JPH11302496A - Polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain heat meltable polymer compositions having high tackiness and cohesion, capable of firmly adhering to various materials irrespective of polar materials or non-polar materials and, in addition, excellent in retention without falling off or slipping off the adherend. SOLUTION: Desired polymer compositions comprises (I) a (hydrogenated) block copolymer having an aromatic vinyl compound based polymer block A and a conjugated diene based polymer block; (II) 0.1-200 pts., based on 100 pts. block copolymer (I), block copolymer having a polymer block C composed of an aromatic vinyl compound and/or an olefin compound and a polymer block D having a structural unit derived from a polymerizable monomer having a functional group consisting of a carboxyl group and/or an acid anhydride group; and (III) 0.1-20 pts., based on 100 pts. block copolymer (II), metal compound comprising a metal oxide, a metal hydroxide and/or a metal salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermoplastic polymer composition which exhibits excellent adhesion to both polar and non-polar materials and has a high cohesive force, and the polymer composition. The present invention relates to a pressure-sensitive adhesive using a material.

[0002]

2. Description of the Related Art A block copolymer having a styrene-based polymer block and a diene-based polymer block (hereinafter sometimes referred to as a "styrene-diene block copolymer") and a hydrogenated product thereof have rubber elasticity at ordinary temperature. Has plasticization and melting by heating, and has excellent handleability and moldability and processability.
Moreover, since it is excellent in flexibility and mechanical properties, it has been widely used in various fields in recent years as a kind of so-called thermoplastic elastic body (thermoplastic elastomer). One of the typical uses of the styrene-diene block copolymer is an adhesive (pressure-sensitive adhesive). The styrene-diene block copolymer is used as a base polymer, and a tackifier resin, a plasticizer (process) Oils and the like are used in the production of pressure-sensitive adhesive sheets or tapes (pressure-sensitive adhesive sheets or tapes), the production of vibration-damping sheets, the adhesive sealants for automobiles, and the like.

[0003] For adhesive products such as adhesives and adhesive tapes, both high adhesive strength and high cohesive strength are required. When the adhesive strength of the adhesive is low, the adhesive cannot be firmly adhered to the adherend and is easily peeled off. On the other hand, if the cohesive force of the pressure-sensitive adhesive is low, the holding power (shear resistance) of the pressure-sensitive adhesive or the pressure-sensitive adhesive product that has adhered to the adherend decreases, causing misalignment in the adherend or falling from the adherend. When a product such as an adhesive or an adhesive tape needs to be peeled off from the adherend, a part of the adhesive remains on the adherend and cannot be removed cleanly. However, adhesive strength and cohesive strength are generally contradictory properties, so it is difficult to combine high adhesive strength and high cohesive strength with an adhesive or an adhesive product, and a polymer composition, Agents and adhesive products have been sought, but no satisfactory products have been obtained.

[0004] Japanese Patent Application Laid-Open No. 7-41636 discloses that
A hot melt adhesive comprising a polymer composition obtained by ion-crosslinking an acid-modified styrene-ethylene-butylene-styrene block copolymer by adding a metal salt or metal oxide thereto and a hot melt adhesive comprising the same are described. In the polymer composition and the hot melt adhesive, the cohesive strength is not improved because the acid-modified styrene-ethylene-butylene-styrene block copolymer is ion-crosslinked using a metal salt or a metal oxide. However, on the other hand, the adhesive force (adhesive force) is remarkably reduced, and both the adhesive force and the cohesive force are not well-balanced. In addition, the adhesive force (adhesive force) of the polymer composition and hot melt adhesive described in this publication greatly depends on the presence or absence of the polarity of the adherend (material), and non-polarity such as polypropylene Has extremely low adhesion to materials.

Further, in the production of adhesive products such as adhesive tapes and adhesive sheets, a method of applying an organic solvent solution of an adhesive or an emulsion to a substrate such as a film or sheet has been widely adopted. However, the method of using an organic solvent solution or emulsion requires a step of dissolving the adhesive in an organic solvent or dispersing in water and a step of drying them after applying them to a base material, which complicates the process.
This leads to a decrease in thermal efficiency and an increase in cost. In addition, when an organic solvent solution of the adhesive is used, there is a problem that the working environment and the global environment are deteriorated by the organic solvent.

[0006]

An object of the present invention is to provide a polymer block mainly composed of an aromatic vinyl compound, such as a styrene-diene block copolymer or a hydrogenated product thereof, and a polymer block mainly composed of a conjugated diene compound. Based on a block copolymer having a coalesced block and / or a block copolymer composed of a hydrogenated product thereof, having good elasticity and flexibility originally possessed by the block copolymer,
Has various properties such as mechanical properties, adheres strongly to both polar and non-polar materials, and has high cohesion and no displacement (high holding power) A polymer composition that can be completely and completely peeled off without leaving the pressure-sensitive adhesive on the adherend when it is necessary to peel the pressure-sensitive adhesive or the pressure-sensitive adhesive product from the adherend, and using the polymer composition To provide an adhesive. further,
An object of the present invention is to easily heat and melt and apply the melt to a base material such as a sheet or a film, without having to be in the form of an organic solvent solution or an emulsion or the like. Products can be manufactured in simple processes without causing pollution or deterioration of the working environment and the global environment.
An object of the present invention is to provide a polymer composition which can be produced safely and economically, and a pressure-sensitive adhesive comprising the polymer composition.

[0007]

The present inventors have made various studies in order to achieve the above object. As a result, a block copolymer having a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound and / or a thermoplastic elastic polymer composed of a hydrogenated product thereof has an aromatic aromatic polymer. A polymer block mainly composed of at least one compound selected from a vinyl compound and an olefin compound and a polymer block having a structural unit derived from a polymerizable monomer having a functional group selected from a carboxyl group and an acid anhydride group. When a block copolymer having at least one metal compound selected from a metal oxide, a metal hydroxide and a metal salt is blended in a specific ratio, the resulting polymer composition has thermoplasticity, heat melting property, Excellent handling properties with good adhesiveness, high adhesive strength and high cohesive strength To exhibit high adhesion to both materials and non-polar materials with a polar, yet good elasticity with the thermoplastic elastic polymer inherent flexibility, mechanical properties,
The inventors have found that various properties such as transparency are maintained, and completed the present invention based on those findings.

