization and ease of handling. Aluminum, isobutylbis (2,6-di-tert-butylphenoxy) aluminum, isobutyl [2,2'-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum and the like are preferable.

Examples of the organic alkali metal compound include alkyllithium and alkyldilithium such as n-butyllithium, sec-butyllithium, isobutyllithium, tert-butyllithium, n-pentyllithium and tetramethylenedilithium; phenyllithium, p. -Aryllithium and aryldilithium such as trilllithium and lithium naphthalene; aralkyllithium and aralkyldilithium such as dilithium produced by the reaction of benzyllithium, diphenylmethyllithium, diisopropenylbenzene and butyllithium; lithium such as lithiumdimethylamide Amid; Examples thereof include lithium alkoxides such as methoxylithium and ethoxylithium. These may be used alone or in combination of two or more. Of these, alkyllithium is preferable because of its high polymerization initiation efficiency, and tert-butyllithium and sec-butyllithium are more preferable, and sec-butyllithium is even more preferable.

The living anionic polymerization is usually carried out in the presence of a solvent that is inert to the polymerization reaction. Examples of the solvent include aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chloroform, methylene chloride and carbon tetrachloride; ethers such as tetrahydrofuran and diethyl ether, and toluene is preferably used.

The block copolymer is, for example, a step of forming a desired polymer block (polymer block (A1), polymer block (B), etc.) at a desired living polymer terminal obtained by polymerizing a monomer. It can be produced by stopping the polymerization reaction after repeating the process a desired number of times. Specifically, for example, in the presence of an organic aluminum compound, the first step and the second polymer block for polymerizing the monomer forming the first polymer block with a polymerization initiator composed of an organic alkali metal compound are used. The active terminal of the obtained polymer is subjected to a multi-step polymerization step including a second step of polymerizing the polymer to be formed and a third step of polymerizing the monomer forming the third polymer block. The acrylic triblock copolymer (I) and the acrylic triblock copolymer (II) can be produced by reacting with alcohol or the like to stop the polymerization reaction. According to the above method, a triblock copolymer composed of a polymer block (A1) -polymer block (B) -polymer block (A2), a polymer block (C1) -polymer block (D) -A triblock copolymer composed of a polymer block (C2) can be produced.

The polymerization temperature is 0 to 100 ° C. when forming the polymer blocks (A1), (A2) and (C1), (C2), and −50 when forming the polymer blocks (B) and (D). ~ 50 ° C. is preferable. When the polymerization temperature is lower than the above range, the progress of the reaction is slowed down, and it takes a long time to complete the reaction. On the other hand, when the polymerization temperature is higher than the above range, the deactivation of the living polymer terminal increases, the molecular weight distribution becomes wide, and a desired block copolymer cannot be obtained. In addition, each polymer block can be polymerized in the range of 1 second to 20 hours.

(Adhesive-imparting resin)
The adhesive composition of the present invention may contain a tackifier resin. By including the tackifier resin in the adhesive composition of the present invention, the adhesiveness, tackiness and compatibility are improved.

As the tackifier resin that can be blended in the pressure-sensitive adhesive composition of the present invention, any of the pressure-sensitive adhesive resins conventionally used in the pressure-sensitive adhesive can be used. Examples of the tackifying resin include rosin-based resins (rosin, rosin derivatives, hydrogenated rosin derivatives, etc.), terpene-based resins, terpene phenol-based resins, (hydrogenated) petroleum-based resins, styrene-based resins, xylene-based resins, and hydrogen. Examples thereof include chemical aromatic copolymers, phenolic resins, and kumaron-indene resins.

In the present invention, the rosin-based resin is an amber-colored, amorphous natural resin obtained from pine, and its main component is a mixture of abietic acid and its isomers. Further, the rosin-based resin also includes those modified by esterification, polymerization, hydrogenation (hereinafter, also referred to as hydrogenation) or the like by utilizing the reactivity of this abietic acid or its isomer. Examples of the rosin-based resin include unmodified rosins (for example, tall rosins, gum rosins, and wood rosins), polymerized rosins, disproportionated rosins, hydrogenated rosins, maleic acid-modified rosins, fumaric acid-modified rosins, and esters thereof (eg, For example, glycerin ester, pentaerythritol ester, methyl ester, ethyl ester, butyl ester, ethylene glycol ester, etc.) and those further modified by hydrogenation and the like can be mentioned. Among these, hydrogenated rosin ester is preferable from the viewpoint of heat resistance and color resistance.

