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
• • 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
  • C09J145/00—Adhesives based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Adhesives based on derivatives of such polymers
• • 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
  • C08F132/00—Homopolymers 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
  • C08F132/08—Homopolymers 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 condensed rings
• • 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
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only 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
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/04—Monomers containing three or four carbon atoms
  • C08F210/06—Propene
• • 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
  • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
• • 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
  • 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
  • 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
  • C08F2420/00—Metallocene catalysts
  • C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor
• • 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
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C

Definitions

• the present invention relates to an olefin resin and a hot melt adhesive.
• the hot melt adhesive is a solvent-free adhesive, which is applied to the adherend by heating and melting, and then solidified by cooling to develop adhesiveness.
• hot melt adhesives have been widely used in various fields because they are excellent in high-speed coating property, quick-curing property, solvent-free property, barrier property, energy saving property, economy, and the like.
• the hot melt adhesive does not use a solvent, the solvent does not volatilize, but since it is made from petroleum products, it contains a small amount of volatile organic compounds derived from them.
• the volatile organic compounds contained in the products can cause adverse health effects and discomfort due to odors. Due to their nature, studies have been made to reduce them (see, for example, Patent Documents 1 and 2).
• the hot melt adhesive does not require a solvent, it has little effect on the environment and health, but it is derived from a volatile organic compound contained in a low molecular weight substance such as a styrene elastomer or a tackifier as a raw material. Odor is a problem, and it is required to further reduce the odor especially for sanitary materials such as paper diapers and masks and daily necessities such as cleaning tools. On the other hand, if low molecular weight substances such as the above-mentioned styrene-based elastomer and tackifier are not blended in order to reduce the odor, the adhesive performance and miscibility with other raw materials will be inferior, which is the basis of hot melt adhesives.
• the problem to be solved by the technique of the present disclosure is to provide an olefin-based resin that has less odor, has excellent affinity with other materials when used as a raw material for a hot melt adhesive, and can improve adhesiveness. There is.
• the olefin resin contains a constituent unit derived from an alicyclic olefin, and the aromatic portion is reduced to a certain amount or less to enhance the linearity of the structure.
• the olefin-based resin of the present disclosure has little odor, and when used as a raw material for a hot melt adhesive, it has excellent compatibility with other materials and can improve adhesiveness.
• the olefin-based resin of the present disclosure contains a structural unit derived from the alicyclic olefin (A), has an aromatic portion of 1% or less, and has a linearity of 70% or more.
• the olefin-based resin of the present disclosure contains a structural unit derived from the alicyclic olefin (A).
• the alicyclic olefin (A) include monocyclic olefins and polycyclic olefins, and polycyclic olefins are preferable.
• the alicyclic olefin (A) preferably has 4 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, and even more preferably 7 to 10 carbon atoms.
• the alicyclic olefin (A) include dicyclopentadiene, cyclopentene, cyclohexene, norbornene and derivatives thereof, and one or more selected from dicyclopentadiene, cyclopentene, cyclohexene, norbornene and derivatives thereof. Is preferable, and one or more selected from dicyclopentadiene, norbornene and derivatives thereof is more preferable, and when the olefin-based resin of the present disclosure is used as a tackifier, dicyclopentadiene is further preferable, and the olefin-based resin of the present disclosure is used. Norbornene is even more preferred when the resin is used as the base polymer.
• the obtained resin is suitable as a tackifier, has high reactivity, and is a straight chain of the obtained resin. Since a resin having a high molecular weight and a high glass transition temperature can be obtained by using norbornene having excellent properties, it is considered that the obtained resin is suitable as a base polymer.
• the derivative include 5-ethylidene-2-norbornene, 5-ethyl-2-norbornene, 5,6-dihydrodicyclopentadiene, tricyclopentadiene, tetracyclopentadiene and the like.
• the odor is less than that of the resin using other monomers, and when it is used as a raw material of a hot melt adhesive, it can be used with other materials. It has excellent compatibility with.
• the olefin-based resin of the present disclosure preferably contains a structural unit derived from an ⁇ -olefin (B) in addition to a structural unit derived from the alicyclic olefin (A).
• a structural unit derived from the alicyclic olefin (A) By containing the ⁇ -olefin (B) in the olefin-based resin of the present disclosure, when used as a raw material for a hot melt adhesive, compatibility with other materials and adhesiveness can be further improved.
