JP2018003035A - Pressure-sensitive adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition containing an acrylic triblock copolymer having no bleed and having excellent transparency, adhesive properties and processability. SOLUTION: The polymer block (A1) and (A2) composed of methacrylic acid ester units and the polymer block (B) composed of acrylic acid ester units are provided, and the total content of (A1) and (A2) is high. A triblock copolymer (I) having an Mw of 35% by mass or less and each of (A1) and (A2) having a Mw of 3000 or more, and polymer blocks (C1) and (C2) composed of methacrylic acid ester units. It has a polymer block (D) composed of acrylic ester units, the total content of (C1) and (C2) is 25% by mass or less, and at least one Mw of (C1) and (C2) is A viscous adhesive composition containing a total of 100 parts by mass of the triblock copolymer (II) of 300 to 3000 and (ii) 1 to 190 parts by mass of a tackifier resin. [Selection diagram] None

Description

  The present invention relates to an adhesive composition containing an acrylic block copolymer suitable for an adhesive or the like.

It has been conventionally known that an acrylic block copolymer or a composition containing an acrylic block copolymer is used as an adhesive.
For example, a methacrylic acid alkyl ester polymer having a glass transition temperature of 110 ° C. or higher and a syndiotacticity of 70% or higher at both ends of a (meth) acrylic acid alkyl ester polymer block having a glass transition temperature of 30 ° C. or lower. A block copolymer composition containing a triblock copolymer having a block bonded thereto, a (meth) acrylic acid alkyl ester diblock copolymer, and a pressure-sensitive adhesive comprising the composition are known (Patent Document 1). reference). Also known is a pressure-sensitive adhesive composition containing a specific diblock copolymer composed of a methacrylic acid alkyl ester polymer block and an acrylic acid alkyl ester polymer block and a (meth) acrylic acid ester triblock copolymer. (See Patent Document 2). In addition, a pressure-sensitive adhesive composition containing a triblock copolymer and a diblock copolymer each comprising a specific alkyl methacrylate ester polymer block and an acrylic acid alkyl ester polymer block is known (Patent Document 3). reference). Furthermore, the melt viscosity at 100 ° C. measured by a triblock copolymer comprising a specific alkyl methacrylate polymer block and an alkyl alkyl ester polymer block and a B-type viscometer is 100,000 mPa · s or less. A pressure-sensitive adhesive composition containing a specific triblock copolymer is known (see Patent Document 4).

Japanese Patent Laid-Open No. 11-323072 Japanese Patent Laid-Open No. 2004-2736 JP 2005-307063 A International Publication No. 2016/121607

  The tackifying resins and plasticizers specifically studied in the pressure-sensitive adhesives and pressure-sensitive adhesive compositions described in the above-mentioned patent documents are limited, and there is still room for improvement in coexistence of pressure-sensitive adhesive properties and workability. . An object of the present invention is to provide an adhesive composition containing an acrylic block copolymer which is free from bleeding and has excellent transparency, adhesive properties and processability.

  As a result of intensive studies to achieve the above object, the present inventors have determined that a specific blend ratio of a specific acrylic triblock copolymer, a specific acrylic triblock copolymer, and a tackifier resin. It was found that an adhesive composition containing an acrylic block copolymer having no bleed and excellent transparency, adhesive properties, and processability can be obtained by using the adhesive composition contained in It was.

According to the invention, the object is
[1] (i) having two polymer blocks (A1) and (A2) composed of methacrylic acid ester units, and one polymer block (B) composed of acrylate ester units, and (A1)-( B)-(A2) having a block structure, a weight average molecular weight of 50,000 to 250,000, a total content of polymer blocks (A1) and (A2) of 35% by mass or less, a polymer An acrylic triblock copolymer (I) in which the weight average molecular weight of each of the blocks (A1) and (A2) is 3000 or more;
(C1)-(D)-(C2) having two polymer blocks (C1) and (C2) composed of methacrylic ester units and one polymer block (D) composed of acrylate units It has a block structure, has a weight average molecular weight of 10,000 to 120,000, a total content of polymer blocks (C1) and (C2) of 25% by mass or less, and polymer blocks (C1) and ( Viscosity containing a total of 100 parts by mass of the acrylic triblock copolymer (II) having a weight average molecular weight of at least 300 and less than 3000 among C2) and (ii) 1 to 190 parts by mass of a tackifying resin Adhesive composition,
[2] (i) having two polymer blocks (A1) and (A2) composed of methacrylic ester units and one polymer block (B) composed of acrylate units, (A1)-(B )-(A2) having a block structure, a weight average molecular weight of 50,000 to 250,000, a total content of the polymer blocks (A1) and (A2) of 35% by mass or less, and a polymer block (A1) and (A2) acrylic triblock copolymer (I) each having a weight average molecular weight of 3000 or more;
(C1)-(D)-(C2) having two polymer blocks (C1) and (C2) composed of methacrylic ester units and one polymer block (D) composed of acrylate units It has a block structure, has a weight average molecular weight of 10,000 to 120,000, a total content of polymer blocks (C1) and (C2) of 25% by mass or less, and polymer blocks (C1) and ( A total of 100 parts by mass with the acrylic triblock copolymer (II) having a weight average molecular weight of at least 300 and less than 3000 among C2), and (ii) 1-190 parts by mass of a tackifying resin, and (iii) ) Adhesive composition containing 80 parts by weight or less of a plasticizer;
Is achieved by providing

  According to the present invention, there can be obtained an adhesive composition containing an acrylic block copolymer which is free from bleeding and has excellent transparency, adhesive properties and processability.

  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” means “methacrylic” and “acrylic”. It is a generic name.

(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 ester units and 1 composed of acrylate units. Two polymer blocks (B), a block structure (A1)-(B)-(A2), a weight average molecular weight of 50,000 to 250,000, and a polymer block (A1) and The total content of (A2) is 35% by mass or less.

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

  Examples of the methacrylic acid ester constituting the structural units of the polymer blocks (A1) and (A2) include, for example, 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 Methacrylic acid ester having no functional group such as isobornyl, phenyl methacrylate, benzyl methacrylate; methoxyethyl methacrylate, ethoxyethyl methacrylate, diethylamino methacrylate Ethyl, 2-hydroxyethyl methacrylate, 2-aminoethyl methacrylate, glycidyl methacrylate, and methacrylic acid esters having a functional group such as tetrahydrofurfuryl methacrylate.

  Among these, from the viewpoint of improving the heat resistance and durability of the obtained polymer, a methacrylate having no functional group is preferred, methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, More preferred are isobornyl methacrylate and phenyl methacrylate, and methyl methacrylate is more preferred in that the phase separation between the polymer blocks (A1) and (A2) and the polymer block (B) becomes clearer and the cohesive force becomes higher. . Polymer block (A1) and (A2) may be comprised from 1 type of these methacrylic acid ester, or may be comprised from 2 or more types. The acrylic triblock copolymer (I) has two polymer blocks (A1) and (A2) as polymer blocks composed of methacrylic acid ester units. These polymer blocks (A1) and The methacrylic acid esters constituting (A2) may be the same or different. Further, the ratio of the methacrylic acid ester units contained in the polymer blocks (A1) and (A2) is preferably 60% by mass or more in each polymer block of the polymer blocks (A1) and (A2). More preferably, it is 90 mass% or more, and more preferably 95 mass% or more. Moreover, 100 mass% may be sufficient as the ratio of the methacrylic acid ester unit of a polymer block (A1) and (A2).

  In addition, the stereoregularity of the methacrylic acid ester unit contained in each polymer block (A1) and (A2) composed of the methacrylic acid ester unit may be the same as or different from each other.

  In the acrylic triblock copolymer (I), the total content of the polymer blocks (A1) and (A2) is 35% by mass or less, preferably 30% by mass or less, and preferably 25% by mass or less. Is more preferable, and it is further more preferable that it is 23 mass% or less. The total content of the polymer blocks (A1) and (A2) is preferably 4% by mass or more, and more preferably 8% by mass or more. When the total content of the polymer blocks (A1) and (A2) is within the above range, the cohesive force is excellent when the acrylic triblock copolymer (I) is contained in the adhesive composition. To improve tack and adhesion. Moreover, it exists in the tendency for the heat-resistant adhesiveness and holding power of this adhesive composition to be more excellent. 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 polymer blocks (A1) and (A2) each have a weight average molecular weight of 3,000 or more, preferably 4,500 or more, and preferably 6,000 or more. More preferred. The weight average molecular weight of each of the polymer blocks (A1) and (A2) is preferably 30,000 or less, and more preferably 25,000 or less.
When the weight average molecular weight of each of the polymer blocks (A1) and (A2) is within the above range, when the acrylic triblock copolymer (I) is contained in the adhesive composition, With excellent handleability, it exhibits excellent cohesion and improves tack and adhesion. Moreover, it exists in the tendency for the heat-resistant adhesiveness and holding power of this adhesive composition to be more excellent. 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 further preferably 80 to 130 ° C. When the glass transition temperature is within this range, the polymer blocks (A1) and (A2) act as physical pseudo-crosslinking points at the normal use temperature of the adhesive, and cohesion is developed. When contained in the adhesive composition, it is excellent in adhesive properties, durability, heat resistance and the like. In addition, the glass transition temperature in this 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 a preferred embodiment 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 an acrylate unit.

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

Among these, from the viewpoint of transparency and flexibility when used as a pressure-sensitive adhesive composition of the general formula _CH 2 = _CH-COOR ¹ (wherein, ^{R 1} represents an organic group having 1 to 10 carbon atoms) Is more preferable, the phase separation between the polymer blocks (A1) and (A2) and the polymer block (B) becomes clear, and the adhesive composition exhibits high cohesive force. Methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, acrylic acid n-hexyl, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, acrylic Isobornyl, cyclohexyl acrylate, phenyl acrylate, such as benzyl acrylate, acrylic acid ester is more preferably without a functional group. From the point that the adhesive composition has moderate tackiness at room temperature and exhibits stable adhesive force over a wide temperature range and a wide peeling speed condition, methyl acrylate, n-butyl acrylate, acrylic At least one selected from 2-ethylhexyl acrylate, n-octyl acrylate and isooctyl acrylate is more preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferable.

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

  In the acrylic triblock copolymer (I), the content of the polymer block (B) is 65% by mass or more, preferably 70% by mass or more, and more preferably 75% by mass or more. 77% by mass or more is more preferable. Moreover, it is preferable that content of a polymer block (B) is 96 mass% or less, and it is more preferable that it is 92 mass% or less. When the content of the polymer block (B) is within the above range, when the acrylic triblock copolymer (I) is used for the adhesive composition, it exhibits excellent cohesive force, Adhesive strength is further improved.

  The glass transition temperature of the polymer block (B) is preferably -100 to 30 ° C, more preferably -80 to 10 ° C, and further preferably -70 to 0 ° C. When the glass transition temperature is within 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 monomer components of each other as long as the effects of the present invention are not impaired. For example, you may have a tapered structure in the boundary of a polymer block (A1) or (A2) and a polymer block (B). Moreover, the polymer block (A1) or (A2) and the polymer block (B) may not contain each other's monomer components.

  Moreover, the said polymer block (A1) and (A2) and a polymer block (B) may contain another monomer unit as needed. Examples of such other monomers include vinyl monomers having a carboxyl group such as (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, and fumaric acid; (meth) acrylamide, (meth) acrylonitrile, Vinyl monomers having functional groups such as vinyl acetate, vinyl chloride, vinylidene chloride; aromatic vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene; butadiene, isoprene, etc. Conjugated diene monomers; olefin monomers such as ethylene, propylene, isobutene and octene; and lactone 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 with respect to the total mass of 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. Have When the acrylic triblock copolymer (I) having such a structure is contained in the adhesive composition, the adhesive force, holding force, and cohesive force tend to be excellent.

