JP2019065179A - Adhesive composition - Google Patents

Abstract

To provide an adhesive composition excellent in adhesion characteristics.SOLUTION: The adhesive composition contains a cyclopentene ring-opened polymer and a tackifier. The tackifier is selected from an aliphatic petroleum resin, an aromatic petroleum resin, an aliphatic-aromatic copolymer-based petroleum resin, a hydrogenated petroleum resin, and an alicyclic petroleum resin. The content of the tackifier is 10-500 pts.wt. based on 100 pts.wt. of the cyclopentene ring-opened polymer.SELECTED DRAWING: None

Description

  The present invention relates to a pressure-sensitive adhesive composition.

  Conventionally, butadiene rubber is widely used as an elastomeric material. Butadiene rubber is a synthetic rubber produced using butadiene as a raw material, and butadiene as the raw material is produced as a by-product in producing ethylene by cracking naphtha. However, in recent years, a method using natural gas such as ethane as a raw material has been expanded as a method for producing ethylene, and a decrease in the production amount of butadiene is expected. Therefore, investigation of synthetic rubber which does not use butadiene as a raw material as a substitute material of butadiene rubber is advanced.

  One of the synthetic rubbers being studied as a substitute material for butadiene rubber is a cyclopentene ring-opened polymer obtained by ring-opening polymerization of cyclopentene. This cyclopentene ring-opened polymer is known to be used as a material for automobile tires and the like. For example, Patent Document 1 discloses a tire rubber composition containing a cyclopentene ring-opened polymer.

WO 2016/060267

  In recent years, as a new application of the cyclopentene ring-opened polymer, an application of a material having an adhesive function is required.

  An object of the present invention is to provide a pressure-sensitive adhesive composition excellent in adhesive properties.

  In order to solve the above problems, one aspect of the present invention provides a pressure-sensitive adhesive composition containing a cyclopentene ring-opened polymer and a tackifier.

  According to one aspect of the present invention, a pressure-sensitive adhesive composition having excellent adhesion properties can be obtained.

  Hereinafter, embodiments of the present invention will be described in detail.

<Adhesive composition>
The pressure-sensitive adhesive composition according to the embodiment of the present invention contains a cyclopentene ring-opened polymer and a tackifier.

<Cyclopentene ring-opened polymer>
The cyclopentene ring-opening polymer contained in the pressure-sensitive adhesive composition of the present embodiment is a polymer containing a repeating unit formed by ring-opening polymerization of cyclopentene as a repeating unit constituting its main chain.

  In this cyclopentene ring-opened polymer, the proportion of repeating units formed by ring-opening polymerization of cyclopentene is preferably 80% by mole or more, more preferably 90% by mole or more, based on all repeating units. It is 95 mol% or more, particularly preferably substantially 100%.

  The cyclopentene ring-opened polymer contained in the pressure-sensitive adhesive composition of the present embodiment contains a repeating unit derived from another monomer copolymerizable with cyclopentene as long as the characteristics of the cyclopentene ring-opened polymer are maintained. May be The proportion of repeating units derived from other copolymerizable monomers is preferably 20 mol% or less, more preferably 10 mol% or less, and more preferably 5 mol% or less, based on all repeating units. It is further preferred that

Other monomers copolymerizable with cyclopentene include monocyclic olefins other than cyclopentene, monocyclic dienes, monocyclic trienes, polycyclic cyclic olefins, polycyclic cyclic olefins, polycyclic cyclic dienes, and polycyclic cyclic trienes. . Examples of monocyclic olefins other than cyclopentene include cyclooctene. Examples of monocyclic dienes include 1,5-cyclooctadiene. Examples of monocyclic trienes include 1,5,9-cyclododecatriene. Moreover, as a polycyclic cyclic olefin, a polycyclic cyclic diene, and a polycyclic cyclic triene, 2-norbornene, dicyclopentadiene, 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene , Tetracyclo [6.2.1.1 ^{3, 6} . Examples of norbornene compounds such as 0 ^2,7 ] dodec-4-ene and the like. The cyclopentene and the other monomers copolymerizable with the above cyclopentene may be substituted or unsubstituted. Moreover, the other monomer copolymerizable with the said cyclopentene may be used individually by 1 type, or may be used combining 2 or more types.

  The molecular weight of the cyclopentene ring-opened polymer is not particularly limited, but is preferably 50,000 to 900,000 as a value of weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography. Preferably it is 100,000-600,000, More preferably, it is 150,000-400,000. When the cyclopentene ring-opening polymer has such a molecular weight, a pressure-sensitive adhesive composition having excellent mechanical strength can be obtained.

  The ratio (Mw / Mn) of weight-average molecular weight (Mw) to number-average molecular weight (Mn) in terms of polystyrene, as measured by gel permeation chromatography, in the cyclopentene ring-opened polymer is not particularly limited, but is preferably Is 4.0 or less, more preferably 3.5 or less, and still more preferably 3.0 or less. By having such Mw / Mn, the characteristic as an adhesive composition obtained can be made more excellent.

  The cis / trans ratio of the double bond present in the repeating unit constituting the cyclopentene ring-opened polymer is not particularly limited, and can be set, for example, in the range of 10/90 to 90/10.

  The method for adjusting the cis / trans ratio of the cyclopentene ring-opened polymer is not particularly limited. For example, a method of controlling the polymerization conditions when polymerizing cyclopentene to obtain the cyclopentene ring-opened polymer is mentioned. Be Specifically, the trans ratio can be increased as the polymerization temperature for polymerizing cyclopentene is increased, and the trans ratio can be increased as the monomer concentration in the polymerization solution is decreased.

  Moreover, the glass transition temperature (Tg) of a cyclopentene ring-opened polymer is not specifically limited, For example, it can adjust to -70 degrees C or less. In addition, adjustment of the glass transition temperature of a cyclopentene ring-opened polymer can be performed, for example by controlling the cis / trans ratio etc. in the double bond which exists in a repeating unit.