In the present invention, the terpene-based resin is an oligomer obtained by polymerizing a raw material containing a terpene-based monomer. Further, the terpene-based resin also includes an oligomer obtained by modifying the oligomer obtained in this manner by hydrogenation or the like. Terpenes generally mean polymers of isoprene (C ₅ H ₈ ) and are classified into _{monoterpenes (C 10} H ₁₆ ), sesquiterpenes (C ₁₅ H ₂₄ ), diterpenes (C ₂₀ H _{32), etc.} To. The terpene-based monomer is a monomer having these as a basic skeleton, and is, for example, α-pinene, β-pinene, dipentene, limonene, myrcene, aloosimene, osimene, α-ferrandrain, α-terpinene, γ. -Terpinene, terpinene, 1,8-cineole, 1,4-cineole, α-terpineneol, β-terpineneol, γ-terpineneol, sabinene, paramentadiens, curenes and the like can be mentioned. Further, the raw material containing terpene monomer, terpene monomer and other copolymerizable monomers, for example coumarone based monomers such as benzofuran (C ₈ H ₆ O); styrene, alpha- Vinyl aromatic compounds such as methylstyrene, vinyltoluene, divinyltoluene, 2-phenyl-2-butene; phenol, cresol, xylenol, propylphenol, norylphenol, hydroquinone, resorcin, methoxyphenol, bromophenol, bisphenol A, bisphenol F Phenolic monomers and the like may be contained. Examples of the oligomer obtained by polymerizing a raw material containing another monomer copolymerizable with the terpene-based monomer include a terpene phenol-based resin and the like. In addition, the oligomer obtained in this way modified by hydrogenation or the like is also included in the terpene resin.

In the present invention, the (hydrogenated) petroleum-based resin is composed of a C ₅ fraction, a C ₉ fraction, _{a purified component of the C 5} fraction, a purified component of the C ₉ fraction, or a mixture of these fractions or purified components. It is an oligomer obtained by polymerizing a raw material. Further, the oligomer obtained in this manner modified by hydrogenation or the like is also included in the above (hydrogenated) petroleum-based resin. Note that the C ₅ fraction, typically, cyclopentadiene, dicyclopentadiene, isoprene, 1,3-pentadiene, 2-methyl-1-butene, 2-methyl-2-butene, 1-pentene, 2-pentene and Cyclopentene and the like are included, and the C ₉ distillate usually contains styrene, allylbenzene, α-methylstyrene, vinyltoluene, β-methylstyrene, indene and the like. In addition, the C ₉ fraction may contain a small amount of the C ₈ fraction and the C _{10 fraction.}

The (hydrogenated) petroleum resin, C ₅ fraction or a C ₅ resin purified components were the raw material, C ₉ fraction or C ₉ resins the purified components to the raw material, C ₅ fraction or purified components thereof the mixture of the C ₉ fraction or a purified component was the raw material is roughly classified into C ₅ -C ₉ copolymer resin. Among these, hydrogenated petroleum-based resins are preferably used from the viewpoint of heat resistance and color resistance.

In the present invention, the aromatic hydrocarbon-based resins such as styrene-based resin, xylene-based resin, hydrogenated aromatic copolymer, and phenol-based resin are, for example, styrene, α-methylstyrene, vinyltoluene, β-methylstyrene, and divinyltoluene. , 2-Phenyl-2-butene, methoxystyrene, t-butylstyrene, chlorostyrene, inden, methylinden, phenol, cresol, xylenol, propylphenol, norylphenol, hydroquinone, resorcin, methoxyphenol, bromophenol, bisphenol A, It is an oligomer obtained by polymerizing a raw material composed of bisphenol F or a mixture thereof. Further, the oligomer obtained in this manner modified by hydrogenation or the like is also included. In addition, Kumaron-inden resin and the like can also be mentioned. Among these, styrene-based resins are preferably used from the viewpoints of compatibility, heat resistance, and color resistance.

These tackifier resins may be contained alone or in combination of two or more. When two or more kinds of these tackifier resins are contained, it is desirable from the viewpoint of excellent adhesive strength and tack balance. The softening point of the tackifier resin is preferably 50 to 160 ° C. from the viewpoint of exhibiting high adhesive strength.

The content of the tackifying resin may be appropriately set according to the intended use, etc., but it is a viscous adhesive layer having high adhesive strength, tackiness and cohesive strength, and high followability and holding power to the biological surface. From the viewpoint of obtaining 100 parts by mass, the amount is preferably 1 to 180 parts by mass, more preferably 2 to 100 parts by mass, and 4 to 80 parts by mass with respect to 100 parts by mass of the acrylic triblock copolymer (I). Is more preferable.

When the tackifier resin is a terpene resin composed of only (hydrogenated) petroleum resin and terpene monomer, it is difficult to increase the content from the viewpoint of compatibility with acrylic triblock copolymers. There is a tendency. From the viewpoint of adhesive strength, tack and cohesive strength, and compatibility, the content of the tackifier resin is preferably 2 to 40 parts by mass with respect to 100 parts by mass of the acrylic triblock copolymer (I). , 2 to 30 parts by mass, more preferably.

(Plasticizer)
The adhesive composition of the present invention may contain a plasticizer. By containing a plasticizer in the adhesive composition of the present invention, an adhesive composition having an excellent balance between adhesive strength and tack can be obtained, and more generally, the adhesive composition as a whole can be obtained. Cost can be reduced.

