JP2020033543A - Electrical insulation tape - Google Patents

Abstract

To provide an electrical insulation tape which is low in odor, suppressed in change in adhesive force with time, and excellent in holding force.SOLUTION: An electrical insulation tape includes a hot-melt sticky adhesive composition and a base material, in which the hot-melt sticky adhesive composition contains an aromatic vinyl block copolymer and a hydrogenated hydrocarbon resin, and when being heated at 65°C for 2 hours, a toluene volatile content amount of the hot-melt sticky adhesive composition is 260 μg/mor less and the total volatile content amount is 15,000 μg/mor less, and when being measured on conditions of a temperature of 23°C, a peeling angle of 180°, and a tensile speed of 300 mm/min, a peeling adhesive force of the hot-melt sticky adhesive composition to a stainless steel plate is 400 N/m or more.SELECTED DRAWING: None

Description

  The present invention relates to an electrical insulating tape, and more particularly, to an electrical insulating tape that has a low odor, suppresses a change in adhesive force over time, and has an excellent holding force.

  Hot-melt adhesives can solidify in a short period of time, enabling efficient bonding of various products, and since they do not require solvents, they are highly adhesive to humans. Since it is an adhesive, it is used in various fields. For example, when manufacturing paper, cardboard, sealing adhesives for packaging films, hygiene products such as disposable diapers and sanitary products, food and clothing, electronic devices, cosmetics, etc. Hot-melt adhesives have been used as adhesives for forming adhesive layers and as adhesives constituting adhesive layers of adhesive tapes and labels.

As the hot melt adhesive, for example, in Patent Document 1, the adhesive comprises a block copolymer A represented by the following general formula (A) and a block copolymer B represented by the following general formula (B). A hot melt adhesive composition comprising a block copolymer composition and a tackifier resin, wherein the weight of the block copolymer A and the block copolymer B in the block copolymer composition A hot melt adhesive composition having a ratio (A / B) of 10/90 to 90/10 and an aromatic monomer unit content of the tackifying resin of 1 to 70% by weight has been proposed. I have.
^{Ar1 a -D a -Ar2 a (A} )
(Ar ^b -D ^b ) nx (B)
(In the general formula (A) and (B), Ar @ 1 ^a and Ar ^b are each an aromatic vinyl polymer block having a weight average molecular weight of 6,000 to 20,000, Ar @ 2 ^a has a weight average molecular weight of 22,000 to 400,000 an aromatic vinyl polymer block, D ^a and D ^b are each a vinyl bond content of 20 mol% of the conjugated diene polymer block, X is the residue of a single bond or a coupling agent , N is an integer of 2 or more.)

  On the other hand, when the hot melt adhesive composition is used for the adhesive of the electrical insulating tape, odor may be a problem, and therefore, while maintaining the holding power and suppressing the deterioration over time, the odor is reduced. Reduction was required.

JP 2010-254833 A

  The present invention has been made in view of such circumstances, and an object of the present invention is to provide an electric insulating tape which has a low odor, suppresses a change in adhesive force with the passage of time, and has excellent holding power.

  The present inventors have conducted studies to achieve the above object, and found that, in an electric insulating tape including a hot-melt adhesive composition and a substrate, aromatic hot-melt adhesive composition was used as the hot-melt adhesive composition. A hot-melt adhesive composition containing a vinyl block copolymer and a hydrogenated hydrocarbon resin, wherein the amount of volatile components in toluene and the total amount of volatile components are suppressed to a predetermined amount or less, and a stainless steel sheet It has been found that the above object can be achieved by using a material having a specific adhesive strength for peeling to the present invention, and the present invention has been completed.

That is, according to the present invention, a hot-melt adhesive composition, and an electrical insulating tape comprising a substrate, wherein the hot-melt adhesive composition is an aromatic vinyl block copolymer, The hot melt adhesive composition contains a hydrogenated hydrocarbon resin and is heated at 65 ° C. for 2 hours. The hot melt adhesive composition has a toluene volatile content of 260 μg / m ³ or less and a total volatile component content of 15, 000 μg / m ³ or less, the peel adhesion of the hot melt adhesive composition to a stainless steel plate measured at a temperature of 23 ° C., a peel angle of 180 °, and a tensile speed of 300 mm / min is 400 N / m. An electrical insulating tape as described above is provided.

In the hot melt adhesive composition for an electric insulating tape of the present invention, the aromatic vinyl block copolymer may be a block copolymer A represented by the following general formula (I) and a block copolymer A represented by the following general formula (II). And the block copolymer B represented by the formula (I).
Ar1-D1-Ar2 (I)
Ar3-D2 (II)
(In the above general formulas (I) and (II), Ar1, Ar2 and Ar3 are each an aromatic vinyl polymer block, and D1 and D2 are each a conjugated diene polymer block.)
In the hot melt adhesive composition in the electric insulating tape of the present invention, the content of the aromatic vinyl monomer unit of the block copolymer A is not larger than the content of the aromatic vinyl monomer unit of the block copolymer B. More than quantity,
The weight average molecular weight (Mw (Ar1)) of the aromatic vinyl polymer block Ar1 of the block copolymer A and the weight average molecular weight (Mw (Ar3)) of the aromatic vinyl polymer block Ar3 of the block copolymer B. Are preferably substantially the same.
In the electrical insulating tape of the present invention, the weight average molecular weight (Mw (Ar2)) of the aromatic vinyl polymer block Ar2 of the block copolymer A and the weight average molecular weight (Mw (Ar1) of the aromatic vinyl polymer block Ar1 are used. )) (Mw (Ar2) / Mw (Ar1)) is preferably in the range of 1 to 7.
In the electric insulating tape of the present invention, it is preferable that the block copolymer B is prepared together with the block copolymer A when preparing the block copolymer A.

Further, in the hot melt adhesive composition in the electrical insulating tape of the present invention, the hydrogenated hydrocarbon resin,
1,3-pentadiene monomer unit 30% by mass to 75% by mass,
Alicyclic monoolefin monomer unit having 4 to 6 carbon atoms, 20% to 50% by mass,
An acyclic monoolefin monomer unit having 4 to 8 carbon atoms in an amount of 5 mass% to 25 mass%,
It is obtained by hydrogenating a hydrocarbon resin containing 0% to 10% by mass of an alicyclic diolefin monomer unit and 0% to 30% by mass of an aromatic monoolefin monomer unit. Is preferred.
In the electrical insulating tape of the present invention, the hydrogenated hydrocarbon resin may be a hydrocarbon resin having a monomer unit content of dicyclopentadiene of 10% by mass or less as the hydrocarbon resin before hydrogenation. And those obtained by hydrogenation.
In the hot melt adhesive composition in the electrical insulating tape of the present invention,
The hydrogenated hydrocarbon resin,
The hydrogenation rate of the olefin is 10% to 80%,
In the case of containing an aromatic monomer unit, the hydrogenation ratio of the aromatic ring is 1% to 30%,
A weight average molecular weight (Mw) of 1,000 to 3,500,
Z average molecular weight (Mz) is 2,000 to 7,000,
The ratio of the Z average molecular weight to the weight average molecular weight (Mz / Mw) is 1.5 to 2.5,
A softening point of 50 ° C. or more;
The 50% by mass toluene solution preferably has a Gardner color number of 3 or less.

Further, in the electric insulating tape of the present invention, it is preferable that the hot melt adhesive composition further contains a softener.
In the electric insulating tape of the present invention, the content of the aromatic vinyl block copolymer is 10% by mass to 70% by mass, the content of the hydrogenated hydrocarbon resin is 20% by mass to 80% by mass, The content ratio is preferably from 0.1% by mass to 30% by mass.

  ADVANTAGE OF THE INVENTION According to this invention, the odor is low, the change of the adhesive force with time is suppressed, and the electrical insulation tape excellent in holding power can be provided.

  The electric insulating tape of the present invention comprises a hot melt adhesive composition and a base material.

(Hot melt adhesive composition)
The hot melt adhesive composition used in the present invention contains an aromatic vinyl block copolymer and a hydrogenated hydrocarbon resin, and is heated at 65 ° C. for 2 hours to evaporate toluene. Peeling from stainless steel sheet, measured under the conditions of a quantity of 260 μg / m ³ or less, a total volatile content of 15,000 μg / m ³ or less, a temperature of 23 ° C., a peeling angle of 180 ° and a tensile speed of 300 mm / min. The adhesive force was controlled to 400 N / m or more.

(Aromatic vinyl block copolymer)
The aromatic vinyl block copolymer used in the present invention is preferably a block copolymer including a specific aromatic vinyl polymer block and a conjugated diene polymer block.

In the present invention, as a block copolymer having such an aromatic vinyl polymer block and a conjugated diene polymer block, a block copolymer A represented by the following general formula (I) and a block copolymer A represented by the following general formula (II) ), And the block copolymer composition containing the block copolymer B represented by the formula (1).
Ar1-D1-Ar2 (I)
Ar3-D2 (II)
(In the above general formulas (I) and (II), Ar1, Ar2 and Ar3 are each an aromatic vinyl polymer block, and D1 and D2 are each a conjugated diene polymer block.)

The block copolymer A is a triblock copolymer having two aromatic vinyl polymer blocks represented by the following general formula (I) and one conjugated diene polymer block.
Ar1-D1-Ar2 (I)
(In the above general formula (I), Ar1 and Ar2 are each an aromatic vinyl polymer block, and D1 is a conjugated diene polymer block.)

  The aromatic vinyl polymer block Ar1 constituting the block copolymer A is a polymer block having an aromatic vinyl monomer unit as a main constituent unit. Examples of the aromatic vinyl monomer used to constitute the aromatic vinyl monomer unit of the aromatic vinyl polymer block Ar1 include styrene; α-methylstyrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene. Alkyl-substituted styrenes such as methylstyrene, 2,4-dimethylstyrene, ethylstyrene and p-tert-butylstyrene; halogen-substituted styrenes such as 4-chlorostyrene, 2-bromostyrene and 3,5-difluorostyrene; And alkoxy-substituted styrenes such as -methoxystyrene and 3,5-dimethoxystyrene. Among these, a halogen-free aromatic vinyl monomer is preferable, and from the viewpoint that the adhesive force as a pressure-sensitive adhesive can be further improved and that the holding power of an electric insulating tape can be further increased, Styrene and alkyl-substituted styrene are more preferred, and styrene is particularly preferred. These aromatic vinyl monomers can be used alone or in combination of two or more.

  The aromatic vinyl polymer block Ar1 may include a monomer unit other than the aromatic vinyl monomer unit. Examples of the monomer constituting a monomer unit other than the aromatic vinyl monomer unit which can be contained in the aromatic vinyl polymer block Ar1 include 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3. Conjugated diene monomers such as -butadiene and 1,3-pentadiene; The content of monomer units other than the aromatic vinyl monomer unit in the aromatic vinyl polymer block Ar1 is preferably 20% by mass or less, more preferably 10% by mass or less, and substantially. Particularly preferably, it is 0% by mass. That is, the content of the aromatic vinyl monomer unit in the aromatic vinyl polymer block Ar1 is preferably 80% by mass or more, more preferably 90% by mass or more, and substantially 100% by mass. It is particularly preferred that there is.

  The weight average molecular weight (Mw (Ar1)) of the aromatic vinyl polymer block Ar1 is not particularly limited, but can be generally in the range of 5,000 to 100,000, and is preferably 6,000 to 50,000. It is preferably in the range, more preferably in the range of 7,000 to 30,000, and still more preferably in the range of 10,000 to 16,000. By setting Mw (Ar1) in the above range, it is possible to further increase the adhesive force as a pressure-sensitive adhesive while suppressing an increase in melt viscosity, and to further increase the holding power of the electric insulating tape. .

  The molecular weight distribution (Mw (Ar1) / Mn (Ar1)), which is the ratio between the weight average molecular weight (Mw (Ar1)) and the number average molecular weight (Mn (Ar1)) of the aromatic vinyl polymer block Ar1, depends on time. From the viewpoint that the change in the adhesive force can be further reduced, it is preferably 1.5 or less, more preferably 1.2 or less.

  In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of each polymer block, block copolymer and block copolymer composition are expressed in terms of polystyrene as measured by high performance liquid chromatography. You can ask. More specifically, the weight average molecular weight and the number average molecular weight can be measured as high molecular weight in terms of polystyrene by high performance liquid chromatography using tetrahydrofuran as a carrier.

  The conjugated diene polymer block D1 constituting the block copolymer A is a polymer block having a conjugated diene monomer unit as a main constituent unit. The conjugated diene monomer used to form the conjugated diene monomer unit of the conjugated diene polymer block D1 is not particularly limited as long as it is a conjugated diene compound. For example, 1,3-butadiene, isoprene, , 3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene and the like. Among these, as the conjugated diene monomer, a halogen-free conjugated diene monomer is preferable, and from the viewpoint that the adhesive force as a pressure-sensitive adhesive can be further increased and the holding power of the electric insulating tape is further increased. In light of the fact that it can be formed, 1,3-butadiene and / or isoprene are more preferred, and isoprene is particularly preferred. These conjugated diene monomers can be used alone or in combination of two or more. The conjugated diene polymer block D1 constituting the block copolymer A may be one obtained by subjecting a part of the carbon-carbon unsaturated bond to a hydrogenation reaction.

  The conjugated diene polymer block D1 may include a monomer unit other than the conjugated diene monomer unit. Examples of the monomer constituting a monomer unit other than the conjugated diene monomer unit that can be contained in the conjugated diene polymer block D1 include aromatic vinyl monomers such as styrene and α-methylstyrene, and α, β- Examples include unsaturated nitrile monomers, unsaturated carboxylic acid or acid anhydride monomers, unsaturated carboxylic acid ester monomers, and non-conjugated diene monomers. The content of the monomer unit other than the conjugated diene monomer unit in the conjugated diene polymer block D1 is preferably 20% by mass or less, more preferably 10% by mass or less, and substantially 0% by mass. % Is particularly preferred. That is, the content of the conjugated diene monomer unit in the conjugated diene polymer block D1 is preferably 80% by mass or more, more preferably 90% by mass or more, and substantially 100% by mass. Is particularly preferred.

  The content of the monomer unit having a vinyl bond in the monomer units constituting the conjugated diene polymer block D1 is not particularly limited, but is usually 50% by mass or less and 20% by mass or less. Is preferable, and it is especially preferable that it is in the range of 5% by mass to 10% by mass. By setting the content of the monomer unit having a vinyl bond in the above range, the adhesive strength at a low temperature can be further increased.

