Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
  • C08F232/02—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
  • C08F232/04—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F236/20—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/04—Non-macromolecular additives inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J165/00—Adhesives based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Adhesives based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

• the present invention relates to a polymer having an alicyclic structure, a method for producing the same, and a composition containing the same.
• Polymers having an alicyclic structure in the main chain are generally known as materials exhibiting the properties of high glass transition temperature (Tg), high optical transparency, low shrinkage, low hygroscopicity and low birefringence. It is widely used in optical lenses, optical films, and the like.
• Patent Document 1 discloses a retardation film containing a cyclic olefin copolymer having a structural unit derived from ethylene and a structural unit derived from a norbornene compound and having a Tg in the range of 110°C to 175°C. ing.
• a cyclic olefin copolymer as described in Patent Document 1 is produced by ring-opening polymerization of a norbornene-based compound followed by hydrogenation.
• Patent Documents 2 and 3 disclose polymers having such alicyclic structures.
• the present invention provides a novel polymer having an alicyclic structure that can be used as an adhesive, a method for producing the same, and a composition containing the same.
• ⁇ Aspect 9>> A method for producing a polymer having an alicyclic structure according to aspect 5 or 6, comprising copolymerizing a monomer having a cycloalkene structure, a linear or branched ⁇ -olefin, and a diene.
• ⁇ Aspect 10>> A method for producing a polymer having an alicyclic structure according to any one of aspects 7 to 9, wherein a transition metal complex-based catalyst and an organoaluminumoxy compound-based co-catalyst are used.
• ⁇ Aspect 11>> A method for producing a polymer having an alicyclic structure according to aspect 10, wherein a phenolic compound is used as a cocatalyst modifier.
• ⁇ Aspect 12>> A pressure-sensitive adhesive composition comprising at least the polymer having an alicyclic structure according to any one of aspects 1 to 6, a cross-linking agent, and a cross-linking accelerator.
• ⁇ Aspect 14>> A pressure-sensitive adhesive sheet comprising a film substrate and a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive composition according to aspect 12 or 13.
• the polymer having an alicyclic structure of the present disclosure has a heat of crystal fusion of 30.0 J/g or less and a glass transition temperature of 20° C. or less. That is, the polymer having this alicyclic structure has a very low glass transition temperature and low crystallinity as compared with polymers having other alicyclic structures.
• Conventional polymers having an alicyclic structure often have a glass transition temperature of 100° C. or higher, and the polymer having an alicyclic structure of the present embodiment has such a conventional alicyclic structure. It has a significantly lower glass transition temperature than polymers with A polymer having an alicyclic structure with a relatively low glass transition temperature has also been reported in the prior art, but the polymer having such an alicyclic structure has crystallinity.
• Polymers having an alicyclic structure have not been used as adhesives in the past. was found to be useful as an adhesive. In addition, it was found that in a specific embodiment, it can be used as a reworkable pressure-sensitive adhesive that can be easily peeled off once adhered to an adherend. Further, it has been found that in certain embodiments this reworkability can be maintained even when the adhesive is exposed to elevated temperatures.
• the glass transition temperature of the polymer having an alicyclic structure is 20° C. or less, 10° C. or less, 0° C. or less, ⁇ 10° C. or less, ⁇ 15° C. or less, and ⁇ 20° C. when measured by the method described in Examples. ° C. or lower, or -25 ° C. or lower, -70 ° C. or higher, -50 ° C. or higher. It may be -40°C or higher, -30°C or higher, or -25°C or higher.
• the glass transition temperature of a polymer having an alicyclic structure is preferably lower when used as an adhesive, but should be in the range of -70°C to 20°C, or -40°C to 0°C. can be done. By setting the glass transition temperature of the polymer within the above range, suitable adhesion to various adherends can be exhibited.
• the heat of crystal fusion of the polymer having an alicyclic structure is 30.0 J/g or less, 20.0 J/g or less, 15.0 J/g or less, 10.0 J when measured by the method described in Examples. /g or less, 5.0 J/g or less, 3.0 J/g or less, or 1.0 J/g or less, or 0.1 J/g or more.
• the heat of crystal fusion of a polymer having an alicyclic structure is preferably lower when used as an adhesive, but is 0.1 J/g to 30.0 J/g, or 0.1 J/g to 20 It can be in the range of .0 J/g or less.
• the iodine value of the polymer having an alicyclic structure when measured by the method described in Examples, is 50 g/100 g or less, 40 g/100 g or less, 30 g/100 g or less, 20 g/100 g or less, 15 g/100 g or less, Or it may be 10 g / 100 g or less, 0.0 g / 100 g or more, 0.5 g / 100 g or more, 1.0 g / 100 g or more, 3.0 g / 100 g or more, or 5.0 g / 100 g or more good.