  The weight average molecular weight of the acrylic triblock copolymer (I) is 50,000 to 250,000. From the point of cohesive force and handling at the time of manufacture, it is preferably 60,000 to 250,000, more preferably 100,000 to 230,000, and 130,000 to 210,000. Is more preferable. If the weight average molecular weight of the acrylic triblock copolymer (I) is less than 50,000, the cohesive force may be poor. Moreover, when a weight average molecular weight exceeds 250,000, there exists a possibility that the handleability at the time of manufacture may be inferior.

  The molecular weight distribution (Mw / Mn) of the acrylic triblock copolymer (I) is preferably 1.0 to 1.5, and more preferably 1.0 to 1.4. In addition, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in this specification are the weight average molecular weight and number average molecular weight in terms of standard polystyrene determined by gel permeation chromatography (GPC) measurement.

(Acrylic triblock copolymer (II))
The acrylic triblock copolymer (II) contained in the adhesive composition of the present invention comprises at least two polymer blocks (C1) and (C2) composed of methacrylic acid ester units, and an acrylic acid ester unit. At least one polymer block (D), having a (C1)-(D)-(C2) block structure, having a weight average molecular weight of 30,000 to 100,000, The total content of C1) and (C2) is 25% by mass or less, and the weight average molecular weight of at least one of the polymer blocks (C1) and (C2) is 300 or more and less than 3000.

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

  Specific examples of the methacrylic acid ester which is the structural unit of the polymer blocks (C1) and (C2) are the structural units of the polymer blocks (A1) and (A2) of the acrylic triblock copolymer (I). Same as methacrylic acid ester.

  Among these, from the viewpoint of improving the heat resistance and durability of the obtained polymer, a methacrylate having no functional group is preferred, methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, More preferred are isobornyl methacrylate and phenyl methacrylate, and methyl methacrylate is more preferred because the phase separation between the polymer blocks (C1) and (C2) and the polymer block (D) becomes clearer and the cohesive force becomes higher. . Polymer block (C1) and (C2) may be comprised from 1 type of these methacrylic acid ester, or may be comprised from 2 or more types. The proportion of methacrylic acid ester units 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 more preferably 95% by mass or more. Even more preferred. Moreover, 100 mass% may be sufficient as the ratio of the methacrylic acid ester unit of a polymer block (C1) and (C2).

  In the acrylic triblock copolymer (II), the total content of the polymer blocks (C1) and (C2) is 25% by mass or less, preferably 20% by mass or less, and preferably 10% by mass or less. It is more preferable. Moreover, it is preferable that content of polymer block (C1) and (C2) is 3 mass% or more, and it is more preferable that it is 5 mass% or more. When the total content of the polymer blocks (C1) and (C2) is within the above range, the cohesive force is impaired when the acrylic triblock copolymer (II) is contained in the adhesive composition. However, tack and workability tend to be further improved.

  The glass transition temperature of the polymer blocks (C1) and (C2) is preferably 60 to 140 ° C, more preferably 70 to 130 ° C, and further preferably 80 to 130 ° C. When the glass transition temperature is within this range, the polymer blocks (C1) and (C2) act as physical pseudo-crosslinking points at the normal use temperature of the adhesive, and cohesion is developed. When contained in the adhesive composition, it is excellent in adhesive properties, durability, heat resistance and the like.

  The acrylic triblock copolymer (II) preferably 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. Moreover, it is preferable that it is 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 resulting acrylic triblock copolymer (II) tends to have excellent cohesive strength. When the weight average molecular weight of at least one of the polymer blocks (C1) and (C2) is less than 3,000, the resulting acrylic triblock copolymer (II) has a low melt viscosity, There exists a tendency which is excellent in productivity at the time of manufacturing an adhesive composition.

  Among the block structures (C1)-(D)-(C2), the polymer block (C1) preferably has a weight average molecular weight of 300 or more and less than 3,000, more preferably 500 or more and less than 2,000. preferable. The weight average molecular weight of the polymer block (C2) is preferably 3,000 or more and 10,000 or less, and more preferably 3,000 or more and 7,000 or less. By being in the said range, it is excellent in a viscosity, cohesion force, and the handleability at the time of manufacture.

  In addition, the stereoregularity of the methacrylic acid ester unit 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 an acrylate unit.

  The specific example of the acrylic acid ester which becomes a structural unit of the said polymer block (D) is the same as that of the acrylic acid ester which becomes a structural unit of the polymer block (B) of an acryl-type triblock copolymer (I).

Among these, from the viewpoint of transparency and flexibility when used as a pressure-sensitive adhesive composition of the general formula _CH 2 = _CH-COOR ¹ (wherein, ^{R 1} represents an organic group having 1 to 10 carbon atoms) In view of the fact that the polymer block (C1) and the polymer block (D2) and the polymer block (D) are clearly separated, the adhesive composition exhibits high cohesive force. 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, acrylic acid Soboruniru, cyclohexyl acrylate, phenyl acrylate, such as benzyl acrylate, acrylic acid ester is more preferably without a functional group. From the point that the adhesive composition has moderate tackiness at room temperature and exhibits stable adhesive force over a wide temperature range and a wide peeling speed condition, methyl acrylate, n-butyl acrylate, acrylic At least one selected from 2-ethylhexyl acid, n-octyl acrylate and isooctyl acrylate is more preferable, and n-butyl acrylate is particularly preferable.

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

  In the acrylic triblock copolymer (II), the content of the polymer block (D) is 75% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more. . Moreover, it is preferable that content of a polymer block (D) is 97 mass% or less, and it is more preferable that it is 95 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 cohesive force is not impaired, and the tack and Workability is further improved.

  The glass transition temperature of the polymer block (D) is preferably −100 to 30 ° C., more preferably −80 to 10 ° C., and further preferably −70 to 0 ° C. When the glass transition temperature is within 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 monomer components of each other as long as the effects of the present invention are not impaired. For example, you may have a tapered structure in the boundary of a polymer block (C1) or (C2), and a polymer block (D). Moreover, the polymer block (C1) or (C2) and the polymer block (D) may not contain each other's monomer components.

  The polymer blocks (C1) and (C2) and the polymer block (D) may contain other monomer units as necessary. Specific examples of such other monomers include other single monomers contained in the polymer blocks (A1) and (A2) and the polymer block (B) of the acrylic triblock copolymer (I) as necessary. It is the same as that of the other monomer illustrated as what is used for a monomer unit. When each polymer block contains these other monomers, the content thereof is preferably 20% by mass or less, more preferably 10% by mass with respect to the total mass of 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. Have When the acrylic triblock copolymer (II) having such a structure is included in the adhesive composition, tack and workability tend to be further improved.

  The weight average molecular weight of the acrylic triblock copolymer (II) is 10,000 to 120,000. From the point of cohesive force and handling 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 more preferable. If the weight average molecular weight of the acrylic triblock copolymer (II) is less than 10,000, the cohesive force may be inferior. Moreover, when a weight average molecular weight exceeds 120,000, there exists a possibility that it may be inferior to the handleability at the time of manufacture.

  The molecular weight distribution of the acrylic triblock copolymer (II) is preferably 1.0 to 1.5, and more preferably 1.0 to 1.4.

  The acrylic triblock copolymer (II) preferably has a melt viscosity at 100 ° C. measured by a B-type viscometer of 100,000 mPa · s or less. 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) becomes a property having low fluidity instead of a solid state at room temperature (about 25 ° C.), and when added to the adhesive composition There is a tendency to be excellent in workability.

  In the adhesive composition of the present invention, the mass ratio between the acrylic triblock copolymer (I) and the acrylic triblock copolymer (II) is not particularly limited. In order to combine the adhesive properties with a good balance, it is preferable that the acrylic triblock copolymer (I): acrylic triblock copolymer (II) = 100: 1 to 100: 500, More preferably, it is ˜100: 300.

  The production method of the acrylic triblock copolymer (I) and the acrylic triblock copolymer (II) used in the present invention is particularly limited as long as a polymer satisfying the conditions of the present invention concerning the chemical structure is obtained. The method according to a known method can be adopted without being done. In general, as a method of obtaining a block copolymer having a narrow molecular weight distribution, a method of living polymerizing monomers as constituent units is used. Examples of such living polymerization methods include a method of living polymerization using an organic rare earth metal complex as a polymerization initiator (see JP 06-93060 A), and an alkali metal or alkaline earth using an organic alkali metal compound as a polymerization initiator. Living anionic polymerization in the presence of mineral salts such as salts of metal salts (see Japanese Patent Publication No. 05-507737), Living anionic polymerization using organic alkali metal compound as polymerization initiator in the presence of organoaluminum compound (Refer to JP-A-11-335432), atom transfer radical polymerization method (ATRP) (see Macromolecular Chemistry and Physics, 2000, 201, p. 1108 to 1114).

  Among the above production methods, the method of living anion polymerization using an organoalkali metal compound as a polymerization initiator in the presence of an organoaluminum compound makes the resulting block copolymer highly transparent, has little residual monomer and has an odor. In addition, when used as an adhesive composition, the generation of bubbles after bonding can be suppressed, which is preferable. Furthermore, the molecular structure of the methacrylic acid ester polymer block is highly syndiotactic, which has the effect of increasing the heat resistance of the adhesive composition, and is capable of living polymerization under relatively mild temperature conditions. In production, it is also preferable in that the environmental load (mainly the electric power applied to the refrigerator for controlling the polymerization temperature) is small.

As the organoaluminum compound, for example, the following general formula (1)
AlR ² R ³ R ⁴ (1)
(In the formula (1), R ² , R ³ and R ⁴ each independently have an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent. 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 any one of the groups described above, and R ³ and R ⁴ are combined to form an aryleneoxy group which may have a substituent. An aluminum compound is mentioned.

  As the organoaluminum compound represented by the general formula (1), isobutyl bis (2,6-di-tert-butyl-4-methylphenoxy) is used from the viewpoints of high living property of polymerization and easy handling. Preferred examples include aluminum, isobutylbis (2,6-di-tert-butylphenoxy) aluminum, isobutyl [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, and the like.

  Examples of the organic alkali metal compounds include alkyl lithium and alkyl dilithium such as n-butyl lithium, sec-butyl lithium, isobutyl lithium, tert-butyl lithium, n-pentyl lithium, and tetramethylene dilithium; phenyl lithium, p -Aryllithium and aryldilithium such as tolyllithium and lithium naphthalene; aralkyllithium and aralkyldilithium such as dilithium produced by the reaction of benzyllithium, diphenylmethyllithium, diisopropenylbenzene and butyllithium; lithium such as lithium dimethylamide Amides; lithium alkoxides such as methoxy lithium and ethoxy lithium, and the like. These may be used alone or in combination of two or more. Of these, alkyl lithium is preferable because of high polymerization initiation efficiency, among which tert-butyl lithium and sec-butyl lithium are more preferable, and sec-butyl lithium is more preferable.

  The living anion polymerization is usually performed in the presence of a solvent inert to the polymerization reaction. Examples of the solvent include aromatic hydrocarbons such as benzene, 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. It is done.

  The block copolymer includes, 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 monomers. After repeating the desired number of times, it can be produced by stopping the polymerization reaction. Specifically, for example, in the presence of an organoaluminum compound, a first step of polymerizing a monomer that forms the first polymer block with a polymerization initiator composed of an organic alkali metal compound, the second polymer block The active terminal of the polymer obtained through a multi-step polymerization step including a second step of polymerizing the monomer to be formed and a third step of polymerizing the monomer to form the third polymer block Acrylic triblock copolymer (I) and acrylic triblock copolymer (II) can be produced by reacting with an alcohol or the like to stop the polymerization reaction. According to the above method, a triblock copolymer comprising polymer block (A1) -polymer block (B) -polymer block (A2), polymer block (C1) -polymer block (D). -A triblock copolymer comprising 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 preferred. When the polymerization temperature is lower than the above range, the progress of the reaction is slow, 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 ends increases, the molecular weight distribution becomes wide, and the desired block copolymer cannot be obtained. Each polymer block can be polymerized in the range of 1 second to 20 hours.