That is, the present invention provides (i) a polymer block (A) mainly composed of an aromatic vinyl compound and a polymer block (B) mainly composed of a conjugated diene compound.
And at least one block copolymer (I) selected from a block copolymer having the formula (I) and a hydrogenated product thereof; a polymer block (C) mainly comprising at least one compound selected from an aromatic vinyl compound and an olefin compound And a block copolymer (II) having a polymer block (D) having a structural unit derived from a polymerizable monomer having a functional group selected from a carboxyl group and an acid anhydride group; and a metal oxide and a metal. A polymer composition containing at least one metal compound (III) selected from a hydroxide and a metal salt, wherein (ii) the block copolymer (I)
The block copolymer (II) was added in an amount of 0.1 part by weight to 100 parts by weight.
And (iii) 0.1 to 20 parts by weight of the metal compound (III) based on 100 parts by weight of the block copolymer (II). Characteristic polymer composition. And the present invention
An adhesive comprising the polymer composition.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The block copolymer (I) used in the polymer composition of the present invention is, as described above, a polymer block (A) mainly composed of an aromatic vinyl compound [hereinafter referred to as “aromatic vinyl polymer block (A)”. And a block copolymer having a polymer block (B) mainly composed of a conjugated diene compound [hereinafter referred to as a “conjugated diene polymer block (B)”] and at least one hydrogenated product thereof.
Consists of seeds.

The aromatic vinyl compound constituting the aromatic vinyl polymer block (A) in the block copolymer (I) includes, for example, styrene, α-methylstyrene,
β-methylstyrene, o-, m-, p-methylstyrene, t-butylstyrene, 2,4,6-trimethylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, 1,3- Vinyl naphthalene, vinyl anthracene,
And vinyl aromatic compounds such as indene and acetonaphthylene. The aromatic vinyl polymer block (A) may have a structural unit composed of only one kind of the above-mentioned aromatic vinyl compound, or may have a structural unit composed of two or more kinds. Among them, it is preferable that the aromatic vinyl polymer block (A) is mainly composed of structural units derived from styrene.

The aromatic vinyl polymer block (A) may have a small amount of a structural unit composed of another copolymerizable monomer together with a structural unit composed of an aromatic vinyl compound. The ratio of the structural unit composed of the polymerizable monomer is
3 based on the weight of the aromatic vinyl polymer block (A)
It is preferably at most 0% by weight, more preferably at most 10% by weight. In this case, other copolymerizable monomers include, for example, 1-butene, pentene, hexene,
Examples include ionic polymerizable monomers such as butadiene, isoprene, and methyl vinyl ether.

The conjugated diene compound constituting the conjugated diene polymer block (B) in the block copolymer (I) includes isoprene, butadiene, hexadiene, 2,3-dimethyl-1,3-butadiene, 3-
Examples thereof include pentadiene, and the conjugated diene polymer block (B) may be composed of one type of these conjugated diene compounds or may be composed of two or more types. Among them, the conjugated diene polymer block (B) is preferably composed of one or both of isoprene and butadiene.

The bonding form of the conjugated diene compound in the conjugated diene polymer block (B) is not particularly limited. For example, 1,2- and / or 1,4-bonds for butadiene, and 1,2-bonds for isoprene,
A 3,4-bond and / or a 1,4-bond can be adopted, and any of these bond forms may be employed. Among them, when the conjugated diene polymer block (B) is formed from isoprene, or when it is formed from isoprene and butadiene, the 3,4-bond and the 1,2-bond in the conjugated diene compound polymer block are used. Is preferably 1 to 95 mol%.

When the conjugated diene polymer block (B) has structural units derived from two or more kinds of conjugated diene compounds, their bonding forms are random, tapered, partially block-like, or Or a combination of two or more of the above.

The bonding form between the aromatic vinyl polymer block (A) and the conjugated diene polymer block (B) in the block copolymer (I) is not particularly limited, and may be linear, branched, radial, or a combination thereof. May be any of the bonding forms in which two or more of them are combined, and are preferably linear bonding forms. As an example of the block copolymer (I) having a linear bond form, when an aromatic vinyl polymer block (A) is represented by A and a conjugated diene polymer block (B) is represented by B, Diblock copolymer represented by AB, triblock copolymer represented by ABA or BAB, ABAB or BAB
-A tetrablock copolymer represented by A, or A and B
And a polyblock copolymer in which 5 or more are linked linearly. Among them, the elasticity is that the block copolymer (I) is a diblock copolymer represented by AB and / or a triblock copolymer represented by ABA. It is preferable from the viewpoint of mechanical properties, adhesiveness and cohesiveness.

In the block copolymer (I), part or all of the unsaturated double bond in the conjugated diene polymer block (B) is hydrogenated (B) because of its good heat resistance and weather resistance. (Hereinafter sometimes referred to as “hydrogenation”). At that time, the hydrogenation rate of the conjugated diene polymer block (B) is preferably 50 mol% or more, more preferably 60 mol% or more, and 70 mol% or more.
More preferably, it is at least mol%.

In the block copolymer (I), the content of the structural unit derived from the aromatic vinyl compound is 5 to 75% by weight based on the total weight before hydrogenation.
It is preferable in terms of its elasticity, flexibility, mechanical properties and the like, and more preferably 5 to 45% by weight.

Furthermore, in the block copolymer (I), the molecular weights of the aromatic vinyl polymer block (A) and the conjugated diene polymer block (B) are not particularly limited. The number average molecular weight of the polymer block (A) is in the range of 500 to 100,000, and the number average molecular weight of the conjugated diene polymer block (B) is 2,500.
It is preferably from 0 to 400,000. In addition, the total number average molecular weight of the block copolymer (I) before hydrogenation is preferably in the range of 3,000 to 500,000 from the viewpoint of mechanical properties, moldability, and the like. . In addition, the number average molecular weight referred to in the present specification refers to a value determined from a standard polystyrene calibration curve by gel permeation chromatography (GPC).

The method for producing the block copolymer (I) is not particularly limited and can be produced by a conventionally known method. For example, ionic polymerization methods such as anionic polymerization and cationic polymerization,
It may be produced by any of a single-site polymerization method and a radical polymerization method. In the case of the anionic polymerization method, for example, using an alkyllithium compound or the like as a polymerization initiator, in an inert organic solvent such as n-hexane or cyclohexane, successively polymerize an aromatic vinyl compound and a conjugated diene compound to obtain a desired compound. After producing a block copolymer having a molecular structure and a molecular weight, adding ethylene oxide or propylene oxide, then adding an active hydrogen compound such as alcohols, carboxylic acids and water to terminate the polymerization. Can be. And
The block copolymer produced as described above is preferably hydrogenated in an inert organic solvent in the presence of a hydrogenation catalyst according to a known method to obtain a hydrogenated block copolymer (I). it can.

As described above, the block copolymer (II) used in the polymer composition of the present invention contains at least one selected from an aromatic vinyl compound and an olefin compound.
A polymer block (C) mainly composed of a kind of compound;
It is a block copolymer having a polymer block (D) having a structural unit derived from a polymerizable monomer having a functional group selected from a carboxyl group and an acid anhydride group.

The polymer block (C) in the block copolymer (II) may be composed of an aromatic vinyl compound alone or an olefin compound alone, and may be composed of both an aromatic vinyl compound and an olefin compound. Or may be composed of at least one of an aromatic vinyl compound and an olefin compound and a small amount of another copolymerizable monomer.