  The cyclopentene ring-opening polymer may have a molecular structure consisting of only carbon atoms and hydrogen atoms, but may contain atoms other than carbon atoms and hydrogen atoms in the molecular structure. More specifically, a modifying group containing an atom selected from the group consisting of atoms of group 15 of the periodic table, atoms of group 16 of the periodic table, and silicon atoms may be contained.

  As such a modifying group, a modifying group containing an atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom and a silicon atom is preferable, and among these, a nitrogen atom, an oxygen atom, More preferred is a modifying group containing an atom selected from the group consisting of and silicon atoms, and more preferred is a modifying group containing silicon atoms.

  Examples of the nitrogen atom-containing modifying group include an amino group, a pyridyl group, an imino group, an amido group, a nitro group, a urethane bonding group, or a hydrocarbon group containing these groups. Examples of the modifying group containing an oxygen atom include a hydroxyl group, a carboxylic acid group, an ether group, an ester group, a carbonyl group, an aldehyde group, an epoxy group, or a hydrocarbon group containing these groups. As the modifying group containing a phosphorus atom, a phosphoric acid group, a phosphino group, or a hydrocarbon group containing these groups is exemplified. Examples of the modifying group containing a sulfur atom include a sulfonyl group, a thiol group, a thioether group, or a hydrocarbon group containing these groups. Examples of the modifying group containing a silicon atom include an alkylsilyl group, an oxysilyl group, or a hydrocarbon group containing these groups.

  Further, the modifying group may be a modifying group containing a plurality of the groups described above. Among these, from the viewpoint of improving the heat aging resistance of the cyclopentene ring-opened polymer, amino group, pyridyl group, imino group, amido group, hydroxyl group, carboxylic acid group, aldehyde group, epoxy group, oxysilyl group, or these groups Are preferred, among which an oxysilyl group is particularly preferred. In addition, an oxysilyl group means group which has a silicon-oxygen bond.

  Specific examples of the oxysilyl group include an alkoxysilyl group, an aryloxysilyl group, an acyloxysilyl group, an alkylsiloxysilyl group, an arylsiloxysilyl group, and a hydroxysilyl group. Among these, an alkoxysilyl group to a cyclopentene ring-opened polymer is preferable.

  The alkoxysilyl group is a group formed by bonding one or more alkoxy groups to a silicon atom, and specific examples thereof include trimethoxysilyl group, (dimethoxy) (methyl) silyl group, (methoxy) (dimethyl) silyl Group, triethoxysilyl group, (diethoxy) (methyl) silyl group, (ethoxy) (dimethyl) silyl group, (dimethoxy) (ethoxy) silyl group, (methoxy) (diethoxy) silyl group, tripropoxysilyl group, tributoxy A silyl group etc. are mentioned.

  The aryloxysilyl group is a group formed by bonding one or more aryloxy groups to a silicon atom, and specific examples thereof include triphenoxysilyl group, (diphenoxy) (methyl) silyl group, (phenoxy) (dimethyl) A silyl group, (diphenoxy) (ethoxy) silyl group, (phenoxy) (diethoxy) silyl group etc. are mentioned. Among these, the (diphenoxy) (ethoxy) silyl group and the (phenoxy) (diethoxy) silyl group are also classified as alkoxysilyl groups because they have alkoxy groups in addition to aryloxy groups.

  The acyloxysilyl group is a group formed by combining one or more acyloxy groups with a silicon atom, and specific examples thereof include a triacyloxysilyl group, (diacyloxy) (methyl) silyl group, (acyloxy) (dimethyl) A silyl group etc. are mentioned.

  The alkylsiloxysilyl group is a group formed by combining one or more alkylsiloxy groups with a silicon atom, and specific examples thereof include a tris (trimethylsiloxy) silyl group, a trimethylsiloxy (dimethyl) silyl group, a triethylsiloxy ( Diethyl) silyl group, tris (dimethylsiloxy) silyl group and the like can be mentioned.

  The arylsiloxysilyl group is a group formed by combining one or more arylsiloxy groups with a silicon atom, and specific examples thereof include tris (triphenylsiloxy) silyl group, triphenylsiloxy (dimethyl) silyl group, tris (Diphenylsiloxy) silyl group etc. are mentioned.

  The hydroxysilyl group is a group formed by bonding one or more hydroxy groups to a silicon atom, and specific examples thereof include a trihydroxysilyl group, (dihydroxy) (methyl) silyl group, (hydroxy) (dimethyl) silyl group , (Dihydroxy) (ethoxy) silyl group, (hydroxy) (diethoxy) silyl group and the like. Among these, the (dihydroxy) (ethoxy) silyl group and the (hydroxy) (diethoxy) silyl group have an alkoxy group in addition to the hydroxy group, and therefore they are also classified as an alkoxy silyl group.

  When the cyclopentene ring-opening polymer has such a modifying group, the introducing position of the modifying group is not particularly limited, but from the viewpoint of further enhancing the introducing effect, it has a modifying group at the end of the polymer chain Is preferred.

  When the cyclopentene ring-opened polymer has a modifying group at the end of the polymer chain, both polymer chain ends (both ends even if the modifying group is introduced only at one polymer chain end (one end) A modified group may be introduced into the terminal), or a mixture of these may be used. Furthermore, these may be mixed with an unmodified cyclopentene ring-opened polymer in which a specific modifying group is not introduced at the polymer chain terminal.

When the cyclopentene ring-opened polymer has a modifying group at the end of the polymer chain, the introduction ratio of the modifying group at the polymer chain end of the cyclopentene ring-opened polymer is not particularly limited, for example, a modifying group is introduced The value of the percentage of the cyclopentene ring-opened polymer chain end number / cyclopentene ring-opened polymer chain number can be adjusted to 60% or more. The method for measuring the introduction ratio of the modifying group to the polymer chain terminal is not particularly limited. For example, the peak area ratio corresponding to the modifying group determined by ¹ H-NMR spectrum measurement, and gel permeation chromatography It can be determined from the number average molecular weight determined from the graph.