Examples of such plasticizers include phthalates such as dibutylphthalate, din-octylphthalate, bis (2-ethylhexyl) phthalate, bis (2-ethylhexyl) terephthalate, din-decylphthalate, and diisodecylphthalate; Adiponic acid esters such as bis (2-ethylhexyl) adipate, diisodecyl adipate, din-octyl adipate; sebacic acid esters such as bis (2-ethylhexyl) sebacate, din-butyl sebacate; bis (2-ethylhexyl) azelate, etc. Azelaic acid esters; citrate esters such as tributyl acetyl citrate; paraffins such as chlorinated paraffins; glycols such as polypropylene glycol; epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; trioctyl Phthalate esters such as phosphate and triphenyl phosphate; subphosphate esters such as triphenyl phosphite; esterified products of adipic acid and 1,3-butylene glycol, esterified products of benzoic acid and dipropylene glycol, etc. Classes; sugar derivatives such as sculose isobutyrate; low molecular weight polymers such as low molecular weight polybutene, low molecular weight polyisobutylene, low molecular weight polyisoprene; acrylic oligomers such as n-butyl polyacrylate and 2-ethylhexyl polyacrylate; Diana Paraffin-based oils such as process oil PW series (manufactured by Idemitsu Kosan Co., Ltd.), SUNPURE LW70 and P series (manufactured by Nippon Sun Oil Co., Ltd.); Oil: Aroma-based oils such as JSO AROMA790 (manufactured by Nippon Sun Oil Co., Ltd.) and Vivatec500 (manufactured by H & R) can be mentioned. These plasticizers may be contained alone or in combination of two or more.

The content of the plasticizer may be appropriately set according to the intended use, etc., but a viscous adhesive composition having no bleeding and excellent transparency can be obtained, and the viscous property has high followability and holding power to the biological surface. From the viewpoint of obtaining an adhesive layer, the amount is preferably 1 to 40 parts by mass and more preferably 1 to 25 parts by mass with respect to 100 parts by mass of the acrylic triblock copolymer (I).

The adhesive composition of the present invention contains other polymers, softeners, heat stabilizers, light stabilizers, antistatic agents, flame retardants, foaming agents, colorants, as long as the effects of the present invention are not impaired. Additives such as a dye, a refractive index adjuster, a filler, a curing agent, and an antistatic agent may be contained. These other polymers and additives may be contained alone or in combination of two or more.

Other polymers include, for example, acrylic resins such as polymethyl methacrylate and (meth) acrylic acid ester copolymers (excluding acrylic triblock copolymers (I) and (II)); polyethylene, ethylene. -Olefin resins such as vinyl acetate copolymer, polypropylene, polybutene-1, poly-4-methylpentene-1, polynorbornene; ethylene ionomer; polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, AS Sterite resins such as resins, ABS resins, AES resins, AAS resins, ACS resins, MBS resins; styrene-methyl methacrylate copolymers; polyesters such as polyethylene terephthalate, polybutylene terephthalate, polylactic acid; nylon 6, nylon 66, Polyamide such as polyamide elastomer; polycarbonate; polyvinyl chloride; polyvinylidene chloride; polyvinyl alcohol; ethylene-vinyl alcohol copolymer; polyacetal; vinylidene fluoride; polyurethane; modified polyphenylene ether; polyphenylene sulfide; silicone rubber modified resin; acrylic rubber Silicon-based rubbers; styrene-based thermoplastic polymers such as SEPS, SEBS, and SIS; olefin-based rubbers such as IR, EPR, and EPDM. Among these, from the viewpoint of compatibility with the acrylic triblock copolymer (I) contained in the adhesive composition, acrylic resins (acrylic triblock copolymer (I) and (II). ), Ethylene-vinyl acetate copolymer, AS resin, polylactic acid, polyvinylidene fluoride and styrene-based thermoplastic elastomer are preferable, and (meth) acrylic acid ester copolymer (acrylic triblock copolymer (I)). ) And (II) are excluded) are more preferable.

Examples of the filler include inorganic fibers such as glass fiber and carbon fiber, and organic fibers; inorganic fillers such as calcium carbonate, talc, titanium oxide, silica, clay, barium sulfate, and magnesium carbonate; carbon black and the like. .. The inclusion of these fillers imparts durability, heat resistance and weather resistance to the resulting adhesive composition.

When the adhesive composition of the present invention contains an anti-adhesive agent, improvement in handleability may be expected. Examples of the anti-sticking agent include fatty acids such as stearic acid and palmitic acid; fatty acid metal salts such as calcium stearate, zinc stearate, magnesium stearate, potassium palmitate, and sodium palmitate; polyethylene wax, polypropylene wax, and montanic acid. Waxes such as waxes; low molecular weight polyolefins such as low molecular weight polyethylene and low molecular weight polypropylene; acrylic resin powders; polyorganosiloxanes such as dimethylpolysiloxane; octadecylamine, alkyl phosphate, fatty acid esters, ethylene bisstearylamide, etc. Examples thereof include amide-based resin powder, fluororesin powder such as ethylene tetrafluoride resin, molybdenum disulfide powder, silicone resin powder, silicone rubber powder, and silica.

The method for producing the adhesive composition of the present invention is not particularly limited, and for example, each component is usually mixed or kneaded using a known mixing or kneading device such as a kneader ruder, an extruder, a mixing roll, and a Banbury mixer. It can be manufactured by mixing at a temperature in the range of ~ 250 ° C. Further, it may be produced by dissolving each component in an organic solvent, mixing the components, and then distilling off the organic solvent. The obtained adhesive composition can be used by being melted by heating, or may be dissolved in a solvent and used as a solution type adhesive. Examples of the solvent include toluene, ethyl acetate, ethylbenzene, methylene chloride, chloroform, tetrahydrofuran, methyl ethyl ketone, dimethyl sulfoxide, toluene-ethanol mixed solvent and the like. Of these, toluene, ethylbenzene, ethyl acetate and methyl ethyl ketone are preferable.
When the adhesive composition of the present invention is used by heating and melting, it is preferable that the melt viscosity is low from the viewpoint of processability and handleability. On the other hand, from the viewpoint of achieving both the adhesive properties of the adhesive composition and high holding power (creep resistance), it is preferable that the melt viscosity is high.

