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
  • C08F236/04—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 conjugated
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/04—Reduction, e.g. hydrogenation
• • 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
  • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
• • 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
  • C09J11/08—Macromolecular 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
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; 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
  • C09J201/00—Adhesives based on unspecified macromolecular compounds

Definitions

• the present invention provides a hydrocarbon resin capable of giving a hot-melt pressure-sensitive adhesive composition excellent in holding power and low-temperature performance, a hydride obtained by hydrogenating this, and a hot-melt pressure-sensitive adhesive using these. It relates to an agent composition.
• Hydrocarbon resins obtained by copolymerizing aliphatic monomers such as monoolefinic unsaturated hydrocarbons and chain conjugated diolefins and, if necessary, with aliphatic monomers are known. Such hydrocarbon resins are used, for example, as tackifying resins for forming hot-melt adhesive compositions.
• the glass transition temperature (Tg) is -50 ° C. to 160 ° C.
• the number average molecular weight is 3000 or less
• the Z average molecular weight is 9000 or less
• gel permeation chromatography Hydrocarbon resins are disclosed having an oligomer content of 55% by weight or less as measured by GPC) and an oligomer content of 38% by weight or less as measured by high resolution thermogravimetric analysis (TGA).
• the hydrocarbon resin for example, when used as a tackifying resin for forming a hot-melt adhesive composition, in addition to having excellent holding power, has good properties even in a low-temperature environment. From the viewpoint of exhibiting, it is required that the low temperature performance is also excellent, and the technology disclosed in the above Patent Document 1 is not necessarily sufficient in these characteristics.
• the present invention has been made in view of such circumstances, and an object of the present invention is to provide a hydrocarbon resin capable of giving a hot-melt pressure-sensitive adhesive composition excellent in holding power and low-temperature performance. Another object of the present invention is to provide a hydrogenated product obtained by hydrogenating such a hydrocarbon resin, and a hot-melt pressure-sensitive adhesive composition using the same.
• the present inventors have made studies to achieve the above objects, and found that the number average molecular weight (Mn), the weight average molecular weight (Mw), the Z average molecular weight (Mz), the ratio of the weight average molecular weight to the number average molecular weight (Mw /Mn), the ratio of the Z-average molecular weight to the weight-average molecular weight (Mz/Mw), and the ratio of the peak top molecular weight (Mp) to the weight-average molecular weight (Mw) where the softening point is in a specific range (Mp/Mw ) is controlled in the range of 0.3 or more and less than 0.7.
• a hydrocarbon resin comprising an aliphatic monomer unit, or an aliphatic monomer unit and an aromatic monomer unit
• the number average molecular weight (Mn) is in the range of 400 to 3000
• the weight average molecular weight (Mw) is in the range of 700 to 6000
• Z-average molecular weight (Mz) is in the range of 1500 to 20000
• the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn) is in the range of 1.0 to 4.0
• the ratio of the Z-average molecular weight to the weight-average molecular weight (Mz/Mw) is in the range of 1.0 to 4.0
• the ratio (Mp/Mw) of the peak top molecular weight (Mp) to the weight average molecular weight (Mw) is in the range of 0.3 or more and less than 0.7
• a hydrocarbon resin is provided characterized by a softening point temperature in the range of 80-150°C.
• the hydrocarbon resin of the present invention contains 1,3-pentadiene monomer units of 1 to 70% by mass, 1 to 30% by mass of alicyclic monoolefin monomer units having 4 to 6 carbon atoms, 0 to 50% by mass of acyclic monoolefin monomer units having 4 to 8 carbon atoms, It preferably contains 0 to 10% by mass of alicyclic diolefin monomer units and 0 to 40% by mass of aromatic monoolefin monomer units.
• the hydrocarbon resin of the present invention preferably has an aliphatic monomer unit content of 50% by mass or more.
• the hydrocarbon resin of the present invention preferably has a peak top molecular weight (Mp) in the range of 500-4000.
• a hydride obtained by hydrogenating the above hydrocarbon resin is provided.
• a hot-melt pressure-sensitive adhesive composition containing the hydrocarbon resin and/or the hydride.
• the hot-melt pressure-sensitive adhesive composition of the present invention preferably further contains a thermoplastic elastomer.
• a hydrocarbon resin capable of giving a hot-melt pressure-sensitive adhesive composition excellent in holding power and low-temperature performance, a hydride obtained by hydrogenating such a hydrocarbon resin, and these It is possible to provide a hot melt adhesive composition using.