When the polymer block (C) is composed of two or more kinds of monomers of an aromatic vinyl compound and an olefin compound, their bonding forms are random, tapered and partially block. Shape or a combination of two or more thereof

Examples of the aromatic vinyl compound which can constitute the polymer block (C) include styrene, α-methylstyrene, β-methylstyrene, o-, m-, p-methylstyrene, t-butylstyrene, 2,4,6-trimethylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, 1,3-vinylnaphthalene, vinylanthracene, indene, vinyl aromatic compounds such as acetonaphthylene, and the like. Polymer block (C)
May have a structural unit composed of one or more of the above-mentioned aromatic vinyl compounds.

Examples of the olefin compound that can constitute the polymer block (C) include olefins having 2 to 10 carbon atoms and diene hydrocarbon compounds.
Specific examples include ethylene, propylene, isobutylene, pentene, hexene, octene, butadiene, isoprene and the like. When the polymer block (C) has a structural unit composed of a diene-based hydrocarbon such as butadiene or isoprene, it is preferable to form the olefin by hydrogenation.

Among the above, the polymer block (C)
Is a polymer block composed of one or more of polymers such as polystyrene, polyethylene, polypropylene, polyisobutylene, polybutene, polyisoprene, polybutadiene, and hydrogenated products thereof. ) And the block copolymer (I) are preferable, since the compatibility with the block copolymer (I) is improved, and a polymer composition and a pressure-sensitive adhesive having excellent transparency, high cohesion, and excellent transparency are obtained.

The polymer block (D) in the block copolymer (II) is a polymerizable monomer having a functional group selected from a carboxyl group and an acid anhydride group. (D-1) "]. The polymer block (D) may be composed of only a structural unit derived from the functional group-containing monomer (d-1), but the adhesiveness, cohesive strength, transparency, From the viewpoint of corrosion resistance and the like, a functional group-containing monomer (d-1) and a polymerizable monomer having no carboxyl group and no acid anhydride group [hereinafter referred to as "other monomer (d-2)" That is, a polymer having a structural unit derived from the functional group-containing monomer (d-1) and a structural unit derived from the other monomer (d-2). It is preferably a united block.

At that time, in the block copolymer (II),
Adhesiveness of a polymer composition and a pressure-sensitive adhesive obtained using the same,
From the viewpoint of cohesion, transparency, wettability, corrosion resistance, etc., the ratio of the carboxyl group and / or the acid anhydride group based on the structural unit derived from the functional group-containing monomer (d-1) [carboxyl group and acid anhydride group Is preferably in the range of 0.1 to 50 mol% based on all structural units (all monomer units) constituting the polymer block (D). More preferably, it is in the range of 0.1 to 20 mol%. The ratio of the structural units derived from the other monomer (d-2) in the polymer block (D) is determined by the total structural units (all monomer units) constituting the polymer block (D).
Is preferably 50 to 99.9 mol%, more preferably 80 to 99.9 mol%, based on the
The functional group-containing monomer (d-) in the polymer block (D)
When the ratio of the carboxyl group and / or the acid anhydride group based on the structural unit derived from 1) is less than 0.1 mol%,
The cohesive strength of the polymer composition and the pressure-sensitive adhesive and the wettability to the adherend are easily reduced. On the other hand, if it exceeds 50 mol%, the adhesion and the non-polar resin are easily reduced. Become.

The functional group-containing monomer (d-1) constituting the polymer block (D) includes a carboxyl group and / or
Alternatively, any monomer having an acid anhydride group and having a polymerizable carbon-carbon double bond can be used and is not particularly limited. Among them, the functional group-containing monomer (d-
Preferred specific examples of 1) include acrylic acid, methacrylic acid, crotonic acid, oleic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride, fumaric anhydride, itaconic anhydride and the like. .
The polymer block (D) may have a structural unit derived from only one type of the functional group-containing monomer (d-1) or may have a structural unit derived from two or more types. Is also good. Among them, the structural unit derived from the functional group-containing monomer (d-1) in the polymer block (D) is a structural unit derived from acrylic acid, methacrylic acid, and maleic anhydride. It is preferable from the viewpoints of properties and cohesiveness.

The copolymer in which the polymer block (D) has a structural unit derived from the functional group-containing monomer (d-1) and a structural unit derived from another monomer (d-2) If the other monomer (d-2) is composed of a metal compound, the other monomer (d-2) is copolymerizable with the functional group-containing monomer (d-1) and has no carboxyl group or acid anhydride group. Desirably, the monomer is a monomer having no functional group that causes an ionic bond reaction or other reaction with (III), and particularly (meth) acrylate, (meth) acrylonitrile and derivatives thereof. preferable. Other monomers (d-
Specific examples of the case where 2) is a (meth) acrylate are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acryl. Pentyl acid, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, octadecyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic acid Examples thereof include 2-ethylhexyl and glycidyl (meth) acrylate. The polymer block (D) may have, as a structural unit derived from another monomer (d-2), a structural unit derived from only one of the above monomers, or two or more types. May have a structural unit derived from

The polymer block (D) has a structural unit derived from the functional group-containing monomer (d-1) and another monomer (d-2).
In the case of having a structural unit derived from the above, the bonding form thereof may be random, tapered, partially block-shaped, or a combination of two or more thereof. Among them, it is preferable that the polymer composition and the pressure-sensitive adhesive using the polymer composition have a random bonding form because the cohesiveness and the tackiness of the polymer composition and the pressure-sensitive adhesive using the same are improved and the production is easy.

The bonding form between the polymer block (C) and the polymer block (D) in the block copolymer (II) is not particularly limited, and may be linear, branched, radial, or two or more of them. Any combination of bonding forms may be used, and a linear bonding form is preferable. As an example of the block copolymer (II) having a linear bond form, when the polymer block (C) is represented by C and the polymer block (D) is represented by D, it is represented by CD. Diblock copolymers, triblock copolymers represented by CDC or DCD, tetrablock copolymers represented by CDCD, or C and D And a polyblock copolymer in which 5 or more are linked linearly. Among them, compatibility with the block copolymer (I), elasticity, mechanical properties, adhesiveness, cohesiveness, block copolymer (II) of the polymer composition and the pressure-sensitive adhesive prepared using the same ), The block copolymer (II) is a diblock copolymer represented by CD,
Alternatively, a triblock copolymer represented by CDC or DCD is preferable.

In the block copolymer (II), the molecular weights of the polymer block (C) and the polymer block (D) are not particularly limited, but the number average molecular weight of the polymer block (C) is 1,000 to 100, 000, more preferably 2,500 to 50,000, and the number average molecular weight of the polymer block (D) is 1,000 to 100,000. More preferably, it is more preferably in the range of 2,500 to 50,000. The total number average molecular weight of the block copolymer (II) is preferably in the range of 2,000 to 200,000, and more preferably in the range of 5,000 to 100,000. When the block copolymer (II) in which the number average molecular weight of the polymer block (C) and the polymer block (D) and the total number average molecular weight of the block copolymer (II) are in the above-mentioned range is used, The miscibility with the polymer (I) and the mechanical properties, adhesiveness, cohesiveness and the like of the polymer composition and the pressure-sensitive adhesive using the same are excellent.