• the carbon number of the ⁇ -olefin (B) is preferably 2 to 10, and more preferably 2 to 8.
• the ⁇ -olefin (B) is preferably one or more selected from linear ⁇ -olefins and branched ⁇ -olefins.
• the number of carbon atoms of the linear ⁇ -olefin is preferably 2 to 6, more preferably 2 to 4, and the number of carbon atoms of the branched ⁇ -olefin is preferably 5 to 8 and more preferably 5 to 6. preferable.
• the specific ⁇ -olefin (B) shall be one or more selected from ethylene, propylene, butene, 3-methyl-1-butene, 4-methyl-1-pentene and 2-ethyl-1-hexene.
• an olefin resin when used as a tackifier, it is important that it is amorphous, has a low molecular weight, and has a high glass transition temperature (Tg), and the ⁇ -olefin (B) is propylene or 4-methyl-1. -Pentene is more preferred.
• an olefin resin is used as a base polymer, it is important to have a high molecular weight and a relatively high glass transition temperature (Tg), and ethylene and propylene are more preferable as the ⁇ -olefin (B).
• dicyclopentadiene or a derivative thereof is used as the alicyclic olefin (A)
• it is preferably one or more selected from propylene and 4-methyl-1-pentene
• norbornene and its derivatives are used as A
• it is preferably one or more selected from ethylene and propylene, and more preferably propylene from the viewpoint of compatibility.
• the olefin-based resin of the present disclosure contains a structural unit derived from the alicyclic olefin (A), but when used as a tackifier, it contains a structural unit derived from the alicyclic olefin (A).
• the amount is preferably 50 mol% or more, more preferably 60 mol% or more, further preferably 70 mol% or more, still more preferably 80 mol% or more.
• the upper limit may be 100 mol%, and when a structural unit derived from ⁇ -olefin (B) is contained, 90 mol% or less is preferable, and 85 mol% or less is more preferable.
• the content of the structural unit derived from the alicyclic olefin (A) is preferably 1 mol% or more, more preferably 2 mol% or more, and further preferably 3 mol% or more. Preferably, 4 mol% or more is even more preferable. Further, 40 mol% or less is preferable, 38 mol% or less is more preferable, 35 mol% or less is further preferable, and 30 mol% or less is further preferable. From the viewpoint of compatibility, the content of the structural unit derived from the alicyclic olefin (A) is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 15 mol% or more. , 20 mol% or more is even more preferable.
• the content of the constituent unit derived from the ⁇ -olefin (B) of the olefin resin of the present disclosure is preferably 3 to 50 mol%, more preferably 10 to 40 mol%, still more preferably 15 to 30 mol%. 15 to 20 mol% is even more preferable. The range is particularly good when used as a tackifier.
• the content of the structural unit derived from ⁇ -olefin (B) is preferably 60 to 99 mol%, more preferably 62 to 98 mol%, and 65 to 97 mol%. Even more preferably, 70 to 96 mol% is even more preferable.
• the content of the structural unit derived from the ⁇ -olefin (B) is preferably 60 to 95 mol%, more preferably 62 to 90 mol%, and further preferably 62 to 85 mol%. Preferably, 62-80 mol% is even more preferred.
• the molar ratio [(A) / (B)] of the alicyclic olefin (A) to the ⁇ -olefin (B) is preferably 40/60 to 100/0 when used as a tackifier. It is more preferably 50/50 to 100/0, further preferably 60/40 to 100/0, even more preferably 70/30 to 95/5, and 80/60 to 95/5. Is even more preferable.
• the molar ratio [(A) / (B)] of the alicyclic olefin (A) to the ⁇ -olefin (B) is 1/99 to 40/60. Is preferable.
• it is preferably 10/90 to 40/60, more preferably 15/85 to 40/60, and even more preferably 20/80 to 40/60.
• it when used as a base polymer, it is preferably 1/99 to 30/70, and when used as a component having both the properties of a base polymer and a tackifier, it is 5/95 to 40/60. Is preferable.
• the olefin resin of the present disclosure has an aromatic portion of 1% or less, preferably 0.5% or less, more preferably 0.1% or less, further preferably 0.05% or less, and 0%. Is even more preferable.
• the content of the aromatic moiety in the entire olefin resin can be estimated by measuring the aromatic hydrogen.
• Aromatic hydrogen can be obtained from the ratio of the peak area integrated value to the proton bonded to unsaturated carbon in 1 H-NMR measurement of the resin after the hydrogenation reaction, and specifically, the method described in Examples.