The adhesive composition of the present invention is preferably used in the form of an article (for example, a laminated body such as a laminated film or a laminated sheet) containing a base material and an adhesive layer composed of the adhesive composition. ..

In order to form the adhesive layer, when the adhesive composition of the present invention is used by heating and melting, for example, a hot melt coating method, a T-die method, an inflation method, a calendar molding method, a lamination method and the like are used. It can be used to form a sheet or film. For example, a viscous adhesive layer can be formed by melt-coating a heat-melted adhesive composition on a film or sheet of a heat-resistant material such as polyethylene terephthalate using, for example, a hot melt coater. When the melt viscosity of the adhesive composition of the present invention is high, for example, when the melt viscosity at 180 ° C. exceeds 20,000 mPa · s, it is heated and melted at a higher temperature, so that the T-die is used. A hot melt coating method in which the heated melt is applied onto the substrate in a non-contact manner is preferable from the viewpoint of controlling the thickness of the adhesive layer, homogeneity, and the heat resistance required for the substrate.

When the adhesive composition of the present invention is dissolved in a solvent and used, for example, a heat-resistant material such as polyethylene terephthalate or a flat plate or roll such as a steel belt is used as a base material, and a bar coater or a roll is used on the flat plate or roll. A method in which a roll coater, a die coater, a comma coater or the like is used to apply a solution in which a viscous adhesive composition containing an acrylic triblock copolymer (I) or the like is dissolved in a solvent, and the solvent is removed by drying. A viscous adhesive layer can be formed using (solution casting method).

The method for removing the solvent by drying is not particularly limited, and a conventionally known method can be used, but it is preferable to perform drying in a plurality of steps. When drying is performed in multiple stages, the first stage is dried at a relatively low temperature in order to suppress foaming due to the rapid volatilization of the solvent, and the second and subsequent stages are sufficiently dried. A method of drying at a high temperature is more preferable in order to remove the solvent.
The concentration of the adhesive composition containing the acrylic triblock copolymer (I) in the above solution is appropriately determined in consideration of the solubility of the composition in the solvent, the viscosity of the obtained solution, and the like. The preferred lower limit is 5% by mass, and the preferred upper limit is 70% by mass.

The article of the present invention can be obtained by laminating a base material and a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition of the present invention. The adhesive layer may be laminated in direct contact with the base material, or may be laminated with the base material via another layer such as a primer layer or an adhesion promoting layer.
Examples of the base material used in the article of the present invention include papers such as impregnated paper, coated paper, high-quality paper, kraft paper, Japanese paper, and glassin paper; polyester films such as polyethylene terephthalate and polybutylene terephthalate, polyethylene and polypropylene, and the like. Polyethylene film, polyvinyl chloride film, polycarbonate film, polyurethane film such as polyether urethane and polyester urethane, amide polymer film such as polyether polyamide block polymer, plastic film such as cellophane film; foam; non-woven fabric, woven cloth, Fabrics such as knitted fabrics; laminated bodies of two or more of these; and the like. As the material of the fabrics, natural materials, synthetic resin materials, recycled resin materials and various materials in which these are appropriately combined can be used, and among them, polyester, polyurethane, polyethylene, polypropylene, polyamide, acrylic resin and the like are used as raw materials. Non-woven fabrics, woven fabrics, knitted fabrics and the like can be used. For these base materials, it is preferable to select a cloth such as a non-woven fabric in order to prevent stuffiness and whitening when applied to the skin surface. For example, a non-woven fabric made of polyurethane, polyamide or polyester may be used. Suitable. Further, the film may be laminated with a woven fabric or a non-woven fabric. The base material may be subjected to a mold release treatment such as a silicone resin or a fluororesin, or other surface treatment.

The thickness of the base material can be appropriately selected in consideration of physical properties such as elongation, tensile strength, workability, feel at the time of application, and airtightness of the affected area, but is usually about 5 μm to 1 mm. When the thickness of the base material is as thin as about 5 μm to 30 μm, it is placed on a surface opposite to one side of the base material provided with the adhesive layer (hereinafter referred to as the other side). A peelable carrier film (usually a film made of a thermoplastic resin) layer may be provided.
When the base material is a woven fabric, the thickness thereof is preferably 50 μm to 1 mm, more preferably 100 μm to 800 μm, and the basis weight is ^{preferably 300 g / m 2} or less from the viewpoint of followability to the skin, more preferably. Is preferably 200 g / m ² or less, more preferably 150 g / m ² or less.

When the base material is a plastic film, the thickness thereof is preferably 10 μm to 300 μm, more preferably 12 μm to 200 μm. When the base material is a plastic film, one side surface or the other side of the base material is used for the purpose of improving the anchoring property of the adhesive layer made of the adhesive composition of the present invention and the base material. Or both sides thereof may be subjected to a treatment such as sandblasting treatment or corona treatment.