• the hydrocarbon resin of the present invention is a hydrocarbon resin comprising an aliphatic monomer unit, or an aliphatic monomer unit and an aromatic monomer unit,
• the number average molecular weight (Mn) is in the range of 400 to 3000
• the weight average molecular weight (Mw) is in the range of 700 to 6000
• Z-average molecular weight (Mz) is in the range of 1500 to 20000
• the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn) is in the range of 1.0 to 4.0
• the ratio of the Z-average molecular weight to the weight-average molecular weight (Mz/Mw) is in the range of 1.0 to 4.0
• the ratio (Mp/Mw) of the peak top molecular weight (Mp) to the weight average molecular weight (Mw) is in the range of 0.3 or more and less than 0.7, It has a softening point temperature in the range of 80 to 150°C.
• the hydrocarbon resin of the present invention contains at least aliphatic monomer units, and may contain aromatic monomer units in addition to aliphatic monomer units.
• Aliphatic monomers for forming the aliphatic monomer units may be those containing no aromatic ring and containing at least unsaturated hydrocarbons. Examples of such aliphatic monomers include , 1,3-pentadiene, alicyclic monoolefin monomers having 4 to 6 carbon atoms, acyclic monoolefin monomers having 4 to 8 carbon atoms, alicyclic diolefin monomers, etc. can. Further, in the present invention, a mixture containing these aliphatic monomers may be added to the polymerization reaction system when producing the hydrocarbon resin.
• the aliphatic monomer contained in the mixture is used as a monomer unit component constituting the hydrocarbon resin.
• the addition-polymerizable components other than the aliphatic monomer contained in the mixture may also be used as constituent components of the monomer units of the hydrocarbon resin, and the non-addition-polymerizable component may be used as a solvent during polymerization.
• a mixture containing such an aliphatic monomer for example, a C5 fraction containing 1,3-pentadiene, cyclopentene, isobutylene, etc. as an aliphatic monomer can be preferably used.
• the hydrocarbon resin preferably contains, as aliphatic monomer units, 1,3-pentadiene units and alicyclic monoolefin monomer units having 4 to 6 carbon atoms. It may further contain 8 acyclic monoolefin monomer units and 8 cycloaliphatic diolefin monomer units.
• the content of the 1,3-pentadiene monomer unit in the hydrocarbon resin is not particularly limited, but is preferably 1 to 70% by mass, more preferably 15 to 68% by mass, and still more preferably 30 to 66% by mass. % by weight, particularly preferably 42 to 64% by weight.
• the cis/trans isomer ratio in 1,3-pentadiene may be any ratio and is not particularly limited.
• An alicyclic monoolefin having 4 to 6 carbon atoms forming an alicyclic monoolefin monomer unit having 4 to 6 carbon atoms has one ethylenically unsaturated bond and a non-aromatic ring in its molecular structure. It is a hydrocarbon compound having 4 to 6 carbon atoms and having the structure Specific examples of alicyclic monoolefins having 4 to 6 carbon atoms include cyclobutene, cyclopentene, cyclohexene, methylcyclobutene, methylcyclopentene and the like.
• the content of the alicyclic monoolefin monomer unit having 4 to 6 carbon atoms in the hydrocarbon resin is not particularly limited, but is preferably 1 to 30% by mass, more preferably 5 to 28% by mass, More preferably 9 to 27% by mass, still more preferably 11 to 26% by mass, particularly preferably 13 to 21% by mass.
• the hot-melt pressure-sensitive adhesive composition has excellent holding power and low-temperature performance. be able to.
• the ratio of each compound corresponding to this may be any ratio and is not particularly limited, but it is preferable that at least cyclopentene is included, and 4 carbon atoms
• the ratio of cyclopentene in the alicyclic monoolefins of 1 to 6 is more preferably 50% by mass or more, still more preferably 80% by mass or more, and particularly preferably substantially 100% by mass.
• An acyclic monoolefin having 4 to 8 carbon atoms forming an acyclic monoolefin monomer unit having 4 to 8 carbon atoms has one ethylenically unsaturated bond in its molecular structure and has a ring structure. It is a chain hydrocarbon compound having 4 to 8 free carbon atoms.