• the iodine value of the polymer having an alicyclic structure may be 0.0 g/100 g or more and 50 g/100 g or less, or 3.0 g/100 g or more and 20 g/100 g or less.
• the iodine value is a numerical value expressed by converting the amount of halogen that reacts with 100 g of a substance into grams of iodine, and is a measure of the amount of residual unsaturated bonds. It becomes a cross-linking point when used. When the iodine value is within the above range, appropriate cross-linking is formed when the polymer having a cyclic structure is used as an adhesive.
• a polymer having this alicyclic structure exhibits high heat resistance while having a very low glass transition temperature.
• the 5% weight loss temperature of a polymer having an alicyclic structure is described in Examples. may be 300°C or higher, 330°C or higher, 360°C or higher, 380°C or higher, 400°C or higher, 410°C or higher, or 420°C or higher, 500°C or lower, 450°C or lower, Or it may be 430° C. or lower.
• the higher the 5% weight loss temperature of the polymer having an alicyclic structure the better the heat resistance.
• the repeating unit of the polymer having an alicyclic structure is not particularly limited as long as it has an alicyclic structure in its main chain and has the physical properties as described above.
• the weight-average molecular weight of the polymer having an alicyclic structure when measured by the method described in Examples, may be 2000 or more, 3000 or more, 5000 or more, or 8000 or more, 30000 or less, 20000 or less, It may be 15000 or less, or 12000 or less.
• the weight average molecular weight of the polymer having an alicyclic structure may be, for example, 2000 or more and 30000 or less, or 5000 or more and 15000 or less. From the viewpoint of enhancing heat resistance and mechanical strength as a material, the weight average molecular weight of the polymer is preferably 2000 or more.
• the polymer having an alicyclic structure includes at least a first repeating unit having an alicyclic structure and a second repeating unit derived from a linear or branched ⁇ -olefin.
• the polymer having an alicyclic structure can further contain a third repeating unit having an alkenyl group- and/or alkenylene group-containing structure.
• the polymer having an alicyclic structure can further have other repeating units such as a fourth repeating unit and a fifth repeating unit, as long as the physical properties described above can be obtained.
• the other repeating units are preferably hydrocarbon-based repeating units, but may contain heteroatoms such as oxygen atoms, nitrogen atoms, etc., to the extent that they are useful in adhesives.
• the method for introducing the first repeating unit having an alicyclic structure is not particularly limited, for example, two methods can be mentioned.
• a first method for example, a method of cyclizing an ⁇ , ⁇ -diene can be mentioned.
• a second method is a method using a cycloalkene.
• a polymer having an alicyclic structure into which the first repeating unit is introduced can have the physical properties described above.
• Examples of the ⁇ , ⁇ -diene used in the first method include linear or branched ones having 5 to 12 or 5 to 8 carbon atoms, such as 1,5-hexadiene, 1,6 -heptadiene, 1,7-octadiene, 2-methyl-1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene and the like.
• Cycloalkenes used in the second method include 5- to 8-membered cycloalkenes, specifically cyclopentene, cyclohexene, cycloheptene, and the like.
• the 5- to 8-membered cycloalkene may have a substituent in its alicyclic structure as long as the physical properties described above can be obtained. Examples of the substituent include a methyl group and an ethyl group. can be mentioned.
• a polycyclic cycloalkene when a polycyclic cycloalkene is used, the resulting polymer tends to have a high glass transition temperature due to its rigidity. Therefore, it is preferable to use a monocyclic cycloalkene.
• the first repeating unit can contain an alicyclic structure and a hydrocarbon group, but can also contain heteroatoms such as oxygen atoms, nitrogen atoms, etc., to the extent that they are useful in adhesives.
• the first repeat unit can have a structure such as, for example:
• the repeating unit of formula (A-1) can be derived, for example, from 1,5-hexadiene, and the repeating unit of formula (A-2) can be derived, for example, from 1,7-octadiene.
• the repeating unit of formula (A-3) can be derived, for example, from cyclopentene, and the repeating unit of formula (A-4) can be derived, for example, from cyclohexene.
• the polymer having an alicyclic structure may contain 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, or 80 mol% or more of the first repeating unit, and 95 mol% or less, It may be contained at 90 mol% or less, 85 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, or 50 mol% or less.
• the polymer having an alicyclic structure may contain the first repeating unit at 30 mol% or more and 95 mol% or less, or 60 mol% or more and 90 mol% or less. This content ratio is determined by NMR as described in Examples. By setting the first repeating unit within the above range, the polymer has excellent heat resistance.