If the thickness of the base material is smaller than 5 μm, the strength and handleability of the article containing the adhesive layer (typically, the adhesive sheet or film) is lowered, and when used as a biological surface adhesive, for example. It becomes difficult to attach it to the skin, and it may be torn by contact with other members or the like, or it may be peeled off from the skin in a short time by contact with water such as bathing. Further, if the thickness of the base material is too large (more than 1 mm), for example, when it is used as a biological surface adhering material, it becomes difficult to follow the movement of the skin, and it peels off at the edge of the article including the adhesive layer. Since it becomes easy to form a trigger, it may be peeled off from the skin in a short time, or the feeling of discomfort during application may increase.

When the article of the present invention is used as a biological surface adhesive, the article may further contain a locally administrable pharmaceutically active agent.
Topical pharmaceutically active agents include, for example, antibacterial agents, antifungal agents, anti-inflammatory agents (steroidal anti-inflammatory drugs, non-steroidal anti-inflammatory drugs (NSAIDs), etc.), vitamins, effective oils, moisturizers, etc. Can be mentioned. More specific topically administrable pharmaceutically active agents include, for example, iodine, povidone iodine, silver, salicylic acid or a salt thereof, acetylsalicylic acid or a salt thereof, chlorhexidine (eg, chlorhexidine gluconate), sulfacetamide and a salt thereof, erythromycin, etc. Neomycin, polymyxin, bacitracin, letapamulin, mupirocin, gentamycin, maphenide, lidocaine, tetracycline, benzoic acid, cyclopyroxolamine, undesicylene alkanolamide, bihonazole, chlorhexidine, econazole, ketoconazole, miconazole, thioconazole, terubinate , Timor, sulfacetamide, almond oil, argan oil, avocado oil, camelina oil, palm oil, jojoba oil, rose oil, sesame oil, shea butter, hemp oil, macadamia nut oil, lanolin, vitamins such as vitamin A, vitamin A palmitate, Vitamin B3, vitamin C, and tocopherols and esters thereof, such as α-tocopherol and α-tocopherol acetate.
Topically administrable pharmaceutically active agents can be included in the article in appropriate amounts depending on their use. For example, with respect to 100 parts by mass of the acrylic triblock copolymer (I) contained in the adhesive composition of the present invention, 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, and 5 parts by mass or less. , 2 parts by mass or less, or 1 part by mass or less can be used.

The article of the present invention can be preferably used as a biological surface adhering material. The biological surface adhering material of the present invention can be used, for example, for pharmaceuticals, veterinary medicine, and surgical treatment. For example, a biological surface adhering material can be used as a wound dressing used to cover the wound to treat the wound. The biosurface adhering material also stabilizes a catheter, a needle for intravenous injection, a needle for inter-arterial injection (inter-arterial) that is at least partially inserted into the subject (eg, into the subject's lumen). Therefore, it can be used by covering the catheter, the needle for intravenous injection, or the needle for inter-arterial injection (inter-arterial) and placing it on the surface of the living body. The biological surface adhering material can also be used to secure the medical device to the subject.

Specific examples of the biological surface adhesive of the present invention include analgesic and anti-inflammatory agents (plasters, paps), ischemic heart disease therapeutic agents, female hormone replacement agents, bronchial dilators, cancerous pain relievers, quitting aids, and sensation. Percutaneous absorbents such as patches, antipruritic patches, and keratin softeners; first-aid adhesive plasters (with bactericides), surgical dressing / surgical tapes, adhesive plasters, hemostatic bonds, human excrement treatment fitting tapes (artificial anal fixation tape), Various tape applications such as suturing tape, antibacterial tape, fixed taping, self-adhesive bandage, oral mucosa sticking tape, sports tape, hair removal tape; beauty application such as face pack, eye moisturizing sheet, keratin peeling pack; cooling sheet , Thermal cairo and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In Production Examples 1 to 8 shown below, the monomers and other compounds were dried and purified by a conventional method, degassed with nitrogen, and used. In addition, the transfer and supply of the monomer and other compounds to the reaction system was carried out in a nitrogen atmosphere.

In the following production examples, the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the polymer (polymer forming the block) and the acrylic triblock copolymer are polystyrene by GPC. It was calculated by the converted molecular weight. The measuring devices and conditions used in GPC are as follows.
[GPC measurement equipment and conditions]
・ Equipment: GPC equipment "HLC-8020" manufactured by Tosoh Corporation
-Separation column: "TSKgel GMHXL", "G4000HXL" manufactured by Tosoh Corporation
And "G5000HXL" are connected in series.-Eluent: tetrahydrofuran-Eluent flow rate: 1.0 ml / min-Column temperature: 40 ° C.
-Detection method: Differential refractometer (RI)

Further, in the following example, the content of each polymer block in the block copolymer was ^{determined by 1} H-NMR measurement. ^{1 The} measuring equipment and conditions used in the 1 H-NMR measurement are as follows.

[ ¹ Equipment and conditions for 1 H-NMR measurement]
・ Equipment: Nuclear magnetic resonance equipment "JNM-ECX400" manufactured by JEOL Ltd.
・ Deuterated solvent: Deuterated chloroform
^{1 In the} H-NMR spectrum, the signals around 3.6 ppm and 4.0 ppm are hydrogen atoms bonded to carbon atoms adjacent to oxygen atoms contained in the ester group of methyl methacrylate, respectively (-OC H _3). ) and it is attributed to the hydrogen atom bonded to a carbon atom adjacent to the oxygen atom contained in the ester group of the acrylic acid n- butyl units _{(-O-C H 2 -CH 2} -CH 2 -CH 3), the integrated value The content of each polymer block was determined by the ratio of.