• acyclic monoolefins having 4 to 8 carbon atoms include butenes such as 1-butene, 2-butene and isobutylene (2-methylpropene); 1-pentene, 2-pentene, 2-methyl-1 -pentenes such as butene, 3-methyl-1-butene and 2-methyl-2-butene; hexenes such as 1-hexene, 2-hexene and 2-methyl-1-pentene; 1-heptene and 2-heptene , 2-methyl-1-hexene and other heptenes; 1-octene, 2-octene, 2-methyl-1-heptene, diisobutylene (2,4,4-trimethyl-1-pentene and 2,4,4- octenes such as trimethyl-1-pentene);
• the content of the acyclic monoolefin monomer unit having 4 to 8 carbon atoms in the hydrocarbon resin is not particularly limited, but is preferably 0 to 50% by mass, more preferably 1 to 50% by mass, More preferably 10 to 45% by mass, particularly preferably 14 to 40% by mass, particularly preferably 15 to 37% by mass, most preferably 16 to 35% by mass.
• the hot-melt pressure-sensitive adhesive composition has excellent holding power and low-temperature performance. be able to.
• the ratio of each corresponding compound may be any ratio and is not particularly limited, but at least 2-methyl-2-butene , isobutylene, and diisobutylene, and 2-methyl-2-butene, isobutylene, and diisobutylene in the acyclic monoolefin having 4 to 8 carbon atoms. More preferably, the proportion of the total amount is 50% by mass or more.
• An alicyclic diolefin forming an alicyclic diolefin monomer unit is a hydrocarbon compound having two or more ethylenically unsaturated bonds and a non-aromatic ring structure in its molecular structure.
• Specific examples of alicyclic diolefins include cyclopentadiene polymers such as cyclopentadiene and dicyclopentadiene, methylcyclopentadiene polymers, and methylcyclopentadiene polymers.
• the content of the alicyclic diolefin monomer units in the hydrocarbon resin is not particularly limited, but is preferably 0 to 10% by mass, more preferably 0.03 to 5% by mass, and still more preferably 0. 0.05 to 4% by weight, particularly preferably 0.08 to 3% by weight.
• the hot-melt pressure-sensitive adhesive composition can be made more excellent in holding power and low-temperature performance.
• the hydrocarbon resin of the present invention includes 1,3-pentadiene monomer units, alicyclic monoolefin monomer units having 4 to 6 carbon atoms, aromatic monoolefin monomer units, and 4 to 4 carbon atoms. It may contain monomer units other than 8 acyclic monoolefin monomer units and alicyclic diolefin monomer units.
• Such other monomers forming such other monomer units are not particularly limited as long as they are addition-polymerizable compounds that can be addition-copolymerized with 1,3-pentadiene or the like.
• Such other monomers include, for example, 1,3-butadiene, 1,2-butadiene, isoprene, 1,3-hexadiene, 1,4-pentadiene, and other monomers having 4 carbon atoms other than 1,3-pentadiene.
• alicyclic monoolefins having 7 or more carbon atoms such as cycloheptene
• acyclic monoolefins having carbon atoms other than 4 to 8 such as ethylene, propylene and nonene;
• the content of other monomer units in the hydrocarbon resin is usually in the range of 0-30% by mass, preferably 0-25% by mass, more preferably 0-20% by mass.
• the content of the aliphatic monomer units in the hydrocarbon resin is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass. 80% by mass or more, particularly preferably 80% by mass or more.
• the hydrocarbon resin of the present invention may contain aromatic monomer units in addition to aliphatic monomer units.
• aromatic monomer for forming the aromatic monomer unit may have an aromatic ring and can be copolymerized with an aliphatic monomer. mers.
• a mixture containing aromatic monomers such as aromatic monoolefin monomers may be added to the polymerization reaction system during the production of the hydrocarbon resin.
• the aromatic monomer contained in the mixture is used as a component of the monomer units constituting the hydrocarbon resin.
• the addition-polymerizable components other than the aromatic monomer contained in the mixture may also be used as constituent components of the monomer units of the hydrocarbon resin, and the non-addition-polymerizable component may be used as a solvent during polymerization.
• a mixture containing such an aromatic monomer for example, a C9 fraction containing a styrene compound, an indene compound, etc. as the aromatic monomer can be preferably used.
• Aromatic monoolefin monomers are aromatic compounds that have one ethylenically unsaturated bond in their molecular structure.
• aromatic monoolefins include styrene compounds such as styrene, ⁇ -methylstyrene, ⁇ -methylstyrene and vinyltoluene; indene compounds such as indene and 1-methylindene; and coumarone.
• the content of aromatic monoolefin monomer units in the hydrocarbon resin is not particularly limited, but is preferably 0 to 40% by mass, more preferably 3 to 35% by mass, and still more preferably 8 to 25% by mass. %, particularly preferably 11 to 19% by weight.