• a second repeating unit derived from a linear or branched ⁇ -olefin provides a low glass transition temperature to the polymer having an alicyclic structure.
• the ⁇ -olefin into which the second repeating unit is introduced includes, for example, an ⁇ -olefin having 4 to 18 carbon atoms, from the viewpoint that the heat of crystal fusion of the resulting polymer can be lowered.
• Alpha-olefins having 4 to 12 carbon atoms, 5 to 10 carbon atoms or 6 to 8 carbon atoms may be mentioned.
• ⁇ -olefin to introduce the second repeating unit propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1- Dodecene and the like can be mentioned.
• a polymer having an alicyclic structure obtained by copolymerizing such an ⁇ -olefin with a monomer from which the first repeating unit is derived has very low crystallinity.
• the second repeat units Formulas (B-1) and (B-2) below are derived from 1-hexene and 1-octene, respectively, but such comparison It is believed that the relatively long side chain alkyl group reduces the crystallinity of the polymer having an alicyclic structure.
• the ⁇ -olefin may have a low carbon number.
• the second repeating unit can also contain a hydrocarbon group, but can also contain heteroatoms such as oxygen atoms, nitrogen atoms, etc., to the extent that they are useful in adhesives.
• the polymer having an alicyclic structure may contain 3 mol% or more, 5 mol% or more, 8 mol% or more, 10 mol% or more, 15 mol% or more, 30 mol% or more, or 50 mol% or more of the second repeating unit, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 15 mol% or less.
• the polymer having an alicyclic structure may contain the second repeating unit at 3 mol % or more and 70 mol % or less, or 10 mol % or more and 40 mol % or less. This content ratio is determined by NMR as described in Examples. By setting the second repeating unit within the above range, the desired glass transition temperature and heat of crystal fusion can be imparted to the polymer.
• the third repeating unit having an alkenyl group and/or alkenylene group-containing structure is an optional repeating unit, and this repeating unit is an unsaturated bond (especially a carbon-carbon triple bond (unsaturated bonds excluding
• the third repeating unit can contain unsaturated bonds and hydrocarbon groups, but can also contain heteroatoms such as oxygen atoms, nitrogen atoms, etc., to the extent that they are useful in adhesives.
• a polymer having an alicyclic structure has an unsaturated bond, it acts as a cross-linking point when used as an adhesive, for example.
• the third repeating unit can be introduced into the polymer having an alicyclic structure by the ⁇ , ⁇ -diene that did not undergo the cyclization reaction. Therefore, in the case of the first method, monomers for introducing the third repeating unit include the above ⁇ , ⁇ -dienes that can be used to introduce the first repeating unit. However, even in the case of the first method, a third repeating unit can be further introduced by using the following diene. The following diene is preferably different from the above ⁇ , ⁇ -diene.
• the third repeating unit can be introduced by copolymerizing a diene, for example, in the case of the second method in which the first repeating unit is introduced from a cycloalkene.
• dienes include linear or branched conjugated dienes, non-conjugated dienes, and polyenes having 3 to 20 carbon atoms, 3 to 12 carbon atoms, or 4 to 8 carbon atoms.
• the polymer having an alicyclic structure has a third repeating unit of 0 mol% or more, 0.1 mol% or more, 0.5 mol% or more, 1.0 mol% or more, 1.5 mol% or more, 3.0 mol% or more, Or it may contain 5.0 mol% or more, 15 mol% or less, 10 mol% or less, 8.0 mol% or less, 5.0 mol% or less, 3.0 mol% or less, 2.0 mol% or less, or 1.5 mol% or less may be included in
• the polymer having an alicyclic structure may contain 0 mol % or more and 20 mol % or less, or 0.5 mol % or more and 10 mol % or less of the third repeating unit. This content ratio is determined by NMR as described in Examples.
• the polymer having an alicyclic structure obtained by the production method of the present disclosure may be the polymer having an alicyclic structure described above, and the polymer having an alicyclic structure obtained by the production method of the present disclosure With respect to the structure of , the above structure described with respect to the polymer having an alicyclic structure of the present disclosure can be referred to.
• a method for producing a polymer having an alicyclic structure comprises copolymerizing a monomer that introduces the first repeating unit as described above and a monomer that introduces the second repeating unit.
• a polymer having an alicyclic structure obtained by such a production method can have a lower glass transition temperature and crystallinity than other polymers having an alicyclic structure.
• the first method uses a cyclization reaction of an ⁇ , ⁇ -diene and the second method uses a cycloalkane. At least a method exists.