  The weight average molecular weight (Mw (D1)) of the conjugated diene polymer block D1 is not particularly limited, but can be generally in the range of 70,000 to 190,000, and in the range of 80,000 to 160,000. Is preferably within the range of 85,000 to 140,000, and more preferably 110,000 to 130,000. By setting Mw (D1) in the above range, it is possible to further increase the adhesive force as a pressure-sensitive adhesive while suppressing an increase in melt viscosity, and to further increase the holding force of the electric insulating tape. .

  The molecular weight distribution (Mw (D1) / Mn (D1)), which is the ratio of the weight average molecular weight (Mw (D1) to the number average molecular weight (Mn (D1))) of the conjugated diene polymer block D1, is determined by the adhesion with time. From the viewpoint that the change in force can be further reduced, it is preferably 1.5 or less, more preferably 1.2 or less.

  The aromatic vinyl polymer block Ar2 constituting the block copolymer A is a polymer block having an aromatic vinyl monomer unit as a main constituent unit. As the aromatic vinyl monomer used to constitute the aromatic vinyl monomer unit of the aromatic vinyl polymer block Ar2, the same aromatic vinyl monomer as the above-mentioned aromatic vinyl polymer block Ar1 can be used.

  Further, the aromatic vinyl polymer block Ar2 may include a monomer unit other than the aromatic vinyl monomer unit, and may include a monomer unit other than the aromatic vinyl monomer unit that can be included in the aromatic vinyl polymer block Ar2. Examples of the monomer constituting the above monomer unit include those similar to the above-mentioned aromatic vinyl polymer block Ar1, and the content thereof can be the same.

  The weight average molecular weight (Mw (Ar2)) of the aromatic vinyl polymer block Ar2 may be larger than the weight average molecular weight (Mw (Ar1)) of the aromatic vinyl polymer block Ar1 constituting the block copolymer A. It may be about the same as Mw (Ar1). In the present invention, the ratio (Mw (Ar2) / Mw (Mw (Ar2) / Mw (Mw (Ar2))) of the weight average molecular weight (Mw (Ar2)) of the aromatic vinyl polymer block Ar2 to the weight average molecular weight (Mw (Ar1)) of the aromatic vinyl polymer block Ar1. Ar1))) is preferably in the range of 1 to 7, more preferably in the range of 1 to 5, and even more preferably in the range of 1.2 to 4. It is particularly preferred that it is in the range of 5 to 3. By setting the ratio of the weight average molecular weight in the above range, it is possible to further increase the adhesive force as a pressure-sensitive adhesive and further increase the holding power of the electric insulating tape.

  The weight average molecular weight (Mw (Ar2)) of the aromatic vinyl polymer block Ar2 is not particularly limited, but can be generally in the range of 5,000 to 120,000, and is preferably in the range of 9,000 to 100,000. It is preferably within the range, more preferably within the range of 4,000 to 90,000. By setting Mw (Ar2) within the above range, it is possible to further increase the adhesive force as a pressure-sensitive adhesive while suppressing the decrease in productivity due to the increase in the molecular weight, and to increase the holding force of the electric insulating tape. Can be more enhanced.

  The molecular weight distribution (Mw (Ar2) / Mn (Ar2)), which is the ratio between the weight average molecular weight (Mw (Ar2)) and the number average molecular weight (Mn (Ar2)), of the aromatic vinyl polymer block Ar2 is determined by the adhesive force over time. Is preferably 1.5 or less, and more preferably 1.2 or less, from the viewpoint that the change in can be made smaller.

  The block copolymer A is a triblock copolymer composed of the above-described aromatic vinyl polymer block Ar1, conjugated diene polymer block D1, and aromatic vinyl polymer block Ar2, and has a weight average molecular weight (MwA), The weight average molecular weight of the entire block copolymer A can be generally in the range of 80,000 to 400,000, preferably in the range of 90,000 to 300,000, and more preferably 100,000. It is more preferably in the range of from 250,000 to 250,000, still more preferably in the range of 110,000 to 220,000, and particularly preferably in the range of 150,000 to 190,000. By setting the weight average molecular weight (MwA) of the block copolymer A in the above range, it is possible to further increase the adhesive force as a pressure-sensitive adhesive while suppressing an increase in melt viscosity. The holding power can be further increased.

  The molecular weight distribution (Mw / Mn) of the block copolymer A, that is, the molecular weight distribution of the entire block copolymer A is 1.5 or less from the viewpoint that the change in adhesive force with time can be further reduced. And more preferably 1.2 or less.

  The content of the aromatic vinyl monomer unit of the block copolymer A (the ratio of the aromatic vinyl monomer unit to all the monomer units constituting the block copolymer A) is usually from 15% by mass to In the range of 75% by mass, preferably in the range of 17% to 60% by mass, more preferably in the range of 18% to 50% by mass, and more preferably in the range of 20% to 35% by mass. More preferably, it is within the range. By setting the content of the aromatic vinyl monomer unit within the above range, the adhesive force as the adhesive agent can be further increased, and the holding force of the electric insulating tape can be further increased.

  In the present invention, the content of the aromatic vinyl monomer unit of the block copolymer A is preferably larger than the content of the aromatic vinyl monomer unit of the block copolymer B described later. Specifically, the ratio of the aromatic vinyl monomer unit content of the block copolymer A to the aromatic vinyl monomer unit content of the block copolymer B (the aromatic vinyl monomer unit of the block copolymer A) Monomer unit content / aromatic vinyl monomer unit content of block copolymer B) is preferably in the range of 1.1 to 5, and more preferably in the range of 1.5 to 4. More preferably, it is more preferably in the range of 1.75 to 3.5. By setting the above ratio in the above range, the adhesive force as the adhesive agent can be further increased, and the holding force of the electric insulating tape can be further increased.

  Further, the content of the block copolymer A in the block copolymer composition (the content of the block copolymer A in the block copolymer composition including the block copolymer A and the block copolymer B) Amount) can be generally in the range of 10% by mass to 90% by mass, preferably in the range of 15% by mass to 60% by mass, and more preferably in the range of 20% by mass to 50% by mass. More preferably, it is more preferably 35% by mass to 45% by mass. By setting the content of the block copolymer A in the block copolymer composition to the above range, the adhesive force as a pressure-sensitive adhesive can be further increased, and the holding power of the electric insulating tape is further increased. be able to.

  In the present invention, the block copolymer A constituting the block copolymer composition may be composed of only one type of block copolymer A having a substantially single structure. However, it may be composed of two or more types of block copolymers A having substantially different configurations.

The block copolymer B is a diblock copolymer represented by the following general formula (II) and having one aromatic vinyl polymer block and one conjugated diene polymer block.
Ar3-D2 (II)
(In the general formula (II), Ar3 is an aromatic vinyl polymer block, and D2 is a conjugated diene polymer block.)

  The aromatic vinyl polymer block Ar3 constituting the block copolymer B is a polymer block having an aromatic vinyl monomer unit as a main constituent unit. The aromatic vinyl monomer used to constitute the aromatic vinyl monomer unit of the aromatic vinyl polymer block Ar3 is the same as the aromatic vinyl polymer block Ar1 constituting the block copolymer A. Things.

  In addition, the aromatic vinyl polymer block Ar3 may include a monomer unit other than the aromatic vinyl monomer unit, and may include a monomer unit other than the aromatic vinyl monomer unit that can be included in the aromatic vinyl polymer block Ar3. Examples of the monomer constituting the monomer unit include those similar to the aromatic vinyl polymer block Ar1 constituting the block copolymer A, and the content thereof may be the same.

  In the present invention, the type of the monomer used to form the monomer unit constituting the aromatic vinyl polymer block Ar3 constitutes the aromatic vinyl polymer block Ar1 of the block copolymer A. It is preferable that the type of the monomer used to form the monomer unit is the same, and the content ratio of each monomer unit forming the aromatic vinyl polymer block Ar3 is the same as that of the block copolymer. It is preferable that the content ratio of each monomer unit constituting the aromatic vinyl polymer block Ar1 of the united product A is substantially the same. Since the monomer units constituting the aromatic vinyl polymer block Ar3 and the monomer units constituting the aromatic vinyl polymer block Ar1 of the block copolymer A are substantially the same, the block copolymerization The compatibility between the coalesced A and the block copolymer B can be increased, whereby the adhesive strength as a pressure-sensitive adhesive can be further increased, and the holding power of the electric insulating tape can be further increased. it can.

  In the present invention, the weight average molecular weight (Mw (Ar3)) of the aromatic vinyl polymer block Ar3 constituting the block copolymer B is such that the aromatic vinyl polymer block Ar3 constitutes the block copolymer A. It is preferable that the weight average molecular weight (Mw (Ar1)) of Ar1 is substantially the same. In this case, it suffices that Mw (Ar3) and Mw (Ar1) have such a relationship that it can be determined that they are substantially the same, but the ratio of these weight average molecular weights (Mw (Ar3) / Mw) (Ar1)) is preferably in the range of 0.95 to 1.05, more preferably in the range of 0.98 to 1.02, and particularly preferably 1.00. When Mw (Ar3) and Mw (Ar1) are substantially the same, the compatibility between the block copolymer A and the block copolymer B can be increased, and the adhesive As a result, the adhesive force can be further increased, and the holding force of the electrical insulating tape can be further increased.

  In addition, the molecular weight distribution (Mw (Ar3) / Mn (Ar3)), which is the ratio of the weight average molecular weight (Mw (Ar3)) to the number average molecular weight (Mn (Ar3)) of the aromatic vinyl polymer block Ar3, is the same as that of the block. From the viewpoint that the compatibility between the polymer A and the block copolymer B can be enhanced, and thereby the adhesive strength as a pressure-sensitive adhesive can be further increased, the aromatic vinyl polymer constituting the block copolymer A can be improved. It is preferable that the molecular weight distribution (Mw (Ar1) / Mn (Ar1)) of the united block Ar1 is substantially the same, that is, [Mw (Ar3) / Mn (Ar3)] / [Mw (Ar1) / Mn ( Ar1)] is preferably in the range of 0.95 to 1.05, more preferably in the range of 0.98 to 1.02, and particularly preferably 1.00.

  The conjugated diene polymer block D2 constituting the block copolymer B is a polymer block having a conjugated diene monomer unit as a main constituent unit. Examples of the conjugated diene monomer used for forming the conjugated diene monomer unit of the conjugated diene polymer block D2 include the same conjugated diene polymer block D1 as the block copolymer A. .

  Further, the conjugated diene polymer block D2 may contain a monomer unit other than the conjugated diene monomer unit, and may be a monomer other than the conjugated diene monomer unit which can be contained in the conjugated diene polymer block D2. Examples of the monomer constituting the unit include those similar to the conjugated diene polymer block D1 constituting the block copolymer A, and the content thereof may be the same.

  In the present invention, the type of the monomer used to form the monomer unit constituting the conjugated diene polymer block D2 is a monomer constituting the conjugated diene polymer block D1 of the block copolymer A. It is preferably the same as the type of the monomer used to form the body unit, and the content ratio of each monomer unit forming the conjugated diene polymer block D2 is preferably the same as that of the block copolymer A. It is preferable that the content ratio of each monomer unit constituting the conjugated diene polymer block D1 is substantially the same. Since the monomer units constituting the conjugated diene polymer block D2 and the monomer units constituting the conjugated diene polymer block D1 of the block copolymer A are substantially the same, the block copolymer A And the compatibility with the block copolymer B can be enhanced, whereby the adhesive force as the adhesive agent can be further increased, and the holding power of the electric insulating tape can be further increased.

  In the present invention, the weight average molecular weight (Mw (D2)) of the conjugated diene polymer block D2 constituting the block copolymer B is the same as that of the conjugated diene polymer block D1 constituting the block copolymer A. Preferably, it is substantially the same as the weight average molecular weight (Mw (D1)). In this case, it suffices that Mw (D2) and Mw (D1) have a relationship that can be determined to be substantially the same, but the ratio of these weight average molecular weights (Mw (D2) / Mw (D1)) is preferably in the range of 0.95 to 1.05, more preferably in the range of 0.98 to 1.02, and particularly preferably 1.00. When Mw (D2) and Mw (D1) are substantially the same, the compatibility between the block copolymer A and the block copolymer B can be increased, and thus, the adhesive As a result, the adhesive force can be further increased, and the holding force of the electrical insulating tape can be further increased.

  The molecular weight distribution (Mw (D2) / Mn (D2)), which is the ratio of the weight average molecular weight (Mw (D2)) to the number average molecular weight (Mn (D2)), of the conjugated diene polymer block D2 is also known as the block weight. From the viewpoint that the compatibility between the coalesced A and the block copolymer B is enhanced, thereby increasing the adhesive force as a pressure-sensitive adhesive, and further increasing the holding power of the electric insulating tape, It is preferable that the molecular weight distribution (Mw (D1) / Mn (D1)) of the conjugated diene polymer block D1 constituting the copolymer A is substantially the same as that of [Mw (D2) / Mn (D2)]. ] / [Mw (D1) / Mn (D1)] is preferably in the range of 0.95 to 1.05, more preferably in the range of 0.98 to 1.02. 00 is particularly preferred.

  The block copolymer B is a diblock copolymer composed of the above-mentioned aromatic vinyl polymer block Ar3 and conjugated diene polymer block D2, and has a weight average molecular weight (MwB), that is, the entire block copolymer B. Can usually be in the range of 80,000 to 300,000, preferably in the range of 85,000 to 250,000, and in the range of 90,000 to 230,000. Is more preferably in the range of 95,000 to 200,000, and particularly preferably in the range of 120,000 to 150,000. By setting the weight average molecular weight (MwB) of the block copolymer B to the above range, it is possible to further increase the adhesive force as a pressure-sensitive adhesive while suppressing an increase in melt viscosity. The holding power can be further increased.

  The molecular weight distribution (Mw / Mn) of the block copolymer B, that is, the molecular weight distribution of the block copolymer B as a whole is 1.5 or less from the viewpoint that the change in adhesive force with time can be reduced. And more preferably 1.2 or less.

  The content of the aromatic vinyl monomer unit of the block copolymer B (the ratio of the aromatic vinyl monomer unit to all the monomer units constituting the block copolymer B) is usually from 8% by mass to Within a range of 50% by mass, preferably within a range of 10% by mass to 40% by mass, more preferably within a range of 12% by mass to 30% by mass, and more preferably within a range of 12% by mass to 17% by mass. It is more preferred that there be. By setting the content of the aromatic vinyl monomer unit within the above range, the adhesive force as the adhesive agent can be further increased, and the holding force of the electric insulating tape can be further increased.

  In the present invention, the block copolymer B constituting the block copolymer composition may be composed of only one type of block copolymer B having a substantially single structure. However, it may be composed of two or more block copolymers B having substantially different configurations.