• the number average molecular weight (Mn) of the hydrocarbon resin of the present invention is in the range of 400 to 3000, preferably in the range of 450 to 2500, more preferably in the range of 500 to 2000, still more preferably in the range of 700 to 1500.
• the weight average molecular weight (Mw) of the hydrocarbon resin of the present invention is in the range of 700 to 6000, preferably in the range of 900 to 5000, more preferably in the range of 1000 to 4000, still more preferably in the range of 1500 to 3300. is.
• the Z-average molecular weight (Mz) of the hydrocarbon resin of the present invention is in the range of 1500 to 20000, preferably in the range of 1800 to 15000, more preferably in the range of 2000 to 10000, still more preferably in the range of 3000 to 8300. is.
• the ratio of weight average molecular weight to number average molecular weight (Mw/Mn) of the hydrocarbon resin of the present invention is in the range of 1.0 to 4.0, preferably in the range of 1.1 to 3.5, more preferably It is in the range of 1.2 to 3.2, more preferably in the range of 1.5 to 3.0.
• the ratio of Z-average molecular weight to weight-average molecular weight (Mz/Mw) of the hydrocarbon resin of the present invention is in the range of 1.0 to 4.0, preferably in the range of 1.1 to 3.5. , more preferably in the range of 1.2 to 3.0, more preferably in the range of 1.4 to 2.8.
• Hydrocarbon resin number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), ratio of weight average molecular weight to number average molecular weight (Mw/Mn) and ratio of Z average molecular weight to weight average molecular weight (Mz/Mw) By setting Mz/Mw) within the above range, the compatibility with the base polymer can be enhanced when the hot-melt pressure-sensitive adhesive composition is formed, and as a result, excellent holding power can be obtained. can.
• Hydrocarbon resin number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), ratio of weight average molecular weight to number average molecular weight (Mw/Mn) and ratio of Z average molecular weight to weight average molecular weight ( Mz/Mw) can be obtained as a value converted to polystyrene by gel permeation chromatography using tetrahydrofuran as a developing solvent.
• the number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz) of the hydrocarbon resin the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn) and the weight average molecular weight
• the ratio (Mp/Mw) of the peak top molecular weight (Mp) to the weight average molecular weight (Mw) of the hydrocarbon resin is 0.3 or more , less than 0.7.
• the ratio (Mp/Mw) of the peak top molecular weight (Mp) to the weight average molecular weight (Mw) of the hydrocarbon resin is in the range of 0.3 or more and less than 0.7, so that the hot melt viscosity It can be excellent in holding power and low-temperature performance when made into an adhesive composition. If the ratio (Mp/Mw) of the peak top molecular weight (Mp) to the weight average molecular weight (Mw) is too low, the anti-blocking property is remarkably lowered. On the other hand, if the ratio (Mp/Mw) of the peak top molecular weight (Mp) to the weight average molecular weight (Mw) is too high, the low temperature performance will deteriorate.
• the ratio (Mp/Mw) of the peak top molecular weight (Mp) to the weight average molecular weight (Mw) may be in the range of 0.3 or more and less than 0.7, preferably in the range of 0.4 to 0.68. , more preferably in the range of 0.45 to 0.66, more preferably in the range of 0.5 to 0.64.
• the peak top molecular weight (Mp) of the hydrocarbon resin is not particularly limited, but is preferably in the range of 500 to 4000, more preferably in the range of 700 to 3000, still more preferably in the range of 800 to 2500, particularly preferably It is in the range of 900-2200.
• the ratio (Mp/Mw) of the peak top molecular weight (Mp) to the weight average molecular weight (Mw) is measured by gel permeation chromatography using tetrahydrofuran as a developing solvent. It is determined by determining the average molecular weight (Mw) and the peak top molecular weight (Mp) and calculating the ratio (Mp/Mw).
• the peak top molecular weight (Mp) is the molecular weight at which the detection value (elution amount) is the maximum in the GPC chart obtained by gel permeation chromatography measurement, and Mp/Mw is such a detection value (elution amount ) represents the relationship between the peak top molecular weight (Mp) which is the maximum molecular weight and the weight average molecular weight (Mw).
• Mp/Mw value tends to contain a relatively large amount of low-molecular-weight components
• a larger Mp/Mw value tends to contain a larger amount of high-molecular-weight components.