The method for producing the block copolymer (II) is not particularly limited. For example, it can be produced as follows. That is, the monomer component constituting the polymer block (C) [or the polymer block (D)] is converted to thio-S-
Carboxylic acid, 2-acetylthioethylthiol, 10-
Radical polymerization in the presence of a compound having a mercapto group in the molecule such as acetylthiodecanethiol, etc., and the resulting polymer is treated with an alkali such as sodium hydroxide or ammonia, or an acid such as hydrochloric acid or sulfuric acid. Thus, a polymer having a mercapto group at one end is prepared, and a polymer block (D) is formed in the presence of the polymer.
[Or polymer block (C)] is subjected to radical polymerization of a monomer component constituting the block copolymer (I).
I) can be obtained. In the above, a functional group-containing monomer (d-1) is preferably used as a monomer component during the production of the polymer constituting the polymer block (D), preferably the functional group-containing monomer (d-1) By using and another monomer (d-2), a carboxyl group and / or an acid anhydride group can be introduced into the polymer block (D).
According to this method, the block copolymer (II) having the target number average molecular weight and molecular weight distribution can be easily and efficiently produced.

Further, the polymer composition and the pressure-sensitive adhesive of the present invention are selected from metal oxides, metal hydroxides and metal salts together with the above-mentioned block copolymer (I) and block copolymer (II). Contains at least one metal compound (III) as an essential component. Metal compound (III)
Generates an ionic bonding reaction, a coordination bonding reaction, and the like with a carboxyl group and / or an acid anhydride group contained in the polymer block (D) constituting the block copolymer (II), and has a crosslinking action. And the like to improve the cohesion of the polymer composition and the pressure-sensitive adhesive of the present invention.

As the metal compound (III), an ionic bond reaction and a coordinate bond reaction between a carboxyl group and / or an acid anhydride group contained in the polymer block (D) in the block copolymer (II). Metal oxides that can cause
Any metal hydroxide and metal salt can be used. Among them, in the present invention, as the metal compound (III), an alkali metal, an alkaline earth metal, and I-th of the periodic table
At least one metal compound selected from the group consisting of oxides, hydroxides and salts of metals of Group B, Group IIB, Group III, Group IV and Group VIII is preferably used. Specific examples of the metal compound (III) preferably used in the present invention include:
Zinc oxide, titanium oxide, magnesium oxide, calcium oxide, aluminum oxide, cobalt oxide, nickel oxide, copper oxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, calcium carbonate, magnesium carbonate, aluminum hydroxide, hydroxide Examples thereof include calcium, zinc acetate, aluminum acetate, and di-i-propoxy-bis (2,4-pentanedione) titanate. One or more of the above-mentioned metal compounds can be used. Among them, in the present invention, as the metal compound (III), zinc oxide, magnesium oxide, aluminum oxide, calcium carbonate, calcium hydroxide, aluminum hydroxide, and zinc acetate are more preferably used from the viewpoint of reactivity.

The polymer composition and the pressure-sensitive adhesive of the present invention are used in an amount of 100 parts by weight of the block copolymer (I).
The block copolymer (II) is contained in a proportion of 0.1 to 200 parts by weight, particularly preferably in a proportion of 10 to 100 parts by weight. Block copolymer (I) 10
When the blending ratio of the block copolymer (II) is less than 0.1 part by weight with respect to 0 part by weight, the cohesive strength of the polymer composition and the pressure-sensitive adhesive is not improved, while the block copolymer (II) Exceeds 200 parts by weight, the adhesiveness and heat resistance of the polymer composition and the pressure-sensitive adhesive are reduced.

The polymer composition and the pressure-sensitive adhesive of the present invention contain 0.1 to 20 parts by weight of the metal compound (III) based on 100 parts by weight of the block copolymer (II). In particular, it is preferably contained at a ratio of 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight. Block copolymer (II) 100
The mixing ratio of the metal compound (III) is 0.1 part by weight.
When the amount is less than 1 part by weight, the cohesive strength of the polymer composition and the pressure-sensitive adhesive is not improved, while the mixing ratio of the metal compound (III) is 2
If the amount exceeds 0 parts by weight, the adhesiveness, mechanical properties, and the like of the polymer composition and the adhesive will decrease.

The polymer composition of the present invention containing the block copolymer (I), the block copolymer (II) and the metal compound (III) has excellent adhesiveness, cohesive strength, elasticity,
Utilizing various properties such as flexibility, mechanical properties, and transparency,
It can be effectively used as an adhesive, a sealing agent, a molding material, a coating agent, an adhesive for a laminated structure, etc., and is particularly useful as an adhesive. When the polymer composition of the present invention is used as an adhesive, the block copolymer (I), the block copolymer (II) and the metal compound (II)
The adhesive may be prepared using only I). However, the block copolymer (I) and the block copolymer (II)
It is preferable to prepare a pressure-sensitive adhesive by using a tackifier resin and / or a plasticizer, which has been widely used in the past, together with the metal compound (III) and the pressure-sensitive adhesive, cohesiveness, and handleability. As a result, it is possible to obtain a pressure-sensitive adhesive that is more excellent in wettability to an adherend.

When a tackifier resin is used in the pressure-sensitive adhesive of the present invention, the type of tackifier resin is not particularly limited, and any of tackifier resins conventionally used in pressure-sensitive adhesives can be used. Are coumarone-indene resin, phenol resin, p-tert-butylphenol-acetylene resin, phenol formaldehyde resin, terpene phenol resin, polyterpene resin, xylene-formaldehyde resin, synthetic polyterpene resin, aromatic hydrocarbon resin, and fat Group hydrocarbon resins, oligomeric resins of monoolefins and diolefins, hydrogenated terpene resins,
Hydrogenated aromatic hydrocarbon resin, hydrogenated aliphatic hydrocarbon resin, alicyclic saturated hydrocarbon resin, polybutene, polyhydric alcohol ester of rosin, hydrogenated rosin, hydrogenated wood rosin, hydrogenated rosin and monoalcohol Alternatively, an ester with a polyhydric alcohol, a turpentine-based tackifying resin, and the like can be given. These tackifier resins may be used alone or in combination of two or more. Among them, in the pressure-sensitive adhesive of the present invention, as a tackifying resin, hydrogenated terpene resin, hydrogenated aliphatic hydrocarbon resin, hydrogenated aromatic hydrocarbon resin, alicyclic saturated hydrocarbon resin is compatible, It is preferably used from the viewpoint of adhesiveness.

The ratio of the tackifier resin used in the pressure-sensitive adhesive is 1 to 100 parts by weight of the block copolymer (I).
0 to 400 parts by weight, preferably 100 to 30 parts by weight.
More preferably, it is 0 parts by weight. When the use ratio of the tackifier resin is within the above range, a pressure-sensitive adhesive excellent in tackiness, cohesive strength (holding power), flexibility, handleability, wettability and the like can be obtained.