(Tackifying resin)
The adhesive composition of the present invention includes a tackifying resin. By including the tackifier resin in the adhesive composition of the present invention, the adhesion, tack, and compatibility are improved. In addition, in the adhesive composition of this invention, it is one preferable aspect that the plasticizer mentioned later is not contained.

  As the tackifying resin that can be blended in the adhesive composition of the present invention, any of the tackifying resins conventionally used in pressure-sensitive adhesives can be used and is not particularly limited. For example, a rosin resin (rosin, Rosin derivatives, hydrogenated rosin derivatives, etc.), terpene resins, terpene phenol resins, (hydrogenated) petroleum resins, styrene resins, xylene resins, hydrogenated aromatic copolymers, phenol resins, coumarone-indene resins And so on.

  In the present invention, the rosin-based resin is an amber, amorphous natural resin obtained from pine, and its main component is a mixture of abietic acid and its isomers. Also, the rosin resins include those modified by esterification, polymerization, hydrogenation, etc. utilizing the reactivity of abietic acid or its isomers. For example, unmodified rosin (eg, tall rosin, gum rosin, and wood rosin), polymerized rosin, disproportionated rosin, hydrogenated rosin, maleic acid modified rosin, fumaric acid modified rosin, and esters thereof (eg, glycerin ester, pentane) Erythritol ester, methyl ester, ethyl ester, butyl ester, ethylene glycol ester and the like) and those modified by hydrogenation (hereinafter also referred to as hydrogenation). To hydrogenated rosin esters are preferably used.

In the present invention, the terpene resin is an oligomer obtained by polymerizing a raw material containing a terpene monomer. Further, the terpene resin also includes an oligomer obtained by hydrogenating and modifying the oligomer thus obtained. The terpene generally means a polymer of isoprene (C ₅ H ₈ ), and is classified into monoterpene (C ₁₀ H ₁₆ ), sesquiterpene (C ₁₅ H ₂₄ ), diterpene (C ₂₀ H ₃₂ ), and the like. The The terpene monomer is a monomer having these as a basic skeleton, for example, α-pinene, β-pinene, dipentene, limonene, myrcene, alloocimene, ocimene, α-ferrane drain, α-terpinene, γ. -Terpinene, terpineolene, 1,8-cineole, 1,4-cineole, α-terpineneol, β-terpineneol, γ-terpineneol, sabinene, paramentadienes, and carenes. The raw material containing the terpene monomer includes other monomers copolymerizable with the terpene monomer, for example, a coumarone monomer such as benzofuran (C ₈ H ₆ O); styrene, α- 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 A phenolic monomer such as the above may be contained. Examples of the oligomer obtained by polymerizing a raw material containing another monomer copolymerizable with the terpene monomer include terpene phenol resins. Further, the terpene resin also includes those obtained by modifying the oligomer thus obtained by hydrogenation.

In the present invention a (hydrogenated) petroleum resin consists C ₅ fraction, C ₉ fraction, C purified components of ₅ fraction, purified components of C ₉ fraction, or a mixture thereof fractions or purified components It is an oligomer obtained by polymerizing raw materials. Further, the above-obtained (hydrogenated) petroleum-based resin includes those obtained by modifying the oligomer obtained in this manner by hydrogenation or the like. 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, the C ₉ fraction, usually, styrene, allyl benzene, alpha-methyl styrene, vinyl toluene, include β- methylstyrene and indene. Also, the C ₉ fraction might contain small amounts of C ₈ fraction and 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 And C ₉ fraction or a mixture of purified components thereof are roughly classified into C ₅ -C ₉ copolymer resins. Among these, hydrogenated petroleum resins are preferably used from the viewpoints of heat resistance and color resistance.

  In the present invention, aromatic hydrocarbon resins such as styrene resins, xylene resins, hydrogenated aromatic copolymers, and phenol resins are, for example, styrene, α-methylstyrene, vinyltoluene, β-methylstyrene, divinyltoluene. 2-phenyl-2-butene, methoxystyrene, t-butylstyrene, chlorostyrene, indene, methylindene, phenol, cresol, xylenol, propylphenol, norylphenol, hydroquinone, resorcin, methoxyphenol, bromophenol, bisphenol A, It is an oligomer obtained by polymerizing a raw material comprising bisphenol F or a mixture thereof. In addition, those obtained by modifying the oligomer thus obtained by hydrogenation are also included. Other examples include coumarone-indene resin. Among these, a styrene resin is preferably used particularly from the viewpoint of compatibility, heat resistance, and color resistance.

  These tackifier resins may be included singly or in combination of two or more. When two or more types of these tackifying resins are contained, it is desirable in terms of excellent adhesion and tack balance. Moreover, about the softening point of the said tackifying resin, the thing of 50-160 degreeC is preferable from the point which expresses high adhesive force.

  Content of tackifying resin is 1-190 mass parts with respect to a total of 100 mass parts of acrylic triblock copolymer (I) and acrylic triblock copolymer (II). When the tackifying resin is a rosin resin, terpene phenol resin, styrene resin, xylene resin, hydrogenated aromatic copolymer, phenol resin, coumarone-indene resin, etc., the content of the tackifying resin is within the above range. When it exists, it is excellent in the balance of the adhesive force of an adhesive composition, tack, and cohesive force. From the viewpoint of achieving higher adhesion, tack and cohesion, the content of the tackifying resin is 100 parts by mass in total of the acrylic triblock copolymer (I) and the acrylic triblock copolymer (II). On the other hand, it is preferably 10 to 180 parts by mass, and more preferably 15 to 170 parts by mass.

On the other hand, if the tackifying resin is a terpene resin composed only of (hydrogenated) petroleum resin and terpene monomer, the content is increased from the viewpoint of compatibility with the acrylic triblock copolymer. It tends to be difficult. From the viewpoint of adhesive strength, tack and cohesive strength, and compatibility, the content of the tackifying resin is 100 parts by mass in total of the acrylic triblock copolymer (I) and the acrylic triblock copolymer (II). On the other hand, it is preferable that it is 2-40 mass parts, and it is more preferable that it is 2-30 mass parts.

(Plasticizer)
The adhesive composition of the present invention may contain a plasticizer. By including a plasticizer in the adhesive composition of the present invention, an adhesive composition having an excellent balance between adhesive force and tack can be obtained. Can reduce the cost.

  Examples of such plasticizers include, for example, phthalic acid esters such as dibutyl phthalate, di n-octyl phthalate, bis (2-ethylhexyl) phthalate, bis (2-ethylhexyl) terephthalate, di n-decyl phthalate, diisodecyl phthalate; Adipates such as bis (2-ethylhexyl) adipate, diisodecyl adipate, di-n-octyl adipate; sebacates such as bis (2-ethylhexyl) sebacate, di-n-butyl sebacate; bis (2-ethylhexyl) azelate Azelaic acid esters; citrate esters such as acetyltributyl citrate; paraffins such as chlorinated paraffin; glycols such as polypropylene glycol; epoxy such as epoxidized soybean oil and epoxidized linseed oil Vegetable oils; phosphate esters such as trioctyl phosphate and triphenyl phosphate; phosphites such as triphenyl phosphite; esterified products of adipic acid and 1,3-butylene glycol, benzoic acid and dipropylene glycol Ester oligomers such as low molecular weight polybutene, low molecular weight polyisobutylene, low molecular weight polyisoprene and other low molecular weight polymers; acrylic oligomers such as poly (n-butyl acrylate) and poly (2-ethylhexyl acrylate); Diana Process Oil PW Paraffinic oils such as series (made by Idemitsu Kosan Co., Ltd.), SUNPURE LW70 and P series (made by Nippon Sun Oil Co., Ltd.); SUNPURE N90 and NX90, SUNTHENE series (made by Nippon Sun Oil Co., Ltd.) Naphthenic oils; JSO AROMA790 (manufactured by Japan Sun Oil Co., Ltd.), Vivatec500 (H & R Co., Ltd.) aromatic oil and the like, these are used alone or in combination.

  The content of the plasticizer is preferably 80 parts by mass or less, and 70 parts by mass or less with respect to 100 parts by mass in total of the acrylic triblock copolymer (I) and the acrylic triblock copolymer (II). More preferably, it is more preferably 60 parts by mass or less. When the content of the plasticizer is in the above range, an adhesive composition having no bleeding and excellent transparency can be obtained. In addition, in order to obtain the effect by including a plasticizer in the adhesive composition, the total amount of acrylic triblock copolymer (I) and acrylic triblock copolymer (II) is 100 parts by mass. On the other hand, it is usually desirable to contain 5 parts by mass or more.

  The adhesive composition of the present invention is a polymer, softener, heat stabilizer, light stabilizer, antistatic agent, flame retardant, foaming agent, colorant, as long as the effects of the present invention are not impaired. Additives such as a staining agent, a refractive index adjusting agent, a filler, a curing agent, and an anti-sticking agent may be contained. These other polymers and additives may be included singly or in combination of two or more.

  Examples of other polymers include acrylic resins such as polymethyl methacrylate and (meth) acrylic acid ester copolymers; polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polybutene-1, and poly-4-methyl. Olefin resins such as pentene-1 and polynorbornene; ethylene ionomers; polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin, etc. Styrene resin; Styrene-methyl methacrylate copolymer; Polyester resin such as polyethylene terephthalate, polybutylene terephthalate and polylactic acid; Polyamide such as nylon 6, nylon 66 and polyamide elastomer; Polycarbonate; Polyvinyl chloride; Polyvinyl alcohol; Ethylene-vinyl alcohol copolymer; Polyacetal; Polyvinylidene fluoride; Polyurethane; Modified polyphenylene ether; Polyphenylene sulfide; Silicone rubber modified resin; Acrylic rubber; Silicone rubber; Sstyrene such as SEPS, SEBS, SIS Thermoplastic elastomers; olefin 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 resin, ethylene-vinyl acetate copolymer, AS resin, polylactic acid, Polyvinylidene fluoride and styrenic thermoplastic elastomer are preferred, and (meth) acrylic acid ester copolymers are more preferred.

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

  When a hardener is included in the adhesive composition of the present invention, it can be suitably used as a curable adhesive. Examples of the curing agent include photocuring agents such as UV curing agents, thermosetting agents, and the like, and examples include benzoins, benzoin ethers, benzophenones, anthraquinones, benzyls, acetophenones, and diacetyls. . Specifically, benzoin, α-methylol benzoin, α-t-butyl benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin-n-propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, α-methylol benzoin methyl ether, α -Methoxybenzoin methyl ether, benzoin phenyl ether, benzophenone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, benzyl, 2,2-dimethoxy-1,2-diphenylethane-1-one (2,2 -Dimethoxy-2-phenylacetophenone), diacetyl and the like. A hardening | curing agent may be contained individually by 1 type, and 2 or more types may be contained.

  From the viewpoint of enhancing the effect of the curing agent, for example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, itaconic acid, acrylic acid ester, methacrylic acid, Esters such as acid esters, crotonic acid esters and maleic acid esters; acrylamides; methacrylamides; acrylamide derivatives such as N-methylol acrylamide, N-hydroxyethyl acrylamide and N, N- (dihydroxyethyl) acrylamide; N-methylol methacrylamide; Methacrylamide derivatives such as N-hydroxyethyl methacrylamide and N, N- (dihydroxyethyl) methacrylamide; vinyl esters; vinyl ethers; mono-N-vinyl derivatives; monomers such as styrene derivatives; An oligomer containing a body as a constituent component may be further contained in the adhesive composition of the present invention. From the viewpoint of enhancing durability, esters such as acrylic acid esters, methacrylic acid esters, crotonic acid esters, and maleic acid esters; vinyl ethers; styrene derivatives; and oligomers containing the aforementioned monomers as constituents are preferred. In addition to these monomers, a cross-linking agent composed of a bifunctional or higher functional monomer or oligomer may be further contained.