  In the present invention, the block copolymer B is preferably prepared together with the block copolymer A when preparing the block copolymer A. Specifically, as described in detail in a manufacturing method described later, first, after obtaining a block copolymer B, a part of the obtained block copolymer B is further subjected to an aromatic vinyl polymer block Ar2. It is preferable that the block copolymer B and the block copolymer A are simultaneously prepared by a method of obtaining the block copolymer A by bonding

  In the present invention, as the aromatic vinyl block copolymer, it is preferable to use a block copolymer composition containing the block copolymer A and the block copolymer B described above. , May be composed of only the block copolymer A and the block copolymer B, but may include a block copolymer other than the block copolymer A and the block copolymer B. Examples of such a block copolymer include an aromatic vinyl-conjugated diene-aromatic vinyl triblock copolymer and a radial aromatic vinyl-conjugated diene block copolymer having a structure different from that of the block copolymer A. Examples include, but are not limited to: In the block copolymer component, the amount occupied by the block copolymer other than the block copolymer A and the block copolymer B is preferably 20% by mass or less, more preferably 10% by mass or less.

  In the block copolymer component consisting of the block copolymer A, the block copolymer B, and the block copolymer other than the block copolymer A and the block copolymer B which may be optionally contained, the block copolymer component The proportion occupied by the aromatic vinyl monomer unit with respect to the whole (hereinafter, sometimes referred to as “the total content of the aromatic vinyl monomer unit”) is determined by the adhesive strength as the adhesive agent. From the viewpoint that it is possible to increase the holding power of the electrical insulating tape, it is preferable to be in the range of 10% by mass to 50% by mass, and in the range of 13% by mass to 40% by mass. More preferably, it is more preferably in the range of 15% by mass to 37% by mass, and particularly preferably in the range of 17% by mass to 35% by mass.

  The total content of the aromatic vinyl monomer units is determined based on the content of the aromatic vinyl monomer units of each block copolymer constituting the block copolymer composition, and By adjusting, it is possible to easily adjust. In addition, if all the polymer components constituting the block copolymer composition are composed of only an aromatic vinyl monomer unit and a conjugated diene monomer unit, Rubber Chem. Technol. , 45, 1295 (1972), when the block copolymer is ozonolyzed and then reduced with lithium aluminum hydride, the conjugated diene monomer unit is decomposed and the aromatic vinyl monomer is decomposed. Since only the unit portion can be taken out, the entire aromatic vinyl monomer unit content can be easily measured.

  The weight average molecular weight (Mw) of the aromatic vinyl block copolymer as a whole used in the present invention, that is, a block copolymer composition containing the above-described block copolymer A and block copolymer B is used. In some cases, the weight average of the entire block copolymer component consisting of the block copolymer A, the block copolymer B, and the block copolymer other than the block copolymer A and the block copolymer B that may be optionally contained. The molecular weight is preferably in the range of 80,000 to 400,000, more preferably in the range of 85,000 to 280,000, and more preferably in the range of 90,000 to 250,000. More preferred.

  The method for producing the block copolymer composition containing the above-described block copolymer A and block copolymer B is not particularly limited. For example, it can be produced by separately producing each block copolymer according to a conventional polymerization method and mixing them according to a conventional method such as kneading or solution mixing.

  In the present invention, the compatibility between the block copolymer A and the block copolymer B is further increased, whereby the adhesive force as an adhesive is further increased, and the holding power of the electric insulating tape is further increased. From the viewpoint that the block copolymer B can be obtained, specifically, first, after obtaining a block copolymer B, a part of the obtained block copolymer B is further converted to an aromatic vinyl. A method of obtaining the block copolymer A by binding the polymer block Ar2 is preferable.

More specifically, it is preferable to manufacture using a manufacturing method including the following steps (1) to (5).
(1): a step of polymerizing an aromatic vinyl monomer using a polymerization initiator in a solvent (2): a solution containing an aromatic vinyl polymer having an active terminal obtained in the above step (1) (3) adding a conjugated diene monomer to the solution containing the aromatic vinyl-conjugated diene block copolymer having an active terminal obtained in the above step (2); Step (4) of adding the aromatic vinyl-conjugated diene block copolymer having a terminal so as to be less than 1 molar equivalent based on the active terminal of the block copolymer to form a block copolymer B: Step (4): Step (5) of adding an aromatic vinyl monomer to the obtained solution to form a block copolymer A: recovering a polymer component from the solution obtained in the above step (4)

  In the above production method, first, an aromatic vinyl monomer is polymerized in a solvent using a polymerization initiator (step (1)). As the polymerization initiator used, generally, for an aromatic vinyl monomer and a conjugated diene monomer, an organic alkali metal compound known to have anionic polymerization activity, an organic alkaline earth metal compound, Organic lanthanoid-based rare earth metal compounds and the like can be used. As the organic alkali metal compound, an organic lithium compound having one or more lithium atoms in a molecule is particularly preferably used, and specific examples thereof include ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, organic monolithium compounds such as sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, stilbenelithium, dialkylaminolithium, diphenylaminolithium, ditrimethylsilylaminolithium, methylenedilithium, tetramethylenedilithium, hexamethylene Organic dilithium compounds such as dilithium, isoprenyldilithium, and 1,4-dilithio-ethylcyclohexane; and organic trilithium compounds such as 1,3,5-trilithiobenzene and the like. It is. Among these, an organic monolithium compound is particularly preferably used.

  Examples of the organic alkaline earth metal compound used as a polymerization initiator include, for example, n-butylmagnesium bromide, n-hexylmagnesium bromide, ethoxy calcium, calcium stearate, t-butoxystrontium, ethoxy barium, isopropoxy barium, ethyl mercapto barium, Examples include t-butoxybarium, phenoxybarium, diethylaminobarium, barium stearate, and ethylbarium. Specific examples of other polymerization initiators include a composite catalyst comprising a lanthanoid-based rare earth metal compound containing neodymium, samarium, gadolinium, etc./alkylaluminum/alkylaluminum halide / alkylaluminum hydride, titanium, vanadium, samarium, gadolinium. And those having a living polymerization property in an organic solvent such as a metallocene-type catalyst containing the same. These polymerization initiators may be used alone or in a combination of two or more.

  The amount of the polymerization initiator to be used may be determined according to the molecular weight of each target block copolymer, and is not particularly limited, but is usually 0.01 to 20 mmol per 100 g of all monomers used. Preferably, it is 0.05 to 15 mmol, more preferably 0.1 to 10 mmol.

  The solvent used for the polymerization is not particularly limited as long as it is inert to the polymerization initiator. For example, a chain hydrocarbon solvent, a cyclic hydrocarbon solvent, or a mixed solvent thereof is used. Examples of the chain hydrocarbon solvent include n-butane, isobutane, 1-butene, isobutylene, trans-2-butene, cis-2-butene, 1-pentene, trans-2-pentene, cis-2-pentene, and n-pentane And linear alkane and alkene having 4 to 6 carbon atoms such as isopentane, neo-pentane and n-hexane. Specific examples of the cyclic hydrocarbon solvent include aromatic compounds such as benzene, toluene, and xylene; and alicyclic hydrocarbon compounds such as cyclopentane and cyclohexane. These solvents may be used alone or as a mixture of two or more.

  The amount of the solvent used for the polymerization is not particularly limited, but the concentration of all block copolymers in the solution after the polymerization reaction is usually 5% by mass to 60% by mass, preferably 10% by mass to 55% by mass, and more preferably. Is set to be 20% by mass to 50% by mass.

  In order to control the structure of each polymer block of each block copolymer, a Lewis base compound may be added to a reactor used for polymerization. Examples of the Lewis base compound include ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether; Tertiary amines; alkali metal alkoxides such as potassium-t-amyl oxide and potassium-t-butyl oxide; phosphines such as triphenylphosphine; These Lewis base compounds are used alone or in combination of two or more, and are appropriately selected within a range not to impair the object of the present invention.

  The timing of adding the Lewis base compound at the time of the polymerization reaction is not particularly limited, and may be appropriately determined according to the target structure of each block copolymer. For example, it may be added in advance before starting polymerization, or may be added after polymerizing some polymer blocks, and further, may be added in advance before starting polymerization, and then partially added. It may be further added after polymerizing the polymer block.

  The polymerization reaction temperature is usually 10C to 150C, preferably 30C to 130C, more preferably 40C to 90C. The time required for the polymerization varies depending on the conditions, but is usually within 48 hours, preferably 0.5 to 10 hours. The polymerization pressure is not particularly limited, as long as the polymerization is carried out at a pressure sufficient to maintain the monomer and the solvent in the liquid phase in the above-mentioned polymerization temperature range.

  By polymerizing an aromatic vinyl monomer using a polymerization initiator in a solvent under the conditions described above, a solution containing an aromatic vinyl polymer having an active terminal can be obtained. The aromatic vinyl polymer having the active terminal constitutes the aromatic vinyl polymer block Ar1 of the block copolymer A and the aromatic vinyl polymer block Ar3 of the block copolymer B. Therefore, the amount of the aromatic vinyl monomer used at this time is determined according to the desired weight average molecular weight of these polymer blocks.

  The next step is a step of adding a conjugated diene monomer to a solution containing an aromatic vinyl polymer having an active terminal obtained as described above (step (2)). By the addition of the conjugated diene monomer, a conjugated diene polymer chain is formed from the active terminal, and a solution containing an aromatic vinyl-conjugated diene block copolymer having an active terminal is obtained. In this case, the amount of the conjugated diene monomer used is such that the obtained conjugated diene polymer chain is the same as the conjugated diene polymer block D1 of the target block copolymer A and the conjugated diene polymer block D2 of the block copolymer B. Determined to have a weight average molecular weight.

  In the next step, a polymerization terminator is added to the solution containing the active terminal aromatic vinyl-conjugated diene block copolymer obtained as described above, and the active terminal aromatic vinyl-conjugated diene block copolymer is added. It is added so as to be less than 1 molar equivalent to the active terminal of the union (step (3)). When a polymerization terminator is added to a solution containing an aromatic vinyl-conjugated diene block copolymer having an active end, the active end of the aromatic vinyl-conjugated diene block copolymer having an active end is inactivated, and as a result, Thus, a block copolymer B which is an aromatic vinyl-conjugated diene diblock copolymer is formed.

  The polymerization terminator added in this step is not particularly limited, and a conventionally known polymerization terminator can be used without any particular limitation. Particularly preferred polymerization terminators include alcohols such as methanol, ethanol, propanol, butanol, and isopropanol.

  The amount of the polymerization terminator added in this step is an amount that is less than 1 molar equivalent with respect to the active terminal of the aromatic vinyl-conjugated diene block copolymer having an active terminal. In order to perform the next step of forming the block copolymer A, an aromatic vinyl-conjugated diene block copolymer having an active terminal can be left in the solution. The amount of the polymerization terminator is preferably from 0.10 molar equivalent to 0.90 molar equivalent, more preferably from 0.15 molar equivalent to 0.70 molar equivalent, based on the active terminal of the polymer. Since the amount of the polymerization terminator added in this step determines the amount of the block copolymer B, the amount of the polymerization terminator depends on the composition of the target block copolymer component. You only have to decide.

  The reaction conditions for the polymerization termination reaction are not particularly limited, and may be usually set in the same range as the polymerization reaction conditions described above.

  In the next step, an aromatic vinyl monomer is added to the solution obtained as described above (step (4)). When an aromatic vinyl monomer is added to the solution, an aromatic vinyl polymer chain is formed from the terminal of the aromatic vinyl-conjugated diene block copolymer having an active terminal remaining without reacting with the polymerization terminator. . This aromatic vinyl polymer chain constitutes the aromatic vinyl polymer block Ar2 of the block copolymer A. Therefore, the amount of the aromatic vinyl monomer used at this time is determined according to the target weight average molecular weight of the aromatic vinyl polymer block Ar2. By the step of adding the aromatic vinyl monomer, an aromatic vinyl-conjugated diene-aromatic vinyl triblock copolymer, which constitutes the block copolymer A, is formed. A solution containing the union A and the block copolymer B is obtained. Before the step of adding the aromatic vinyl monomer, a conjugated diene monomer was added to a solution containing an aromatic vinyl-conjugated diene block copolymer having an active terminal that did not react with the polymerization terminator. It may be added. When the conjugated diene monomer is added in this manner, the weight average molecular weight of the conjugated diene polymer block D1 of the block copolymer A can be increased as compared with the case where no conjugated diene monomer is added.

  In the next step, the desired polymer component is recovered from the solution obtained as described above (step (5)). The method of recovery may be in accordance with a conventional method, and is not particularly limited. For example, after completion of the reaction, if necessary, a polymerization terminator such as water, methanol, ethanol, propanol, hydrochloric acid, or citric acid is added, and if necessary, an additive such as an antioxidant is added. The solution can be recovered by applying a known method such as a direct drying method or steam stripping to the solution. When the polymer component is recovered as a slurry by applying steam stripping or the like, the polymer component is dehydrated using an arbitrary dehydrator such as an extruder-type squeezer to obtain a crumb having a water content of a predetermined value or less, and further, The crumb may be dried using any dryer such as a band dryer or an expansion extrusion dryer.

  As described above, a block copolymer composition containing the above-described block copolymer A and block copolymer B can be obtained.

In the present invention, the aromatic vinyl block copolymer contains a block copolymer B represented by the above general formula (II) and a block copolymer C represented by the following general formula (III). A block copolymer composition may be used.
(Ar4-D3) _n -X (III)
(In the general formula (III), Ar4 is an aromatic vinyl polymer block, D3 is a conjugated diene polymer block, X is a residue of a single bond or a coupling agent, and n is 2 or more. Is an integer.)

  The aromatic vinyl polymer block Ar4 constituting the block copolymer C is a polymer block having an aromatic vinyl monomer unit as a main constituent unit. The aromatic vinyl monomer used to constitute the aromatic vinyl monomer unit of the aromatic vinyl polymer block Ar4 is the same as the aromatic vinyl polymer block Ar1 constituting the block copolymer A. Things.

  Further, the aromatic vinyl polymer block Ar4 may include a monomer unit other than the aromatic vinyl monomer unit, and may include a monomer unit other than the aromatic vinyl monomer unit that can be included in the aromatic vinyl polymer block Ar4. Examples of the monomer constituting the monomer unit include those similar to the aromatic vinyl polymer block Ar1 constituting the block copolymer A, and the content thereof may be the same.

  The weight average molecular weight (Mw (Ar4)) of the aromatic vinyl polymer block Ar1 constituting the block copolymer C is not particularly limited, but the aromatic vinyl polymer block Ar1 constituting the block copolymer A is not limited. Can be appropriately adjusted in the same range as the weight average molecular weight (Mw (Ar1)) of the above.