The evaluation of the adhesive tape having the adhesive layer made of the adhesive composition was carried out by the following method.

[Loop tack characteristics]
A loop having a width of 25 mm and a length of 100 mm so that the adhesive layer comes to the outside in a 50% RH atmosphere at 23 ° C. on an adhesive tape having a 25 μm-thick adhesive layer produced by the method described later. A 25 mm wide PMMA plate (Deraglass A999, manufactured by Asahi Kasei Techno Plus Co., Ltd.) installed in the direction intersecting the loop is attached to a loop tack tester (“LT-1000” manufactured by ChemInstruments), and described in PSTC-16. The tack value (maximum value at the time of peeling) was measured according to the method. It can be judged that the better the evaluation result of the loop tack, the better the followability.

[Constant load holding force]
A PMMA plate (Deraglass A999, Asahi Kasei) at a temperature of 23 ° C. was prepared by a method described below and has a 25 μm-thick adhesive layer (15 mm × 150 mm) so that the attachment area is 15 mm × 100 mm. It was pasted on (manufactured by Techno Plus Co., Ltd.), and the rest was folded with the adhesive surface inside. The PMMA board was fixed horizontally with the side to which the adhesive tape was attached facing down, and then a weight with a load of 100 g was hung from the folded portion at a temperature of 23 ° C. and left to stand 60 minutes later. The peeling length was determined. If it was peeled off within 60 minutes, the peeling time was calculated.

[Acrylic residue (PMMA board)]
An adhesive tape having a 25 μm-thick adhesive layer produced by the method described later is reciprocated twice using a rubber roller with a load of 2 kg and attached to a PMMA plate (Deraglass A999, manufactured by Asahi Kasei Techno Plus Co., Ltd.). After being attached and stored at 23 ° C. and 50% RH for 24 hours, it was peeled off in the 180 ° direction at a peeling rate of 300 mm / min, and then the surface of the PMMA plate was observed to evaluate the presence or absence of adhesive residue. When there was no adhesive residue, it was set to "N", and when there was no adhesive residue, it was set to "Y".

[Edge lift]
An adhesive layer of an adhesive tape (25 mm × 75 mm) having an adhesive layer having a thickness of 25 μm prepared by the method described later was placed in contact with the distal forearm of a person. The edge lift was visually evaluated after 48 hours. If there was no part lifted from the skin, it was evaluated as "none", and if there was a part lifted from the skin, it was evaluated as "yes".

[Glue residue (skin)]
After the above-mentioned edge lift evaluation, the skin was peeled from the skin at a peeling speed of 230 cm / min in the 180 ° direction, and then the skin surface was observed to evaluate the presence or absence of adhesive residue on the skin. When there was no adhesive residue, it was evaluated as "none", and when there was adhesive residue, it was evaluated as "yes".

<< Production Example 1 >> [Production of acrylic triblock copolymer (I-1)]
(1) A three-way cock was attached to a 3 L three-necked flask, the inside was replaced with nitrogen, and then 1409 g of toluene and 32.7 g of 1,2-dimethoxyethane were added while stirring at room temperature, followed by isobutylbis (2,). 6-di-t-Butyl-4-methylphenoxy) Add 48.6 g of a toluene solution containing 24.5 mmol of aluminum, and add 1.50 g of a cyclohexane solution of sec-butyllithium containing 2.55 mmol of sec-butyllithium. added.
(2) Subsequently, 22.7 g of methyl methacrylate was added thereto. The reaction solution was initially colored yellow, but became colorless after stirring at room temperature for 60 minutes. A small amount was sampled, and the weight average molecular weight of the obtained polymethyl methacrylate was determined by GPC measurement by the above method.
(3) Subsequently, the internal temperature of the reaction solution was cooled to −30 ° C., 434 g of n-butyl acrylate was added dropwise over 2 hours, and after the addition was completed, the mixture was stirred at −30 ° C. for 5 minutes.
(4) Further, 29.4 g of methyl methacrylate was added thereto, and the mixture was stirred overnight at room temperature.
(5) After adding 15 g of methanol to stop the polymerization reaction, the obtained reaction solution was poured into 15 kg of methanol to precipitate a liquid precipitate. Then, the liquid precipitate was collected and dried to obtain 440 g of an acrylic triblock copolymer (I-1). The weight average molecular weight of the obtained acrylic triblock copolymer (I-1) was determined by GPC measurement by the above method. In addition, the total content of the polymer block composed of methyl methacrylate units in the acrylic triblock copolymer (I-1) was determined by the above-mentioned ^{1 H-NMR measurement.}

≪Manufacturing examples 2-8≫
Acrylic block copolymer (I) is the same as in Production Example 1 except that the amount of each monomer added in Production Example 1 (2), (3) and (4) is changed as shown in Table 1. -2)-(I-7) and (II-1) were produced, respectively.