  The synthesis method of the cyclopentene ring-opened polymer is not particularly limited as long as the target polymer can be obtained, and may be synthesized according to a conventional method. For example, a cyclopentene ring-opened polymer can be synthesized by the method described below.

  That is, the cyclopentene ring-opened polymer includes, for example, cyclopentene in the presence of a polymerization catalyst containing a Group 6 transition metal compound (A) of the periodic table and an organoaluminum compound (B) represented by the following general formula (1) It can be obtained by ring-opening polymerization of the monomer contained.

(R ¹ ) _3-x Al (OR ² ) _x (1)
(In the above general formula (1), R ¹ and R ² each represent a hydrocarbon group having 1 to 20 carbon atoms, and x is 0 <x <3.)

  The periodic table group 6 transition metal compound (A) is a compound having a periodic table (long period periodic table, hereinafter the same) group 6 transition metal atom, and specifically, a chromium atom, a molybdenum atom, or tungsten It is a compound having an atom. Among these, a compound having a molybdenum atom or a compound having a tungsten atom is preferable, and in particular, a compound having a tungsten atom is more preferable from the viewpoint of high solubility in cyclopentene. In addition, compounds having a periodic table group 6 transition metal atom are not particularly limited, and halides, alcoholates, arylates, oxide compounds and the like of periodic table group 6 transition metal atoms may be mentioned, and among these, polymerization activity is From the viewpoint of being high, halides are preferred.

  As a specific example of such periodic table group 6 transition metal compound (A), molybdenum compounds such as molybdenum pentachloride, molybdenum oxo tetrachloride, molybdenum (phenyl imide) tetrachloride; tungsten hexachloride, tungsten oxotetrachloride, Tungsten compounds such as tungsten (phenyl imide) tetrachloride, monocatecholate tungsten tetrachloride, bis (3,5-ditertiary butyl) catecholate tungsten dichloride, bis (2-chloroetherate) tetrachloride, tungsten oxo tetraphenolate and the like And the like.

  The amount of the periodic table group 6 transition metal compound (A) used is 1: 100 to 1: 200,000 in molar ratio of "group 6 transition metal atom in polymerization catalyst: monomer containing cyclopentene" It is preferably in the range of 1: 200 to 1: 150,000, more preferably 1: 500 to 1: 100,000. If the amount of the periodic table group 6 transition metal compound (A) used is too small, the polymerization reaction may not proceed sufficiently. On the other hand, if the amount is too large, removal of the catalyst residue from the cyclopentene ring-opened polymer may be difficult, and the adhesive properties of the resulting pressure-sensitive adhesive composition may be reduced.

The organoaluminum compound (B) is a compound represented by the above general formula (1). Specific examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ and R ² in the general formula (1) include a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an isobutyl group, and an n-butyl group. Alkyl groups such as t-butyl group, n-hexyl group and cyclohexyl group; aryl groups such as phenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 2,6-diisopropylphenyl group and naphthyl group And the like. The groups represented by R ¹ and R ² in the compound represented by the general formula (1) may be the same or different, but the cis ratio of the resulting cyclopentene ring-opened polymer is Among R ¹ and R ² , at least R ² is preferably an alkyl group formed by continuously bonding 4 or more carbon atoms, in particular, n-butyl. It is more preferable that it is a group, 2-methyl-pentyl group, n-hexyl group, cyclohexyl group, n-octyl group or n-decyl group.

In the above general formula (1), x is 0 <x <3. That is, in the general formula (1), the composition ratio of R ¹ and OR ² can take any value in each range of 0 <3-x <3 and 0 <x <3, respectively. From the viewpoint of being able to increase the polymerization activity and controlling the cis ratio of the resulting cyclopentene ring-opened polymer within the above-mentioned preferred range, x is preferably 0.5 <x <1.5.

The organoaluminum compound (B) represented by the above general formula (1) can be synthesized, for example, by the reaction of trialkylaluminum with an alcohol as shown in the following general formula (2).
(R ¹ ) ₃ Al + _x R ² OH → (R ¹ ) _3-x Al (OR ² ) _x + (R ¹ ) _x H (2)
Incidentally, x in the general formula (1) can be arbitrarily controlled by defining the reaction ratio of the corresponding trialkylaluminum and alcohol as shown in the general formula (2).

  The amount of the organoaluminum compound (B) used varies depending on the type of the organoaluminum compound (B) to be used, but relative to the Group 6 transition metal atom of the periodic table Group 6 transition metal compound (A) Preferably, it is a ratio of 0.1 to 100 times mol, more preferably 0.2 to 50 times mol, still more preferably 0.5 to 20 times mol. If the amount of the organoaluminum compound (B) used is too small, the polymerization activity may be insufficient. If it is too large, side reactions tend to occur easily during ring-opening polymerization.

  The ring-opening polymerization reaction may be carried out without a solvent or in solution. The solvent used when conducting the ring-opening polymerization reaction in a solution is not particularly limited as long as it is a solvent which is inert in the polymerization reaction and can dissolve cyclopentene used in the ring-opening polymerization or the above-mentioned polymerization catalyst. For example, hydrocarbon solvents or halogen solvents may be mentioned. Specific examples of hydrocarbon solvents include, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; aliphatic hydrocarbons such as n-hexane, n-heptane and n-octane; cyclohexane, cyclopentane, methyl Alicyclic hydrocarbons such as cyclohexane; and the like. Further, specific examples of the halogen-based solvent include alkyl halogens such as dichloromethane and chloroform; and aromatic halogens such as chlorobenzene and dichlorobenzene.