• the polymer having an alicyclic structure to be produced contains the third repeating unit
• the third repeating unit in order to introduce the third repeating unit into the polymer, among the ⁇ , ⁇ -diene,
• the diene is further copolymerized to introduce the third repeating unit. There are two methods.
• the amount of the monomer used for introducing the first repeating unit is 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, or It may be 80% by mass or more, 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less. .
• the amount of the monomer used for introducing the first repeating unit may be 30% by mass or more and 95% by mass or less, or 60% by mass or more and 90% by mass or less, based on 100% by mass of all the monomers.
• the amount of the monomer used for introducing the second repeating unit is 3% by mass or more, 5% by mass or more, 8% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, based on 100% by mass of the total monomers.
• % by mass or more or may be 30% by mass or more, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, or 15% by mass or less may be
• the amount of the monomer used for introducing the second repeating unit may be 3% by mass or more and 70% by mass or less, or 10% by mass or more and 40% by mass or less, based on 100% by mass of all the monomers.
• the amount of the monomer used for introducing the third repeating unit is 0% by mass or more, 0.1% by mass or more, 0.5% by mass or more, 1.0% by mass or more, based on 100% by mass of the total monomers. 1.5% by mass or more, 3.0% by mass or more, or 5.0% by mass or more, and 15% by mass or less, 10% by mass or less, 8.0% by mass or less, and 5.0% by mass or less , 3.0% by mass or less, 2.0% by mass or less, or 1.5% by mass or less.
• the amount of the monomer used for introducing the third repeating unit may be 0% by mass or more and 15% by mass or less, or 0% by mass or more and 5.0% by mass, out of 100% by mass of the total monomers. .
• the polymerization catalyst used in the production method of the present disclosure is not particularly limited as long as a polymer having an alicyclic structure as described above can be obtained. It can be used in combination with a compound co-catalyst. These catalysts can be used by being carried on a particulate carrier.
• transition metal complexes include transition metal compounds of Groups 4 to 6 of the periodic table that have the ability to polymerize olefins.
• transition metal compounds for example, transition metal halides, transition metal alkylates, transition metal alkoxylates, and non-crosslinkable or crosslinkable metallocene compounds of groups 4 to 6 of the periodic table can be used.
• the transition metal compounds of Groups 4 to 6 of the periodic table include transition metal compounds of Group 4 of the periodic table.
• Specific examples of the transition metal compounds of Group 4 of the periodic table include titanium tetrachloride, dimethyl titanium dichloride, Tetrabenzyltitanium, tetrabenzylzirconium, tetrabutoxytitanium can be mentioned.
• non-crosslinkable or crosslinkable metallocene compounds include transition metal compounds of Group 4 of the periodic table containing two ligands having a cyclopentadienyl skeleton (especially titanium, zirconium, and hafnium). can be done.
• ligands having a cyclopentadienyl skeleton include a cyclopentadienyl group; a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, and a tetramethylcyclopentadienyl group.
• pentamethylcyclopentadienyl group pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclopenta dienyl group, alkyl-substituted cyclopentadienyl group such as hexylcyclopentadienyl group; indenyl group; 4,5,6,7-tetrahydroindenyl group; and fluorenyl group.
• These groups may have substituents such as halogen atoms and trialkylsilyl groups.
• the amount of the transition metal compound used is not particularly limited as long as a polymer having an appropriate molecular weight can be obtained. It may be 1.00 parts by mass or less, 0.50 parts by mass or less, 0.10 parts by mass or less, or 0.05 parts by mass or less. .
• the transition metal compound may be used in an amount of 0.001 parts by mass or more and 1.00 parts by mass or less, or 0.01 parts by mass or more and 0.10 parts by mass or less with respect to 100 parts by mass of the monomer.
• the organic aluminum oxy compound is a compound containing an Al--O--Al bond and an organic group in the molecule, and is known as a co-catalyst used in the polymerization of olefins.
• the number of Al—O—Al bonds in the organoaluminumoxy compound can range from 1 to 100, or from 1 to 50.
• Examples of organic groups include hydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups, and aralkyl groups.
• organoaluminum oxy compounds having an alkyl group are also called aluminoxanes, particularly methylaluminoxane (MAO) or modified methylaluminoxane (modified MAO) in which part of the structure of MAO is modified with trialkylaluminum such as triisobutylaluminum. is particularly suitable as the organoaluminum oxy compound.
• the amount of the organoaluminumoxy compound to be used is not particularly limited as long as a polymer having an appropriate molecular weight can be obtained. 01 parts by mass or more, or 0.02 parts by mass or more, 10.0 parts by mass or less, 5.0 parts by mass or less, 1.0 parts by mass or less, or 0.5 parts by mass or less good.