In Examples and Comparative Examples, the following were used as the tackifier resin, the plasticizer, and the base material.
(Adhesive-imparting resin)
-Product name "Foral 85E" manufactured by Eastman, hydrogenated rosin ester-Product name "YSresin SX100" manufactured by Yasuhara Chemical Co., Ltd., aromatic hydrocarbon resin (plasticizer)
-Product name "Acronal LR8820" manufactured by BASF, poly n-butyl acrylate (n-butyl polyacrylate) oligomer (acrylic oligomer)
-Product name "Arphon UP1000" manufactured by Toagosei Co., Ltd., acrylate oligomer (acrylic oligomer)
-Product name "SAIB-100" manufactured by Eastman, sucrose acetate isobutyrate (base material)
-Polyethylene terephthalate film: Toyobo ester film E5000, thickness 50 μm
-Base material A: Polyurethane-based non-woven fabric (weight: approx. 80 g / m ² )
-Base material B: Polyurethane-based non-woven fabric (approx. 40 g / m ² ) laminated with polyurethane film (approx. 30 μm) -Base material C: Polyester-based non-woven fabric (approx. Approx. 40g / m ² )

<< Example 1 >>
The acrylic triblock copolymer (I-1) obtained in Production Example 1 and the acrylic triblock copolymer (II-1) obtained in Production Example 8 have a mass ratio shown in Table 2 below. And, these were dissolved in toluene so that the total of these became 35% by mass, and a toluene solution containing 35% by mass of the adhesive composition was prepared. The obtained toluene solution was coated on the above-mentioned polyethylene terephthalate film by a coater so that the thickness of the adhesive layer after drying was 25 μm, and then the film was heat-treated at 100 ° C. for 3 minutes to dry the adhesive. An adhesive tape, which is an article containing an adhesive layer in which the adhesive layer is formed on a polyethylene terephthalate film, is produced, and loop tack characteristics, constant load holding force, and adhesive residue (PMMA) are produced by the above method. Board) was evaluated.

<< Examples 2 to 18, Comparative Examples 1 to 6 >>
An adhesive tape having a thickness of 25 μm was prepared in the same manner as in Example 1 except that the composition of the adhesive composition was changed to the composition shown in Table 2, and the loop tack characteristics and determination were determined by the above method. The load holding force and the adhesive residue (PMMA plate) were evaluated.

As shown in Table 2, the adhesive tapes shown in Examples 1 to 18 made of the adhesive composition of the present invention had good loop tack characteristics and constant load holding force.

On the other hand, as in Comparative Example 1, the acrylic triblock copolymer has a weight average molecular weight smaller than the range of the present invention, and the total content of the polymer blocks (A1) and (A2) is also larger than the range of the present invention. It can be seen that when coalescing (I-5) is used, the loop tack characteristics tend to be significantly deteriorated.

Further, when an acrylic triblock copolymer (I-6) having a weight average molecular weight smaller than the range of the present invention is used as in Comparative Example 2, both the loop tack property and the constant load holding force are deteriorated. It turns out to be easy. In addition, a slight amount of adhesive residue was confirmed, indicating that the cohesive force tends to be small.

Further, when an acrylic triblock copolymer (I-7) having a total content of the polymer blocks (A1) and (A2) larger than the range of the present invention is used as in Comparative Example 3, a loop is used. It can be seen that the tack characteristics tend to be significantly deteriorated.

Further, even when the tackifier resin and the plasticizer are blended as in Comparative Example 4, the weight average molecular weight is smaller than the range of the present invention, and the total content of the polymer blocks (A1) and (A2) is also high. It can be seen that when an acrylic triblock copolymer (I-5) larger than the range of the present invention is used, both the loop tack property and the constant load holding force tend to deteriorate. In addition, a slight amount of adhesive residue was confirmed, indicating that the cohesive force tends to be small.

Further, as in Comparative Example 5, even when the tackifier resin and the plasticizer are blended, the loop is also obtained when the acrylic triblock copolymer (I-6) having a molecular weight smaller than the range of the present invention is used. It can be seen that both the tack characteristics and the constant load holding force tend to deteriorate. In addition, a slight amount of adhesive residue was confirmed, indicating that the cohesive force tends to be small.

Further, even when the tackifier resin and the plasticizer are blended as in Comparative Example 6, the total content of the polymer blocks (A1) and (A2) is larger than the range of the present invention. It can be seen that both the loop tack characteristic and the constant load holding force tend to deteriorate even when the coalescence (I-7) is used.

<< Manufacturing Examples 9 and 10 >>
According to the composition of the adhesive composition shown in Table 3, the acrylic triblock copolymer (I) was added to the kneader set at 170 ° C. and uniformly melted, and then the temperature of the kneader was set to 160 ° C. The acrylic triblock copolymer (II) was put into a kneader and melt-kneaded so that these mixtures became uniform to prepare a viscous adhesive composition.

<< Manufacturing Examples 11 and 14 >>
According to the composition of the adhesive composition shown in Table 3, the acrylic triblock copolymer (I) was added to the kneader set at 170 ° C. and uniformly melted, and then the temperature of the kneader was set to 160 ° C. The acrylic triblock copolymer (II) was put into a kneader and melt-kneaded so that these mixtures became uniform. Then, the temperature of the kneader was set to 150 ° C., the tackifier resin was added to the melt-kneaded product in the kneader, and the mixture was melt-kneaded so as to be uniform to prepare a pressure-sensitive adhesive composition.