  The conjugated diene polymer block D3 constituting the block copolymer C is a polymer block having a conjugated diene monomer unit as a main constituent unit. Examples of the conjugated diene monomer used for forming the conjugated diene monomer unit of the conjugated diene polymer block D3 include the same as the conjugated diene polymer block D1 forming the block copolymer A. .

  In addition, the conjugated diene polymer block D3 may include a monomer unit other than the conjugated diene monomer unit, and may include a monomer other than the conjugated diene monomer unit that can be included in the conjugated diene polymer block D3. Examples of the monomer constituting the unit include those similar to the conjugated diene polymer block D1 constituting the block copolymer A, and the content thereof may be the same.

  The weight average molecular weight (Mw (D3)) of the conjugated diene polymer block D3 constituting the block copolymer C is not particularly limited, but the weight of the conjugated diene polymer block D1 constituting the block copolymer A is not limited. In the same range as the average molecular weight (Mw (D1)), it can be appropriately adjusted.

  The method for producing the block copolymer composition containing the block copolymer B and the block copolymer C is not particularly limited, but includes, for example, the above-described block copolymer A and the block copolymer B containing the block copolymer A and the block copolymer B. In the step (3) of the method for producing a block copolymer composition, a method in which a part of a polymerization terminator is used instead of a part of a polymerization terminator is exemplified.

  The coupling agent is not particularly limited, and any bifunctional or higher functional coupling agent can be used. Examples of the bifunctional coupling agent include bifunctional halogenated silanes such as dichlorosilane, monomethyldichlorosilane, and dimethyldichlorosilane; bifunctional alkoxysilanes such as diphenyldimethoxysilane and diphenyldiethoxysilane; dichloroethane and dibromoethane Difunctional tin halides such as dichlorotin, monomethyldichlorotin, dimethyldichlorotin, monoethyldichlorotin, diethyldichlorotin, monobutyldichlorotin, dibutyldichlorotin and the like. Dibromobenzene, benzoic acid, CO, 2-chloropropene and the like; Examples of trifunctional coupling agents include trifunctional halogenated alkanes such as trichloroethane and trichloropropane; trifunctional halogenated silanes such as methyltrichlorosilane and ethyltrichlorosilane; methyltrimethoxysilane, phenyltrimethoxysilane, and the like. Trifunctional alkoxysilanes such as phenyltriethoxysilane; and the like. Examples of the tetrafunctional coupling agent include tetrafunctional halogenated alkanes such as carbon tetrachloride, carbon tetrabromide, and tetrachloroethane; tetrafunctional silanes such as tetrachlorosilane and tetrabromosilane; tetramethoxysilane; Tetrafunctional alkoxysilanes such as tetraethoxysilane; tetrafunctional tin halides such as tetrachlorotin and tetrabromotin; and the like. Examples of the coupling agent having five or more functional groups include 1,1,1,2,2-pentachloroethane, perchloroethane, pentachlorobenzene, perchlorobenzene, octabromodiphenyl ether, and decabromodiphenyl ether. One of these coupling agents may be used alone, or two or more thereof may be used in combination.

  In step (3), in addition to the block copolymer B and the block copolymer C, the block represented by the general formula (I) may be used, for example, by using a polymerization terminator together with a coupling agent. It may further contain copolymer A. Alternatively, the composition may further contain the block copolymer A by mixing with the block copolymer composition containing the block copolymer A represented by the general formula (I).

(Hydrogenated hydrocarbon resin)
The hot melt adhesive composition used in the present invention contains the above-mentioned aromatic vinyl block copolymer and a hydrogenated hydrocarbon resin.

  The hydrogenated hydrocarbon resin used in the present invention is, as a hydrocarbon resin before hydrogenation, an alicyclic monoolefin monomer having 30 to 75% by mass of 1,3-pentadiene monomer unit and 4 to 6 carbon atoms. Body unit 20 mass% to 50 mass%, C4 to C8 acyclic monoolefin monomer unit 5 mass% to 25 mass%, alicyclic diolefin monomer unit 0 mass% to 10 mass%, It is preferable to use one containing an aromatic monoolefin monomer unit of 0% by mass to 30% by mass, and hydrogenate this.

  The content of the 1,3-pentadiene monomer unit in the hydrocarbon resin before hydrogenation is within a range of 30% by mass to 75% by mass, and within a range of 25% by mass to 65% by mass. Is preferably in the range of 30% by mass to 60% by mass, more preferably in the range of 35% by mass to 55% by mass, and more preferably in the range of 43% by mass to 53% by mass. Is particularly preferred. By keeping the content of the 1,3-pentadiene monomer unit in the above range, the odor can be further reduced while the holding force of the electrical insulating tape is kept high and the change in the adhesive force with time is effectively suppressed. Can be.

  The alicyclic monoolefin having 4 to 6 carbon atoms is a hydrocarbon compound having 4 to 6 carbon atoms having one ethylenically unsaturated bond and a non-aromatic ring structure in its molecular structure. Specific examples of the alicyclic monoolefin having 4 to 6 carbon atoms include cyclobutene, cyclopentene, cyclohexene, methylcyclobutene, methylcyclopentene, and the like.

  The content of the alicyclic monoolefin monomer unit having 4 to 6 carbon atoms in the hydrocarbon resin before hydrogenation is in the range of 20% by mass to 50% by mass, and 20% by mass to 45% by mass. Is more preferably within a range of 25% by mass to 40% by mass. By keeping the content of the alicyclic monoolefin monomer unit having 4 to 6 carbon atoms in the above range, while keeping the holding power of the electrical insulating tape high, while effectively suppressing the change in the adhesive strength over time, Odor can be further reduced.

  The alicyclic monoolefin having 4 to 6 carbon atoms can be used alone or in combination of two or more. When two or more kinds are used in combination, the ratio of each compound is arbitrary. Although it is not particularly limited, it is preferable to include at least cyclopentene, and it is more preferable that the proportion of cyclopentene in the alicyclic monoolefin having 4 to 6 carbon atoms is 50% by mass or more.

  The acyclic monoolefin having 4 to 8 carbon atoms is a chain hydrocarbon compound having 4 to 8 carbon atoms having one ethylenically unsaturated bond in its molecular structure and having no ring structure. Specific examples of the acyclic monoolefin having 4 to 8 carbon atoms include butenes such as 1-butene, 2-butene and isobutylene (2-methylpropene); 1-pentene, 2-pentene and 2-methyl-1 -Pentenes such as -butene, 3-methyl-1-butene and 2-methyl-2-butene; hexenes such as 1-hexene, 2-hexene and 2-methyl-1-pentene; 1-heptene and 2-heptene 1-octene, 2-octene, 2-methyl-1-heptene, diisobutylene (2,4,4-trimethyl-1-pentene, 2,4,4- Octenes such as trimethyl-1-pentene);

  The content of the acyclic monoolefin monomer unit having 4 to 8 carbon atoms in the hydrocarbon resin before hydrogenation is in the range of 5% by mass to 25% by mass, and 6% by mass to 25% by mass. Is preferably within the range of 7% by mass to 25% by mass, and more preferably within the range of 7% by mass to 12% by mass. By keeping the content of the acyclic monoolefin monomer unit having 4 to 8 carbon atoms in the above range, while keeping the holding power of the electric insulating tape high, while effectively suppressing the change in the adhesive strength with time, Odor can be further reduced.

  The acyclic monoolefin having 4 to 8 carbon atoms can be used singly or in combination of two or more. When two or more are used in combination, the ratio of each compound is arbitrary. Although it is not particularly limited, it is preferable that at least one selected from the group consisting of at least 2-methyl-2-butene, isobutylene and diisobutylene is included, and the acyclic monoolefin having 4 to 8 carbon atoms is included. More preferably, the ratio of the total amount of 2-methyl-2-butene, isobutylene and diisobutylene is 50% by mass or more.

  Further, the hydrocarbon resin before hydrogenation used in the present invention may contain an alicyclic diolefin. An alicyclic diolefin is a hydrocarbon compound having two or more ethylenically unsaturated bonds and a non-aromatic ring structure in its molecular structure. Specific examples of the alicyclic diolefin include a cyclopentadiene polymer such as cyclopentadiene and dicyclopentadiene, a methylcyclopentadiene, and a methylcyclopentadiene polymer.

  The content of the alicyclic diolefin monomer unit in the hydrocarbon resin before hydrogenation is in the range of 0% by mass to 10% by mass, and in the range of 0.5% by mass to 4% by mass. Preferably, it is in the range of 0.7% by mass to 3% by mass, more preferably in the range of 0.8% by mass to 2.6% by mass. By keeping the content of the alicyclic diolefin monomer unit in the above range, while keeping the holding power of the electric insulating tape high, effectively suppressing the change in the adhesive force over time, and further reducing the odor. Can be.

  Further, the hydrocarbon resin before hydrogenation used in the present invention may contain an aromatic monoolefin. An aromatic monoolefin is an aromatic compound having one ethylenically unsaturated bond in its molecular structure. Specific examples of the aromatic monoolefin include styrene, α-methylstyrene, vinyltoluene, indene, cumarone, and the like.

  The content of the aromatic monoolefin monomer unit in the hydrocarbon resin before hydrogenation is in the range of 0% by mass to 30% by mass, and may be in the range of 0% by mass to 28% by mass. Preferably, it is in the range of 0% by mass to 26% by mass, more preferably in the range of 0% by mass to 18% by mass. By keeping the content of the aromatic monoolefin monomer unit in the above range, it is possible to further reduce the odor while keeping the holding power of the electric insulating tape high and effectively suppressing the change in the adhesive strength with the passage of time. it can.

  Examples of the hydrocarbon resin before hydrogenation include a 1,3-pentadiene monomer unit, an alicyclic monoolefin monomer unit having 4 to 6 carbon atoms, and an acyclic monoolefin monomer unit having 4 to 8 carbon atoms. In addition to the monomer units, alicyclic diolefin monomer units, and aromatic monoolefin monomer units, other monomer units may be contained as long as the effects of the present invention are not impaired.

  The other monomer used for constituting such another monomer unit is not particularly limited as long as it is a compound having addition polymerizability that can be addition-copolymerized with 1,3-pentadiene or the like. Examples of such other monomers include, for example, carbon atoms other than 1,3-pentadiene such as 1,3-butadiene, 1,2-butadiene, isoprene, 1,3-hexadiene, and 1,4-pentadiene. Unsaturated hydrocarbons having 6 to 6 carbon atoms; alicyclic monoolefins having 7 or more carbon atoms such as cycloheptene; acyclic monoolefins having 4 to 8 carbon atoms such as ethylene, propylene and nonene;

  The content of the other monomer units in the hydrocarbon resin before hydrogenation is usually in the range of 0% by mass to 30% by mass, and may be in the range of 0% by mass to 25% by mass. More preferably, it is in the range of 0% by mass to 20% by mass.

  The method for producing the hydrocarbon resin before hydrogenation is not particularly limited, and includes, for example, a method of addition-polymerizing a monomer mixture containing a monomer forming the above-mentioned monomer unit. A method based on addition polymerization using a Friedel Crafts type cationic polymerization catalyst is preferred.

  As a method by addition polymerization using a Friedel-Crafts type cationic polymerization catalyst, for example, an aluminum halide (A) and a halogenated hydrocarbon (B1) having a tertiary carbon atom bonded to a halogen atom are described below. And a halogenated hydrocarbon (B) selected from the group consisting of a halogenated hydrocarbon (B2) in which a halogen atom is bonded to a carbon atom adjacent to a carbon-carbon unsaturated bond, and a monomer mixture is added. Examples of the method include polymerization.

Specific examples of the aluminum halide (A) include aluminum chloride (AlCl ₃ ) and aluminum bromide (AlBr ₃ ). Among these, aluminum chloride is preferably used from the viewpoint of versatility and the like. The amount of the aluminum halide (A) used is not particularly limited, but is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the monomer mixture. It is.

  Halogenated hydrocarbons selected from the group consisting of halogenated hydrocarbons in which halogen atoms are bonded to tertiary carbon atoms (B1) and halogenated hydrocarbons in which halogen atoms are bonded to carbon atoms adjacent to carbon-carbon unsaturated bonds (B2) The use of the hydrocarbon (B) in combination with the aluminum halide (A) has the effect of further increasing the activity of the polymerization catalyst.

  Specific examples of the halogenated hydrocarbon (B1) in which a halogen atom is bonded to a tertiary carbon atom include t-butyl chloride, t-butyl bromide, 2-chloro-2-methylbutane, triphenylmethyl chloride, and the like. Among these, t-butyl chloride is preferred because of its excellent balance between activity and ease of handling.

  Examples of the unsaturated bond in the halogenated hydrocarbon (B2) in which a halogen atom is bonded to a carbon atom adjacent to the carbon-carbon unsaturated bond include a carbon-carbon double bond and a carbon-carbon triple bond, and an aromatic ring And the like. Specific examples of such a compound include benzyl chloride, benzyl bromide, (1-chloroethyl) benzene, allyl chloride, 3-chloro-1-propyne, 3-chloro-1-butene, 3-chloro-1-butyne, Cinnamon chloride and the like. Among these, benzyl chloride is preferred because of its excellent balance between activity and ease of handling.

  The halogenated hydrocarbon (B) may be used alone or in combination of two or more. The amount of the halogenated hydrocarbon (B) used is preferably in the range of 0.05 to 50, more preferably in the range of 0.1 to 10 in a molar ratio to the aluminum halide (A).

  In performing the polymerization reaction, the order in which the respective components of the monomer mixture and the polymerization catalyst are added to the polymerization reactor is not particularly limited, and may be added in any order, but from the viewpoint of favorably controlling the polymerization reaction. A part of the monomer components constituting the monomer mixture and aluminum halide (A) are added in advance to the polymerization reactor, and a part of the monomer components constituting the monomer mixture; It is preferable that after the aluminum halide (A) is brought into contact in advance, the remainder of the monomer components constituting the monomer mixture is added to the polymerization reactor to start the polymerization reaction. In this case, at least an alicyclic monoolefin having 4 to 6 carbon atoms is used as a part of the monomer component constituting the monomer mixture, and is added to the aluminum halide (A) and the polymerization reactor in advance. Then, an alicyclic monoolefin having 4 to 6 carbon atoms and aluminum halide (A) are brought into contact with each other in advance to obtain a mixture thereof, and then the remaining monomer component constituting the monomer mixture is removed. More preferably, it is added to the polymerization reactor to start the polymerization reaction.