• the amount of the organoaluminumoxy compound used may be 0.001 parts by mass or more and 10.0 parts by mass or less, or 0.01 parts by mass or more and 1.0 parts by mass or less with respect to 100 parts by mass of the monomer. .
• solvent> The production method of the present disclosure can be carried out by solution polymerization, and a hydrocarbon-based solvent can be used as a solvent therefor.
• the amount of solvent to be used is not particularly limited as long as the reaction can proceed without problems, and those skilled in the art can appropriately set the amount of solvent to be used.
• hydrocarbon media include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane.
• aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.
• aromatic hydrocarbons such as toluene can be mentioned.
• a cocatalyst modifier is used during the polymerization reaction to prevent excessive chain transfer reaction during the polymerization reaction and further improve the activity of the cocatalyst, thereby increasing the polymer to a high molecular weight. I found out that I can make it. As a result, it was possible to obtain a polymer having an alicyclic structure with high heat resistance while maintaining a low glass transition temperature.
• promoter modifiers include phenol compounds, silanol compounds, and water.
• Phenolic compounds include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, pentafluorophenol, 2,2′-methylenebis(6-tert-butyl-4-ethylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 4, 4′-butylidenebis(6-tert-butyl-m-cresol), 2,4,6-tris(3′,5′-di-tert-butyl-4′-hydroxybenzyl)mesitylene and the like.
• silanol compounds include triethylsilanol, t-butyldimethylsilanol, triphen
• the amount of co-catalyst modifier used is not particularly limited as long as a polymer having an appropriate molecular weight can be obtained. 010 parts by mass or more, or 0.020 parts by mass or more, and 3.0 parts by mass or less, 2.0 parts by mass or less, 1.0 parts by mass or less, or 0.5 parts by mass or less good.
• the amount of co-catalyst modifier used may be 0.001 parts by mass or more and 3.0 parts by mass or less, or 0.010 parts by mass or more and 1.0 parts by mass or less with respect to 100 parts by mass of the monomer. .
• the temperature at which the polymerization is carried out is not particularly limited as long as a polymer having an appropriate molecular weight can be obtained. °C or lower, 80 °C or lower, 50 °C or lower, or 30 °C or lower.
• the temperature during polymerization may be -50°C or higher and 150°C or lower, or -30°C or higher and 30°C or lower.
• the atmosphere for polymerization may be under normal pressure, under reduced pressure, or under increased pressure. Polymerization may also be carried out in an inert atmosphere, such as under a nitrogen atmosphere.
• the time for the polymerization is sufficient as long as a polymer with an appropriate molecular weight is obtained, for example 10 to 1000 minutes, particularly 60 to 600 minutes.
• the production method of the present disclosure can further include a step of adding a polymerization inhibitor to terminate the above polymerization step.
• a polymerization inhibitor examples include alcohols such as methanol.
• the production method of the present disclosure can include a washing step of washing the polymer obtained as described above with an acid or base to remove the polymerization catalyst and co-catalyst.
• the production method of the present disclosure can include a drying step for removing the solvent used in the polymerization step.
• the pressure-sensitive adhesive composition of the present disclosure contains a polymer having an alicyclic structure as described above or a polymer having an alicyclic structure obtainable by the production method described above.
• the pressure-sensitive adhesive composition containing a polymer having an alicyclic structure can further contain a cross-linking agent, and can further contain a cross-linking accelerator.
• the adhesive physical properties of the adhesive sheet obtained from the adhesive composition can be adjusted by crosslinking the polymer having an alicyclic structure with a crosslinking agent or the like.
• the cross-linking agent is not particularly limited as long as it can cross-link the unsaturated bonds of the polymer having an alicyclic structure.
• Cross-linking agents metal chelate cross-linking agents, siloxane cross-linking agents, hydroxyl cross-linking agents, thiol cross-linking agents, amine cross-linking agents, sulfur cross-linking agents, nitrile-N-oxide cross-linking agents and the like can be mentioned.
• hydrosilane compounds which are siloxane-based cross-linking agents, can be mentioned in particular, and polyorganohydrogensiloxanes containing two or more hydrosilanes (SiH) in one molecule are preferred.
• the cross-linking agent may be contained in an amount of 0.5 parts by mass or more and 10 parts by mass or less or 1.0 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the polymer having an alicyclic structure. good.
• the cross-linking accelerator is not particularly limited as long as it can promote the cross-linking reaction. Accelerators, amine catalysts, dithiocarbamate cross-linking accelerators, radical initiator compounds, Lewis acid compounds and the like can be mentioned. When a siloxane-based cross-linking agent is used as the cross-linking agent, it is preferable to use a platinum-based compound as the cross-linking accelerator.