  When an anti-sticking agent is included in the adhesive composition of the present invention, improvement in handleability can 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, montanic acid Waxes such as low molecular weight wax; low molecular weight polyolefin such as low molecular weight polyethylene and low molecular weight polypropylene; acrylic resin powder; polyorganosiloxane such as dimethylpolysiloxane; octadecylamine, alkyl phosphate, fatty acid ester, ethylenebisstearylamide, etc. Examples thereof include amide resin powder, fluororesin powder such as ethylene tetrafluoride resin, molybdenum disulfide powder, silicone resin powder, silicone rubber powder, silica and the like.

The method for producing the adhesive composition of the present invention is not particularly limited. For example, each component is usually 100 by using a known mixing or kneading apparatus such as a kneader ruder, an extruder, a mixing roll, or a Banbury mixer. It can manufacture by mixing at the temperature in the range of -250 degreeC. Moreover, after dissolving each component in an organic solvent and mixing, you may manufacture by distilling off this organic solvent. The obtained adhesive composition can be used by heating and melting, or it 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.
In addition, when using the adhesive composition of this invention heat-melting, it is preferable that a melt viscosity is low from a viewpoint of workability and handleability. On the other hand, it is preferable that the melt viscosity is high from the viewpoint of achieving both the adhesive properties of the adhesive composition and high holding power (creep resistance).

  The pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive in the form of a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition or a laminate (for example, a laminated film or a sheet) including the pressure-sensitive adhesive layer. It is suitably used for adhesive products.

  In order to form the above-mentioned adhesive layer, when the adhesive composition of the present invention is heated and melted, for example, a hot melt coating method, a T-die method, an inflation method, a calendar molding method, a lamination method, etc. It can be formed into a sheet shape or a film shape. For example, the pressure-sensitive adhesive layer can be formed on a film or sheet of a heat-resistant material such as polyethylene terephthalate using a method of melt-coating the heat-melted adhesive composition using 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, in order to heat and melt at a higher temperature, A hot melt coating method in which the heated melt is applied on the support in a non-contact manner is preferable from the viewpoints of thickness control of the adhesive layer, homogeneity, and heat resistance necessary for the support. Further, when the adhesive composition of the present invention is used by dissolving in a solvent, 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 support, and a bar coater, A solution in which a composition containing an acrylic triblock copolymer (I), an acrylic triblock copolymer (II), and a tackifying resin is dissolved in a solvent using a roll coater, a die coater, a comma coater, or the like The adhesive layer can be formed using a method (solution casting method) in which the solvent is removed by coating and drying.

  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 stages. When drying is performed in a plurality of stages, the first stage of drying is performed at a relatively low temperature in order to suppress foaming due to rapid volatilization of the solvent. In order to remove the solvent, a method of drying at a high temperature is more preferable.

  The concentration of the composition containing the acrylic triblock copolymer (I), the acrylic triblock copolymer (II), and the tackifier resin in the above solution is the solubility of the composition in the solvent, and the resulting solution The lower limit is preferably 5% by mass, and the preferable upper limit is 70% by mass.

  The laminate is obtained by laminating an adhesive layer composed of the adhesive composition of the present invention and various base materials such as paper, cellophane, plastic material, cloth, wood, and metal. A base material layer made of a transparent material is suitable because the adhesive composition of the present invention is excellent in transparency and weather resistance, so that a transparent laminate can be obtained. As the base material layer made of a transparent material, polyethylene terephthalate, triacetyl cellulose, polyvinyl alcohol, cycloolefin resin, styrene-methyl methacrylate copolymer, polypropylene, polyethylene, polyvinyl chloride, ethylene-vinyl acetate copolymer , A copolymer of a polymer such as polycarbonate, polymethyl methacrylate, polyethylene or polypropylene and various monomers, a mixture of two or more of these polymers, and a substrate layer made of glass, etc. It is not limited.

  As a structure of the said laminated body, the two-layer structure of the adhesive layer and base material layer which consist of an adhesive composition of this invention, for example, Two base material layers and the adhesive composition of this invention 3 layer constitution (base material layer / adhesive layer / base material layer) with two different adhesive layers (the base material layer and the adhesive composition of the present invention) a) and a four-layer configuration of an adhesive layer (b) and a base material layer (base material layer / adhesive layer (a) / adhesive layer (b) / base material layer), base material layer and book A four-layer structure (base layer / adhesive layer (a ) / Adhesive layer (c) / base material layer), 3 base material layers and 2 adhesive layers composed of the adhesive composition of the present invention (base material layer / adhesion) (Attachment layer / base material layer / adhesive layer / base material layer) and the like, but is not limited thereto.

  Although it does not restrict | limit especially as thickness ratio of the said laminated body, From the adhesiveness of an adhesive product obtained, durability, and handleability, it is the range of base material layer / adhesive layer = 1 / 1000-1000 / 1. It is preferable that it is in the range of 1/200 to 200/1.

  When the laminate is produced, the adhesive layer and the base material layer may be formed and then bonded together by a lamination method or the like, or the adhesive layer may be directly formed on the base material layer. Good. Moreover, a layered structure may be manufactured as a coextruded film or a coextruded sheet by forming a layer structure at one time by coextruding the adhesive layer and the base material layer.

  In the laminated body of this invention, in order to improve the adhesive force of a base material layer and an adhesive bond layer, you may give surface treatments, such as a corona discharge process and a plasma discharge process, to the surface of a base material layer previously. Moreover, you may form an anchor layer in the surface of at least one of the said adhesive layer and a base material layer using resin etc. which have adhesiveness.

  Examples of the resin used for the anchor layer include ethylene-vinyl acetate copolymers, ionomers, block copolymers (for example, styrene triblock copolymers such as SIS and SBS, and diblock copolymers). Examples thereof include an ethylene-acrylic acid copolymer and an ethylene-methacrylic acid copolymer. The anchor layer may be a single layer or two or more layers.

  In the case of forming the anchor layer, the method is not particularly limited. For example, a method of forming the anchor layer by applying a solution containing the resin to the base material layer, a composition containing the resin to be the anchor layer, and the like. And a method of forming an anchor layer on the surface of the base material layer by T-die or the like after heating and melting.

  When the anchor layer is formed, the anchor layer and the adhesive layer may be integrally laminated on the surface of the base material layer by co-extrusion of the resin used as the anchor layer and the adhesive composition of the present invention. Further, the anchor layer resin and the adhesive composition may be sequentially laminated on the surface of the base material layer. Furthermore, when the base material layer is a plastic material, the plastic material and anchor to be the base material layer The resin forming the layer and the adhesive composition may be coextruded at the same time.

  The adhesive which consists of an adhesive composition of this invention can be used for various uses. Moreover, the adhesive layer which consists of this adhesive composition can be used alone as an adhesive sheet, and the laminated body containing this adhesive layer can also be applied to various uses. For example, for surface protection, masking, binding, packaging, office, label, decoration / display, bonding, dicing tape, sealing, anticorrosion / waterproof, medical / hygiene, glass Adhesives and adhesives for scattering prevention, electrical insulation, electronic equipment holding and fixing, semiconductor manufacturing, optical display films, adhesive optical films, electromagnetic wave shields, or sealing materials for electrical and electronic parts A tape, a film, or a sheet is exemplified. Specific examples are given below.

  Adhesives for surface protection, adhesive tapes or films can be used for various materials such as metal, plastic, rubber, and wood. Specifically, paint parts, metal parts during plastic processing and deep drawing, automotive parts It can be used for surface protection of optical members. Examples of the automobile member include a painted outer plate, a wheel, a mirror, a window, a light, and a light cover. Examples of the optical member include various image display devices such as a liquid crystal display, an organic EL display, a plasma display, and a field emission display; a polarizing film, a polarizing plate, a retardation plate, a light guide plate, a diffusion plate, an optical disc constituting film such as a DVD;・ Precise fine coated face plate for optical applications.

  Masking adhesives, tapes, films, etc. include: masking when manufacturing printed circuit boards and flexible printed circuit boards; masking when plating and soldering on electronic equipment; manufacturing of vehicles such as automobiles, vehicles and architecture Examples include painting, printing, and masking when giving up on civil engineering work.

Examples of binding applications include wire harnesses, electric wires, cables, fibers, pipes, coils, windings, steel materials, ducts, plastic bags, foods, vegetables, and grooms.
Examples of packaging applications include heavy goods packaging, export packaging, cardboard box sealing, can seals, and the like.

The office use includes general office use, sealing, book repair, drafting, and memo.
Examples of label usage include price, product display, tag, POP, sticker, stripe, name plate, decoration, and advertisement.

  The labels include paper, processed paper (paper subjected to aluminum vapor deposition, aluminum lamination, varnishing, resin processing, etc.), paper such as synthetic paper; cellophane, plastic material, cloth, wood and metal The label which uses a film etc. as a base material is mentioned. Specific examples of the substrate include, for example, high-quality paper, art paper, cast paper, thermal paper, foil paper; polyethylene terephthalate film, polyvinyl chloride film, OPP film, polylactic acid film, synthetic paper, synthetic paper thermal, overlamination A film etc. are mentioned. Especially, the adhesive composition of this invention can be used suitably for the label using the base material which consists of a transparent material at the point which is excellent in transparency and a weather resistance. Moreover, since the adhesive composition of this invention has few discoloration with time, it can be used suitably for the thermal label which uses thermal paper or synthetic paper thermal as a base material.

  Examples of the adherend of the label include plastic products such as plastic bottles and foamed plastic cases; paper and cardboard products such as cardboard boxes; glass products such as glass bottles; metal products; and other inorganic material products such as ceramics. It is done.

  A label made of a laminate comprising an adhesive layer made of the adhesive composition of the present invention has little increase in adhesion during storage at a temperature slightly higher than room temperature (for example, 40 ° C.), and can be peeled off without any adhesive residue after use. it can. Moreover, it can be bonded to the adherend even at a low temperature (−40 to + 10 ° C.) and does not peel off even when stored at a low temperature (−40 to + 10 ° C.).

Examples of decoration / display applications include danger display stickers, line tapes, wiring markings, phosphorescent tapes, and reflective sheets.
Examples of adhesive optical film applications include polarizing films, polarizing plates, retardation films, viewing angle widening films, brightness enhancement films, antireflection films, antiglare films, color filters, light guide plates, diffusion films, prism sheets, electromagnetic wave shielding films , Near-infrared absorbing film, functional composite optical film, ITO bonding film, impact resistance imparting film, brightness enhancement film, visibility enhancement film, etc. The optical film etc. which were made are mentioned. Such an adhesive optical film includes a film in which an adhesive layer made of the adhesive composition of the present invention is formed on a protective film used for protecting the surface of the optical film. The pressure-sensitive adhesive optical film is suitably used for various image display devices such as liquid crystal display devices, PDPs, organic EL display devices, electronic paper, game machines, and mobile terminals.

Examples of electrical insulation applications include protective coating or insulation of coils, interlayer insulation such as motors and transformers, and the like.
Electronic device holding and fixing applications include carrier tape, packaging, CRT fixing, splicing, rib reinforcement, and the like.

Examples of semiconductor manufacturing include protection of silicone wafers.
Examples of bonding applications include various bonding fields, automobiles, trains, electrical equipment, printing plate fixing, construction, nameplate fixing, general household use, rough surfaces, uneven surfaces, and adhesion to curved surfaces.

Sealing applications include heat insulation, vibration proofing, waterproofing, moisture proofing, soundproofing or dustproof sealing.
Examples of the anticorrosion / waterproofing include gas, water pipe corrosion prevention, large-diameter pipe corrosion prevention, and civil engineering building corrosion prevention.