• the aromatic portion of the olefin-based resin of the present disclosure is in the range where the aromatic hydrogen is 1% or less, preferably in the range of 0.5% or less, and more preferably in the range of 0.1% or less.
• the range of 0.05% or less is more preferable, and the range of aromatic hydrogen of 0% is even more preferable.
• the aromatic portion of the olefin-based resin of the present disclosure may be a portion derived from an aromatic monomer, a portion obtained by modifying a non-aromatic monomer to have aromaticity, a decomposition product of the resin after polymerization, or the like. Be done. By setting the aromatic portion in the above range, the odor can be further reduced.
• the volatile component contained in the olefin resin of the present disclosure is preferably 10 ppm or less, more preferably 5 ppm or less, further preferably 3 ppm or less, further preferably 2 ppm or less, still more preferably 1 ppm or less.
• the component of the compound having 10 or less carbon atoms contained in the olefin resin of the present disclosure is preferably 2 ppm or less, more preferably 1 ppm or less, further preferably 0.5 ppm or less, and even more preferably 0.3 ppm. The following is even more preferable, and 0.1 ppm or less is even more preferable.
• the olefin-based resin of the present disclosure may be a hydrogenated olefin-based resin.
• the alicyclic olefin (A) as a raw material has two or more unsaturated bonds, or a monomer having two or more unsaturated bonds other than the alicyclic olefin (A) and the ⁇ -olefin (B) When used, it is preferably a hydrogenated olefin resin.
• the hydrogenated olefin-based resin has further improved chemical stability and thermal stability, and further reduces odor. In particular, aromatic odors are reduced.
• the glass transition temperature of the olefin resin of the present disclosure is preferably ⁇ 40 to 120 ° C.
• 20 to 120 ° C. is preferable, 30 to 100 ° C. is more preferable, 50 to 80 ° C. is even more preferable, and 50 to 70 ° C. is even more preferable.
• -40 to 80 ° C is preferable, -40 to 60 ° C is more preferable, -40 to 50 ° C is further preferable, and -40 to 20 ° C is preferable. Even more preferable.
• the temperature is preferably -40 to 100 ° C, more preferably -20 to 100 ° C, and further preferably -20 to 80 ° C. It is more preferably ⁇ 20 to 60 ° C., even more preferably ⁇ 20 to 40 ° C.
• the number average molecular weight (Mn) of the olefin resin of the present disclosure is preferably 100 to 100,000. Among them, when used as a component having properties as a tackifier, 100 to 2,000 is more preferable, 200 to 1,000 is more preferable, and 200 to 500 is even more preferable. Further, when used as a component having the properties of a base polymer of a hot melt adhesive, 1,000 to 100,000 is more preferable.
• the weight average molecular weight (Mw) of the olefin resin of the present disclosure is preferably 300 to 200,000.
• a component having properties as a tackifier when used as a component having properties as a tackifier, 300 to 5,000 is more preferable, 500 to 3,000 is more preferable, 600 to 2,000 is even more preferable, and 600 to 1, 200 is even more preferred. Further, when used as a component having the properties of a base polymer of a hot melt adhesive, 5,000 to 200,000 is more preferable, and when used as a base polymer, 20,000 to 200,000 is further preferable. More preferably 000 to 40,000, and even more preferably 5,000 to 100,000 when used as a component having both the properties of a base polymer and a tackifier.
• the Z average molecular weight (Mz) of the olefin resin of the present disclosure is preferably 500 to 500,000.
• ком ⁇ онент having properties as a tackifier 700 to 20,000 is more preferable, 1,000 to 7,000 is more preferable, and 1,200 to 4,000 is even more preferable. Further, when used as a component having the properties of a base polymer of a hot melt adhesive, 10,000 to 500,000 is more preferable.
• the molecular weight distribution (Mw / Mn) of the olefin resin of the present disclosure is preferably 2.5 or more, and more preferably 3.0 or more.
• the molecular weight distribution (Mz / Mw) is preferably 1.5 or more, more preferably 2.0 or more, further preferably more than 2.5, and more than 3.0. Is even more preferable.
• the compatibility and adhesiveness with other materials can be further improved when used as a raw material for a hot melt adhesive. Specifically, for example, by setting Mw / Mn in the above range, it is possible to develop the tack of the hot melt adhesive, and by setting Mz / Mw in the above range, the holding power of the hot melt adhesive Can be expressed.