  The amount of the alicyclic monoolefin having 4 to 6 carbon atoms, which is brought into contact with the aluminum halide (A) in advance, is preferably at least 5 times (mass ratio) the amount of the aluminum halide (A). Alicyclic monoolefin: aluminum halide (A) 6 ", preferably in the range of 5: 1 to 120: 1, more preferably in the range of 10: 1 to 100: 1, and still more preferably 15: 1. It is in the range of 1-80: 1. By setting the mass ratio in the above range, the catalytic activity can be further increased.

  When the aluminum halide (A) and the alicyclic monoolefin having 4 to 6 carbon atoms are brought into contact with each other in advance, the order of charging them is not particularly limited. Aluminum (A) may be charged, or conversely, an alicyclic monoolefin having 4 to 6 carbon atoms may be charged into aluminum halide (A). Since mixing is usually exothermic, a suitable diluent can be used. As a diluent, a solvent described below can be used.

  As described above, after the aluminum halide (A) and the alicyclic monoolefin having 4 to 6 carbon atoms are brought into contact with each other in advance to prepare a mixture, the remaining monomer component constituting the monomer mixture is removed. Added. Further, it is preferable to further mix the halogenated hydrocarbon (B) together with the rest of the monomer components constituting the monomer mixture, and the order of charging them is not particularly limited.

  From the viewpoint of better controlling the polymerization reaction, it is preferable to carry out the polymerization reaction by adding a solvent to the polymerization reaction system. The type of the solvent is not particularly limited as long as it does not inhibit the polymerization reaction, but a saturated aliphatic hydrocarbon or an aromatic hydrocarbon is preferable. Examples of the saturated aliphatic hydrocarbon used as the solvent include n-pentane, n-hexane, 2-methylpentane, 3-methylpentane, n-heptane, 2-methylhexane, 3-methylhexane, and 3-ethylpentane , 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 2,2,3-trimethylbutane, 2,2,4-trimethylpentane A chain saturated aliphatic hydrocarbon having 5 to 10 carbon atoms; a cyclic saturated aliphatic hydrocarbon having 5 to 10 carbon atoms, such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane. Examples of the aromatic hydrocarbon used as a solvent include aromatic hydrocarbons having 6 to 10 carbon atoms, such as benzene, toluene, and xylene. The solvent may be used alone or as a mixed solvent of two or more. The amount of the solvent to be used is not particularly limited, but is preferably in the range of 10 parts by mass to 1,000 parts by mass, and more preferably in the range of 50 parts by mass to 500 parts by mass with respect to 100 parts by mass of the monomer mixture. Is more preferable. For example, a mixture of an addition-polymerizable component and a non-addition-polymerizable component such as a mixture of cyclopentane and cyclopentene derived from the C5 fraction is added to the polymerization reaction system, and the addition-polymerizable component is added in a single amount. The non-addition polymerizable component may be used as a solvent, and the non-addition polymerizable component may be used as a solvent.

  The polymerization temperature at the time of performing the polymerization reaction is not particularly limited, but is preferably in the range of −20 ° C. to 100 ° C., and more preferably in the range of 10 ° C. to 70 ° C. If the polymerization temperature is too low, the polymerization activity may be reduced and the productivity may be inferior. If the polymerization temperature is too high, the color of the unmodified resin obtained may be inferior. The pressure at which the polymerization reaction is performed may be under atmospheric pressure or under pressure. The polymerization reaction time can be appropriately selected, and is usually selected in the range of 10 minutes to 12 hours, preferably 30 minutes to 6 hours.

  When a desired polymerization conversion is obtained, the polymerization reaction can be stopped by adding a polymerization terminator such as methanol, an aqueous sodium hydroxide solution, or an aqueous ammonia solution to the polymerization reaction system.

  Further, in the method for producing a hydrocarbon resin before hydrogenation, in addition to the above-described polymerization step, another step may be included as necessary. As other steps, for example, after the polymerization step, a polymerization terminator is added in the polymerization step to remove the catalyst residue which is generated when the polymerization catalyst is inactivated and which is insoluble in the solvent, is removed by filtration or the like. After the polymerization reaction is stopped in the process or the polymerization process, the unreacted monomer and solvent are removed, and the low molecular weight oligomer component is further removed by steam distillation or the like, and the hydrocarbon resin is cooled. And the like in which the compound is recovered in a solid state.

  Further, as another step, after the catalyst residue removal step and before the recovery step, the catalyst residue removal mixture after removing the catalyst residue insoluble in the solvent is brought into contact with the adsorbent to obtain an adsorbent-treated mixture. A processing step may be employed. By having the contact treatment step, the odor in the case of forming the electric insulating tape can be further reduced.

  The adsorbent used in the contact treatment step is not particularly limited, and may be a chemical adsorbent or a physical adsorbent. Chemical adsorbents include zinc-based adsorbents such as basic zinc carbonate, zinc oxide, zinc sulfate, zinc laurate, zinc stearate, and zinc myristate; and zirconium-based adsorption such as zirconium oxide, zirconium hydroxide, and zirconium phosphate. Manganese-based adsorbents such as manganese dioxide, cobalt-based adsorbents such as cobalt chloride, copper-based adsorbents such as copper chloride and copper oxide, and amine-based adsorbents such as polyamine compounds.

  Examples of the physical adsorbent include zeolite-based adsorbents generally referred to as a group of hydrous aluminosilicate minerals such as sodium aluminum silicate, silicon dioxide, magnesium oxide, silica gel, silica / alumina, aluminum silicate, activated alumina, acid clay, and activated clay. , Dawsonite compounds, hydrotalcite compounds and the like.

  As the adsorbent, one type may be used alone, or two or more types may be used in combination. When two or more adsorbents are used in combination, two or more chemical adsorbents may be used in combination, two or more physical adsorbents may be used in combination, and one or more chemical adsorbents may be used. The agent and one or more physical adsorbents may be used in combination. For example, a physical adsorbent may carry a chemical adsorbent. It is preferable to use a chemical adsorbent, more preferably use a zinc-based adsorbent, and particularly preferably use basic zinc carbonate, from the viewpoint of further reducing the odor when forming the electric insulating tape.

  The method of contacting the catalyst residue removal mixture with the adsorbent in the contact treatment step is not particularly limited. For example, the catalyst residue removal mixture and the adsorbent are allowed to coexist in an appropriately selected container, and the mixture is agitated, if necessary, and brought into contact with a batch processing method, or the adsorbent is filled in a packed tower in advance, and And a continuous treatment method in which the mixture for removing the catalyst residue is passed through and contacted.

  The amount of the adsorbent used when the catalyst residue-removed mixture and the adsorbent are brought into contact by a batch treatment method is not particularly limited, but is based on 100 parts by mass of the hydrocarbon resin before hydrogenation contained in the catalyst residue-removed mixture. Preferably it is 0.01 part by mass to 5.0 parts by mass, more preferably 0.03 parts by mass to 3.0 parts by mass, still more preferably 0.05 parts by mass to 2.0 parts by mass.

  The temperature at which the catalyst residue removal mixture is brought into contact with the adsorbent is not particularly limited, but is usually selected within the range of 10 ° C to 70 ° C. The treatment time is also not particularly limited, but is usually 0.1 hour to Selected within 2 hours.

  When the catalyst residue removal mixture and the adsorbent are brought into contact with each other by a batch treatment method, if necessary, the adsorbent may be removed from the catalyst residue removal mixture by filtration or the like, or the catalyst residue removal mixture may be adsorbed from the catalyst residue removal mixture. May be subjected to the next step without removing the.

  The hydrogenated hydrocarbon resin used in the present invention is obtained by hydrogenating the above-mentioned hydrocarbon resin before hydrogenation.

  The hydrogenated hydrocarbon resin preferably has an olefin hydrogenation rate (hereinafter, sometimes simply referred to as hydrogenation rate) of preferably 10% to 80%, more preferably 30% to 80%, and still more preferably. It is 30% to 70%, particularly preferably 40% to 60%. The hydrogenation rate of the olefin means a ratio of hydrogenated non-aromatic carbon-carbon double bonds to all non-aromatic carbon-carbon double bonds of the hydrocarbon resin before hydrogenation. By setting the hydrogenation rate in the above range, the odor can be further reduced while the holding force of the electrical insulating tape is kept high and the change in the adhesive force with time is effectively suppressed.

  When the hydrogenated hydrocarbon resin contains an aromatic monomer unit, the hydrogenation rate of the aromatic ring is preferably 1% to 30%, more preferably 6% to 18%, and still more preferably. Is 7% to 15%. The hydrogenation rate of the aromatic ring means the proportion of hydrogenated aromatic rings in the total aromatic rings of the hydrocarbon resin before hydrogenation.

The hydrogenation rate of the above-mentioned olefin or aromatic ring can be determined from the difference between the amount of olefin or the amount of aromatic ring contained in each of the hydrocarbon resin before hydrogenation and the hydrogenated hydrocarbon resin after hydrogenation. These can be determined by ¹ H-NMR spectrum measurement.

  The weight average molecular weight (Mw) of the hydrogenated hydrocarbon resin is preferably from 1,000 to 3,500, more preferably from 1,500 to 3,400, still more preferably from 1,800 to 3,300, and particularly preferably. Is from 2,100 to 2,800. When the weight average molecular weight (Mw) is in the above range, the compatibility with the aromatic vinyl block copolymer can be further increased, whereby the adhesive force as a pressure-sensitive adhesive can be further increased. As a result, the holding power of the electrical insulating tape can be further increased.

  Further, the Z-average molecular weight (Mz) of the hydrogenated hydrocarbon resin is preferably from 2,000 to 7,000, more preferably from 3,200 to 6,800, still more preferably from 3,900 to 6,600. Yes, particularly preferably 4,300 to 5,700. When the Z-average molecular weight (Mz) is in the above range, compatibility with the aromatic vinyl block copolymer can be further increased, and thereby, the adhesive strength of the electric insulating tape can be further increased.

  In the present invention, the weight-average molecular weight (Mw) and the Z-average molecular weight (Mz) of the hydrogenated hydrocarbon resin can be determined as values in terms of polystyrene, as measured by high performance liquid chromatography. More specifically, the weight average molecular weight and the Z average molecular weight can be measured as high molecular weight in terms of polystyrene by high performance liquid chromatography using tetrahydrofuran as a carrier.

  The ratio (Mz / Mw) of the Z average molecular weight to the weight average molecular weight of the hydrogenated hydrocarbon resin is preferably 1.5 to 2.5, more preferably 1.6 to 2.4, and still more preferably 1.65 to 2.5. 2.35. By setting the ratio of the Z-average molecular weight to the weight-average molecular weight in the above range, the compatibility with the aromatic vinyl block copolymer can be further increased, whereby the adhesive strength as a tacky adhesive can be further increased. In addition, the holding power of the electrical insulating tape can be further increased.

  The Gardner color number of a 50% by mass toluene solution of the hydrogenated hydrocarbon resin is preferably 3 or less, more preferably 2 or less. When the Gardner color number is in this range, the hot melt adhesive composition can have excellent hue. As a method for measuring the Gardner color number, there is a method in which a 50% by mass toluene solution is prepared for a hydrogenated hydrocarbon resin to be a sample, and the Gardner color number of the prepared toluene solution is measured according to JIS K0071-2.

  The softening point of the hydrogenated hydrocarbon resin is not particularly limited, but is preferably 50 ° C. or higher, and more preferably 50 ° C. or higher, from the viewpoint that the compatibility with the aromatic vinyl block copolymer can be further improved. C. to 125.degree. C., more preferably 60 to 115.degree. C., particularly preferably 80 to 110.degree. The softening point of the hydrogenated hydrocarbon resin can be measured according to JIS K6863.

  Obtained by subtracting the mixed aniline point of the hydrocarbon resin before hydrogenation from the difference between the mixed aniline points (MMAP) of the hydrogenated hydrocarbon resin before and after hydrogenation, that is, the mixed aniline point of the hydrogenated hydrocarbon resin, The difference between the mixed aniline points is preferably 5 ° C. or less, more preferably 4 ° C. or less, and even more preferably 3.5 ° C. or less. By setting the difference in the mixed aniline point to the above range, the compatibility with the aromatic vinyl block copolymer can be further increased, whereby the adhesive force as a pressure-sensitive adhesive can be further increased, The holding power of the electrical insulating tape can be further increased.

  The lower limit of the difference between the mixed aniline points is preferably as low as possible from the viewpoint of further increasing the adhesive strength as a pressure-sensitive adhesive, but may be, for example, 0 ° C. or higher. Here, the mixed aniline point is the lowest temperature at which a mixed solution of aniline, a measurement sample and methylcyclohexane (volume ratio 2: 1: 1) exists as a uniform solution. The measurement of the mixed aniline point can be performed according to JIS K 2256 by using methylcyclohexane instead of heptane.

  The mixed aniline point of the hydrogenated hydrocarbon resin is preferably 40C to 120C, more preferably 45C to 110C, and even more preferably 50C to 100C. By setting the mixed aniline point in the above range, the compatibility with the aromatic vinyl block copolymer can be further increased, and thereby, the adhesive force as a pressure-sensitive adhesive can be further increased, and The holding power of the tape can be further increased.

  The method for producing the hydrogenated hydrocarbon resin is not particularly limited, and includes a method of hydrogenating the hydrocarbon resin before hydrogenation. Hydrogenation of the hydrocarbon resin before hydrogenation can be performed by bringing the hydrocarbon resin before hydrogenation into contact with hydrogen in the presence of a hydrogenation catalyst.

  Examples of the hydrogenation catalyst include JP-A-58-43412, JP-A-60-26024, JP-A-64-24826, JP-A-1-138257, and JP-A-7-41550. Those described may be used and may be homogeneous or heterogeneous catalysts.

  Examples of the homogeneous catalyst include, for example, a combination of cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, and tetrabutoxytitanate / dimethylmagnesium. A catalyst system comprising a combination of a transition metal compound and an alkali metal compound; a noble metal complex catalyst such as dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, and chlorotris (triphenylphosphine) rhodium; .

  Examples of the heterogeneous catalyst include those in which a hydrogenation catalyst metal such as Ni or Pd is supported on a carrier. Examples of the carrier include silica, alumina, silica / alumina, diatomaceous earth, and the like. Of these, Ni catalysts supported on silica are preferred.

  The hydrogenation reaction may be performed directly on the hydrocarbon resin before hydrogenation, or may be performed in an organic solvent by dissolving the hydrocarbon resin before hydrogenation in an organic solvent. From the viewpoint of operability, a method of directly performing the process on the hydrocarbon resin before hydrogenation is preferable. The organic solvent used for dissolving the hydrocarbon resin before hydrogenation is not particularly limited as long as it is inert to the catalyst. Hydrogen solvents are preferably used.