• the cross-linking accelerator is contained in the adhesive composition in an amount of 0.001 parts by mass or more, 0.005 parts by mass or more, or 0.01 parts by mass or more with respect to 100 parts by mass of the polymer having an alicyclic structure. 1.00 parts by mass or less, 0.50 parts by mass or less, 0.10 parts by mass or less, or 0.05 parts by mass or less.
• the crosslinking accelerator is contained in an amount of 0.001 to 1.00 parts by mass or 0.005 to 0.05 parts by mass with respect to 100 parts by mass of the polymer having an alicyclic structure. may be
• the pressure-sensitive adhesive composition may contain an acetylene derivative from the viewpoint of extending the pot life of the pressure-sensitive adhesive composition.
• the acetylene derivative preferably has no heteroatoms and halogens, for example, 2-butyne (27° C.), 1-pentyne (40° C.), 2-pentyne (56° C.), 4-methyl-1-pentyne. (61° C.), 3,3-dimethyl-1-butyne (38° C.), 2-hexyne (84° C.), 3-hexyne (82° C.), diphenylacetylene (300° C.).
• the inside of a parenthesis shows a boiling point.
• acetylene derivatives it is preferable to use a compound having a carbon-carbon triple bond in the molecule from the viewpoint of cross-linking efficiency. In addition, it does not volatilize easily when blended in the pressure-sensitive adhesive composition, and has a boiling point of 70 from the viewpoint of reducing the acetylene derivative remaining in the pressure-sensitive adhesive sheet by quickly volatilizing it in the drying process during the preparation of the pressure-sensitive adhesive sheet.
• acetylene derivatives that are ⁇ 120°C is preferred.
• the acetylene derivative may be contained in an amount of 10 parts by mass or more, 100 parts by mass or more, 500 parts by mass or more, or 1000 parts by mass or more with respect to 100 parts by mass of the cross-linking accelerator.
• the content may be 5000 parts by mass or less, 3000 parts by mass or less, or 1000 parts by mass or less.
• the acetylene derivative may be contained in an amount of 10 parts by mass or more and 10000 parts by mass or less, or 100 parts by mass or more and 5000 parts by mass or less with respect to 100 parts by mass of the cross-linking accelerator.
• the gel fraction of the adhesive layer obtained from the adhesive composition may be 50% or more, 60% or more, 65% or more, 70% or more, 75% or more, or 80% or more, 98% or less, It may be 95% or less, 93% or less, 90% or less, or 85% or less.
• the gel fraction of the adhesive layer obtained from the adhesive composition may be 50% or more and 98% or less, or 70% or more and 95% or less.
• the gel fraction can be measured by the method described in Examples.
• the pressure-sensitive adhesive composition contains a silane coupling agent, an antistatic agent, an ultraviolet absorber, an antioxidant, a tackifying resin, a plasticizer, an antifoaming agent, a filler, as long as the effects of the present invention are not impaired.
• Ingredients selected from agents, stabilizers, softeners, and wettability modifiers may be included.
• the pressure-sensitive adhesive sheet of the present disclosure has a pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition as described above.
• the pressure-sensitive adhesive sheet include a pressure-sensitive adhesive sheet formed only from a pressure-sensitive adhesive layer, a double-sided pressure-sensitive adhesive sheet having a substrate and pressure-sensitive adhesive layers formed on both sides of the substrate, and a substrate and a pressure-sensitive adhesive layer on one side of the substrate.
• a pressure-sensitive adhesive sheet having a formed pressure-sensitive adhesive layer is mentioned.
• the base material those that can be normally used as a base material for adhesive sheets can be used.
• substrates include polyolefins, polyvinyl chloride, polyvinylidene chloride, polychlorotrifluoroethylene, polytetrafluoroethylene, saturated or unsaturated polyesters, polyamides, polyimides, polyacrylonitrile, polymethyl methacrylate, polycarbonates, Polyphenylene sulfide, polyetheretherketone, polyethylene naphthalate, nonwovens, wovens, paper, metals, glasses, ceramics, foams, and laminates of two or more of these may be mentioned.
• the thickness of the substrate varies depending on the application and the like, and is not particularly limited, but is 5 ⁇ m or more and 200 ⁇ m or less.
• the substrate may be a release-treated substrate.
• the pressure-sensitive adhesive sheet has substrates arranged on both sides of the pressure-sensitive adhesive layer, at least one of the substrates is a release-treated substrate, and the release-treated substrate is applied when adhering to the adherend.
• the substrate is removed.