When a plasticizer (softening agent) is used in the pressure-sensitive adhesive of the present invention, the type of the plasticizer is not particularly limited, and any of the plasticizers conventionally used in pressure-sensitive adhesives can be used. Process oils such as paraffin-based process oils and naphthalene-based process oils;
Examples thereof include phthalic acid derivatives represented by (2-ethylhexyl) phthalate, vegetable oil-based plasticizers (softening agents), lanolin, liquid polybutene, and liquid polyacrylates. One of these plasticizers (softening agents) or Two or more types can be used. The ratio of the plasticizer (softening agent) used is 1 to 100 parts by weight of the block copolymer (I).
The amount is preferably from 300 to 300 parts by weight, more preferably from 20 to 100 parts by weight. When the use ratio of the plasticizer (softening agent) is in the above range, an adhesive having excellent adhesiveness, cohesive strength, handleability, wettability and the like can be obtained. If the use ratio of the plasticizer (softening agent) is more than 300 parts by weight, bleeding becomes severe and the quality of the pressure-sensitive adhesive is liable to deteriorate.

An adhesive and an adhesive product such as an adhesive tape or an adhesive film obtained using the adhesive are required to be temporarily adhered to an adherend, and to be peeled cleanly after use. There are various types that are required to be semi-permanently adhered to an adherend (ones that are not peeled off from the adherend after being adhered), and their use modes and uses are various.
Therefore, in preparing the pressure-sensitive adhesive of the present invention, the above-mentioned block copolymer (I), block copolymer (II),
Metal compound (III), tackifier resin, plasticizer content, type, compounding ratio, the presence or absence and type of other components, the amount, etc. are appropriately selected within the scope of the present invention, and each application and It is preferable to adjust to one suitable for the mode of use.
However, regardless of the mode of use of the pressure-sensitive adhesive or the pressure-sensitive adhesive product, when the pressure-sensitive adhesive and the pressure-sensitive adhesive product are adhered to the adherend using the pressure-sensitive adhesive force, the pressure-sensitive adhesive and the pressure-sensitive adhesive product have high adhesive force and high cohesion. It is desirable.

The polymer composition and the pressure-sensitive adhesive of the present invention may contain, if necessary, other thermoplastic polymers (for example, polyolefin resins such as polypropylene and polyethylene, styrene resins and polyphenylene ether resins), fillers,
One or more of other components such as a pigment, an antioxidant, a thermal deterioration inhibitor, an ultraviolet absorber, a flame retardant, and a fragrance may be contained.

The method for preparing the polymer composition and the pressure-sensitive adhesive of the present invention is not particularly limited, and the block copolymer (I), the block copolymer (II), the metal compound (III) and, if necessary, used. Any method can be used as long as it can uniformly mix the tackifier resin, plasticizer, and other components, and usually a melt-kneading method is used. Melt kneading can be performed using, for example, a melt kneading apparatus such as a single screw extruder, a twin screw extruder, a kneader, and a Banbury mixer.
By kneading at a temperature of 270 ° C. for about 3 to 30 minutes, the polymer composition of the present invention can be obtained. Among them, in preparing the polymer composition and the pressure-sensitive adhesive of the present invention, the block copolymer (II) is melted in the above-mentioned temperature range, the metal compound (III) is added thereto, and the mixture is kneaded. After an ionic bond reaction [crosslinking reaction of the block copolymer (II)] or the like is caused between the copolymer (II) and the metal compound (III), the block copolymer (I) or other residue is added thereto. A method of mixing and melt-kneading the components is preferably employed, whereby it is possible to obtain a polymer composition and a pressure-sensitive adhesive that are more excellent in the adhesive property and the cohesive force balance property, and the adhesion to polar resins and nonpolar resins. it can.

As described above, the polymer composition of the present invention comprises
It can be effectively used as an adhesive, a sealing agent, a molding material, a coating agent, an adhesive for a laminated structure, etc., and is particularly useful as an adhesive. When an adhesive product comprising an adhesive layer such as an adhesive tape, an adhesive film, an adhesive sheet and the like and a substrate is produced using an adhesive comprising the polymer composition of the present invention, an adhesive (a double-sided adhesive) is used. Heat-melted, or dissolved in a suitable organic solvent (for example, toluene, benzene, or other hydrocarbon-based solvent) or dispersed in water to form a liquid state. Various plastics (for example, polyolefins such as polypropylene, polyethylene, ethylene-vinyl acetate copolymer, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamide, vinyl chloride resin, etc.), rubber, paper, cloth, rubber cloth, resin impregnation Coated on various substrates consisting of cloth, glass plate, metal plate, wood, etc. by an appropriate method according to a conventional method By cooling or solidifying the adhesive layer in a molten state, or by drying to remove an organic solvent or water, various adhesive products having an adhesive layer on a substrate can be manufactured. .
In particular, since the pressure-sensitive adhesive of the present invention has an excellent property of hot-meltability, in producing the above-mentioned pressure-sensitive adhesive product,
It is preferable to adopt a method in which the pressure-sensitive adhesive of the present invention is heated and melted to be in a liquid state and applied to a substrate without using an organic solvent or water, whereby the working environment and the natural environment associated with the use of the organic solvent are used. In addition, the problem of contamination can be prevented, and a drying process after coating is not required, so that the process can be simplified and the cost can be reduced.

When the polymer composition of the present invention is used as a sealing agent or the like, it can be used in the same manner as a conventionally known sealing agent. Further, when the polymer composition of the present invention is used for the production of molded articles, various molding methods generally used for thermoplastic polymers,
For example, various molded products can be manufactured by any molding method such as injection molding, extrusion molding, press molding, blow molding, calendar molding, and casting.

The polymer composition and the pressure-sensitive adhesive of the present invention can be used with various other materials (eg, plastic, rubber, metal, wood, ceramic,
(Paper, cloth, etc.) can be firmly adhered (adhered) to the molten material, so that it can be used effectively to produce various laminated structures (composite structures) by sticking such other materials. can do. At that time, the type of the other material is not particularly limited and may be any.The number of layers in the laminated structure, the thickness of each layer, the shape, the structure, and the like are not particularly limited, and may be determined according to the application. You can decide.

[0048]

EXAMPLES The present invention will be described below in more detail with reference to examples and the like, but the present invention is not limited thereto. In the following Examples and Comparative Examples, the adhesive strength of the adhesive tape,
The measurement or evaluation of the holding power and the transparency (haze value) were performed as follows.

[Adhesive Strength of Adhesive Tape] (1) Adhesive Strength to Stainless Steel Plate: A stainless steel plate (width × length × thickness = 40 mm × 150 mm × 2 mm) was manufactured in the following Examples or Comparative Examples. Adhesive tape is adhered and “JIS-Z-0237, 8. Adhesive strength (18
Adhesion to stainless steel plate (g / 10mm) according to the test method specified in “0 degree peeling method”).
Was measured. (2) Adhesive strength to polypropylene plate: polypropylene plate (width x length x thickness = 40 mm x 150 mm x 2 m
m), the adhesive tape obtained in the following example or comparative example was adhered thereto, and the test specified in “JIS-Z-0237, 8. Adhesive force (180 ° peeling method)” was performed. According to the method, the adhesive strength (g / 10 mm) to the polypropylene plate was measured.