  In addition, as a compound having the above-described modifying group and having one olefinic carbon-carbon double bond having metathesis reactivity in the polymerization reaction system of ring-opening polymerization reaction, modifying group-containing olefinically unsaturated carbonization Hydrogen (C) may be present. A modifying group can be introduced at the polymer chain end of the cyclopentene ring-opened polymer by the presence of such a modifying group-containing olefinically unsaturated hydrocarbon (C). For example, when introducing an oxysilyl group at the polymer chain end of the cyclopentene ring-opened polymer, an oxysilyl group-containing olefinically unsaturated hydrocarbon may be present in the polymerization reaction system.

  As an example of such an oxysilyl group-containing olefinic unsaturated hydrocarbon, vinyl (trimethoxy) silane, which is to introduce a modifying group only to one end (one end) of the polymer chain of the cyclopentene ring-opened polymer, Vinyl (triethoxy) silane, allyl (trimethoxy) silane, allyl (methoxy) (dimethyl) silane, allyl (triethoxy) silane, allyl (ethoxy) (dimethyl) silane, styryl (trimethoxy) silane, styryl (triethoxy) silane, 2- Alkoxysilane compounds such as styrylethyl (triethoxy) silane, allyl (triethoxysilylmethyl) ether, allyl (triethoxysilylmethyl) (ethyl) amine; vinyl (triphenoxy) silane, allyl (triphenoxy) silane, allyl (phenoxy) ) Aryloxysilane compounds such as dimethyl) silane; vinyl (triacetoxy) silane, allyl (triacetoxy) silane, allyl (diacetoxy) methylsilane, acyloxysilane compounds such as allyl (acetoxy) (dimethyl) silane; allyltris (trimethylsiloxy) Alkylsiloxysilane compounds such as silanes; arylsiloxysilane compounds such as allyltris (triphenylsiloxy) silanes; 1-allylheptamethyltrisiloxane, 1-allylonamethyltetrasiloxane, 1-allylonamethylcyclopentasiloxane, 1-allyl And polysiloxane compounds such as undecamethylcyclohexasiloxane; and the like. In addition, 1,4-bis (trimethoxysilyl) -2-butene, 1,4-bis (tril) as a unit for introducing a modifying group to both ends (both ends) of the polymer chain of cyclopentene ring-opened polymer Alkoxysilane compounds such as ethoxysilyl) -2-butene and 1,4-bis (trimethoxysilylmethoxy) -2-butene; aryloxysilane compounds such as 1,4-bis (triphenoxysilyl) -2-butene; Acyloxysilane compounds such as 1,4-bis (triacetoxysilyl) -2-butene; alkylsiloxysilane compounds such as 1,4-bis [tris (trimethylsiloxy) silyl] -2-butene; 1,4-bis Arylsiloxysilane compounds such as [tris (triphenylsiloxy) silyl] -2-butene; 1,4-bis (heptamethyltrisiloxy) -2-b Emissions, 1,4-bis (undecapeptide methylcyclohexanol siloxy) -2-butene polysiloxane compounds such; and the like.

  The amount of use of the modified group-containing olefinically unsaturated hydrocarbon (C) such as the oxysilyl group-containing olefinically unsaturated hydrocarbon may be appropriately selected according to the molecular weight of the cyclopentene ring-opened polymer to be produced. For example, it can be in the range of 1/100 to 1 / 100,000 in molar ratio to the monomer containing cyclopentene used for polymerization, preferably 1/200 to 1 / 50,000, more preferably Is in the range of 1/300 to 1 / 10,000. The modified group-containing olefinically unsaturated hydrocarbon (C) acts as a molecular weight modifier in addition to the action of introducing a modified group to the polymer chain terminal of the cyclopentene ring-opened polymer.

  When the above-mentioned modifying group is not introduced into the cyclopentene ring-opened polymer, 1-butene, 1-pentene, 1- as a molecular weight modifier in order to adjust the molecular weight of the cyclopentene ring-opened polymer to be obtained. Monoolefin compounds such as hexene and 1-octene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl A diolefin compound such as 1,5-hexadiene may be added to the polymerization reaction system. The amount of use of the molecular weight modifier may be appropriately selected from the same range as that of the above-mentioned olefin-unsaturated hydrocarbon-containing hydrocarbon (C).

  The polymerization reaction temperature is not particularly limited, but is preferably -100 ° C. or more, more preferably -50 ° C. or more, still more preferably -20 ° C. or more, particularly preferably 0 ° C. or more. The upper limit of the polymerization reaction temperature is not particularly limited, but is preferably less than 100 ° C, more preferably less than 90 ° C, still more preferably less than 80 ° C, and particularly preferably less than 70 ° C. The polymerization reaction time is not particularly limited, but is preferably 1 minute to 72 hours, more preferably 10 minutes to 20 hours.

  Moreover, it replaces with the method using the polymerization catalyst containing the periodic table group 6 transition metal compound (A) and the organic aluminum compound (B) shown by General formula (1), and a ruthenium carbene complex is used as a polymerization catalyst. The cyclopentene ring-opened polymer can also be produced by a method of ring-opening polymerization of a cyclopentene-containing monomer in the presence of a ruthenium carbene complex.

  The ruthenium carbene complex is not particularly limited as long as it is a catalyst for ring opening polymerization of cyclopentene. Specific examples of the ruthenium carbene complex preferably used include bis (tricyclohexylphosphine) benzylideneruthenium dichloride, bis (triphenylphosphine) -3,3-diphenylpropenylideneruthenium dichloride, (3-phenyl-1H-indene-1 -Ylidene) bis (tricyclohexylphosphine) ruthenium dichloride, bis (tricyclohexylphosphine) t-butylvinylidene ruthenium dichloride, bis (1,3-diisopropylimidazolin-2-ylidene) benzylidene ruthenium dichloride, bis (1,3-dicyclohexylimidazoline) -2-ylidene) benzylidene ruthenium dichloride, (1,3-dimesitylimidazolin-2-ylidene) (tricyclohexylphosphine) benzyl Ruthenium dichloride, (1,3-dimesitylimidazolidin-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, bis (tricyclohexylphosphine) ethoxymethylideneruthenium dichloride, (1,3-dimesitylimidazolidine -2-ylidene) (tricyclohexylphosphine) ethoxymethylidene ruthenium dichloride and the like can be mentioned.