  Examples of the hydrocarbon-based solvent include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as n-pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decalin; Among these, cyclic aromatic hydrocarbons and alicyclic hydrocarbons are preferred. These organic solvents can be used alone or in combination of two or more. As the organic solvent, the solvent used for polymerization of the hydrocarbon resin before hydrogenation may be used as it is.

  The method for bringing the hydrocarbon resin before hydrogenation into contact with hydrogen in the presence of the hydrogenation catalyst is not particularly limited. For example, the hydrocarbon resin before hydrogenation and the hydrogenation catalyst coexist in an appropriately selected container. Then, if necessary, stirring and batch treatment method of contacting with hydrogen, or filling the hydrogenation catalyst in advance in a packed tower, and flowing hydrogen resin before hydrogenation, A continuous treatment method in which the contact is performed can be given.

  The hydrogenation reaction can be performed according to a conventional method, and by appropriately adjusting the reaction conditions such as the type of the hydrogenation catalyst and the reaction temperature, the ratio of the hydrogenation of the hydrocarbon resin before hydrogenation can be adjusted. . For example, by using a homogeneous catalyst as the hydrogenation catalyst, the ratio of hydrogenation of the obtained hydrogenated hydrocarbon resin can be made relatively high. In this case, the homogeneous catalyst is a ruthenium homogeneous catalyst. It is preferably used. The reaction temperature is preferably from 100 ° C to 200 ° C, more preferably from 130 ° C to 195 ° C.

  Further, by using a heterogeneous catalyst as the hydrogenation catalyst, the ratio of the obtained hydrogenated hydrocarbon resin can be relatively reduced. In this case, as the heterogeneous catalyst, a nickel heterogeneous catalyst is used. It is preferably used. The reaction temperature is preferably from 150C to 300C, more preferably from 180C to 260C.

  The hydrogen pressure in the hydrogenation reaction is, in terms of absolute pressure, usually in the range of 0.01 MPa to 10 MPa, preferably in the range of 0.05 MPa to 6 MPa, and more preferably in the range of 0.1 MPa to 5 MPa.

  After completion of the hydrogenation reaction, if necessary, the hydrogenation catalyst is removed from the reaction solution by centrifugation or filtration. The centrifugation method and filtration method are not particularly limited as long as the used catalyst can be removed. In the case of filtration, pressure filtration or suction filtration may be used, and from the viewpoint of efficiency, it is preferable to use a filter aid such as diatomaceous earth and perlite. If necessary, a catalyst deactivator such as water or alcohol can be used, or an adsorbent such as activated clay or alumina can be added.

  The hydrogenation rate of the olefin of the hydrogenated hydrocarbon resin, the hydrogenation rate of the aromatic ring, the weight average molecular weight (Mw), the Z average molecular weight (Mz), the ratio of the Z average molecular weight to the weight average molecular weight (Mz / Mw), The softening point, the Gardner color number, the difference between the mixed aniline points (MMAP) before and after hydrogenation, and the like can be adjusted by appropriately adjusting the production conditions and the like in the above-described blending and production method.

(Hot melt adhesive composition)
The hot melt adhesive composition used in the present invention contains the above-mentioned aromatic vinyl block copolymer and the above-mentioned hydrogenated hydrocarbon resin.

The hot-melt adhesive composition used in the present invention has a toluene volatile content of 260 μg / m ³ or less and a total volatile component content of 15,000 μg / m when heated at 65 ° C. for 2 hours. m ³ or less. 65 ° C., definitive when heated under the conditions of 2 hours, toluene volatile content is preferably from 240 [mu] g / ^{m 3} or less, more preferably 200 [mu] g / ^{m 3} or less, more preferably 180 [mu] g / ^{m 3} or less, the lower limit Is not particularly limited, but is usually 1 μg / m ³ or more. The total amount of volatile components when heated at 65 ° C. for 2 hours is preferably 15,000 μg / m ³ or less, more preferably 14,000 μg / m ³ or less, and the lower limit is not particularly limited. Is usually 1,000 μg / m ³ or more. The amount of volatile components of toluene and the total amount of volatile components when heated at 65 ° C. for 2 hours are described in, for example, JASO (Japan Automotive Engineering Standards) M902 (2007) “Automotive parts—interior materials—volatile organic compounds”. It can be measured in accordance with the “emission measurement method”.

  Furthermore, the hot-melt adhesive composition used in the present invention has a peel adhesion to a stainless steel plate of 400 N / m or more, measured at a temperature of 23 ° C., a peel angle of 180 °, and a tensile speed of 300 mm / min. It was done. The peel adhesion to a stainless steel plate measured under the conditions of a temperature of 23 ° C., a peel angle of 180 ° and a tensile speed of 300 mm / min is, for example, according to PSTC-101 (180 ° peel adhesion test by the US Adhesive Tapes Commission). Can be measured. The peel adhesion to a stainless steel plate, measured at a temperature of 23 ° C., a peel angle of 180 °, and a tensile speed of 300 mm / min, is preferably 450 N / m or more, more preferably 500 N / m or more, and still more preferably. Is 530 N / m or more, and the upper limit is not particularly limited, but is usually 700 N / m or less.

  According to the present invention, when heated at 65 ° C. for 2 hours, the amount of volatile components of toluene and the total amount of volatile components are controlled in the above ranges, and the temperature is 23 ° C., the peel angle is 180 °, and By using a hot-melt adhesive composition whose peel adhesion to a stainless steel plate is controlled to 400 N / m or more, which is measured at a tensile speed of 300 mm / min, the electric insulating tape is reduced in odor and high in odor. It has adhesive strength and can suppress change in adhesive strength over time. When heating at 65 ° C. for 2 hours, the amount of volatile components of toluene and the total amount of volatile components are set to the above ranges. As a method for suppressing volatile components due to thermal degradation, a hydrogenated hydrocarbon resin is used. A method in which a hydrogenated hydrocarbon resin having a specific composition range described above is obtained by hydrogenating a pre-hydrogenated hydrocarbon resin, and the hydrogenation rate of the olefin of the hydrogenated hydrocarbon resin is set to the above-described preferable range, and hot melt. Method of using a block copolymer composition containing the above-described block copolymer A and block copolymer B as an aromatic vinyl block copolymer in order to obtain excellent adhesive properties that can be produced by a method And is achieved by using

  In the hot melt adhesive composition used in the present invention, the content ratio of the aromatic vinyl block copolymer and the hydrogenated hydrocarbon resin is not particularly limited, but is based on 100 parts by mass of the aromatic vinyl block copolymer. The content ratio of the hydrogenated hydrocarbon resin is preferably 50 parts by mass to 500 parts by mass, more preferably 80 parts by mass to 400 parts by mass, and still more preferably 100 parts by mass to 300 parts by mass. With respect to the aromatic vinyl block copolymer, by setting the content of the hydrogenated hydrocarbon resin in the above range, the hot-melt pressure-sensitive adhesive composition can further increase the adhesive strength as an adhesive, The holding force of the electrical insulating tape can be further increased, and the change in the adhesive force over time can be more effectively suppressed.

  Further, the hot melt adhesive composition used in the present invention preferably further contains a softening agent. As the softening agent, a conventionally known softening agent added to the hot melt adhesive composition is used. Agents can be used. Specific examples include aromatic, paraffinic or naphthenic process oils; liquid polymers such as polybutene and polyisobutylene; and the like. One type of softener may be used alone, or two or more types may be used in combination. In the hot melt adhesive composition used in the present invention, the content of the softener is 500 parts by mass or less, preferably 10 parts by mass to 350 parts by mass, based on 100 parts by mass of the aromatic vinyl block copolymer. Parts by mass, more preferably 30 parts by mass to 250 parts by mass. By containing the softener in the above content ratio, the hot melt adhesive composition can be easily applied at a relatively low temperature, so that the production of the electrical insulating tape is easier. Things.

  In addition, when the hot melt adhesive composition used in the present invention further contains a softener in addition to the aromatic vinyl block copolymer and the hydrogenated hydrocarbon resin, the content ratio of these components is preferred. Is preferably as follows. That is, the content ratio of the aromatic vinyl block copolymer is preferably 10% by mass to 60% by mass, more preferably 20% by mass to 57.5% by mass, and still more preferably 30% by mass to 55% by mass. is there. Further, the content ratio of the hydrogenated hydrocarbon resin is preferably 20% by mass to 80% by mass, more preferably 20% by mass to 65% by mass, and still more preferably 30% by mass to 60% by mass. The content ratio of the softener is preferably 0.1% by mass to 30% by mass, more preferably 0.1% by mass to 25% by mass, and further preferably 5% by mass to 20% by mass. By setting the content ratio of the aromatic vinyl block copolymer, the content ratio of the hydrogenated hydrocarbon resin, and the content ratio of the softener to the above ranges, the hot melt pressure-sensitive adhesive composition has an adhesive force as an adhesive. And the holding power of the electrical insulating tape can be further increased, and the change in the adhesive strength over time can be suppressed more effectively.

  Further, the hot melt adhesive composition used in the present invention may contain other compounding agents such as a wax, an antioxidant, a heat stabilizer, an ultraviolet absorber, and a filler. The hot melt adhesive composition used in the present invention is preferably a solvent-free composition containing no solvent.

  The wax that can be blended in the hot melt adhesive composition used in the present invention is not particularly limited. For example, polyethylene wax, ethylene vinyl acetate copolymer wax, polyethylene oxide wax, paraffin wax, microcrystalline wax, Fischer- Tropsh wax, oxidized Fischer-Tropsh wax, hydrogenated castor oil wax, polypropylene wax, by-product polyethylene wax, hydroxylated stearamide wax, and the like can be used. One type of wax may be used alone, or two or more types may be used in combination. The content of the wax in the hot melt adhesive composition is not particularly limited, but is preferably 10 to 200 parts by mass, more preferably 20 to 150 parts by mass, based on 100 parts by mass of the aromatic vinyl block copolymer. Department. When the content of the wax is within this range, the obtained hot melt adhesive composition has particularly excellent coating easiness, so that the production of the electric insulating tape becomes easier.

  The antioxidant that can be added to the hot melt adhesive composition used in the present invention is not particularly limited. For example, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl)] Propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-p-cresol, di-t-butyl-4-methylphenol and the like Hindered phenol compounds; thiodicarboxylate esters such as dilauryl thiopropionate; phosphites such as tris (nonylphenyl) phosphite; The amount of the antioxidant is not particularly limited, but is usually 10 parts by mass or less, preferably 0.5 to 5 parts by mass, per 100 parts by mass of the aromatic vinyl block copolymer. The antioxidants may be used alone or in a combination of two or more.

  In preparing the hot melt adhesive composition used in the present invention, in addition to the aromatic vinyl block copolymer and the hydrogenated hydrocarbon resin, and, if necessary, a softener and other components added The method of mixing is not particularly limited, but from the viewpoint of performing the mixing more efficiently, and from the viewpoint of controlling the amount of volatile components of toluene and the amount of all volatile components within the above range, without using a solvent, kneading each component, etc. Is preferred. The temperature at which the melt mixing is performed is not particularly limited, but preferably 220 ° C. or lower, more preferably 200 ° C. or lower, and still more preferably 180 ° C. or lower. By performing the melt mixing in the above, the amount of volatile components of toluene and the amount of all volatile components can be appropriately controlled within the above range. As a mixing method, from the viewpoint of more appropriately controlling the amount of volatile components of toluene and the total amount of volatile components, the aromatic vinyl block copolymer and the hydrogenated hydrocarbon resin are mixed with the aromatic vinyl block copolymer 100. With respect to parts by mass, after melt-mixing at a ratio of 50 to 100 parts by mass of the hydrogenated hydrocarbon resin, the remaining components including the hydrogenated hydrocarbon resin (excluding components containing a relatively large amount of volatile components such as a softener, A preferred method is to add and melt-mix the remaining components, and finally add a component containing a relatively large amount of volatile components (eg, a softener) and melt-mix. In addition, at the time of melt mixing, melt mixing using a twin-screw extruder is preferred from the viewpoint of more appropriately controlling the amount of volatile components of toluene and the amount of all volatile components. In the melt mixing using a twin-screw extruder, in the first half of the twin-screw extruder, the aromatic vinyl block copolymer and the hydrogenated hydrocarbon resin, with respect to 100 parts by mass of the aromatic vinyl block copolymer , 50 to 100 parts by mass of a hydrogenated hydrocarbon resin, melt-mixing them, and in the middle part of a twin-screw extruder, the remaining components including the hydrogenated hydrocarbon resin (the volatile components such as a softener are removed). Add the remaining components excluding the components containing a relatively large amount) and melt-mix them. Is preferred.

(Base material)
The substrate used in the present invention is not particularly limited, and examples thereof include fiber fabrics such as organic fiber fabrics, inorganic fiber fabrics, and organic / inorganic fiber fabrics; organic fiber nonwoven fabrics and inorganic fibers. Nonwoven fabrics such as nonwoven fabrics and nonwoven fabrics made of organic / inorganic fibers; and plastic films such as PVC, polyester, and polypropylene. The thickness of the substrate is not particularly limited and may be appropriately determined depending on the use of the electric insulating tape, but is usually about 1 μm to 1000 μm.

(Electrical insulation tape)
The electric insulating tape of the present invention includes a hot melt adhesive composition and a base material.
The electrical insulating tape of the present invention is not particularly limited as long as it includes a hot melt adhesive composition and a substrate, and is not particularly limited. Examples include those in which a pressure-sensitive adhesive layer made of a melt-adhesive composition is formed. In addition, when a fiber cloth, nonwoven fabric, or the like is used as the base material, the pressure-sensitive adhesive layer formed of the hot melt adhesive composition may be formed on the surface of the base material. It is not necessary that the pressure-sensitive adhesive layer composed of the melt adhesive composition is such that such a base material is impregnated with the hot melt adhesive composition. Alternatively, the hot-melt adhesive composition is impregnated in a fiber cloth or nonwoven fabric, but the pressure-sensitive adhesive layer composed of the hot-melt adhesive composition is not formed on the surface. It may be.

  The method for producing the electrical insulating tape of the present invention is not particularly limited. For example, a method of applying a molten hot melt adhesive composition to at least a part of the surface of a substrate, or dissolving or dispersing in a solvent. After applying the hot-melt adhesive composition to at least a part of the substrate surface, the solvent is removed by heating or the like. Alternatively, when a fiber cloth or nonwoven fabric is used as the substrate, a method of impregnating at least a part of the substrate with the molten hot-melt adhesive composition or a hot solution dissolved or dispersed in a solvent is used. The electrical insulating tape of the present invention can also be produced by a method in which the solvent is removed by heating or the like after at least part of the base material is impregnated with the melt adhesive composition.