• the number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz) of the hydrocarbon resin the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn) and the weight average molecular weight
• the ratio of the Z-average molecular weight (Mz/Mw), the ratio (Mp/Mw) of the peak top molecular weight (Mp) to the weight average molecular weight (Mw) of the hydrocarbon resin depends on the type and amount of the monomer used for polymerization, and the polymerization It can be adjusted according to conditions.
• the ratio (Mp/Mw) of the peak top molecular weight (Mp) to the weight average molecular weight (Mw) of the hydrocarbon resin depends on the method of adjusting the type and amount of the monomer used for polymerization and the amount of polymerization catalyst used. , a method of adjusting the polymerization temperature, and a method of adjusting the mixing temperature and mixing time when the polymerization catalyst is previously mixed in the volatile solvent.
• the ratio (Mp/Mw) of the peak top molecular weight (Mp) to the weight average molecular weight (Mw) of the hydrocarbon resin tends to decrease as the amount of the polymerization catalyst used increases and the polymerization temperature increases. It is in.
• the softening point of the hydrocarbon resin of the present invention is in the range of 80 to 150°C, preferably in the range of 85 to 145°C, more preferably in the range of 90 to 140°C, more preferably in the range of 90 to 100°C. be.
• the softening point of hydrocarbon resin can be measured according to JIS K6863.
• the method for producing the hydrocarbon resin of the present invention is not particularly limited, but includes a method of addition polymerization of a monomer mixture for constituting the hydrocarbon resin.
• a method by addition polymerization using is preferably exemplified.
• the Friedel-Crafts-type cationic polymerization catalyst is not particularly limited, but may include halides such as aluminum, iron, tantalum, zirconium, tin, beryllium, boron, antimony, gallium, bismuth and molybdenum.
• aluminum halides such as aluminum chloride (AlCl 3 ) and aluminum bromide (AlBr 3 ) are suitable.
• the amount of the Friedel-Crafts-type cationic polymerization catalyst used is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, with respect to 100 parts by mass of the monomer mixture used for polymerization. It is preferably 0.5 to 2.0 parts by mass, particularly preferably 0.7 to 1.7 parts by mass.
• a halogenated hydrocarbon may be used in combination with the Friedel-Crafts-type cationic polymerization catalyst from the viewpoint that the catalytic activity can be further enhanced.
• halogenated hydrocarbons include halogenated hydrocarbons in which a halogen atom is bonded to a tertiary carbon atom such as t-butyl chloride, t-butyl bromide, 2-chloro-2-methylbutane, triphenylmethyl chloride; benzyl Carbon-carbon unsaturated bonds such as chloride, benzyl bromide, (1-chloroethyl)benzene, allyl chloride, 3-chloro-1-propyne, 3-chloro-1-butene, 3-chloro-1-butyne, cinnamon chloride, etc.
• halogenated hydrocarbon in which a halogen atom is bonded to the carbon atom adjacent to; Among these, t-butyl chloride and benzyl chloride are preferred from the viewpoint of excellent balance between catalytic activity and handleability.
• Halogenated hydrocarbons may be used singly or in combination of two or more.
• the amount of halogenated hydrocarbon used is preferably in the range of 0.05 to 50, more preferably in the range of 0.1 to 10, in terms of molar ratio to the Friedel-Crafts-type cationic polymerization catalyst.
• a volatile solvent to the polymerization reaction system and carry out the polymerization reaction.
• the type of volatile solvent is not particularly limited as long as it does not interfere with the polymerization reaction, but saturated aliphatic hydrocarbons or aromatic hydrocarbons are suitable.
• saturated aliphatic hydrocarbons examples include n-pentane, n-hexane, 2-methylpentane, 3-methylpentane, n-heptane, 2-methylhexane, 3-methylhexane, 3-ethylpentane, 2,2 - C5-C10 compounds such as dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 2,2,3-trimethylbutane and 2,2,4-trimethylpentane chain saturated aliphatic hydrocarbons; cyclic saturated aliphatic hydrocarbons having 5 to 10 carbon atoms such as cyclopentane, cyclohexane, cycloheptane and cyclooctane; Examples of aromatic hydrocarbons include aromatic hydrocarbons having 6 to 10 carbon atoms such as benzene, toluene and xylene.
• Volatile solvents may be used singly or in combination of two or more.
• the amount of the volatile solvent used is not particularly limited, but is preferably 10 to 1,000 parts by mass, more preferably 50 to 500 parts by mass, based on 100 parts by mass of the monomer mixture used for polymerization.
• the order of adding the respective components of the monomer mixture and the polymerization catalyst to the polymerization reactor is not particularly limited, and may be added in any order, from the viewpoint of good control of the polymerization reaction.