<< Manufacturing Example 12 >>
According to the composition of the adhesive composition shown in Table 3, the acrylic triblock copolymer (I) was put into a kneader set at 170 ° C. and uniformly melted. After that, the temperature of the kneader is set to 150 ° C., the tackifier resin is added to the melt-kneaded product in the kneader to melt-knead the mixture so that the mixture becomes uniform, and then a plasticizer is further added to form the mixture. A pressure-sensitive adhesive composition was prepared by melt-kneading so as to be uniform.

<< Manufacturing Examples 13 and 15 >>
According to the composition of the adhesive composition shown in Table 3, the acrylic triblock copolymer (I) was added to the kneader set at 170 ° C. and uniformly melted, and then the temperature of the kneader was set to 160 ° C. The acrylic triblock copolymer (II) was put into a kneader and melt-kneaded so that these mixtures became uniform. After that, the temperature of the kneader is set to 150 ° C., the tackifier resin is added to the melt-kneaded product in the kneader to melt-knead the mixture so that the mixture becomes uniform, and then a plasticizer is further added to form the mixture. A pressure-sensitive adhesive composition was prepared by melt-kneading so as to be uniform.

<< Manufacturing Example 16 >>
According to the composition of the adhesive composition shown in Table 3, the acrylic triblock copolymer (I) was added to the kneader set at 160 ° C. and uniformly melted, and then the temperature of the kneader was changed to 150 ° C. The acrylic triblock copolymer (II) was put into a kneader and melt-kneaded so that these mixtures became uniform to prepare a viscous adhesive composition.

<< Manufacturing Examples 17 and 18 >>
According to the composition of the adhesive composition shown in Table 3, the acrylic triblock copolymer (I) was added to the kneader set at 160 ° C. and uniformly melted, and then the temperature of the kneader was changed to 150 ° C. The acrylic triblock copolymer (II) was put into a kneader and melt-kneaded so that these mixtures became uniform. After that, the temperature of the kneader is set to 140 ° C., the tackifier resin is added to the melt-kneaded product in the kneader to melt-knead the mixture so that the mixture becomes uniform, and then a plasticizer is further added to form the mixture. A pressure-sensitive adhesive composition was prepared by melt-kneading so as to be uniform.

<< Examples 19 to 25, Comparative Examples 7 to 9 >>
The adhesive layer obtained by hot-melt coating the adhesive compositions obtained in Production Examples 9 to 18 is melt-coated ^{on the substrate shown in Table 3 so as to have a concentration of 40 g / cm 2.} An adhesive tape, which is an article containing the above, was produced.

As for Examples 19 to 25, as a result of the edge lift evaluation, there was no portion where the adhesive tape was lifted from the skin, and even when the adhesive tape was peeled from the skin in the 180 ° direction, adhesive residue was confirmed on the skin. Was not done. On the other hand, in Comparative Examples 7 to 9, as a result of the edge lift evaluation, the edge portion was remarkably peeled off and lifted from the skin, and even when the adhesive tape was peeled off from the skin in the 180 ° direction, it was attached to the skin. It was confirmed that a small amount of glue remained.

≪Reference example≫
Testing was conducted in accordance with Commission Regulation (EU) No 10/2011 on plastic materials and products intended for contact with food. Using the adhesive composition obtained in Production Example 9, a hot press (preheating 3 minutes, pressing time 1 minute) was performed at 170 ° C. under the condition of 50 MPa, and then a cooling press (50 MPa, 1 minute) was performed. , Created a press sheet. Using the obtained sheet, a surface having a predetermined size (area 6 dm ² ) was cut so as to be exposed, and used as a test sample. This test sample was immersed in an extraction solvent (10% ethanol water or 3% acetic acid water) and allowed to stand at 40 ° C. for 10 days. Then, the extraction solvent was removed, and the total solid content weight was calculated. In both the case of 10% ethanol water and the case of 3% acetic acid water, the total solid content weight was ^{less than 1 mg / dm 2} , and there were almost no components to be extracted. From the reference example, the adhesive composition within the scope of the present invention can reduce the amount of components transferred to the adherend, and is suitable in fields such as the medical field where high quality and a high management system are required. Can be used for.

Claims (6)

Two polymer blocks (A1) and (A2) consisting of methacrylic acid ester units and
It has one polymer block (B) composed of acrylic acid ester units, and has a (A1)-(B)-(A2) block structure.
The total content of the polymer blocks (A1) and (A2) is 7% by mass or more and 20% by mass or less.
Weight average molecular weight is 150,000-400,000,
Acrylic triblock copolymer (I)
Adhesive composition containing. Two polymer blocks (C1) and (C2) consisting of methacrylic acid ester units and
It has one polymer block (D) composed of acrylic acid ester units, and has a (C1)-(D)-(C2) block structure.
The total content of the polymer blocks (C1) and (C2) is 5% by mass or more and 15% by mass or less.
Weight average molecular weight is 10,000-120,000,
Acrylic triblock copolymer (II)
The adhesive composition according to claim 1, further comprising. The adhesive composition according to claim 1 or 2, further comprising a tackifier resin. The adhesive composition according to any one of claims 1 to 3, further comprising a plasticizer. With the base material
An article comprising an adhesive layer comprising the adhesive composition according to any one of claims 1 to 4. A biological surface adhering material comprising the article according to claim 5.