  The amount of the ruthenium carbene complex used can be in the range of 1: 2,000 to 1: 2,000,000 by molar ratio of metal ruthenium in the catalyst and the monomer containing cyclopentene, preferably 1 The ratio is preferably in the range of 5,000 to 1: 1,500,000, more preferably 1: 10,000 to 1: 1,000,000. If the amount of the ruthenium carbene complex used is too small, the polymerization reaction may not proceed sufficiently. On the other hand, when the amount is too large, removal of the catalyst residue from the obtained cyclopentene ring-opened polymer becomes difficult, and the adhesive properties of the pressure-sensitive adhesive composition may be deteriorated.

  When using a ruthenium carbene complex as a polymerization catalyst, the ring-opening polymerization reaction may be performed without a solvent or may be performed in a solution. As a solvent used when performing ring-opening polymerization reaction in solution, a polymerization catalyst containing the periodic table group 6 transition metal compound (A) described above and the organoaluminum compound (B) represented by the general formula (1) can be used. The same solvent (hydrocarbon-based solvent, halogen-based solvent, etc.) as used can be used.

  Moreover, the polymerization reaction temperature and the polymerization reaction time in the case of using a ruthenium carbene complex as a polymerization catalyst are the same as those of the periodic table group 6 transition metal compound (A) and the organic aluminum compound (B) represented by the general formula (1). The polymerization reaction temperature and the polymerization reaction time in the case of using a polymerization catalyst containing

  And, a method using a polymerization catalyst containing the periodic table group 6 transition metal compound (A) and the organoaluminum compound (B) represented by the general formula (1), or a method using a ruthenium carbene complex as the polymerization catalyst If desired, an antioxidant such as a phenol-based stabilizer, a phosphorus-based stabilizer, or a sulfur-based stabilizer may be added to the cyclopentene ring-opening polymer obtained by The addition amount of the antiaging agent may be appropriately determined according to the type and the like. Furthermore, if desired, an extender oil may be blended. When cyclopentene ring-opened polymer is obtained as the polymer solution, in order to recover the polymer from the polymer solution, a known recovery method may be adopted, for example, after separating the solvent by steam stripping or the like, It is possible to employ a method of filtering off the solid and drying it to obtain a solid rubber.

  The pressure-sensitive adhesive composition of the present embodiment may contain other elastomer components in addition to the cyclopentene ring-opened polymer. As an elastomer component other than a cyclopentene ring-opened polymer, for example, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene- Propylene-styrene block copolymer, polybutadiene rubber, styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, ethylene propylene diene rubber (EPDM), polyisoprene rubber, natural rubber and the like. . These elastomer components can be used alone or in combination of two or more.

  When the pressure-sensitive adhesive composition of the present embodiment contains another elastomer component, the content of the cyclopentene ring-opened polymer is, from the viewpoint of making the effect of the present invention more remarkable, the cyclopentene ring-opened polymer and Preferably it is 30 weight% or more, More preferably, it is 50 weight% or more, More preferably, it is 70 weight% or more with respect to the total elastomer component which is the sum total with another elastomer component.

  The pressure-sensitive adhesive composition according to the embodiment of the present invention includes a tackifier in addition to the above-described cyclopentene ring-opened polymer. The tackifier can act as a tackifier for the cyclopentene ring-opened polymer or the elastomer component containing the cyclopentene ring-opened polymer, and can impart the adhesive properties of the resulting pressure-sensitive adhesive composition.

  The tackifier is not particularly limited, and examples thereof include natural resin-based tackifying resins and synthetic resin-based tackifying resins.

  Examples of natural resin-based tackifying resins include rosin-based resins and terpene-based resins.

  Examples of rosin-based resins include rosins such as gum rosin, tall rosin and wood rosin; modified rosins such as hydrogenated rosins, disproportionated rosins and polymerized rosins; rosin esters such as glycerin esters of modified rosins and pentaerythritol esters; It is illustrated.

  As a terpene resin, aromatic modified terpene resin, hydrogenated terpene resin, terpene phenol resin etc. are illustrated other than terpene resin of alpha-pinene type, beta-pinene type, dipentene (limonene) type and the like.

  Examples of synthetic resin-based tackifying resins include polymerization-based tackifying resins and condensation-based tackifying resins.

  As a polymerization tackifying resin, aliphatic (C5 series) petroleum resin, aromatic (C9 series) petroleum resin, aliphatic aromatic copolymer (C5 / C9 series) petroleum resin, hydrogenated petroleum resin, fat Petroleum resins such as cyclic petroleum resins; coumarone-indene resins; pure monomer petroleum resins such as styrene-based resins and substituted styrene-based resins; Examples of condensation tackifying resins include phenol resins such as alkylphenol resins and rosin-modified phenol resins, and xylene resins.

  The petroleum resins mentioned as the above-mentioned polymeric tackifying resins include those which are acid-modified (acid-modified petroleum resins) and those which do not contain styrene (non-styrene-based petroleum resins). The alicyclic petroleum resins include those to which hydrogen is added (hydrogenated alicyclic petroleum resins). Furthermore, aliphatic petroleum resins include dicyclopentadiene.

  The above-described tackifiers can be used alone or in combination of two or more.

  In addition, as a tackifier contained in the pressure-sensitive adhesive composition, a synthetic resin-based tackifying resin is preferable, a polymer-based tackifying resin is more preferable, and a fat-based tackifying resin is more preferable, from the viewpoint of reliably imparting excellent adhesive properties to the pressure-sensitive adhesive composition. Petroleum resins such as aliphatic (C5) petroleum resin, aromatic (C9) petroleum resin, aliphatic aromatic copolymer (C5 / C9) petroleum resin, hydrogenated petroleum resin, alicyclic petroleum resin, etc. Are more preferred.