• the thickness of the adhesive layer may be 5 ⁇ m or more and 200 ⁇ m or less, or 10 ⁇ m or more and 100 ⁇ m or less.
• the method for producing the adhesive sheet is not particularly limited, but for example, a method of forming an adhesive layer by applying an adhesive composition onto a substrate and drying it can be mentioned.
• the coating method of the adhesive composition include various coating methods such as roll coating, gravure coating, reverse coating, spray coating, dip roll coating, bar coating, knife coating, lip coating and die coating.
• the adhesive composition contains a solvent
• it is dried at 50 to 150°C for 1 to 30 minutes to remove the solvent and form an adhesive layer.
• another base material is attached to the surface of the pressure-sensitive adhesive layer on which the base material is not provided. After that, if necessary, a curing period may be provided.
• Example 1 Polymer having an alicyclic structure>> ⁇ Example 1: First method> A 500 mL flask equipped with a magnetic stir bar was purged with nitrogen. The flask was charged with a cocatalyst modified methylaluminoxane toluene solution (MMAO-3A: manufactured by Tosoh Finechem, 80 mmol in terms of Al), and a cocatalyst modifier 2,6-di-tert-butyl-p-cresol ( 1.5 mmol) was added and stirred at room temperature for 30 minutes.
• MMAO-3A cocatalyst modified methylaluminoxane toluene solution
• 2,6-di-tert-butyl-p-cresol 1.5 mmol
• 1,5-hexadiene (425 mmol) was added as a monomer for introducing the first repeating unit and 1-hexene (75 mmol) as a monomer for introducing the second repeating unit. After the flask was cooled and the reaction system reached 0° C., it was stirred for an additional 30 minutes.
• a mixed solution of zirconocene dichloride (0.1 mmol) and toluene (74.2 mL) was added to the flask to initiate the reaction.
• the reaction temperature was maintained at 0° C. and the reaction was carried out for 9 hours, after which the reaction was stopped by adding methanol (5 mL) as a polymerization inhibitor to the flask.
• the reactant was added dropwise to a mixed solution of methanol (1 L) and 1M hydrochloric acid (50 mL) to obtain a precipitate of a polymer having an alicyclic structure from which metal components were removed. This was collected and the collected polymer precipitate was dried at 100° C. for 5 hours to obtain the polymer of Example 1.
• Example 2 A polymer of Example 2 was obtained in the same manner as in Example 1 except that 1,7-octadiene was used instead of 1,5-hexadiene.
• Example 3 Second method> A 500 mL flask equipped with a magnetic stir bar was purged with nitrogen. To the flask, a cocatalyst modified methylaluminoxane toluene solution (80 mmol in terms of Al) and a cocatalyst modifier 2,6-di-tert-butyl-p-cresol (1.5 mmol) were added. for 30 minutes.
• a cocatalyst modified methylaluminoxane toluene solution 80 mmol in terms of Al
• a cocatalyst modifier 2,6-di-tert-butyl-p-cresol 1.5 mmol
• Example 4 A polymer of Example 4 was obtained in the same manner as in Example 3, except that cyclohexene was used instead of cyclopentene.
• Example 5 A polymer of Example 5 was obtained in the same manner as in Example 1, except that 1-octene was used instead of 1-hexene.
• Example 6 A polymer of Example 6 was obtained in the same manner as in Example 1 except that 200 mmol of 1,5-hexadiene and 300 mmol of 1-hexene were used.
• Example 7 A polymer of Example 7 was obtained in the same manner as in Example 1 except that 450 mmol of 1,5-hexadiene, 50 mmol of 1-hexene, and 0.5 mmol of zirconocene dichloride were used.
• Example 8 A polymer of Example 8 was obtained in the same manner as in Example 3 except that 300 mmol of cyclopentene and 200 mmol of 1-hexene were used.
• Example 9 A polymer of Example 9 was obtained in the same manner as in Example 3 except that 275 mmol of cyclopentene, 175 mmol of 1-hexene and 50 mmol of 1,3-butadiene were used.
• Example 10 A polymer of Example 10 was obtained in the same manner as in Example 1 except that 50 mmol of 1,5-hexadiene and 450 mmol of 1-hexene were used.
• Example 11 A polymer of Example 11 was obtained in the same manner as in Example 1 except that 490 mmol of 1,5-hexadiene and 10 mmol of 1-hexene were used.
• Comparative Example 1 A polymer of Comparative Example 1 was obtained in the same manner as in Example 1, except that 500 mmol of 1,5-hexadiene was used and 1-hexene was not used.