[Holding force of pressure-sensitive adhesive tape] Using a pressure-sensitive adhesive tape manufactured in the following Examples or Comparative Examples, a test temperature of 40
° C (Examples 1-4, Comparative Examples 1 and 2) or 6
At 0 ° C. (Example 5 and Comparative Example 3) and under a load of 1 kg, a 1 hour test was conducted according to the test method specified in “JIS-Z-0237, 11. Holding force”, and then 1 hour. The displacement distance of the adhesive tape later was measured, or when the adhesive tape dropped one hour before, the drop time was measured to evaluate the holding power of the adhesive tape.

[Transparency of Pressure-Sensitive Adhesive Tape] The pressure-sensitive adhesive tapes manufactured in the following Examples and Comparative Examples were measured using
The haze value of the pressure-sensitive adhesive tape was measured to evaluate the transparency. The higher the haze value, the lower the transparency.

The contents of the block copolymer (I) or a modified product thereof used in the following Examples and Comparative Examples are as follows. Block copolymer (I-1) : 40/60 (weight ratio) of a triblock copolymer composed of a polystyrene block-polyisoprene block-polystyrene block and a diblock copolymer composed of a polystyrene block-polyisoprene block. Hydrogenated product of the blend (number-average molecular weight of the entire hydrogenated product 100,000, styrene content = 13
% By weight, hydrogenation rate in polyisoprene block = 98
%). Block copolymer (I-2) : hydrogenated triblock copolymer consisting of polystyrene block-polyisoprene / butadiene copolymer block-polystyrene block (number average molecular weight 100,000, styrene content = 30)
% By weight, weight ratio of isoprene / butadiene = 45/5
5. Hydrogenation rate in polyisoprene / butadiene block = 98%). Block copolymer (IV) : a maleic anhydride-modified product of the above block copolymer (I-1) (maleic anhydride content: 0.8% by weight).

Reference Example 1 [Block copolymer (II-1)
(Manufacture of Polypropylene Block-Diblock Copolymer Consisting of Ethyl Acrylate / Acrylic Acid Copolymer Block)] (1) Polypropylene (“Mitsubishi Noblen MH8” manufactured by Mitsubishi Chemical Corporation) is supplied to a twin-screw extruder. The mixture was melt-kneaded at 420 ° C. and thermally decomposed to produce a polypropylene having a double bond at a terminal. (2) 100 kg of the polypropylene having a double bond at the terminal obtained in the above (1), 500 kg of toluene and 3.8 kg of thio-S-acetic acid were put into a reactor, and the inside thereof was sufficiently purged with nitrogen. 0.38 kg of '-azobisisobutyronitrile was added and reacted at 90 ° C. for 6 hours to prepare a polypropylene having a thioacetyl group at a terminal. (3) 60 kg of the polypropylene having a terminal thioacetyl group obtained in the above (2) was added to 100 kg of toluene.
Is dissolved in a mixed solvent of 20 kg of n-butanol and 1 kg of a 7% n-butanol solution of sodium hydroxide, and reacted at the reflux temperature of toluene in nitrogen for 2 hours to obtain a polypropylene having a mercapto group at the terminal. Manufactured.

(4) 50 kg of the polypropylene having a terminal mercapto group obtained in the above (3) was added to toluene 1
Dissolved in 74 kg, and ethyl acrylate 48.9 k
g and 1.1 kg of acrylic acid, add
C., the rate of polymerization of ethyl acrylate is about 1 hour
1,1′-azobis (cyclohexane-1-carbonitrile) was added so as to be 0%, and the reaction was stopped when the conversion reached 95%. By removing the solvent and unreacted monomers from the resulting reaction solution, a diblock copolymer consisting of a polypropylene block-ethyl acrylate / acrylic acid copolymer block was obtained [hereinafter referred to as “block copolymer”. (II-1)]]. (5) The block copolymer (II-
Number average molecular weight of polypropylene block in 1) =
10,000, the number average molecular weight of the ethyl acrylate / acrylic acid copolymer block was 9,500, and the total number average molecular weight was 19,500. The molar ratio of the structural unit derived from ethyl acrylate to the structural unit derived from acrylic acid in the ethyl acrylate / acrylic acid copolymer block of the block copolymer (II-1) = 9.
7: 3.

<< Reference Example 2 >> [Block copolymer (II-
2) (Polystyrene block-n-butyl acrylate /
Production of Diblock Copolymer Consisting of Acrylic Acid Copolymer Block) (1) 75 kg of styrene was charged into a 90-liter polymerization tank, and the temperature was raised to 90 ° C. under a nitrogen atmosphere. Thirty minutes later, 32 g of thio-S-acetic acid was added, and a 7% by weight toluene solution of a radical polymerization initiator (“V-65” manufactured by Wako Pure Chemical Industries, Ltd.) was added at a rate of 430 ml / hour. A 6% by weight solution of S-acetic acid in toluene was added to 75
Polymerization was started by adding at a rate of 0 ml / hour, and when the polymerization rate (polymer conversion rate) reached 40%, the polymerization was stopped and the inside of the polymerization tank was cooled. By removing solvent and unreacted monomers from the resulting viscous liquid,
Polystyrene having a number average molecular weight of 10,000 and having a thio-S-acetic acid ester group at a terminal was obtained. (2) 30 kg of the polystyrene obtained in the above (1),
30 kg of toluene and 15 kg of butanol were charged into a 90-liter reaction tank, and 153 ml of a 10% by weight methanol solution of sodium hydroxide was added at 70 ° C. under a nitrogen atmosphere to carry out transesterification of a thio-S-acetate ester group at a polystyrene end. Was done. After 2 hours, 30 g of acetic acid
Was added to the reaction vessel to terminate the reaction. By removing the solvent from the reaction solution thus obtained, polystyrene having a mercapto group at a terminal was obtained.

(3) n-butyl acrylate 117.9
kg, 2.1 kg of acrylic acid, 280 kg of toluene and 30 kg of polystyrene having a mercapto group at the end obtained in the above (2) were charged into a 500-liter polymerization tank, and the inside of the polymerization tank was sufficiently purged with nitrogen at 70 ° C. A 2% by weight toluene solution of a radical polymerization initiator (“V-70” manufactured by Wako Pure Chemical Industries, Ltd.) was added to the polymerization tank at a rate of 270 ml / hour to start polymerization, and the polymerization rate (polymer conversion rate)
Reached 95%, the polymerization was stopped. By removing the solvent and unreacted monomers from the resulting reaction solution, the polystyrene block-acrylic acid n
A diblock copolymer comprising -butyl / acrylic acid copolymer block was obtained [hereinafter referred to as "block copolymer (II
-2) "]. (4) The block copolymer (II-
Number average molecular weight of polystyrene block in 2) = 1
000, the number average molecular weight of the n-butyl acrylate / acrylic acid copolymer block was 40,000, and the total number average molecular weight was 50,000. Further, in the n-butyl acrylate / acrylic acid copolymer block of this block copolymer (II-2), the molar ratio of structural units derived from n-butyl acrylate: structural units derived from acrylic acid = 97: It was 3.