  The content of tackifier is 10 to 500 parts by weight, preferably 50 to 350 parts by weight, more preferably 70 to 250 parts by weight per 100 parts by weight of the cyclopentene ring-opened polymer contained in the pressure-sensitive adhesive composition of the present embodiment. It is a weight part. When the content of the tackifier is in the above range, the adhesive properties of the pressure-sensitive adhesive composition can be sufficiently obtained.

<Other ingredients>
Further, the pressure-sensitive adhesive composition of the present embodiment may be a softener, an antioxidant, an activator, a wax, a heat stabilizer, an ultraviolet ray absorber, according to a conventional method, in addition to the components described above. Necessary amounts of additives such as an agent, a filler and a solvent can be compounded.

  The softener is not particularly limited, and examples thereof include extender oils such as aromatic process oils, paraffinic process oils and naphthenic process oils; liquid polymers such as polybutene and polyisobutylene; and the like. Moreover, the compounding quantity of a softener can be suitably set according to the characteristic of a softener, and the characteristic calculated | required by an adhesive composition.

  As the antioxidant, for example, 2,6-di-tert-butyl-p-cresol and pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like Hindered phenolic compounds; thiodicarboxylate esters such as dilauryl thiodipropionate and distearylthiodipropionate; tris (nonylphenyl) phosphite and 4,4'-butylidene-bis (3-methyl-6) And phosphites such as -tert-butylphenyl) ditridecyl phosphite; and the like.

  The compounding quantity of antioxidant can be suitably set according to the characteristic of each antioxidant, or the characteristic calculated | required by the adhesive composition. Moreover, these antioxidants can be used individually or in combination of 2 or more types, respectively.

<Production of Pressure-Sensitive Adhesive Composition>
The pressure-sensitive adhesive composition of the present embodiment can be produced by mixing cyclopentene ring-opened polymer and tackifier, and, if necessary, other components such as an elastomer component and a softener. The method for producing the pressure-sensitive adhesive composition is not particularly limited, and examples thereof include ordinary methods such as an extrusion method, a hot melt method, a coating method, a casting method, a calender method, and a press method.

  If an example is given, a hot-melt method is the method of melt-kneading and manufacturing each component of an adhesive composition at high temperature about 160 degreeC-180 degreeC under nitrogen atmosphere, and is manufactured. Moreover, the casting method is a method of volatilizing a solvent, after apply | coating to a target object what melt | dissolved the adhesive composition in the solvent.

<Application of Pressure-Sensitive Adhesive Composition>
The application of the pressure-sensitive adhesive composition of the present embodiment is not particularly limited, and can be applied to various adhesive and bonding applications. For example, it can be used for adhesive members and tapes of paper diapers and sanitary products and labels of labels it can.

  Moreover, when using the adhesive composition of embodiment as an adhesive of a label, the application of a label is although it does not specifically limit, For example, using as a product label and variable information label to the container packaging of food, a drink, liquors is possible. it can. It can also be used as a label for physical distribution, electricity, batteries, precision instruments, medicines, medicines, cosmetics, toiletries, stationery, OA, for automobiles, and railways.

  Hereinafter, the present invention will be specifically described based on examples. In the following, "parts" and "%" are based on weight unless otherwise noted. In addition, various tests and evaluations were performed according to the following methods.

Molecular weight of cyclopentene ring-opened polymer
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the cyclopentene ring-opened polymer were measured by gel permeation chromatography (GPC). For measurement by GPC, two H-type columns (manufactured by Tosoh Corporation, HZ-M) are connected in series using a GPC system (manufactured by Tosoh Corporation, HLC-8220), and tetrahydrofuran is used as a solvent at a column temperature of 40 ° C. went. As a detector, a differential refractometer (RI-8320, manufactured by Tosoh Corporation) was used. In addition, a weight average molecular weight (Mw) and a number average molecular weight (Mn) were measured as polystyrene conversion value.

<Glass transition temperature (Tg) of cyclopentene ring-opened polymer>
Using a differential scanning calorimeter (DSC, X-DSC7000 manufactured by Hitachi High-Tech Science Co., Ltd.), temperatures from -150 ° C to 40 ° C were measured at a temperature rise of 10 ° C / min.

<Cis / Trans ratio of cyclopentene ring-opened polymer>
^It was determined by ¹³ C-NMR spectroscopy.

<Introduction rate of oxysilyl group in terminal-modified cyclopentene ring-opened polymer>
^The ratio of the peak integral value derived from the oxysilyl group to the peak integral value derived from the carbon-carbon double bond in the terminal-modified cyclopentene ring-opened polymer main chain was determined by ¹ H-NMR spectrum measurement. Based on the ratio of the peak integral value obtained and the measured value of the number average molecular weight (Mn) by GPC, the introduction rate of the oxysilyl group [(the number of cyclopentene ring-opened polymer chain terminal having oxysilyl group introduced / terminal-modified cyclopentene opening The percentage of ring polymer chains) was calculated.

<Adhesive strength evaluation test>
A 20 mm square test piece is prepared as a test piece of the pressure-sensitive adhesive composition. The adhesion was evaluated from the adhesion time of the test piece to the SUS 304 when the 10 mm square SUS 304 was pressed against the test piece with a force of 0.05 N for 3 seconds, and the SUS 304 was pulled up. The test pieces which did not adhere at all were described as 0, the adhesion time was 1 or less for 5 seconds, and the adhesion time was 2 for 5 seconds or more. In addition, 1 and 2 have adhesive force and show that it is suitable as an adhesive material.