  The electrical insulating tape of the present invention has a low odor, suppresses a change in adhesive force over time, and is excellent in holding power. It can be suitably used for applications such as wire harnesses, transformers and electric / electronic devices, automobile drive motors, industrial motors, batteries, and the like.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to only these Examples. “Parts” and “%” are based on mass unless otherwise specified.
Various measurements were performed according to the following methods.

(Weight average molecular weight of each block copolymer in the block copolymer composition and the block copolymer composition)
The molecular weight was determined as high molecular weight in terms of polystyrene by high performance liquid chromatography using tetrahydrofuran as a carrier at a flow rate of 0.35 mL / min. The apparatus used was HLC8220 manufactured by Tosoh Corporation, the column used was three Shodex (registered trademark) KF-404HQ manufactured by Showa Denko Co., Ltd. connected at a column temperature of 40 ° C., and the detector used was a differential refractometer and an ultraviolet detector. Calibration of the molecular weight was performed at 12 points of standard polystyrene (5 to 3 million) manufactured by Polymer Laboratory.

(Content of each block copolymer in the block copolymer composition)
It was determined from the area ratio of peaks corresponding to each block copolymer in the chart obtained by the high performance liquid chromatography.

(Weight average molecular weight of styrene polymer block of block copolymer)
Rubber Chem. Technol. The block copolymer was reacted with ozone and reduced with lithium aluminum hydride to decompose the isoprene polymer block of the block copolymer according to the method described in J. Am. Specifically, the following procedure was performed. That is, 300 mg of a sample was dissolved in a reaction vessel containing 100 mL of dichloromethane treated with a molecular sieve. This reaction vessel was placed in a cooling bath and cooled to -25 ° C, and then ozone generated by an ozone generator was introduced while flowing oxygen at a flow rate of 170 mL / min into the reaction vessel. After a lapse of 30 minutes from the start of the reaction, the gas flowing out of the reaction vessel was introduced into an aqueous potassium iodide solution to confirm that the reaction was completed. Next, 50 mL of diethyl ether and 470 mg of lithium aluminum hydride were charged into another reaction vessel purged with nitrogen, and a solution reacted with ozone was slowly dropped into this reaction vessel while cooling the reaction vessel with ice water. Then, the reaction vessel was placed in a water bath, the temperature was gradually raised, and the mixture was refluxed at 40 ° C. for 30 minutes. Thereafter, while stirring the solution, dilute hydrochloric acid was added dropwise to the reaction vessel little by little, and the dropwise addition was continued until almost no generation of hydrogen was observed. After this reaction, a solid product formed in the solution was filtered off, and the solid product was extracted with 100 mL of diethyl ether for 10 minutes. This extract was combined with the filtrate obtained by filtration, and the solvent was distilled off to obtain a solid sample. The weight average molecular weight of the sample thus obtained was measured in accordance with the above-mentioned method of measuring the weight average molecular weight, and the value was defined as the weight average molecular weight of the styrene polymer block.

(Weight average molecular weight of isoprene polymer block of block copolymer)
From the weight average molecular weights of the block copolymers obtained as described above, the weight average molecular weight of the corresponding styrene polymer block is subtracted, and the weight average molecular weight of the isoprene polymer block is determined based on the calculated value. Was.

(Styrene unit content of block copolymer)
It was determined based on the detection intensity ratio between the differential refractometer and the ultraviolet detector in the above-described high performance liquid chromatography measurement. Note that copolymers having different styrene unit contents were prepared in advance, and a calibration curve was prepared using them.

[Styrene unit content of block copolymer composition (whole)]
It was determined based on the proton NMR measurement.

[Weight average molecular weight, Z average molecular weight and molecular weight distribution (Mz / Mw) of hydrogenated hydrocarbon resin]
The hydrogenated hydrocarbon resin was subjected to gel permeation chromatography analysis to obtain a weight average molecular weight (Mw) and a Z average molecular weight (Mz) in terms of standard polystyrene, and the molecular weight distribution was shown by a ratio of Mz / Mw. In addition, the gel permeation chromatography analysis uses "HLC-8320GPC" manufactured by Tosoh Corporation as a measuring device, and uses a column in which three "TSKgel SuperMultipore HZ" manufactured by Tosoh Corporation are connected, and uses tetrahydrofuran as a solvent. , 40 ° C., and a flow rate of 1.0 mL / min.

[Gardner color number of a 50% by mass solution of a hydrogenated hydrocarbon resin in toluene]
A 50% by mass toluene solution of the hydrogenated hydrocarbon resin was prepared, and the Gardner color number of the solution was measured according to JIS K0071-2. The smaller the value, the better the hue.

[Softening point of hydrogenated hydrocarbon resin (℃)]
The hydrogenated hydrocarbon resin was measured according to JIS K6863.

[Olefin hydrogenation rate of hydrogenated hydrocarbon resin (%)]
For the hydrocarbon resin before hydrogenation and the hydrogenated hydrocarbon resin after hydrogenation, the amount of each olefin was determined by ¹ H-NMR spectrum measurement, and the olefin hydrogenation rate (% ) Was calculated. In the ¹ H-NMR spectrum measurement, deuterated chloroform was used as a solvent, and JMN-AL seriesAL400 (manufactured by JEOL) was used as an NMR measurement device.

(Toluene volatile component amount of hot melt adhesive composition, total volatile component amount)
The hot-melt adhesive composition having a size of about 100 mm × 100 mm × 0.04 mm was measured at 65 ° C. for 2 hours in accordance with JASO M902 (2007) “Automotive parts-interior materials-volatile organic compound emission measurement method”. The amount of volatile components of toluene and the total amount of volatile components when heated under the conditions described above were measured.

(Odor evaluation test of hot melt adhesive composition)
The sensory test of the hot melt adhesive composition was performed according to the odor intensity display method in the odor measurement method issued by the Research Institute for Odor Control. Specifically, first, 10 g of a hot-melt adhesive composition having a size of about 10 mm × 5 mm × 5 mm was placed in a 120 mL heat-resistant container and capped with aluminum foil. Then, the heat-resistant container containing the hot melt adhesive composition was placed in an oven and heated at a temperature of 150 ° C. for 30 minutes, and the odor after heating was confirmed.
The odor was confirmed by a panel of six persons who were not accustomed to the odor of petroleum resin (ie, did not touch the odor of petroleum resin in daily life). In this test, in order to prevent olfactory fatigue, a method of dividing a panel of six persons into two groups of three persons and smelling the odor by one group was adopted. The order of the samples that smell the odor was randomized.
1: Smell that can be finally recognized (detection threshold concentration)
2: Weak smell to understand what smell is (cognitive threshold concentration)
3: Smell that can be easily perceived 4: Strong smell 5: Intense smell The results of the sensory test are as follows. It was determined by averaging. The smaller the value of the sensory test, the better.

[Peeling adhesive strength of hot melt adhesive composition (initial)]
The obtained hot melt adhesive composition is melted at 180 ° C. and applied to a polyester film having a thickness of 50 μm at a thickness of 30 μm to form an adhesive comprising the hot melt adhesive composition. A sample on which an adhesive layer was formed was prepared. Peeling at room temperature by measuring this at 23 ° C. and a tensile speed of 300 mm / min using a stainless steel plate as an adherend according to PSTC-101 (180 ° peeling adhesion test by the US Adhesive Tapes Commission) The adhesive strength (N / m) was evaluated. The larger the value, the better the adhesive strength.

(Peeling adhesive strength after aging of hot melt adhesive composition)
The sample on which the pressure-sensitive adhesive layer prepared above was formed was aged at 65 ° C. for 2 weeks, and a stainless steel plate was used as an adherend at 23 ° C. and a tensile speed of 300 mm / min. The peel adhesion (N / m) after aging at 65 ° C. for 2 weeks was measured by measuring according to PSTC-101 (180 ° peel adhesion test by the American Adhesive Tapes Commission). The smaller the change in the value from the peel adhesive force (initial), the more the change in the adhesive force with time is suppressed, which is desirable.

(Holding force of hot melt adhesive composition)
Using the stainless steel plate as the adherend, the sample having the pressure-sensitive adhesive layer formed as described above was bonded to a 10 × 25 mm adhesive portion according to PSTC-107 Procedure A (holding force test method by the US Adhesive Tapes Committee). At a load of 3.92 × 10 ⁴ Pa and a temperature of 50 ° C., the holding power was evaluated based on the time (minutes) until peeling. The larger the value, the better the holding power.

[Production Example 1]
23.3 kg of cyclohexane, 2.57 mmol of N, N, N ', N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) and 1.10 kg of styrene were added to the pressure-resistant reactor, and the mixture was stirred at 40 ° C. Meanwhile, 85.7 mmol of n-butyllithium was added, and polymerization was carried out for 1 hour while heating to 50 ° C. The polymerization conversion of styrene was 100%. Subsequently, 7.00 kg of isoprene was continuously added to the reactor over 1 hour while controlling the temperature so as to maintain 50 to 60 ° C. After the addition of isoprene was completed, polymerization was carried out for another 1 hour. Thereafter, 60.0 mmol of methanol as a polymerization terminator was added to the reactor to carry out a polymerization termination reaction for 1 hour, and a styrene-isoprene block having an active terminal was obtained. By inactivating a part of the active terminals of the polymer, a styrene-isoprene diblock copolymer serving as a block copolymer B was formed. Thereafter, 1.90 kg of styrene was continuously added over 1 hour while controlling the temperature so as to maintain 50 to 60 ° C. After the addition of styrene was completed, the mixture was further polymerized for 1 hour to form a styrene-isoprene-styrene block copolymer which was a block copolymer A. The polymerization conversion of styrene was 100%. Thereafter, 171.4 mmol of methanol was added as a polymerization terminator and mixed well to terminate the reaction.

  To 100 parts of the reaction solution obtained as described above (containing 30 parts of the polymer component), 0.3 part of 2,6-di-tert-butyl-p-cresol as an antioxidant was added and mixed. The mixed solution was dropped little by little into warm water heated to 85 to 95 ° C. to volatilize the solvent to obtain a precipitate. The precipitate was pulverized and dried at 85 ° C. with hot air to produce Production Example 1. Was recovered. Also, a part of the obtained reaction solution was taken out, and the weight average molecular weight of each polymer contained, the weight ratio of each polymer in the polymer component, and the weight average molecular weight of the styrene polymer block of each block copolymer The weight average molecular weight of the isoprene polymer block of each block copolymer, the styrene unit content of each block copolymer, the styrene unit content of the polymer component (total), and the isoprene polymer block of each block copolymer. The vinyl bond content was determined. Table 1 shows the results.

[Production Example 2]
To the pressure-resistant reactor, 23.3 kg of cyclohexane, 2.36 mmol of TMEDA and 2.40 kg of styrene were added, and while stirring at 40 ° C., 154,1 mmol of n-butyllithium was added, and the temperature was raised to 50 ° C. The polymerization was carried out for 1 hour. The polymerization conversion of styrene was 100% by weight. Subsequently, 7.60 kg of isoprene was continuously added to the reactor over 1 hour while controlling the temperature so as to maintain 50 to 60 ° C. After the addition of isoprene was completed, the polymerization was continued for 1 hour. The polymerization conversion of isoprene was 100%. Next, 25.4 mmol of dimethyldichlorosilane was added as a coupling agent, and a coupling reaction was performed for 2 hours to form a styrene-isoprene-styrene block copolymer to be a block copolymer C. Thereafter, 308.2 mmol of methanol was added as a polymerization terminator, mixed well, and the reaction was stopped to form a styrene-isoprene diblock copolymer serving as a block copolymer B.

  To 100 parts of the reaction solution obtained as described above (containing 30 parts of the polymer component), 0.3 part of 2,6-di-tert-butyl-p-cresol as an antioxidant was added and mixed. The mixed solution was dropped little by little into warm water heated to 85 to 95 ° C. to volatilize the solvent to obtain a precipitate, and the precipitate was pulverized and dried with hot air at 85 ° C. to obtain Production Example 2. Was recovered. Further, a part of the obtained reaction solution was taken out, and each measurement was performed in the same manner as in Production Example 1. Table 1 shows the results.

[Production Example 3]
To the pressure-resistant reactor, 23.3 kg of cyclohexane, 1.27 mmol of TMEDA and 0.90 kg of styrene were added, and while stirring at 40 ° C., 84.5 mmol of n-butyllithium was added, and the temperature was raised to 50 ° C. The polymerization was carried out for 1 hour. The polymerization conversion of styrene was 100%. Subsequently, 8.20 kg of isoprene was continuously added to the reactor over 1 hour while controlling the temperature so as to maintain 50 to 60 ° C. After the addition of isoprene was completed, the polymerization was continued for 1 hour. Thereafter, 0.90 kg of styrene was continuously added over 1 hour while controlling the temperature so as to maintain 50 to 60 ° C. After the addition of styrene was completed, polymerization was carried out for another hour to obtain a styrene-isoprene-styrene block copolymer. The polymerization conversion of styrene was 100%. Thereafter, 169.0 mmol of methanol was added as a polymerization terminator and mixed well to terminate the reaction.

  To 100 parts of the reaction solution obtained as described above (containing 30 parts of the polymer component), 0.3 part of 2,6-di-tert-butyl-p-cresol as an antioxidant was added and mixed. The mixed solution was dropped little by little into warm water heated to 85 to 95 ° C. to volatilize the solvent to obtain a precipitate, and the precipitate was pulverized and dried with hot air at 85 ° C. to obtain Production Example 3. The styrene-isoprene-styrene block copolymer (α3) according to the above was recovered. Further, a part of the obtained reaction solution was taken out, and each measurement was performed in the same manner as in Production Example 1. Table 1 shows the results. In Table 1, the styrene-isoprene-styrene block copolymer (α3) according to Production Example 3 was described as block copolymer A.

[Production Example 4]
A mixture of 50.3 parts of cyclopentane and 37.2 parts of cyclopentene was charged into the polymerization reactor, heated to 60 ° C., and then 1.0 part of aluminum chloride was added to obtain a mixture M1. Subsequently, 49.5 parts of 1,3-pentadiene, 9.2 parts of isobutylene, 0.6 part of C4-C6 unsaturated hydrocarbon, 2.1 parts of dicyclopentadiene, 0.1 part of cyclopentadiene, and C4-C6 saturated. Mixture M2 consisting of 12.0 parts of hydrocarbon and 0.2 part of benzyl butyl chloride were respectively passed through separate lines while maintaining the temperature (60 ° C.) for 60 minutes to obtain the mixture obtained above. Polymerization was carried out while continuously adding to the polymerization reactor containing M1. Thereafter, an aqueous sodium hydroxide solution was added to the polymerization reactor to stop the polymerization reaction. Table 2 shows the types and amounts of the components in the polymerization reactor during the polymerization reaction. The precipitate generated by terminating the polymerization was removed by filtration to obtain a polymer solution containing a resin before modification, an unreacted monomer, and the like.
In addition, a part of the obtained polymer solution was taken out, charged in a distillation still, heated under a nitrogen atmosphere, and the polymerization solvent and unreacted monomers were removed to remove the hydrocarbon resin before hydrogenation. Sampled.