• the polymerization catalyst is added in advance to the volatile solvent and mixed to obtain the polymerization catalyst.
• a preferred method is to prepare the monomer mixture in a volatile solvent and then add the monomer mixture to the polymerization reactor to initiate the polymerization reaction.
• the temperature is preferably 45 to 80°C, more preferably 50 to 78°C, still more preferably 50 to 70°C, and the mixing time is preferably 10 seconds to 4 minutes, more preferably 30 seconds to 3 minutes. is.
• the mixing temperature is preferably substantially the same as the polymerization temperature (for example, the difference between the mixing temperature and the polymerization temperature is within 5°C, preferably within 2°C).
• the polymerization temperature during the polymerization reaction is not particularly limited, it is preferably 50 to 90°C, more preferably 55 to 85°C, and still more preferably 60 to 78°C.
• the polymerization reaction time may be appropriately selected, but it is usually 10 minutes to 12 hours, preferably 30 minutes to 6 hours.
• the polymerization reaction is stopped by adding a polymerization terminator such as methanol, an aqueous sodium hydroxide solution, or an aqueous ammonia solution to the polymerization reaction system when a desired polymerization conversion rate is obtained, thereby obtaining a polymer containing a hydrocarbon resin.
• a polymerization terminator such as methanol, an aqueous sodium hydroxide solution, or an aqueous ammonia solution
• a polymerization terminator may be added to remove the solvent-insoluble catalyst residue generated when the polymerization catalyst is deactivated by filtration or the like.
• the obtained hydrocarbon resin may be converted into a hydride by subjecting the obtained hydrocarbon resin to a hydrogenation reaction for hydrogenating carbon-carbon double bonds in the hydrocarbon resin, if necessary.
• Hydrogenation of the hydrocarbon resin can be carried out by contacting the hydrocarbon resin with hydrogen in the presence of a hydrogenation catalyst.
• the hydrogenation catalyst is not particularly limited, but a nickel catalyst is preferred.
• a catalyst containing, as a main component, a compound in which nickel as a metal is supported on an inorganic compound supported as a carrier is preferred.
• supported inorganic compounds as carriers include silica, alumina, boria, silica-alumina, diatomaceous earth, clay, clay, magnesia, magnesia-silica (silica-magnesium oxide), titania, zirconia and the like.
• magnesia-silica is preferable from the viewpoint of reactivity.
• the hot-melt pressure-sensitive adhesive composition of the present invention contains the above-described hydrocarbon resin of the present invention.
• a hydride obtained by hydrogenating the above-described hydrocarbon resin of the present invention may be contained.
• the hot-melt adhesive composition of the present invention can usually be obtained by blending a thermoplastic elastomer with the hydrocarbon resin and/or its hydride of the present invention.
• thermoplastic elastomer is not particularly limited, but any thermoplastic elastomer that is used as a base polymer for hot-melt pressure-sensitive adhesives can be used without limitation. At least one selected from ethylene-vinyl acetate copolymers, styrene thermoplastic elastomers, and polyolefin thermoplastic elastomers is preferred.
• the ethylene-vinyl acetate copolymer is not particularly limited, but the vinyl acetate monomer unit content is preferably in the range of 10 to 50% by mass, more preferably in the range of 15 to 40% by mass. Preferably, it is more preferably in the range of 15 to 35% by mass.
• the ethylene-vinyl acetate copolymer those having a melt flow rate of 1 to 500 g/10 min are preferably used.
• the ethylene-vinyl acetate copolymer is available as a commercial product. ” and the like can be suitably used.
• the styrene-based thermoplastic elastomer is not particularly limited, and copolymers such as random, block, and graft copolymers of styrene-based monomers and other monomers that can be copolymerized with styrene-based monomers, and such copolymers.
• Coalesced hydrogenates and the like include block copolymers comprising at least one aromatic vinyl polymer block and at least one conjugated diene polymer block.
• block copolymers include styrene-isoprene diblock copolymers, styrene-isoprene-styrene triblock copolymers, isoprene-styrene-isoprene triblock copolymers, styrene-isoprene-styrene- Isoprene tetrablock copolymers, and mixtures thereof can be suitably used.
• the polyolefin-based thermoplastic elastomer is not particularly limited, but includes, for example, an ethylene/ ⁇ -olefin copolymer.
• the ⁇ -olefin to be copolymerized with ethylene to obtain the ethylene/ ⁇ -olefin copolymer is not particularly limited.