<Preparation of diisobutylaluminum mono (n-hexoxide) / toluene solution>
Preparation Example 1
In a nitrogen atmosphere, 88 parts of toluene and 11.7 parts of a 25.4 wt% triisobutylaluminum / n-hexane solution (manufactured by Tosoh Finechem Corp.) were added to a glass container containing a stirrer. The vessel was then cooled to -45 ° C and 1.53 parts of n-hexanol (equimolar to triisobutylaluminum) were slowly added dropwise with vigorous stirring. Then, it was allowed to reach room temperature with stirring to prepare a diisobutylaluminum mono (n-hexoxide) / toluene solution (3.75% by weight).

<Synthesis of cyclopentene ring-opened polymer>
Synthesis Example 1
In a nitrogen atmosphere, 588 parts of a 1.5% by weight WCl ₆ / toluene solution and 3.75% by weight of diisobutylaluminum mono (n-hexoxide) / toluene prepared in Preparation Example 1 in a glass container containing a stirrer. A catalyst solution was obtained by adding 252 parts of the solution and stirring for 15 minutes. Then, 3168 parts of cyclopentene and 41 parts of 1,4-bis (triethoxysilyl) -2-butene are added to a pressure resistant glass reaction vessel with a stirrer under a nitrogen atmosphere, and 840 parts of the catalyst solution prepared above is added to this. In addition, the polymerization reaction was carried out at 25 ° C. for 4 hours. After polymerization reaction for 4 hours, excess ethyl alcohol is added to the pressure resistant glass reaction vessel to stop the polymerization, and then 100 parts of the polymer obtained by the polymerization is an anti-aging agent (trade name "Irganox 1520 L", 0.2 part of Ciba Specialty Chemicals Inc. "Irganox" is a registered trademark was added. Next, the polymer is recovered by coagulating with a large amount of ethanol, and vacuum-dried at 40 ° C. for 3 days to form a ring-opened polymer of cyclopentene as a ring-opened polymer of cyclopentene. There were obtained 370 parts of combined (a1). The weight average molecular weight (Mw) of the obtained both-end modified cyclopentene ring-opened polymer (a1) is 294,000, the glass transition temperature (Tg) is -105 ° C, and the cis / trans ratio is cis / trans = 53/47 The oxysilyl group introduction ratio was 163%.

Synthesis Example 2
In a nitrogen atmosphere, 588 parts of a 1.5% by weight WCl ₆ / toluene solution and 3.75% by weight of diisobutylaluminum mono (n-hexoxide) / toluene prepared in Preparation Example 1 in a glass container containing a stirrer. A catalyst solution was obtained by adding 252 parts of the solution and stirring for 15 minutes. Then, under nitrogen atmosphere, 3158 parts of cyclopentene and 7.8 parts of 1-hexene are added to a pressure resistant glass reaction vessel with a stirrer, to which 840 parts of the catalyst solution prepared above is added, and polymerization is carried out at 0 ° C for 4 hours The reaction was done. After polymerization reaction for 4 hours, excess ethyl alcohol is added to the pressure resistant glass reaction vessel to stop the polymerization, and then 100 parts of the polymer obtained by the polymerization is an anti-aging agent (trade name "Irganox 1520 L", 0.2 part of Ciba Specialty Chemicals Inc. was added. Next, the polymer was coagulated with a large amount of ethanol and recovered, and vacuum dried at 40 ° C. for 3 days to obtain 1092 parts of a non-modified cyclopentene ring-opened polymer (a2) as a cyclopentene ring-opened polymer. The weight average molecular weight (Mw) of the obtained unmodified cyclopentene ring-opened polymer (a2) is 195,000, the glass transition temperature (Tg) is -109 ° C., and the cis / trans ratio is cis / trans = 77/23. there were.

Synthesis Example 3
In a nitrogen atmosphere, 588 parts of a 1.5% by weight WCl ₆ / toluene solution and 3.75% by weight of diisobutylaluminum mono (n-hexoxide) / toluene prepared in Preparation Example 1 in a glass container containing a stirrer. A catalyst solution was obtained by adding 252 parts of the solution and stirring for 15 minutes. Then, 1077 parts of toluene, 1616 parts of cyclopentene and 15.9 parts of 1,4-bis (triethoxysilyl) -2-butene are added to a pressure resistant glass reaction vessel with a stirrer under a nitrogen atmosphere, and the above is prepared as described above. 840 parts of the catalyst solution was added, and a polymerization reaction was carried out at 25 ° C. for 4 hours. After polymerization reaction for 4 hours, excess ethyl alcohol is added to the pressure resistant glass reaction vessel to stop the polymerization, and then 100 parts of the polymer obtained by the polymerization is an anti-aging agent (trade name "Irganox 1520 L", 0.2 part of Ciba Specialty Chemicals Inc. "Irganox" is a registered trademark was added. Next, the polymer is recovered by coagulating with a large amount of ethanol, and vacuum-dried at 40 ° C. for 3 days to form a ring-opened polymer of cyclopentene as a ring-opened polymer of cyclopentene. There were obtained 320 parts of combined (a3). The weight average molecular weight (Mw) of the obtained both-end modified cyclopentene ring-opened polymer (a3) is 277,000, the glass transition temperature (Tg) is -103 ° C, and the cis / trans ratio is cis / trans = 31/69. The oxysilyl group introduction rate was 152%.

<Production and evaluation of test pieces for adhesive strength evaluation>
Example 1
100 parts of ring-opened cyclopentene ring-terminated polymer (a1) obtained in Synthesis Example 1 and aliphatic (C5 series) petroleum resin as a tackifier (trade name “Quintone R 100”, manufactured by Nippon Zeon Co., “QUINTONE” Dissolved 100 parts of toluene in 1133 parts of toluene. The obtained solution was dropped on a polyethylene sheet and vacuum dried at 60 ° C. for 2 days to obtain a test piece (A) for adhesive strength evaluation. And the adhesive force evaluation test was done according to the said method using the obtained test piece (A). The results are shown in Table 1.