  Then, the polymer solution obtained above is supplied as a raw material to a multitubular heat exchange hydrogenation reactor, and the hydrogenated hydrocarbon resin is hydrogenated by hydrogenating the hydrocarbon resin before hydrogenation. Manufactured. The hydrogenation reaction uses a nickel silica catalyst (N108F, manufactured by JGC Catalysts and Chemicals, Inc.) as a hydrogenation catalyst, a hydrogen pressure of 1.5 MPa, a reaction temperature of 220 ° C., and a hydrogen amount of 2 parts (hydrocarbon resin 100 before hydrogenation). Per unit) and the residence time in the reaction tube was 30 minutes. Next, the obtained polymer solution containing the hydrogenated hydrocarbon resin was charged into a distillation still and heated under a nitrogen atmosphere to remove the polymerization solvent and unreacted monomers. Subsequently, while blowing saturated steam at 200 ° C. or higher, low-molecular-weight oligomer components were distilled off, and the molten resin was taken out from the distillation still and allowed to cool to room temperature. Resin (β1) was obtained.

  With respect to the obtained hydrogenated hydrocarbon resin (β1) of Production Example 4, the weight average molecular weight, Z average molecular weight, Mz / Mw, Gardner color number, softening point, and olefin hydrogenation rate were determined. Table 2 shows the measurement results.

[Production Example 5]
A mixture of 34.5 parts of cyclopentane and 28.8 parts of cyclopentene was charged into the polymerization reactor, the temperature was raised to 60 ° C., and 0.7 part of aluminum chloride was added to obtain a mixture M3. Subsequently, 46.1 parts of 1,3-pentadiene, 7.3 parts of isobutylene, 0.6 part of a C4-C6 unsaturated hydrocarbon, 1.1 parts of dicyclopentadiene, 0.1 part of cyclopentadiene, and 14.0 parts of styrene. , And 8.5 parts of a C4-C6 saturated hydrocarbon, and 0.5 part of t-butyl chloride, each through separate lines, maintaining the temperature (80 ° C.) for 60 minutes, Polymerization was carried out while continuously adding to the polymerization reactor containing the mixture M3 obtained above. Thereafter, an aqueous sodium hydroxide solution was added to the polymerization reactor to stop the polymerization reaction. Table 2 shows the types and amounts of the components in the polymerization reactor during the polymerization reaction. The precipitate generated by terminating the polymerization was removed by filtration to obtain a polymer solution containing a resin before modification, an unreacted monomer, and the like.
In addition, a part of the obtained polymer solution was taken out, charged in a distillation still, heated under a nitrogen atmosphere, and the polymerization solvent and unreacted monomers were removed to remove the hydrocarbon resin before hydrogenation. Sampled.

  Then, the polymer solution obtained above is supplied as a raw material to a multitubular heat exchange hydrogenation reactor, and the hydrogenated hydrocarbon resin is hydrogenated by hydrogenating the hydrocarbon resin before hydrogenation. Manufactured. The hydrogenation reaction uses a nickel silica catalyst (N108F, manufactured by JGC Catalysts & Chemicals, Inc.) as a hydrogenation catalyst, a hydrogen pressure of 0.5 MPa, a reaction temperature of 180 ° C., and a hydrogen amount of 1 part (hydrocarbon resin 100 before hydrogenation). Per unit) and the residence time in the reaction tube was 30 minutes. Next, the obtained polymer solution containing the hydrogenated hydrocarbon resin was charged into a distillation still and heated under a nitrogen atmosphere to remove the polymerization solvent and unreacted monomers. Subsequently, while blowing saturated steam at a temperature of 200 ° C. or higher, the low molecular weight oligomer component was distilled off, the molten resin was taken out from the distillation still and allowed to cool to room temperature, whereby the hydrogenated hydrocarbon of Production Example 5 was obtained. Resin (β2) was obtained.

  With respect to the obtained hydrogenated hydrocarbon resin (β2) of Production Example 5, the weight average molecular weight, Z average molecular weight, Mz / Mw, Gardner color number, softening point, and olefin hydrogenation rate were determined. Table 2 shows the measurement results.

[Example 1]
100 parts of the block copolymer composition (α1) obtained in Production Example 1 was charged into a stirring blade-type kneader, and 100 parts of the hydrogenated hydrocarbon resin (β1) obtained in Production Example 4 was added thereto. 10 parts of process oil (trade name "Diana Process Oil NS-90S", manufactured by Idemitsu Kosan Co., Ltd.) and antioxidant (trade name "Irganox 1010", pentaerythritol tetrakis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate], manufactured by BASF Co., Ltd.), and the system was replaced with nitrogen gas. After kneading at 160 to 180 ° C. for 1 hour, hot melt adhesion of Example 1 was performed. A dressing composition was prepared. At the time of kneading, first, the block copolymer composition (α1), the hydrogenated hydrocarbon resin (β1), and the antioxidant are melt-mixed at 160 to 180 ° C. The hot-melt adhesive composition of Example 1 was prepared by adding a naphthenic process oil and continuing the melt-mixing at 160 to 180 ° C (the same applies to each of Examples and Comparative Examples described later). .). And about the obtained hot melt adhesive composition, measurement of the amount of toluene volatile components and total volatile components, an odor evaluation test, peel adhesion (initial), and measurement of peel adhesion and retention after lapse of time were performed. went. Table 3 shows the results.

[Example 2]
Example 1 Example 1 was repeated except that the amount of the hydrogenated hydrocarbon resin (β1) obtained in Production Example 4 was changed from 100 parts to 150 parts, and the amount of the naphthenic process oil was changed from 10 parts to 20 parts. In the same manner as in the above, the hot melt adhesive composition of Example 2 was prepared and evaluated in the same manner. Table 3 shows the results.

[Example 3]
Hot melt adhesive composition of Example 3 in the same manner as in Example 1 except that the amount of the hydrogenated hydrocarbon resin (β1) obtained in Production Example 4 was changed from 100 parts to 90 parts. Was prepared and evaluated in the same manner. Table 3 shows the results.

[Example 4]
Example 1 was repeated except that 100 parts of the block copolymer composition (α2) obtained in Production Example 2 was used instead of 100 parts of the block copolymer composition (α1) obtained in Production Example 1. Similarly, the hot melt adhesive composition of Example 4 was prepared and evaluated similarly. Table 3 shows the results.

[Example 5]
The amount of the block copolymer composition (α1) obtained in Production Example 1 was changed from 100 parts to 50 parts, and 50 parts of the block copolymer composition (α2) obtained in Production Example 2 was used. Except for further use, a hot melt adhesive composition of Example 5 was prepared in the same manner as in Example 1 and evaluated in the same manner. Table 3 shows the results.

[Example 6]
In the same manner as in Example 1 except that 120 parts of the hydrogenated hydrocarbon resin (β2) obtained in Production Example 5 was used instead of 100 parts of the hydrogenated hydrocarbon resin (β1) obtained in Production Example 4. Thus, the hot melt adhesive composition of Example 6 was prepared and similarly evaluated. Table 3 shows the results.

[Comparative Example 1]
Instead of 100 parts of the hydrogenated hydrocarbon resin (β1) obtained in Production Example 4, 100 parts of a non-hydrogenated hydrocarbon resin (trade name “Quinton R100” manufactured by Zeon Corporation) was used, and a naphthenic resin was used. A hot melt adhesive composition of Comparative Example 1 was prepared and evaluated in the same manner as in Example 1 except that no process oil was blended. Table 3 shows the results.

[Comparative Example 2]
A comparison was made except that 100 parts of the styrene-isoprene-styrene block copolymer (α3) obtained in Production Example 3 was used instead of 100 parts of the block copolymer composition (α1) obtained in Production Example 1. In the same manner as in Example 1, the hot melt adhesive composition of Comparative Example 2 was prepared and evaluated in the same manner. Table 3 shows the results.

[Comparative Example 3]
100 parts of the styrene-isoprene-styrene block copolymer (α3) obtained in Production Example 3 was charged into a stirring blade type kneader, and 100 parts of the hydrogenated hydrocarbon resin (β1) obtained in Production Example 4 was added thereto. , Naphthenic process oil (trade name “Diana Process Oil NS-90S”, manufactured by Idemitsu Kosan Co., Ltd.), 10 parts, antioxidant (trade name “Irganox 1010”), pentaerythritol tetrakis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate], 1 part of BASF), and 316.5 parts of toluene as a solvent, and the system was purged with nitrogen gas. The mixture was stirred for 1 hour, and then dried. The hot melt adhesive composition of Comparative Example 3 was prepared by removing toluene by doing. Then, the obtained hot melt adhesive composition was evaluated in the same manner as in Example 1. Table 3 shows the results.

[Comparative Example 4]
In place of 100 parts of the hydrogenated hydrocarbon resin (β1) obtained in Production Example 4, 100 parts of a hydrogenated resin derived from cyclopentadiene (trade name “Imarb P100”, manufactured by Idemitsu Kosan Co., Ltd.) was used, and A hot melt adhesive composition of Comparative Example 4 was prepared and evaluated in the same manner as in Example 1 except that no naphthene-based process oil was blended. Table 3 shows the results.

[Comparative Example 5]
Instead of using 100 parts of the hydrogenated hydrocarbon resin (β1) obtained in Production Example 4, 100 parts of a hydrogenated resin derived from cyclopentadiene (trade name “Escolets 5300” manufactured by ExxonMobil Chemical) was used. In the same manner as in Example 1, the hot melt adhesive composition of Comparative Example 5 was prepared and similarly evaluated. Table 3 shows the results.

From Table 3, it can be seen that when the mixture contains an aromatic vinyl block copolymer and a hydrogenated hydrocarbon resin and is heated at 65 ° C. for 2 hours, the amount of volatile components in toluene is 260 μg / m ³ or less, and A hot-melt adhesive having a component amount of 15,000 μg / m ³ or less and a peel adhesion to a stainless steel plate of 400 N / m or more, measured at a temperature of 23 ° C., a peel angle of 180 °, and a tensile speed of 300 mm / min. According to the adhesive composition, the odor was low, the adhesive strength was high, and the change in the adhesive strength over time was suppressed (Examples 1 to 6).
According to such a hot melt pressure-sensitive adhesive composition, an electrical insulating tape having a low odor, a high adhesive strength, and a suppressed change in adhesive strength over time is provided by combining with a base material. It can be said that it can be done.
On the other hand, when the amount of volatile components of toluene exceeds 260 μg / m ³ or the total amount of volatile components exceeds 15,000 μg / m ³ , the odor is strong, and the change in adhesive force with time is large. The properties were inferior (Comparative Examples 1-4).
When the peel adhesion was less than 400 N / m, the holding power was poor (Comparative Example 5).

Claims (9)

A hot melt adhesive composition, an electrical insulating tape comprising a substrate,
The hot melt adhesive composition contains an aromatic vinyl block copolymer and a hydrogenated hydrocarbon resin,
When heated at 65 ° C. for 2 hours, the hot melt adhesive composition has a toluene volatile content of 260 μg / m ³ or less, and a total volatile component content of 15,000 μg / m ³ or less,
An electrical insulating tape having a peel adhesion to a stainless steel plate of 400 N / m or more of the hot melt adhesive composition measured at a temperature of 23 ° C., a peel angle of 180 °, and a tensile speed of 300 mm / min. 2. The composition according to claim 1, wherein the aromatic vinyl block copolymer includes a block copolymer A represented by the following general formula (I) and a block copolymer B represented by the following general formula (II): 3. An electrical insulating tape as described.
Ar1-D1-Ar2 (I)
Ar3-D2 (II)
(In the above general formulas (I) and (II), Ar1, Ar2 and Ar3 are each an aromatic vinyl polymer block, and D1 and D2 are each a conjugated diene polymer block.) The aromatic vinyl monomer unit content of the block copolymer A is larger than the aromatic vinyl monomer unit content of the block copolymer B,
The weight average molecular weight (Mw (Ar1)) of the aromatic vinyl polymer block Ar1 of the block copolymer A and the weight average molecular weight (Mw (Ar3)) of the aromatic vinyl polymer block Ar3 of the block copolymer B. Is substantially the same.   The ratio (Mw (Ar2)) of the weight average molecular weight (Mw (Ar2)) of the aromatic vinyl polymer block Ar2 of the block copolymer A to the weight average molecular weight (Mw (Ar1)) of the aromatic vinyl polymer block Ar1. 4) The electrical insulating tape according to claim 2, wherein (Mw (Ar1)) is in the range of 1 to 7.   The electrical insulating tape according to claim 2, wherein the block copolymer B is prepared together with the block copolymer A when preparing the block copolymer A. 6. The hydrogenated hydrocarbon resin,
1,3-pentadiene monomer unit 30% by mass to 75% by mass,
Alicyclic monoolefin monomer unit having 4 to 6 carbon atoms, 20% to 50% by mass,
An acyclic monoolefin monomer unit having 4 to 8 carbon atoms in an amount of 5 mass% to 25 mass%,
It is obtained by hydrogenating a hydrocarbon resin containing 0% to 10% by mass of an alicyclic diolefin monomer unit and 0% to 30% by mass of an aromatic monoolefin monomer unit. The electrical insulating tape according to claim 1. The hydrogenated hydrocarbon resin,
The hydrogenation rate of the olefin is 10% to 80%,
In the case of containing an aromatic monomer unit, the hydrogenation ratio of the aromatic ring is 1% to 30%,
A weight average molecular weight (Mw) of 1,000 to 3,500,
Z average molecular weight (Mz) is 2,000 to 7,000,
The ratio of the Z average molecular weight to the weight average molecular weight (Mz / Mw) is 1.5 to 2.5,
A softening point of 50 ° C. or more;
The electrical insulating tape according to claim 6, wherein the 50 mass% toluene solution has a Gardner color number of 3 or less.   The electrical insulating tape according to claim 1, further comprising a softener.   The content of the aromatic vinyl block copolymer is 10% by mass to 70% by mass, the content of the hydrogenated hydrocarbon resin is 20% by mass to 80% by mass, and the content of the softener is 0.1% by mass. The electrical insulating tape according to claim 8, wherein the amount is from 30% by mass.