• ⁇ -olefins having 3 to 20 carbon atoms such as -1-pentene and 1-octene are preferred, ⁇ -olefins having 6 to 8 carbon atoms are more preferred, and 1-octene is even more preferred.
• the ⁇ -olefins may be used singly or in combination of two or more.
• the content ratio of the ⁇ -olefin units in the ethylene/ ⁇ -olefin copolymer is not particularly limited, but the ratio of the ⁇ -olefin units to the total monomer units is preferably 20 to 40 mol%.
• the ethylene/ ⁇ -olefin copolymer those having a melt flow rate of 200 to 1500 g/10 min are preferably used.
• the blending ratio of the thermoplastic elastomer and the hydrocarbon resin and/or hydride thereof in the hot-melt adhesive composition of the present invention is not particularly limited, but is based on 100 parts by mass of the thermoplastic elastomer.
• the hydrocarbon resin and its hydride are preferably 50 to 500 parts by mass, more preferably 80 to 400 parts by mass.
• the hot-melt pressure-sensitive adhesive composition has particularly good holding power and low-temperature performance.
• the hot-melt pressure-sensitive adhesive composition of the present invention may consist solely of the hydrocarbon resin and/or hydrogenated product thereof of the present invention and a thermoplastic elastomer, but may further contain other components. There may be.
• Other components that can be contained in the hot-melt pressure-sensitive adhesive composition include waxes, softeners, antioxidants, tackifying resins other than the hydrocarbon resins and hydrides thereof of the present invention, and polymers other than those mentioned above. , heat stabilizers, UV absorbers, fillers, etc., can be added.
• the hot-melt pressure-sensitive adhesive composition is preferably a solvent-free composition that does not contain a solvent.
• the method of mixing the hydrocarbon resin and/or hydrogenated product thereof, the thermoplastic elastomer, and other components added as necessary is particularly limited.
• examples include a method of dissolving each component in a solvent and uniformly mixing them, then removing the solvent by heating or the like, and a method of melting and mixing each component with a kneader or the like.
• melt mixing is preferable from the viewpoint of more efficient mixing.
• the temperature for melt-mixing is not particularly limited, but is usually in the range of 100 to 200°C.
• the hot-melt pressure-sensitive adhesive composition of the present invention contains the hydrocarbon resin of the present invention and/or its hydride as a tackifying resin, and is therefore excellent in holding power and low-temperature performance. Therefore, the hot-melt pressure-sensitive adhesive composition of the present invention can be applied to adhesion of various members by taking advantage of such properties, and is energy-saving, highly productive, and has high holding power. can be performed.
• the hot-melt pressure-sensitive adhesive composition of the present invention is suitably used, for example, as a pressure-sensitive adhesive for various pressure-sensitive adhesive tapes and labels.
• a pressure-sensitive adhesive layer composed of the hot-melt pressure-sensitive adhesive composition of the present invention on a sheet-like base material that constitutes an adhesive tape or label
• the base material and the hot melt of the present invention are formed. It is suitably used as a pressure-sensitive adhesive tape or label comprising a pressure-sensitive adhesive layer comprising a melt pressure-sensitive adhesive composition.
• the gel permeation chromatography analysis uses "HLC-8320GPC” manufactured by Tosoh Corporation as a measuring device, and uses a column made by connecting three "TSKgel SuperMultiporeHZ” manufactured by Tosoh Corporation, and uses tetrahydrofuran as a solvent. , 40° C. and a flow rate of 1.0 mL/min.
• the resulting hot-melt adhesive composition was melt-coated on a 25 ⁇ m PET film to a thickness of 20 to 30 ⁇ m to obtain a coated sheet. Then, this coated sheet was cut to obtain a test piece. Using the test piece thus obtained, according to PSTC-101 (180° peel adhesion test by the US Adhesive Tape Committee), using a stainless steel plate as the adherend, tensile speed 300 mm / min, The peel adhesion strength (N/10 mm) at room temperature was evaluated by measuring at a temperature of 23°C. The larger the value, the better the peel adhesive strength.
• Loop tack (23°C) of hot-melt adhesive composition Using a test piece obtained in the same manner as above, a stainless steel plate was used as the adherend according to PSTC-16 (loop tack test by the US Adhesive Tape Committee), and the test speed was 300 mm / min. Loop tack (N/25 mm) at room temperature (23°C) was evaluated by measuring at a part of 25 x 25 mm at a temperature of 23°C. The larger the value, the better the loop tack strength (initial adhesive strength).