Example 2
Aliphatic-based (C5 series) petroleum resin (brand name "Quintone R100", manufactured by Nippon Zeon Co., Ltd.) as a tackifier in place of 100 parts, aliphatic aromatic copolymer (C5 / C9 series) petroleum resin (brand name " A test piece for evaluation of adhesive strength (B) was obtained and evaluated in the same manner as in Example 1 except that 100 parts of Quintone DX395 ′ ′ (manufactured by Zeon Corporation, Japan) were used. The results are shown in Table 1.

[Example 3]
Acid-modified aliphatic aromatic copolymer (C5 / C9 series) petroleum resin (C5 / C9 series) in place of 100 parts of aliphatic (C5 series) petroleum resin (trade name "Quintone R100", manufactured by Nippon Zeon Co., Ltd.) as a tackifier A test piece (C) for adhesive strength evaluation was obtained and evaluated in the same manner as in Example 1 except that 100 parts of trade name "Quintone D295" (manufactured by Zeon Corporation, Japan) was used. The results are shown in Table 1.

Example 4
Hydrogenated alicyclic petroleum resin (trade name "Escorez 5300", exxon mobil, in place of 100 parts of aliphatic (C5 series) petroleum resin (trade name "Quintone R100", manufactured by Nippon Zeon Co., Ltd.) as a tackifier. A test piece for evaluation of adhesive strength (D) was obtained and evaluated in the same manner as in Example 1 except that 100 parts of "ESCOREZ" (registered trademark) was used. The results are shown in Table 1.

[Example 5]
Non-styrene based aliphatic aromatic copolymer (C5 / C9 series) petroleum resin (C5 / C9 series) petroleum resin (C5 / C9 series) instead of 100 parts of aliphatic (C5 series) petroleum resin (brand name "Quintone R100", manufactured by Nippon Zeon Co., Ltd.) as tackifier A test piece for evaluation of adhesive strength (E) was obtained in the same manner as in Example 1 except that 100 parts of trade name "Piccotac 6095-E" manufactured by eastman chemical and "PICCOTAC" were registered trademarks were obtained similarly. It was evaluated. The results are shown in Table 1.

[Example 6]
A rosin-based resin (trade name “Pencel GA-100”, manufactured by Arakawa Chemical Co., Ltd., instead of 100 parts of aliphatic (C5 series) petroleum resin (trade name “Quintone R100”, manufactured by Nippon Zeon Co., Ltd.) as a tackifier. Evaluation was made in the same manner as in Example 1 except that 100 parts of "Pencel" was used as a registered trademark was used to obtain a test piece for evaluation of adhesive strength (F). The results are shown in Table 1.

[Example 7]
The procedure is carried out except that 100 parts of the unmodified cyclopentene ring-opened polymer (a2) obtained in Synthesis Example 2 is used in place of 100 parts of the double-end-modified cyclopentene ring-opened polymer (a1) obtained in Synthesis Example 1 In the same manner as Example 2, a test piece (G) for adhesive strength evaluation was obtained and evaluated in the same manner. The results are shown in Table 1.

Example 8
In place of 100 parts of the both-end modified cyclopentene ring-opened polymer (a1) obtained in Synthesis Example 1, except that 100 parts of the both-end modified cyclopentene ring-opened polymer (a3) obtained in Synthesis Example 3 was used, In the same manner as Example 2, a test piece (H) for adhesive strength evaluation was obtained and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 1
The adhesive strength was the same as in Example 1, except that only 100 parts of the both-end modified cyclopentene ring-opened polymer (a1) obtained in Synthesis Example 1 was dissolved in 567 parts of toluene (without tackifier). Evaluation test pieces (I) were obtained and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 2
Comparative Example 1 except that 100 parts of the unmodified cyclopentene ring-opened polymer (a2) obtained in Synthesis Example 2 were used in place of 100 parts of the both-end modified cyclopentene ring-opened polymer (a1) obtained in Synthesis Example 1 In the same manner as Example 1, a test piece (J) for adhesive strength evaluation was obtained and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 3
In place of 100 parts of the both-end modified cyclopentene ring-opened polymer (a1) obtained in Synthesis Example 1, except that 100 parts of the both-end modified cyclopentene ring-opened polymer (a3) obtained in Synthesis Example 3 was used, In the same manner as in Comparative Example 1, a test piece (K) for adhesive strength evaluation was obtained and evaluated in the same manner. The results are shown in Table 1.

  As shown in Table 1, the test piece for evaluation of adhesive strength obtained by adding tackifier to the cyclopentene ring-opened polymer showed adhesive strength and was excellent as a tacky adhesive material (Examples 1 to 4). 8).

  In addition, test pieces for evaluation of adhesive strength using aliphatic aromatic copolymer (C5 / C9 system) or hydrogenated alicyclic petroleum resin as tackifier show good adhesive strength, and a tacky adhesive material Especially excellent as (Examples 2-5, 7, 8).

  On the other hand, the test piece for adhesive force evaluation which did not add the tackifier did not show adhesive force, and was inferior as an adhesive material (comparative examples 1-3).

  From these results, it was found that the pressure-sensitive adhesive composition containing the cyclopentene ring-opened polymer and the tackifier is excellent in adhesive properties.

  Although the present invention has been described above with reference to the embodiments and examples, the present invention is not limited to the specific embodiments and examples, and various modifications may be made within the scope of the invention described in the claims. Variations and modifications are possible.

Claims (3)

  An adhesive composition comprising a cyclopentene ring-opened polymer and a tackifier.   The adhesion according to claim 1, wherein the tackifier is selected from aliphatic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, hydrogenated petroleum resins, and alicyclic petroleum resins. Agent composition.   The pressure-sensitive adhesive composition according to claim 1 or 2, wherein the content of the tackifier is 10 to 500 parts by weight with respect to 100 parts by weight of the cyclopentene ring-opened polymer.