For medical and hygiene applications, analgesic / anti-inflammatory agents (plasters, papps), ischemic heart disease treatments, female hormone supplements, bronchodilators, cancer pain relieving agents, smoking cessation aids, cold patches, antipruritic patches, Percutaneous absorption medicines such as keratin softeners; emergency bandages (with bactericides), surgical dressings / surgical tapes, bandages, hemostatic bonds, human excrement treatment attachment tapes (artificial anal fixation tapes), suture tapes, antibacterial tapes , Fixed taping, self-adhesive dressing, oral mucosa adhesive tape, sports tape, hair removal tape, etc .; cosmetic use such as face pack, moisturizing sheet, exfoliating pack; cooling sheet, thermal warmer, dustproof, Examples include waterproofing and pest capturing.
Examples of electronic / electrical component sealing materials include liquid crystal monitors and solar cells.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In Production Examples 1 to 15 shown below, monomers and other compounds were dried and purified by a conventional method and degassed with nitrogen. Moreover, transfer and supply of monomers and other compounds to the reaction system were performed in a nitrogen atmosphere.

In the following examples, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw / Mn) of the polymer (polymer forming the block) and the block copolymer are obtained by polystyrene conversion molecular weight by GPC. It was. The measuring apparatus 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” and “G5000HXL” manufactured by Tosoh Corporation are connected in series. Eluent: Tetrahydrofuran Eluent flow rate: 1.0 ml / min Column temperature: 40 ° C.
・ Detection method: Differential refractive index (RI)

In the following examples, the content of each polymer block in the block copolymer was determined by ¹ H-NMR measurement. ^The measuring apparatus and conditions used in ¹ H-NMR measurement are as follows.
[Apparatus and conditions for ¹ H-NMR measurement]
・ Device: JEOL Nuclear Magnetic Resonance Device “JNM-LA400”
・ Deuterated solvent: Deuterated chloroform
^{In the 1} H-NMR spectrum, signals near 3.6 ppm and 4.0 ppm are respectively represented by an ester group (—O—CH ₃ ) of a methyl methacrylate unit and an ester group (—O—C H ₂ ) of an acrylate unit. is attributed to -CH ₂ -CH ₂ -CH _3, or _{-O-C H 2 -CH (-CH} 2 -CH 3) -CH 2 -CH 2 -CH 2 -CH 3), each by the ratio of the integrated value The content of the polymer block was determined.
The ratio of the monomer constituting the polymer block (B) in the acrylic triblock copolymers (I-7) to (I-9) is about 4.1 ppm of acrylic acid in the ¹ H-NMR spectrum. n- butyl ester group _{(-O-C H 2 -CH 2} -CH 2 -CH 3) from the signal, and an ester group of 2-ethylhexyl acrylate in the vicinity of 4.2ppm _(-O-C H 2 -CH From the signal derived from (—CH ₂ —CH ₃ ) —CH ₂ —CH ₂ —CH ₂ —CH ₃ ), the content by molar ratio of each monomer is determined by the ratio of the integral values, Based on the molecular weight of the body unit, it was converted into a mass ratio, and the mass ratio of the monomers constituting the polymer block (B) was obtained.

  Evaluation of the pressure-sensitive adhesive tape having the pressure-sensitive adhesive layer made of the adhesive composition was performed by the following method.

[Compatibility]
The compatibility was evaluated by the appearance 24 hours after the production of the pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer having a thickness of 25 μm produced by the method described later. When the adhesive tape was colorless and transparent and no white turbidity was observed, “A” (compatibility: good), and when the unevenness or white turbidity was observed, “B” (compatibility: bad).

[Bleed]
The appearance immediately after the production of the pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer having a thickness of 25 μm produced by the method described later and after 24 hours was observed and evaluated by bleeding of the liquid material from the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape. “A” when no oozing of the liquid material from the surface of the adhesive layer is observed either immediately after production or 24 hours after production, and “b” when liquid material oozes from the tape surface after 24 hours of production. It was.

[Adhesive properties]
The resistance when pressing and peeling the thumb against the adhesive layer surface of the adhesive tape produced by the method described below at 25 ° C. was subjected to a sensory evaluation as a tack feeling, and this was used as an index of the adhesive property. Here, the larger the number, the higher the tackiness (tackiness), “3” being good tackiness and “2” being tackiness, indicating that it is suitable as an adhesive. On the other hand, “1” was not suitable as a pressure-sensitive adhesive with no tackiness.

[Machinability]
The processability of the adhesive composition was evaluated as follows.
(Including acrylic triblock copolymer (I) and acrylic triblock copolymer (II))
Acrylic triblock copolymer (I) is charged into a kneader set at 160 ° C. and uniformly melted, then the kneader temperature is set at 145 ° C., and acrylic triblock copolymer (II) is added to the kneader. The mixture was melt kneaded so that the mixture became uniform. A tackifying resin is added to the melt kneaded product of the acrylic triblock copolymer (I) and the acrylic triblock copolymer (II) in the kneader set at 145 ° C., and the tackifying resin is kneaded. Rareness was evaluated in two stages (i, ii) and used as an index of workability. Evaluation was made as “i” when the tackifier resin was kneaded immediately, and as “ii” when it was not kneaded immediately.
(When acrylic triblock copolymer (II) is not included)
Acrylic triblock copolymer (I) is charged into a kneader set at 160 ° C. and uniformly melted, and then the kneader temperature is set at 145 ° C. to melt the acrylic triblock copolymer (I). A tackifier resin was added to the kneaded product, and evaluation was performed according to the same criteria as described above (how the tackifier resin was kneaded).

[Thermal stability]
The thermal stability was evaluated by observing the appearance of the obtained adhesive tape before and after the heat treatment at 180 ° C. for 3 hours and by the presence or absence of a color change. When the color change could not be confirmed on the appearance before and after the heat treatment, it was “◯”, and when the color change could be confirmed, “△”.

[Melt viscosity]
In the evaluation of workability, the pressure-sensitive adhesive composition prepared by melt kneading was set in a B-type viscometer, and the melt viscosity when heated to 160 ° C. and 180 ° C. was measured. The spindle is No. 29 was used.

[Retention force (creep resistance)]
The measurement was performed according to JIS Z0237. That is, the produced adhesive tape having a thickness of 25 μm was attached to a stainless steel (SUS304) plate (bright annealed product) with a width of 25 mm × a length of 25 mm, a load of 500 g was suspended at a temperature of 60 ° C., and a drop time or 240 minutes later The deviation distance was obtained.

<< Production Example 1 >> [Production of Acrylic Triblock Copolymer (I-1)]
(1) A 3 L three-necked flask was fitted with a three-way cock and the inside was replaced with nitrogen. Then, while stirring at room temperature, 1408 g of toluene and 32.7 g of 1,2-dimethoxyethane were added, followed by isobutylbis (2, 6-di-t-butyl-4-methylphenoxy) 48.6 g of toluene solution containing 24.5 mmol of aluminum, and further 2.39 g of cyclohexane solution of sec-butyllithium containing 4.08 mmol of sec-butyllithium added.
(2) Subsequently, 32.6 g of methyl methacrylate was added thereto. The reaction solution was initially colored yellow, but became colorless after stirring for 60 minutes at room temperature. A small amount was sampled, and the weight average molecular weight of the obtained polymethyl methacrylate was determined by GPC measurement by the method described above.
(3) Subsequently, the internal temperature of the polymerization solution was cooled to −30 ° C., 410 g of n-butyl acrylate was added dropwise over 2 hours, and the mixture was stirred at −30 ° C. for 5 minutes after the completion of the addition.
(4) Furthermore, 45.3 g of methyl methacrylate was added thereto and 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. Thereafter, the liquid precipitate was collected and dried to obtain 445 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 method described above. Further, by ^{1 H-NMR} measurements described above, to determine the total content of the polymer block comprising the acrylic triblock copolymer (I-1) methyl methacrylate units in the.

<< Production Example 2 >> [Production of Acrylic Triblock Copolymer (I-2)]
(1) A 3 L three-necked flask was fitted with a three-way cock and the inside was replaced with nitrogen. Then, while stirring at room temperature, 1409 g of toluene and 32.7 g of 1,2-dimethoxyethane were added, followed by isobutylbis (2, 6-di-t-butyl-4-methylphenoxy) 48.6 g of toluene solution containing 24.5 mmol of aluminum, and further 1.50 g of 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 for 60 minutes at room temperature. A small amount was sampled, and the weight average molecular weight of the obtained polymethyl methacrylate was determined by GPC measurement by the method described above.
(3) Subsequently, the internal temperature of the polymerization solution was cooled to −30 ° C., 434 g of n-butyl acrylate was added dropwise over 2 hours, and the mixture was stirred at −30 ° C. for 5 minutes after the completion of the addition.
(4) Furthermore, 29.4 g of methyl methacrylate was added to this, and it stirred at room temperature overnight.
(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. Thereafter, 440 g of an acrylic triblock copolymer (I-2) was obtained by collecting and drying the liquid precipitate. The weight average molecular weight of the obtained acrylic triblock copolymer (I-2) was determined by GPC measurement using the method described above. Further, by ^{1 H-NMR} measurements described above, to determine the total content of the polymer block comprising the acrylic triblock copolymer (I-2) methyl methacrylate units in the.

<< Production Example 3 >> [Production of Acrylic Triblock Copolymer (I-3)]
(1) A 3 L three-necked flask was fitted with a three-way cock and the inside was replaced with nitrogen. Then, while stirring at room temperature, 1409 g of toluene and 32.7 g of 1,2-dimethoxyethane were added, followed by isobutylbis (2, 6-di-t-butyl-4-methylphenoxy) 48.6 g of toluene solution containing 24.5 mmol of aluminum, and further 1.85 g of cyclohexane solution of sec-butyllithium containing 3.15 mmol of sec-butyllithium. added.
(2) Subsequently, 32.6 g of methyl methacrylate was added thereto. The reaction solution was initially colored yellow, but became colorless after stirring for 60 minutes at room temperature. A small amount was sampled, and the weight average molecular weight of the obtained polymethyl methacrylate was determined by GPC measurement by the method described above.
(3) Subsequently, the internal temperature of the polymerization solution was cooled to −30 ° C., 410 g of n-butyl acrylate was added dropwise over 2 hours, and the mixture was stirred at −30 ° C. for 5 minutes after the completion of the addition.
(4) Furthermore, 45.3 g of methyl methacrylate was added thereto and 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. Thereafter, the liquid precipitate was collected and dried to obtain 445 g of an acrylic triblock copolymer (I-3). The weight average molecular weight of the obtained acrylic triblock copolymer (I-3) was determined by GPC measurement using the method described above. Moreover, the total content of the polymer block which consists of a methylmethacrylate unit in an acrylic type triblock copolymer (I-3) was calculated | required by the < ¹ > H-NMR measurement mentioned above.

<< Production Example 4 >> [Production of Acrylic Triblock Copolymer (I-4)]
(1) A 3 L three-necked flask was fitted with a three-way cock and the inside was replaced with nitrogen. Then, while stirring at room temperature, 1409 g of toluene and 32.7 g of 1,2-dimethoxyethane were added, followed by isobutylbis (2, 6-di-t-butyl-4-methylphenoxy) 48.6 g of a toluene solution containing 24.5 mmol of aluminum, and 2.55 g of a cyclohexane solution of sec-butyllithium containing 4.35 mmol of sec-butyllithium. added.
(2) Subsequently, 43.5 g of methyl methacrylate was added thereto. The reaction solution was initially colored yellow, but became colorless after stirring for 60 minutes at room temperature. A small amount was sampled, and the weight average molecular weight of the obtained polymethyl methacrylate was determined by GPC measurement by the method described above.
(3) Subsequently, the internal temperature of the polymerization solution was cooled to −30 ° C., 360 g of n-butyl acrylate was added dropwise over 2 hours, and the mixture was stirred at −30 ° C. for 5 minutes after the completion of the addition.
(4) Furthermore, 61.5 g of methyl methacrylate was added to this, and it stirred at room temperature overnight.
(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. Thereafter, 450 g of an acrylic triblock copolymer (I-4) was obtained by collecting and drying the liquid precipitate. The weight average molecular weight of the obtained acrylic triblock copolymer (I-4) was determined by GPC measurement using the method described above. Further, by ^{1 H-NMR} measurements described above, to determine the total content of the polymer block comprising the acrylic triblock copolymer (I-4) methyl methacrylate units in the.