• Loop tack (10°C) of hot-melt adhesive composition Using a test piece obtained in the same manner as above, a stainless steel plate was used as the adherend according to PSTC-16 (loop tack test by the US Adhesive Tape Committee), and the test speed was 300 mm / min. Loop tack (N/25 mm) at a low temperature (10°C) was evaluated by measuring at a part of 25 x 25 mm and a temperature of 23°C. The higher the value, the better the low temperature performance.
• Example 1 Manufacture of hydrocarbon resin
• a polymerization reactor was charged with 52.7 parts of cyclopentane as a hydrocarbon solvent, heated to 70° C., then 1.0 part of aluminum chloride as a polymerization catalyst was added, and the temperature (70° C.) was maintained.
• the aluminum chloride was dispersed in the cyclopentane in such a way that some agglomerates remained by mixing for 2 minutes while the mixture was still intact.
• 48.2 parts of 1,3-pentadiene, 15.0 parts of cyclopentene, 35.0 parts of isobutylene, 1.0 part of diisobutylene, and 0.5 parts of dicyclopentadiene were added.
• the polymer solution was placed in a still and heated under a nitrogen atmosphere to remove the polymerization solvent and unreacted monomers to obtain a hydrocarbon resin. Since the amount of unreacted monomer was very small, it can be determined that the monomer composition constituting the obtained hydrocarbon resin is almost the same as the monomer composition used for polymerization (described later. The same applies to Examples 2 to 5 and Comparative Examples 1 to 6.).
• the number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), peak top molecular weight (Mp), molecular weight distribution (Mw/Mn, Mz/Mw), the ratio of the weight average molecular weight (Mw) to the peak top molecular weight (Mp) (Mp/Mw), and the softening point were tested.
• Table 1 shows the results.
• thermoplastic adhesive composition 100 parts of a styrene-isoprene-styrene block copolymer (trade name “Quintac (registered trademark) 3421”, manufactured by Nippon Zeon Co., Ltd.) was put into a stirring blade kneader, and 100 parts of the hydrocarbon resin obtained above was added thereto. part, softener (trade name "Sunpure N100", naphthenic process oil, manufactured by Nippon Sun Oil Co., Ltd.) 10 parts and antioxidant (trade name "Irganox 1010", manufactured by BASF) 1.5 parts After purging the inside of the system with nitrogen gas, the mixture was kneaded at 160 to 180° C. for 1 hour to prepare a hot-melt adhesive composition. Then, the obtained hot-melt pressure-sensitive adhesive composition was measured for peel adhesive strength, loop tack, and holding power. Table 2 shows the results.
• a hot-melt adhesive composition was prepared in the same manner as in Example 1 except that the hydrocarbon resins of Comparative Examples 1 and 2 obtained above were used, and each Tested and evaluated. Table 2 shows the results.
• Examples 2 and 3 Examples except that the types and amounts of components added to the polymerization reactor, the mixing temperature and mixing time when mixing aluminum chloride as a polymerization catalyst, and the polymerization temperature were changed as shown in Table 3 below.
• Hydrocarbon resins of Examples 2 and 3 were obtained in the same manner as in Example 1.
• the C9 fraction mainly contains styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, vinyltoluene and indene as aromatic monomers. shows the amount used in Then, the obtained hydrocarbon resin was tested and evaluated in the same manner as in Example 1. Table 3 shows the results.
• a hot-melt pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the hydrocarbon resins of Examples 2 and 3 obtained above were used. Tested and evaluated. Table 4 shows the results.
• a hot-melt adhesive composition was prepared in the same manner as in Example 1 except that the hydrocarbon resins of Comparative Examples 3 and 4 obtained above were used, and each Tested and evaluated. Table 4 shows the results.
• Example 4 and 5 Examples except that the types and amounts of components added to the polymerization reactor, the mixing temperature and mixing time when mixing aluminum chloride as a polymerization catalyst, and the polymerization temperature were changed as shown in Table 5 below. Hydrocarbon resins of Examples 4 and 5 were obtained in the same manner as in Example 1. Then, the obtained hydrocarbon resin was tested and evaluated in the same manner as in Example 1. Table 5 shows the results.
• a hot-melt pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the hydrocarbon resins of Examples 4 and 5 obtained above were used. Tested and evaluated. Table 6 shows the results.
• a hot-melt adhesive composition was prepared in the same manner as in Example 1 except that the hydrocarbon resins of Comparative Examples 5 and 6 obtained above were used, and each Tested and evaluated. Table 6 shows the results.

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