<< Reference Example 3 >> [Block copolymer (II-
3) Production of (diblock copolymer composed of polypropylene block-ethyl acrylate / maleic anhydride copolymer block)] (1) 50 kg of polypropylene having a mercapto group at the terminal obtained in (3) of Reference Example 1 To toluene 174k
g), and thereto were added 45.3 kg of ethyl acrylate and 4.7 kg of maleic anhydride.
At 90 ° C., a radical polymerization initiator (“V-65” manufactured by Wako Pure Chemical Industries, Ltd.) was added so that the polymerization rate of ethyl acrylate became about 10% per hour, and the polymerization rate became 95%. The reaction was stopped at that time. By removing the solvent and unreacted monomer from the resulting reaction solution, a diblock copolymer consisting of a polypropylene block-ethyl acrylate / maleic anhydride copolymer block was obtained [hereinafter referred to as “block copolymer”. Combined (II-3) "
That]. (2) The block copolymer (II-
Number average molecular weight of polypropylene block in 3) =
10,000, the number average molecular weight of the ethyl acrylate / maleic anhydride copolymer block was 9,500, and the total number average molecular weight was 19,500. In the block copolymer (II-3), the molar ratio of the structural unit derived from ethyl acrylate to the structural unit derived from maleic anhydride in the ethyl acrylate / maleic anhydride copolymer block was 97: 3. there were.

Example 1 (1) 30 parts by weight of the block copolymer (II-1) produced in Reference Example 1 was melted by heating at 180 ° C., and 1.5 parts by weight of zinc oxide was added thereto. The mixture was added and kneaded at the same temperature for 10 minutes while melting. (2) With respect to 31.5 parts by weight of the kneaded product obtained in the above (1), 100 parts by weight of the block copolymer (I-1) and a tackifier resin (hydrogenated aromatic hydrocarbon resin; Arakawa Chemical) 200 parts by weight of "Alcon P-100" manufactured by Co., Ltd., 100 parts by weight of paraffin-based process oil ("Diana Process PW-90" manufactured by Idemitsu Kosan Co., Ltd.) and an antioxidant ("Irganox 1010" manufactured by Ciba Geigy) The mixture was melt-kneaded at 180 ° C. to prepare a polymer composition (adhesive). (3) The polymer composition (adhesive) obtained in (2) above
Was heated and melted at 180 ° C., and coated on a polyethylene terephthalate film (thickness: 50 μm) using a dice type applicator so that the thickness of the pressure-sensitive adhesive layer was 30 μm, to produce a pressure-sensitive adhesive tape. (4) The pressure-sensitive adhesive strength, holding power and transparency (haze value) of the pressure-sensitive adhesive tape obtained in the above (3) were measured or evaluated by the above-mentioned methods, and the results were as shown in Table 1 below.

Example 2 (1) Except that (1) of Example 1 was replaced by 2.0 parts by weight of zinc acetate in place of 1.5 parts by weight of zinc oxide, (1) and (2) of Example 1 were used. A polymer composition (adhesive) was produced in the same manner as in (2). (2) The polymer composition (adhesive) obtained in (1) above
Was used to produce a pressure-sensitive adhesive tape in the same manner as in Example 1 (2), and the pressure-sensitive adhesive strength, holding power, and transparency (haze value) of the pressure-sensitive adhesive tape obtained thereby were measured or evaluated by the above-described method. And as shown in Table 1 below.

Example 3 (1) 30 parts by weight of the block copolymer (II-2) produced in Reference Example 2 was melted by heating at 180 ° C., and 1.5 parts by weight of zinc oxide was added thereto. The mixture was added and kneaded at the same temperature for 10 minutes while melting. (2) With respect to 31.5 parts by weight of the kneaded product obtained in the above (1), 100 parts by weight of the block copolymer (I-1), the same tackifying resin as used in Example 1, a paraffin-based resin The process oil and the antioxidant were added in proportions of 200 parts by weight, 100 parts by weight and 1 part by weight,
The mixture was melt-kneaded at 0 ° C. to produce a polymer composition (adhesive). (3) The polymer composition (adhesive) obtained in (2) above
Was used to produce a pressure-sensitive adhesive tape in the same manner as in Example 1 (3), and the pressure-sensitive adhesive strength, holding power, and transparency (haze value) of the pressure-sensitive adhesive tape obtained were measured or evaluated by the above-described method. And as shown in Table 1 below.

Example 4 (1) 30 parts by weight of the block copolymer (II-3) produced in Reference Example 3 was melted by heating at 180 ° C., and 1.0 part by weight of zinc acetate was added thereto. The mixture was added and kneaded at the same temperature for 10 minutes while melting. (2) With respect to 31.0 parts by weight of the kneaded product obtained in the above (1), 100 parts by weight of the block copolymer (I-1), the same tackifying resin as used in Example 1, a paraffin-based resin The process oil and the antioxidant were added in proportions of 200 parts by weight, 100 parts by weight and 1 part by weight,
The mixture was melt-kneaded at 0 ° C. to produce a polymer composition (adhesive). (3) The polymer composition (adhesive) obtained in (2) above
Was used to produce a pressure-sensitive adhesive tape in the same manner as in Example 1 (3), and the pressure-sensitive adhesive strength, holding power, and transparency (haze value) of the pressure-sensitive adhesive tape obtained were measured or evaluated by the above-described method. And as shown in Table 1 below.

Comparative Example 1 (1) The same tackifier resin, paraffin-based process oil and antioxidant as used in Example 1 were used with respect to 100 parts by weight of the block copolymer (I-1). 2
The polymer compositions (adhesives) were produced by adding 00 parts by weight, 100 parts by weight, and 1 part by weight, and melt-kneading at 180 ° C. (2) The polymer composition (adhesive) obtained in (1) above
Was used to produce a pressure-sensitive adhesive tape in the same manner as in Example 1 (3), and the pressure-sensitive adhesive strength, holding power, and transparency (haze value) of the pressure-sensitive adhesive tape obtained were measured or evaluated by the above-described method. And as shown in Table 1 below.

<< Comparative Example 2 >> (1) To 100 parts by weight of the block copolymer (IV), 1.5 parts by weight of zinc oxide, and the same tackifying resin and paraffin-based process as used in Example 1 200 parts by weight, 100 parts by weight and 1 part by weight of an oil and an antioxidant were added, respectively, and melt-kneaded at 180 ° C. to produce a polymer composition (adhesive). (2) The polymer composition (adhesive) obtained in (1) above
Was used to produce a pressure-sensitive adhesive tape in the same manner as in Example 1 (3), and the pressure-sensitive adhesive strength, holding power, and transparency (haze value) of the pressure-sensitive adhesive tape obtained were measured or evaluated by the above-described method. And as shown in Table 1 below.