<< Production Example 5 >> [Production of Acrylic Triblock Copolymer (I-5)]
(1) A 3 L three-necked flask was fitted with a three-way cock and the inside was replaced with nitrogen. Then, while stirring at room temperature, 1302 g of toluene and 65.1 g of 1,2-dimethoxyethane were added, followed by isobutyl bis (2, 6-di-t-butyl-4-methylphenoxy) 120.0 g of a toluene solution containing 60.3 mmol of aluminum was added, and 4.34 g of a cyclohexane solution of sec-butyllithium containing 7.50 mmol of sec-butyllithium was further added. added.
(2) Subsequently, 53.9 g of methyl methacrylate was added thereto. The reaction solution was initially colored yellow, but became colorless after stirring for 60 minutes at room temperature. A small amount was sampled, and the weight average molecular weight of the obtained polymethyl methacrylate was determined by GPC measurement by the method described above.
(3) Subsequently, the internal temperature of the polymerization solution was cooled to −30 ° C., 360 g of n-butyl acrylate was added dropwise over 2 hours, and the mixture was stirred at −30 ° C. for 5 minutes after the completion of the addition.
(4) Furthermore, 53.9 g of methyl methacrylate was added thereto, and the mixture was stirred overnight at room temperature.
(5) After adding 20 g of methanol to stop the polymerization reaction, the resulting reaction solution was poured into 15 kg of methanol to precipitate a liquid precipitate. Thereafter, 440 g of an acrylic triblock copolymer (I-5) was obtained by collecting and drying the liquid precipitate. The weight average molecular weight of the obtained acrylic triblock copolymer (I-5) was determined by GPC measurement using the method described above. Moreover, the total content of the polymer block which consists of a methylmethacrylate unit in an acryl-type triblock copolymer (I-5) was calculated | required by ¹ H-NMR measurement mentioned above.

<< Production Example 6 >> [Production of Acrylic Triblock Copolymer (I-6)]
(1) A 3 L three-necked flask was fitted with a three-way cock and the inside was replaced with nitrogen. Then, while stirring at room temperature, 1302 g of toluene and 65.1 g of 1,2-dimethoxyethane were added, followed by isobutyl bis (2, 6-di-t-butyl-4-methylphenoxy) 120.0 g of a toluene solution containing 60.3 mmol of aluminum was added, and 4.34 g of a cyclohexane solution of sec-butyllithium containing 7.50 mmol of sec-butyllithium was further added. added.
(2) Subsequently, 69.3 g of methyl methacrylate was added thereto. The reaction solution was initially colored yellow, but became colorless after stirring for 60 minutes at room temperature. A small amount was sampled, and the weight average molecular weight of the obtained polymethyl methacrylate was determined by GPC measurement by the method described above.
(3) Subsequently, the internal temperature of the polymerization solution was cooled to −30 ° C., 315 g of n-butyl acrylate was added dropwise over 2 hours, and the mixture was stirred at −30 ° C. for 5 minutes after the completion of the addition.
(4) Furthermore, 65.9 g of methyl methacrylate was added thereto, and the mixture was stirred overnight at room temperature.
(5) After adding 20 g of methanol to stop the polymerization reaction, the resulting reaction solution was poured into 15 kg of methanol to precipitate a liquid precipitate. Thereafter, 440 g of an acrylic triblock copolymer (I-6) was obtained by collecting and drying the liquid precipitate. The weight average molecular weight of the obtained acrylic triblock copolymer (I-6) was determined by GPC measurement using the method described above. Moreover, the total content of the polymer block which consists of a methyl methacrylate unit in an acryl-type triblock copolymer (I-6) was calculated | required by ¹ H-NMR measurement mentioned above.

<< Production Example 7 >> [Synthesis of Acrylic Triblock Copolymer (I-7)]
(1) A three-way cock was attached to a 2 L three-necked flask and the inside was replaced with nitrogen. Then, while stirring at room temperature, 1035 g of toluene and 31.9 g of 1,2-dimethoxyethane were added, followed by isobutylbis (2, 6-di-t-butyl-4-methylphenoxy) 41.7 g of a toluene solution containing 21.0 mmol of aluminum and 2.41 g of a cyclohexane solution of sec-butyllithium containing 4.11 mmol of sec-butyllithium were added. added.
(2) Subsequently, 28.5 g of methyl methacrylate was added thereto. The reaction solution was initially colored yellow, but became colorless after stirring for 60 minutes at room temperature. A small amount was sampled, and the weight average molecular weight of the obtained polymethyl methacrylate was determined by GPC measurement by the method described above.
(3) Subsequently, the internal temperature of the polymerization solution was cooled to −30 ° C., and 210 g of a mixture of n-butyl acrylate / 2-ethylhexyl acrylate (mass ratio 50/50) was added dropwise over 2 hours, and after completion of the addition Stir at −30 ° C. for 5 minutes.
(4) Furthermore, 31.8 g of methyl methacrylate was added to this, and it stirred at room temperature overnight.
(5) After adding 13.6 g of methanol to stop the polymerization reaction, the resulting reaction solution was poured into 15 kg of methanol to precipitate a white precipitate. Thereafter, the liquid precipitate was collected and dried to obtain 250 g of an acrylic triblock copolymer (I-7). The weight average molecular weight of the obtained acrylic triblock copolymer (I-7) was determined by GPC measurement using the method described above. In addition, the total content of polymer blocks composed of methyl methacrylate units in the acrylic triblock copolymer (I-7) by the ¹ H-NMR measurement described above, n-butyl acrylate / 2-ethylhexyl acrylate The mass ratio of was determined.

<< Synthesis Example 8 >> [Synthesis of Acrylic Triblock Copolymer (I-8)]
(1) A 3-liter cock was attached to a 2 L three-necked flask and the inside was replaced with nitrogen. Then, while stirring at room temperature, 1044 g of toluene and 34.8 g of 1,2-dimethoxyethane were added, followed by isobutylbis (2, 6-di-t-butyl-4-methylphenoxy) 34.0 g of a toluene solution containing 17.1 mmol of aluminum was added, and 1.67 g of a cyclohexane solution of sec-butyllithium containing 2.84 mmol of sec-butyllithium was further added. added.
(2) Subsequently, 22.0 g of methyl methacrylate was added thereto. The reaction solution was initially colored yellow, but became colorless after stirring for 60 minutes at room temperature. A small amount was sampled, and the weight average molecular weight of the obtained polymethyl methacrylate was determined by GPC measurement by the method described above.
(3) Subsequently, the internal temperature of the polymerization solution was cooled to −30 ° C., and 214 g of a mixture of n-butyl acrylate / 2-ethylhexyl acrylate (mass ratio 50/50) was added dropwise over 2 hours. Stir at −30 ° C. for 5 minutes.
(4) Furthermore, 33.8 g of methyl methacrylate was added to this, and it stirred at room temperature overnight.
(5) After adding 10.7 g of methanol to stop the polymerization reaction, the obtained reaction solution was poured into 15 kg of methanol to precipitate a white precipitate. Thereafter, the white precipitate was recovered and dried to obtain 250 g of an acrylic triblock copolymer (I-8). The weight average molecular weight of the obtained acrylic triblock copolymer (I-8) was determined by GPC measurement using the method described above. Moreover, the total content of the polymer block consisting of methyl methacrylate units in the acrylic triblock copolymer (I-8) by the ¹ H-NMR measurement described above, n-butyl acrylate / 2-ethylhexyl acrylate The mass ratio of was determined.

<< Synthesis Example 9 >> [Synthesis of Acrylic Triblock Copolymer (I-9)]
(1) A three-way cock was attached to a 2 L three-necked flask and the inside was replaced with nitrogen. Then, while stirring at room temperature, 1038 g of toluene and 43.5 g of 1,2-dimethoxyethane were added, followed by isobutylbis (2, 6-di-t-butyl-4-methylphenoxy) 37.4 g of toluene solution containing 18.8 mmol of aluminum was added, and 2.90 g of cyclohexane solution of sec-butyllithium containing 4.95 mmol of sec-butyllithium was further added. added.
(2) Subsequently, 25.4 g of methyl methacrylate was added thereto. The reaction solution was initially colored yellow, but became colorless after stirring for 60 minutes at room temperature. A small amount was sampled, and the weight average molecular weight of the obtained polymethyl methacrylate was determined by GPC measurement by the method described above.
(3) Subsequently, the internal temperature of the polymerization solution was cooled to −30 ° C., and 215 g of a mixture of n-butyl acrylate / 2-ethylhexyl acrylate (mass ratio 50/50) was added dropwise over 2 hours. Stir at −30 ° C. for 5 minutes.
(4) Furthermore, 29.4 g of methyl methacrylate was added to this, and it stirred at room temperature overnight.
(5) After adding 13.3 g of methanol to stop the polymerization reaction, the resulting reaction solution was poured into 15 kg of methanol to precipitate a white precipitate. Thereafter, a white precipitate was collected and dried to obtain 250 g of an acrylic triblock copolymer (I-9). The weight average molecular weight of the obtained acrylic triblock copolymer (I-9) was determined by GPC measurement using the method described above. Moreover, the total content of the polymer block consisting of methyl methacrylate units in the acrylic triblock copolymer (I-9) by the ¹ H-NMR measurement described above, n-butyl acrylate / 2-ethylhexyl acrylate The mass ratio of was determined.

<< Production Example 10 >> [Production of Acrylic Triblock Copolymer (II-1)]
(1) A 3 L three-necked flask was fitted with a three-way cock and the inside was replaced with nitrogen. Then, while stirring at room temperature, 1409 g of toluene and 32.7 g of 1,2-dimethoxyethane were added, followed by isobutylbis (2, 48.6 g of toluene solution containing 24.5 mmol of 6-di-t-butyl-4-methylphenoxy) aluminum, and 5.55 g of cyclohexane solution of sec-butyllithium containing 9.44 mmol of sec-butyllithium. added.
(2) Subsequently, 28.8 g of methyl methacrylate was added thereto. The reaction solution was initially colored yellow, but became colorless after stirring for 60 minutes at room temperature. A small amount was sampled, and the weight average molecular weight of the obtained polymethyl methacrylate was determined by GPC measurement by the method described above.
(3) Subsequently, the internal temperature of the polymerization liquid was cooled to −30 ° C., 427 g of n-butyl acrylate was added dropwise over 2 hours, and the mixture was stirred at −30 ° C. for 5 minutes after the completion of the addition.
(4) Furthermore, 9.30 g of methyl methacrylate was added to this, and it stirred at room temperature overnight.
(5) After adding 20 g of methanol to stop the polymerization reaction, the resulting reaction solution was poured into 15 kg of methanol to precipitate a liquid precipitate. Thereafter, 440 g of an acrylic triblock copolymer (II-1) was obtained by collecting the liquid precipitate and drying it. The weight average molecular weight of the obtained acrylic triblock copolymer (II-1) was determined by GPC measurement using the method described above. Moreover, the total content of the polymer block which consists of a methyl methacrylate unit in acrylic type triblock copolymer (II-1) was calculated | required by ¹ H-NMR measurement mentioned above.