• ⁇ Comparative Example 2> A 500 mL flask equipped with a magnetic stir bar was purged with nitrogen. The flask was charged with a cocatalyst modified methylaluminoxane toluene solution (MMAO-3A: manufactured by Tosoh Finechem, 80 mmol in terms of Al), and a cocatalyst modifier 2,6-di-tert-butyl-p-cresol ( 1.5 mmol) was added and stirred at room temperature for 30 minutes.
• MMAO-3A cocatalyst modified methylaluminoxane toluene solution
• 2,6-di-tert-butyl-p-cresol 1.5 mmol
• 1,5-hexadiene 500 mmol
• a mixed gas of propylene and nitrogen propylene concentration 1.5 vol
• Comparative Example 3 A polymer of Comparative Example 3 was obtained in the same manner as in Example 3 except that 145 mmol of 2-norbornene, 345 mmol of 1-hexene and 10 mmol of 1,3-butadiene were used.
• Adhesive sheet>> Each polymer obtained as described above was dissolved in toluene to prepare a polymer solution. Then, with respect to 100 parts by mass of the solid content of the polymer in the solution, a hydrosilane compound (KF-9901: manufactured by Shin-Etsu Chemical Co., Ltd.) as a cross-linking agent in an amount such that the solid content is 3 parts by mass, and 0.5 part as a cross-linking accelerator. 01 parts by mass of a platinum-based compound (CAT-PL-50T: manufactured by Shin-Etsu Chemical Co., Ltd.) was blended and thoroughly mixed to obtain a pressure-sensitive adhesive composition containing a polymer.
• a hydrosilane compound KF-9901: manufactured by Shin-Etsu Chemical Co., Ltd.
• CAT-PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.
• a release-treated polyethylene terephthalate (PET) film was attached to the surface of the adhesive layer opposite to the surface in contact with the polyimide film to obtain an adhesive sheet.
• Tg ⁇ Glass transition temperature
• DSC differential scanning calorimeter
• the iodine value of the polymer was measured according to JIS K 6235:2006.
• the iodine value is a value expressed by converting the amount of halogen that reacts with 100 g of the target substance into grams of iodine, and the unit is "g/100 g".
• the 5% weight loss temperature refers to the temperature at which the weight of the set sample is reduced by 5%.
• the 5% weight loss temperature of the polymer was determined by thermogravimetry/differential thermal analysis (TG-DTA) under the following conditions: Measuring device: STA7220 (manufactured by Hitachi High-Tech Science) Atmosphere: Nitrogen 200ml/min Sample measurement container: Aluminum open cell
• the pressure-sensitive adhesive sheet thus obtained was cut into a size of 25 mm wide ⁇ 100 mm long to obtain a test piece.
• the peel-treated PET film of the obtained test piece was peeled off, and the exposed adhesive layer was adhered to a SUS plate and crimped by three reciprocations of a 2 kg roller, and then left for 20 minutes in a 23° C./50% RH environment. . After that, the edge of the test piece was pulled at a speed of 300 mm/min in the direction of 180° to the SUS plate surface, and the adhesive strength (N/25 mm) was measured.
• AUTOGRAPH AG-X manufactured by Shimadzu Corporation was used as an adhesive force measuring device.
• the pressure-sensitive adhesive sheet thus obtained was cut into a size of 25 mm wide ⁇ 100 mm long to obtain a test piece.
• the peel-treated PET film of the obtained test piece was peeled off, and the exposed adhesive layer was adhered to a SUS plate, pressed with a 2 kg roller back and forth three times, and then left in an environment of 180° C. for 30 minutes. After that, it was left in a 23° C./50% RH environment for 20 minutes, and the end of the test piece was pulled in a direction of 180° with respect to the SUS plate surface at a rate of 300 mm/min to measure the adhesive force.
• the adhesive sheets using the polymers of Examples 1 to 5 all had good reworkability at room temperature and reworkability after the heat resistance test, and were very useful.
• the polymer of Example 6 had relatively few first repeating units and was a relatively soft resin. As a result, the pressure-sensitive adhesive sheet lost reworkability after the heat resistance test.
• the polymer of Example 7 had a low molecular weight and resulted in a relatively soft resin. As a result, the pressure-sensitive adhesive sheet also lost reworkability after the heat resistance test.
• the polymer of Example 8 did not contain a third repeating unit, and as a result, the PSA sheet did not have reworkability, but could adhere relatively strongly to the adherend. did it.
• the polymer of Example 9 contained a relatively large amount of third repeating units and had a high gel fraction. As a result, the adhesive sheet had good reworkability at room temperature, but lost its adhesiveness after the heat resistance test.
• the polymer of Comparative Example 1 did not contain the second repeating unit, had high crystallinity, and had a high glass transition temperature. As a result, it could not be used as an adhesive sheet.

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