Example 5 (1) 50 parts by weight of the block copolymer (II-2) produced in Reference Example 2 was melted by heating at 180 ° C., and 1.5 parts by weight of zinc oxide was added thereto. The mixture was added and kneaded at the same temperature for 10 minutes while melting. (2) With respect to 31.5 parts by weight of the kneaded product obtained in the above (1), 100 parts by weight of the block copolymer (I-2), the same tackifying resin as used in Example 1, a paraffin-based resin The process oil and the antioxidant were added in proportions of 200 parts by weight, 100 parts by weight and 1 part by weight,
The mixture was melt-kneaded at 0 ° C. to produce a polymer composition (adhesive). (3) The polymer composition (adhesive) obtained in (2) above
Was used to produce a pressure-sensitive adhesive tape in the same manner as in Example 1 (3), and the pressure-sensitive adhesive strength, holding power, and transparency (haze value) of the pressure-sensitive adhesive tape obtained were measured or evaluated by the above-described method. And as shown in Table 1 below.

Comparative Example 3 (1) The same tackifying resin, paraffin-based process oil and antioxidant as used in Example 1 were used with respect to 100 parts by weight of the block copolymer (I-2). 2
The polymer compositions (adhesives) were produced by adding 00 parts by weight, 100 parts by weight, and 1 part by weight, and melt-kneading at 180 ° C. (2) The polymer composition (adhesive) obtained in (1) above
Was used to produce a pressure-sensitive adhesive tape in the same manner as in Example 1 (3), and the pressure-sensitive adhesive strength, holding power, and transparency (haze value) of the pressure-sensitive adhesive tape obtained were measured or evaluated by the above-described method. And as shown in Table 1 below.

[0066]

[Table 1]

From the results in Table 1 above, it can be seen that the block copolymer (I), the block copolymer (II) and the metal compound (II)
A polymer composition containing (I), wherein the block copolymer (II) is added to 100 parts by weight of the block copolymer (I).
In the range of 0.1 to 200 parts by weight and the metal compound (III) in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the block copolymer (II). The pressure-sensitive adhesives of Examples 1 to 5 using the polymer composition having excellent adhesiveness, have high adhesion to both a stainless steel plate having a polarity and a non-polar polypropylene plate, and have a cohesive force. It is clear that the adhesive tape was not dropped or slipped from the adherend.

On the other hand, Comparative Example 1 and Comparative Example 1 which did not contain the block copolymer (II) and the metal compound (III) but only blended the block copolymer (I) with the tackifier resin and the process oil. The pressure-sensitive adhesive of No. 3 was obtained in Examples 1 to
The cohesive force is lower than that of the pressure-sensitive adhesive of No. 5, and the pressure-sensitive adhesive tapes obtained using the pressure-sensitive adhesives of Comparative Examples 1 and 3 drop from the adherend one hour before elapse, and the holding power is reduced. It turns out that it is inferior. Furthermore, the block copolymer (1) which does not contain the block copolymer (II) and which is used in the present invention.
The adhesive of Comparative Example 2 using a hydrogenated styrene / diene block copolymer (IV) modified with maleic anhydride instead of styrene was inferior in tackiness, and was made of a stainless steel plate as a polar material and a non-polar It shows that the adhesive strength to any of the polypropylene materials is significantly lower than those of Examples 1 to 5, and the adhesiveness to polypropylene, which is a nonpolar material, is particularly poor.

[0069]

Industrial Applicability The polymer composition of the present invention and the pressure-sensitive adhesive using the same are excellent in tackiness, strongly adhere to various materials regardless of the type and physical properties of the adherend, and are polar materials. High adhesion to both non-polar and non-polar materials. Furthermore, the polymer composition of the present invention and the pressure-sensitive adhesive using the same have high cohesive strength as well as high cohesive strength. Therefore, when the pressure-sensitive adhesive product using the polymer composition and the pressure-sensitive adhesive of the present invention is adhered to an adherend, it has excellent holding power, causes a displacement in the adherend, and causes a drop from the adherend. Absent. Moreover, when the adhesive or the adhesive product needs to be peeled off from the adherend due to the high cohesive force, the adhesive can be completely and completely peeled off without remaining on the adherend. Further, since the polymer composition and the pressure-sensitive adhesive of the present invention are heat-meltable, by applying the melt to a substrate such as a sheet or a film, it is not necessary to form an organic solvent solution or an emulsion. , Which can safely produce adhesive products such as adhesive tapes and adhesive sheets in a simple process and without causing pollution or deterioration of the working environment and the global environment, and drying after applying the adhesive to the base material. An adhesive product can be economically produced in a simple process without any treatment. Further, the polymer composition of the present invention and the pressure-sensitive adhesive prepared using the same have the above-mentioned properties such as good elasticity, flexibility, mechanical properties, and transparency inherently possessed by the block copolymer (I). Has along with the characteristics.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09J 11/06 C09J 11/06 153/00 153/00 153/02 153/02

Claims (6)

[Claims] (I) at least one selected from a block copolymer having a polymer block (A) mainly composed of an aromatic vinyl compound and a polymer block (B) mainly composed of a conjugated diene compound, and a hydrogenated product thereof;
A kind of block copolymer (I); a polymer block (C) mainly composed of at least one compound selected from an aromatic vinyl compound and an olefin compound, and a polymer having a functional group selected from a carboxyl group and an acid anhydride group. (II) having a polymer block (D) having a structural unit derived from a reactive monomer; and at least one metal compound selected from metal oxides, metal hydroxides and metal salts ( III) a polymer composition comprising: (ii) a block copolymer (I)
The block copolymer (II) was added in an amount of 0.1 part by weight to 100 parts by weight.
And (iii) 0.1 to 20 parts by weight of the metal compound (III) based on 100 parts by weight of the block copolymer (II). Characteristic polymer composition. 2. A polymer block (D) constituting a block copolymer (II) comprises a polymerizable monomer having a functional group selected from a carboxyl group and an acid anhydride group, and a carboxyl group and an acid anhydride group. The polymer composition according to claim 1, which is a polymer block comprising a copolymer with a polymerizable monomer having no polymerizable monomer. 3. The method according to claim 1, wherein the polymerizable monomer having no carboxyl group or acid anhydride group is at least one of (meth) acrylate, (meth) acrylonitrile, and a derivative thereof. A polymer composition as described in the above. 4. The method according to claim 1, wherein the metal compound (III) is an alkali metal,
Alkaline earth metals, groups IB, IIB,
The polymer composition according to any one of claims 1 to 3, which is at least one metal compound selected from oxides, hydroxides, and salts of Group III, Group IV, and Group VIII metals. 5. An adhesive comprising the polymer composition according to any one of claims 1 to 4. 6. The pressure-sensitive adhesive according to claim 5, further comprising a tackifier resin and / or a plasticizer.