<< Production Example 11 >> [Production of Acrylic Triblock Copolymer (II-2)]
(1) A 3 L three-necked flask was fitted with a three-way cock and the inside was replaced with nitrogen. Then, while stirring at room temperature, 1409 g of toluene and 32.7 g of 1,2-dimethoxyethane were added, followed by isobutylbis (2, 6-di-t-butyl-4-methylphenoxy) 48.6 g of toluene solution containing 24.5 mmol of aluminum was added, and 3.75 g of cyclohexane solution of sec-butyl lithium containing 6.38 mmol of sec-butyllithium was further added. added.
(2) Subsequently, 31.0 g of methyl methacrylate was added thereto. The reaction solution was initially colored yellow, but became colorless after stirring for 60 minutes at room temperature. A small amount was sampled, and the weight average molecular weight of the obtained polymethyl methacrylate was determined by GPC measurement by the method described above.
(3) Subsequently, the internal temperature of the polymerization solution was cooled to −30 ° C., 428 g of n-butyl acrylate was added dropwise over 2 hours, and the mixture was stirred at −30 ° C. for 5 minutes after the completion of the addition.
(4) Furthermore, 6.20 g of methyl methacrylate was added to this, and it stirred at room temperature overnight.
(5) After adding 20 g of methanol to stop the polymerization reaction, the resulting reaction solution was poured into 15 kg of methanol to precipitate a liquid precipitate. Thereafter, the liquid precipitate was collected and dried to obtain 440 g of an acrylic triblock copolymer (II-2). The weight average molecular weight of the obtained acrylic triblock copolymer (II-2) was determined by GPC measurement using the method described above. Further, by ^{1 H-NMR} measurements described above, to determine the total content of the polymer block comprising the acrylic triblock copolymer (II-2) methyl methacrylate units in the.

<< Production Example 12 >> [Production of Acrylic Triblock Copolymer (II-3)]
(1) A 3 L three-necked flask was fitted with a three-way cock and the inside was replaced with nitrogen. Then, while stirring at room temperature, 1409 g of toluene and 32.7 g of 1,2-dimethoxyethane were added, followed by isobutylbis (2, 6-di-t-butyl-4-methylphenoxy) 48.6 g of toluene solution containing 24.5 mmol of aluminum was added, and 4.50 g of cyclohexane solution of sec-butyl lithium containing 7.65 mmol of sec-butyllithium was further added. added.
(2) Subsequently, 30.1 g of methyl methacrylate was added thereto. The reaction solution was initially colored yellow, but became colorless after stirring for 60 minutes at room temperature. A small amount was sampled, and the weight average molecular weight of the obtained polymethyl methacrylate was determined by GPC measurement by the method described above.
(3) Subsequently, the internal temperature of the polymerization liquid was cooled to −30 ° C., 427 g of n-butyl acrylate was added dropwise over 2 hours, and the mixture was stirred at −30 ° C. for 5 minutes after the completion of the addition.
(4) Furthermore, 7.60 g of methyl methacrylate was added to this, and it stirred at room temperature overnight.
(5) After adding 20 g of methanol to stop the polymerization reaction, the resulting reaction solution was poured into 15 kg of methanol to precipitate a liquid precipitate. Thereafter, 440 g of an acrylic triblock copolymer (II-3) was obtained by collecting and drying the liquid precipitate. The weight average molecular weight of the obtained acrylic triblock copolymer (II-3) was determined by GPC measurement by the method described above. Further, by ^{1 H-NMR} measurements described above, to determine the total content of the polymer block comprising the acrylic triblock copolymer (II-3) methyl methacrylate units in the.

<< Production Example 13 >> [Production of Acrylic Triblock Copolymer (II-4)]
(1) A 3 L three-necked flask was fitted with a three-way cock and the inside was replaced with nitrogen. Then, while stirring at room temperature, 1409 g of toluene and 32.7 g of 1,2-dimethoxyethane were added, followed by isobutylbis (2, 48.6 g of toluene solution containing 24.5 mmol of 6-di-t-butyl-4-methylphenoxy) aluminum, and further 4.95 g of cyclohexane solution of sec-butyllithium containing 8.42 mmol of sec-butyllithium. added.
(2) Subsequently, 32.7 g of methyl methacrylate was added thereto. The reaction solution was initially colored yellow, but became colorless after stirring for 60 minutes at room temperature. A small amount was sampled, and the weight average molecular weight of the obtained polymethyl methacrylate was determined by GPC measurement by the method described above.
(3) Subsequently, the internal temperature of the polymerization liquid was cooled to −30 ° C., 427 g of n-butyl acrylate was added dropwise over 2 hours, and the mixture was stirred at −30 ° C. for 5 minutes after the completion of the addition.
(4) Further, 4.97 g of methyl methacrylate was added thereto, and the mixture was stirred overnight at room temperature.
(5) After adding 20 g of methanol to stop the polymerization reaction, the resulting reaction solution was poured into 15 kg of methanol to precipitate a liquid precipitate. Thereafter, 440 g of an acrylic triblock copolymer (II-4) was obtained by collecting the liquid precipitate and drying it. The weight average molecular weight of the obtained acrylic triblock copolymer (II-4) was determined by GPC measurement using the method described above. Further, by ^{1 H-NMR} measurements described above, to determine the total content of the polymer block consisting of methyl methacrylate units in the acrylic triblock copolymer (II-4).

<< Production Example 14 >> [Production of Acrylic Triblock Copolymer (II-5)]
(1) A 3 L three-necked flask was fitted with a three-way cock and the inside was replaced with nitrogen. Then, while stirring at room temperature, 1409 g of toluene and 32.7 g of 1,2-dimethoxyethane were added, followed by isobutylbis (2, 6-di-t-butyl-4-methylphenoxy) 48.6 g of toluene solution containing 24.5 mmol of aluminum, and 4.43 g of cyclohexane solution of sec-butyllithium containing 7.52 mmol of sec-butyllithium were added. added.
(2) Subsequently, 29.6 g of methyl methacrylate was added thereto. The reaction solution was initially colored yellow, but became colorless after stirring for 60 minutes at room temperature. A small amount was sampled, and the weight average molecular weight of the obtained polymethyl methacrylate was determined by GPC measurement by the method described above.
(3) Subsequently, the internal temperature of the polymerization solution was cooled to −30 ° C., 420 g of n-butyl acrylate was added dropwise over 2 hours, and the mixture was stirred at −30 ° C. for 5 minutes after the completion of the addition.
(4) Furthermore, 15.0 g of methyl methacrylate was added to this, and it stirred at room temperature overnight.
(5) After adding 20 g of methanol to stop the polymerization reaction, the resulting reaction solution was poured into 15 kg of methanol to precipitate a liquid precipitate. Thereafter, the liquid precipitate was collected and dried to obtain 440 g of an acrylic triblock copolymer (II-5). The weight average molecular weight of the obtained acrylic triblock copolymer (II-5) was determined by GPC measurement by the method described above. Moreover, the total content of the polymer block which consists of a methyl methacrylate unit in acrylic type triblock copolymer (II-5) was calculated | required by ¹ H-NMR measurement mentioned above.

<< Production Example 15 >> [Production of Acrylic Triblock Copolymer (II-6)]
(1) A 3 L three-necked flask was fitted with a three-way cock and the inside was replaced with nitrogen. Then, while stirring at room temperature, 1409 g of toluene and 32.7 g of 1,2-dimethoxyethane were added, followed by isobutylbis (2, 6-di-t-butyl-4-methylphenoxy) 48.6 g of toluene solution containing 24.5 mmol of aluminum, and 4.43 g of cyclohexane solution of sec-butyllithium containing 7.52 mmol of sec-butyllithium were added. added.
(2) Subsequently, 29.9 g of methyl methacrylate was added thereto. The reaction solution was initially colored yellow, but became colorless after stirring for 60 minutes at room temperature. A small amount was sampled, and the weight average molecular weight of the obtained polymethyl methacrylate was determined by GPC measurement by the method described above.
(3) Subsequently, the internal temperature of the polymerization solution was cooled to −30 ° C., 414 g of n-butyl acrylate was added dropwise over 2 hours, and the mixture was stirred at −30 ° C. for 5 minutes after the completion of the addition.
(4) Furthermore, 21.2 g of methyl methacrylate was added to this, and it stirred at room temperature overnight.
(5) After adding 20 g of methanol to stop the polymerization reaction, the resulting reaction solution was poured into 15 kg of methanol to precipitate a liquid precipitate. Thereafter, the liquid precipitate was collected and dried to obtain 440 g of an acrylic triblock copolymer (II-6). The weight average molecular weight of the obtained acrylic triblock copolymer (II-6) was determined by GPC measurement by the method described above. Moreover, the total content of the polymer block which consists of a methylmethacrylate unit in acrylic type triblock copolymer (II-6) was calculated | required by ¹ H-NMR measurement mentioned above.

  Block structures of acrylic triblock copolymers (I-1) to (I-9) and acrylic triblock copolymers (II-1) to (II-6) obtained in Production Examples 1 to 15; Weight average molecular weight, molecular weight distribution, total content of PMMA polymer block (polymer block consisting of 100% by mass of methyl methacrylate unit), composition of polymer block (B), polymer block (A1) or (C1) Table 1 shows the weight average molecular weight and the weight average molecular weight of the polymer block (A2) or (C2). In Table 1, PMMA means a polymer block consisting of 100% by mass of methyl methacrylate units, nBA means a block consisting of 100% by mass of n-butyl acrylate units, and nBA / 2EHA means n-butyl acrylate and acrylic. It was a block in which 2-ethylhexyl acid was randomly copolymerized, and the mass ratio was also shown.

Moreover, in the Example and the comparative example, the following were used as tackifying resin and a plasticizer.
(Tackifying resin)
-Product name "Ysertack 311" manufactured by Euro Yser, rosin ester-Product name "Yserack 316" manufactured by Euro Yser, rosin ester-Product name "Pensel D125", manufactured by Arakawa Chemical Industry Co., Ltd., Polymerized rosin ester Kogyo Co., Ltd., polymerized rosin ester, trade name “KE311” manufactured by Arakawa Chemical Industries, Ltd., hydrogenated rosin ester, trade name “Foral 85E” manufactured by Eastman, hydrogenated rosin ester, trade name “Foral AX-E” manufactured by Eastman Rosin acid, trade name “YS polyster T160” manufactured by Yasuhara Chemical Co., Ltd., terpene phenol resin / trade name “YS resin SX100” manufactured by Yasuhara Chemical Co., Ltd., aromatic hydrocarbon resin, trade name “Kri” "Stalex F100" manufactured by Eastman, aromatic hydrocarbon resin / trade name "Arkon P100" manufactured by Arakawa Chemical Industries, Ltd., hydrogenated petroleum resin / trade name "Arkon M100" manufactured by Arakawa Chemical Industries, Ltd., hydrogenated petroleum resin・ Product name "Clearon K4100", manufactured by Yasuhara Chemical Co., Ltd., hydrogenated aromatic modified terpene resin (plasticizer)
・ Brand name “DOP” manufactured by Shin Nippon Rika Co., Ltd., bis (2-ethylhexyl) phthalate ・ Brand name “DOTP” manufactured by Eastman, bis (2-ethylhexyl) terephthalate ・ Brand name “ATBC” manufactured by Asahi Kasei Finechem Co., Ltd. Tributyl acid ・ Product name “K-FLEX DP” manufactured by Kalama chemical, esterified product of benzoic acid and dipropylene glycol ・ Product name “Micryl 105” manufactured by Polychem, poly n-butyl acrylate oligomer ・ Product name “ARUFON UP1171” Toagosei Co., Ltd. Acrylic oligomer made by company, trade name “ARUFON UP1010”, manufactured by Toagosei Co., Ltd.

[Example 1]
The acrylic triblock copolymer (I-3) obtained in Production Example 3 was charged into a kneader set at 160 ° C. and uniformly melted. Thereafter, the temperature of the kneader was set to 145 ° C., and the acrylic triblock copolymer (II-3) obtained in Production Example 12 was charged into the kneader and melt-kneaded so that these mixtures became uniform. Furthermore, “KE311” was added as a tackifying resin to the melt-kneaded product of acrylic triblock copolymer (I-3) and acrylic triblock copolymer (II-3) in a kneader set at 145 ° C. did. “KE311” was immediately kneaded and the processability was good “i”, and a uniform adhesive composition was immediately obtained. Adhesion was achieved by melt-coating the obtained adhesive composition on a polyethylene terephthalate film (Toyobo Ester Film E5000, thickness 50 μm) using a hot melt coater so that the adhesive layer had a thickness of 25 μm. An adhesive tape having a layer formed on a polyethylene terephthalate film was prepared. The tackiness of the obtained adhesive tape was good and was “3”. The appearance 24 hours after the production of the adhesive tape was transparent, and the compatibility was “A”. Further, in any case immediately after the production of the adhesive tape and 24 hours after the production, no bleeding of the liquid material from the surface of the adhesive layer was observed, and the bleeding property was “a”. Further, when the obtained adhesive tape was evaluated for color change before and after heat treatment at 180 ° C. for 3 hours, no color change was observed on the appearance, and the thermal stability was “◯”. The evaluation results are shown in Table 2A.

[Examples 2-91]
The preparation of the adhesive composition and the thickness are the same as in Example 1 except that the composition of the adhesive composition is changed to the composition (A-2 to 91) described in Tables 2A to 2H, respectively. An adhesive tape having a 25 μm adhesive layer formed on a polyethylene terephthalate film was prepared, and the obtained adhesive tape was evaluated. The evaluation results are shown in Tables 2A to 2H. In the case where the adhesive composition contains a plasticizer, a kneaded mixture of the acrylic triblock copolymer (I), the acrylic triblock copolymer (II), and the tackifier resin is kneaded. After producing in this, the adhesive composition is produced by adding a plasticizer to this melt-kneaded material in the kneader set to 145 degreeC.

[Comparative Examples 1 and 2]
The adhesive composition was prepared using a kneader in the same manner as in Example 1 except that the composition of the adhesive composition was changed to the composition (B-1, 2) shown in Table 2A. Since no triblock copolymer (II) was used, when “KE311” was added as a tackifier resin, “KE311” was not immediately kneaded into the melt of the triblock copolymer (I), and was uniform. It took time to melt, and the workability was unfavorable and was “ii”. Adhesion was achieved by melt-coating the obtained adhesive composition on a polyethylene terephthalate film (Toyobo Ester Film E5000, thickness 50 μm) using a hot melt coater so that the adhesive layer had a thickness of 25 μm. An adhesive tape having a layer formed on a polyethylene terephthalate film was prepared. The tackiness of the obtained adhesive tape was good and was “3”. The appearance 24 hours after the production of the adhesive tape was transparent, and the compatibility was “A”. Further, in any case immediately after the production of the adhesive tape and 24 hours after the production, no bleeding of the liquid material from the surface of the adhesive layer was observed, and the bleeding property was “a”. Further, when the obtained adhesive tape was evaluated for color change before and after heat treatment at 180 ° C. for 3 hours, no color change was observed on the appearance, and the thermal stability was “◯”. The evaluation results are shown in Table 2A.

[Comparative Examples 3 to 5]
An adhesive composition was prepared using a kneader in the same manner as in Example 1 except that the composition of the adhesive composition was changed to the composition (B-3 to 5) shown in Table 2B. Since the acrylic triblock copolymer (II) was used, when the tackifying resin was added at 145 ° C., the tackifying resin was immediately kneaded and the processability was good “i”, and the uniform viscosity was immediately An adhesive composition was obtained. Adhesion was achieved by melt-coating the obtained adhesive composition on a polyethylene terephthalate film (Toyobo Ester Film E5000, thickness 50 μm) using a hot melt coater so that the adhesive layer had a thickness of 25 μm. An adhesive tape having a layer formed on a polyethylene terephthalate film was prepared. The obtained adhesive tape had almost no tackiness and was “1”. The appearance 24 hours after the production of the adhesive tape was opaque, and the compatibility was poor and was “B”. Further, in any case immediately after the production of the adhesive tape and 24 hours after the production, no bleeding of the liquid material from the surface of the adhesive layer was observed, and the bleeding property was “a”. Further, when the obtained adhesive tape was evaluated for color change before and after heat treatment at 180 ° C. for 3 hours, Comparative Examples 3 and 5 were “◯” because no color change was observed on the appearance. The change was large and the thermal stability was “Δ”. The evaluation results are shown in Table 2B.

[Comparative Example 6]
An adhesive composition was prepared using a kneader in the same manner as in Example 1 except that the composition of the adhesive composition was changed to the composition (B-6) shown in Table 2D. Since the acrylic triblock copolymer (II) was used, when the tackifying resin was added at 145 ° C., the tackifying resin was immediately kneaded and the workability was good “i”, and the composition was immediately uniform. Things were obtained. Subsequently, the plasticizer was immediately added and kneaded to obtain a uniform adhesive composition. Adhesion was achieved by melt-coating the obtained adhesive composition on a polyethylene terephthalate film (Toyobo Ester Film E5000, thickness 50 μm) using a hot melt coater so that the adhesive layer had a thickness of 25 μm. An adhesive tape having a layer formed on a polyethylene terephthalate film was prepared. The obtained adhesive tape had almost no tackiness and was “1”. The appearance 24 hours after the production of the adhesive tape was transparent, and the compatibility was “A”. Further, in both cases immediately after the production of the pressure-sensitive adhesive tape and 24 hours after the production, bleeding of the liquid material from the surface of the pressure-sensitive adhesive layer was observed, and the bleeding property was “b”. Moreover, when the color change before and behind heat processing for 3 hours was evaluated at 180 degreeC of the obtained adhesive tape, the color change was not able to be confirmed on appearance but thermal stability was "(circle)". The evaluation results are shown in Table 2D.

[Example 92]
The acrylic triblock copolymer (I-3) obtained in Production Example 3 and the acrylic triblock copolymer (I-5) obtained in Production Example 5 were placed in a kneader set at 160 ° C. in Table 2I. It was charged based on the blending ratio and melted uniformly. Thereafter, the temperature of the kneader was set to 145 ° C., and the acrylic triblock copolymer (II-3) obtained in Production Example 12 was introduced into the kneader based on the blending ratio in Table 2I so that these mixtures were uniformly mixed. It melt-kneaded so that it might become. Furthermore, “YS resin SX100” as a tackifying resin was added to the melt-kneaded material in a kneader set at 145 ° C. based on the blending ratio in Table 2I. “YS resin SX100” was immediately kneaded and the processability was good “i”, and a uniform adhesive composition was immediately obtained. The melt viscosity of the obtained adhesive composition was 325,000 mPa · s (160 ° C.) and 65,000 mPa · s (180 ° C.). Thickness of the pressure-sensitive adhesive composition on the polyethylene terephthalate film (Toyobo Ester Film E5000, thickness 50 μm) using a non-contact type hot melt coater (ITW Dynatec, cross coater). The pressure-sensitive adhesive tape having an adhesive layer formed on a polyethylene terephthalate film was prepared by melt coating at 175 ° C. so that the thickness was 25 μm. The tackiness of the obtained adhesive tape was good and was “3”. The appearance 24 hours after the production of the adhesive tape was transparent, and the compatibility was “A”. Further, in any case immediately after the production of the adhesive tape and 24 hours after the production, no bleeding of the liquid material from the surface of the adhesive layer was observed, and the bleeding property was “a”. Further, when the obtained adhesive tape was evaluated for color change before and after heat treatment at 180 ° C. for 3 hours, no color change was observed on the appearance, and the thermal stability was “◯”. The evaluation results are shown in Table 2I. Also, the holding power (creep resistance) was slightly shifted (less than 0.1 mm), and the holding power was high. The evaluation results are shown in Table 2I.

[Examples 93 to 98]
The formulation of the adhesive composition was changed to the formulation (A-93 to A-98) shown in Table 2I, and the plasticizer was added after the tackifying resin was added and mixed uniformly to become uniform. An adhesive composition was prepared by melt kneading in the same manner as in Example 92 except that the mixture was melt-mixed. Then, using a non-contact type hot melt coater (ITW Dynatec, cross coater), an adhesive tape having a 25 μm thick adhesive layer formed on a polyethylene terephthalate film was prepared. evaluated. In Examples 93 to 97, the melt coating temperature was 170 ° C, and in Example 98, 155 ° C. The evaluation results are shown in Table 2I.

  As shown in the above examples, the adhesive composition of the present invention has good processability at the stage of production, and the appearance of the pressure-sensitive adhesive tape obtained therefrom is transparent, has no bleed, and has a pressure-sensitive adhesive property. It was good. On the other hand, when the acrylic triblock copolymer (II), which is an essential component of the present invention, was not used as in Comparative Examples 1 and 2, the processability at the stage of producing the adhesive composition Was bad. Moreover, the external appearance of the adhesive composition containing the tackifying resin of the quantity outside the range of this invention like Comparative Examples 3-5, and the adhesive tape obtained from it were bad, and the adhesive performance was also bad. Further, as in Comparative Example 6, the appearance of the adhesive composition containing a plasticizer in an amount outside the range of the present invention and the pressure-sensitive adhesive tape obtained therefrom are transparent and good, but the plasticizer bleeds on the tape surface. The adhesion performance was also poor. In addition, as Examples 1-18, 22, 25-30, 33, 35-52, 57-74, 80-86, 89-98, hydrogenated rosin ester having excellent heat resistance as a tackifier resin It can also be seen that when an aromatic hydrocarbon-based resin or a hydrogenated petroleum-based resin is used, it is difficult to color even under high-temperature storage, and is more preferable. Further, as in Example 92, when the adhesive composition has a high melt viscosity and no plasticizer is used, it can be seen that the holding force (creep resistance) of the resulting adhesive tape tends to be higher. . Even when a plasticizer is used as in Examples 93 to 97, when the adhesive composition has a high melt viscosity, it can be seen that the holding force (creep resistance) of the resulting adhesive tape tends to be high.

From the above, it can be seen that the adhesive composition of the present invention has good processability, the appearance of the pressure-sensitive adhesive tape obtained therefrom is transparent, has no bleeding, and exhibits excellent performance as a pressure-sensitive adhesive property.

Claims (2)

(I) It has two polymer blocks (A1) and (A2) composed of methacrylic ester units and one polymer block (B) composed of acrylate units, and (A1)-(B)-( A2) having a block structure, a weight average molecular weight of 50,000 to 250,000, a total content of the polymer blocks (A1) and (A2) of 35% by mass or less, and a polymer block (A1) And (A2) an acrylic triblock copolymer (I) having a weight average molecular weight of 3000 or more,
(C1)-(D)-(C2) having two polymer blocks (C1) and (C2) composed of methacrylic ester units and one polymer block (D) composed of acrylate units It has a block structure, has a weight average molecular weight of 10,000 to 120,000, a total content of polymer blocks (C1) and (C2) of 25% by mass or less, and polymer blocks (C1) and ( Viscosity containing a total of 100 parts by mass of the acrylic triblock copolymer (II) having a weight average molecular weight of at least 300 and less than 3000 among C2) and (ii) 1 to 190 parts by mass of a tackifying resin Adhesive composition. (I) It has two polymer blocks (A1) and (A2) composed of methacrylic ester units and one polymer block (B) composed of acrylate units, and (A1)-(B)-( A2) having a block structure, a weight average molecular weight of 50,000 to 250,000, a total content of the polymer blocks (A1) and (A2) of 35% by mass or less, and a polymer block (A1) And (A2) an acrylic triblock copolymer (I) having a weight average molecular weight of 3000 or more,
(C1)-(D)-(C2) having two polymer blocks (C1) and (C2) composed of methacrylic ester units and one polymer block (D) composed of acrylate units It has a block structure, has a weight average molecular weight of 10,000 to 120,000, a total content of polymer blocks (C1) and (C2) of 25% by mass or less, and polymer blocks (C1) and ( A total of 100 parts by mass with the acrylic triblock copolymer (II) having a weight average molecular weight of at least 300 and less than 3000 among C2), and (ii) 1-190 parts by mass of a tackifying resin, and (iii) ) Adhesive composition containing 80 parts by mass or less of a plasticizer.