• the olefin-based resin of the present disclosure has a linearity of 70% or more, preferably 80% or more.
• Linearity is the ratio of alicyclic monomers polymerized in 1,2-bonds, and when one alicyclic monomer unit has two or more unsaturated bonds, the total number of carbon atoms of the alicyclic monomer is X, the number of unsaturated carbon bonds is y, 13
• the olefin-based resin of the present disclosure is obtained by polymerizing a monomer containing an alicyclic olefin (A).
• a metallocene catalyst it is preferable to use a metallocene catalyst. That is, it is preferable to have a step of polymerizing the monomer component containing the alicyclic olefin (A) at 0 to 240 ° C. in the presence of a metallocene catalyst.
• the metallocene catalyst used in this step is a catalyst composed of a metallocene-based transition metal complex as a main catalyst and a co-catalyst, and a scavenger may be used, or the metallocene catalyst may be supported on an inorganic substance or the like.
• a transition metal (titanium, zirconium, hafnium) selected from Group 4 contains a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, and the like.
• a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group is coordinated as one or two ligands, or two of these groups are coordinated by a covalent bond.
• Other examples include those having a ligand such as a hydrogen atom, an oxygen atom, a nitrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an acetylacetonate group, and an amide group.
• Examples of the co-catalyst include alkylaluminoxane compounds and boron compounds.
• alkylaluminoxane compound include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane and the like.
• Examples of the boron compound include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane, and tris (3,4).
• 5-trifluorophenyl) borane tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6- Tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, Phenylbis (pentafluorophenyl) borate, tetrakis (3,5-bistrifluoromethylphenyl) borate and the like can be mentioned.
• Examples of the scavenger include alkylaluminum compounds, and specific examples thereof include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, and triisobutylaluminum.
• the amount of the metallocene-based transition metal complex is preferably 0.1 to 50 mol%, more preferably 1 to 20 mol%, based on all the monomer components including the alicyclic olefin (A).
• the amount of the co-catalyst is preferably 0.2 to 60 mol%, more preferably 2 to 30 mol%, based on all the monomer components including the alicyclic olefin (A).
• two or more kinds of metallocene catalysts may be used, and it is preferable to use two or more kinds in combination. By using a plurality of catalysts in combination, the molecular weight distribution of the obtained olefin resin can be adjusted, and the adhesiveness can be improved while suppressing the odor.
• the polymerization temperature in this step is preferably 0 to 240 ° C., more preferably 20 to 220 ° C., and even more preferably 40 to 200 ° C.
• the method for producing an olefin resin of the present invention preferably includes a step of stripping.
• the stripping step which is the main step, may be carried out after the polymerization of the olefin resin, or may be carried out after the hydrogenation step described below.
• an inert gas such as nitrogen or argon gas as a medium, and it is more preferable to use nitrogen.
• the interface between the gas and the resin in the container is renewed by stirring or the like, and the gas in the container is renewed with an inert gas medium to make the resin volatile. Remove impurities.
• stripping treatment can be performed at 150 to 300 ° C. for 0.5 to 5 hours at a flow rate of 1 to 1000 L / min of nitrogen with respect to 100 g of the olefin resin.
• the stripping temperature is preferably 100 to 300 ° C, more preferably 150 to 300 ° C, and even more preferably 150 to 250 ° C.
• the time for stripping may be selected optimally depending on the amount of resin and the size of the container used, but is preferably 0.1 to 20 hours, more preferably 0.5 to 10 hours, and 0. .5-5 hours is more preferred.
• the optimum flow rate of nitrogen when stripping with nitrogen may be selected according to the size of the container used, but 0.1 to 20 L / min is used for 100 g of the olefin resin. Preferably, 1 to 10 L / min is more preferable.
• an olefin resin having less odor and suitable as a raw material for a hot melt adhesive can be efficiently obtained.
• the method for producing an olefin-based resin of the present invention that is, the olefin-based resin obtained by polymerizing a monomer component containing an alicyclic olefin (A) at 0 to 240 ° C.
• the obtained resin Since it has little odor by itself, it does not require excessive stripping conditions. Further, when the olefin resin obtained in the polymerization step satisfies the condition that the aromatic portion is 1% or less and the linearity is 70% or more, the odor of the resin itself is further reduced, which is excessive. No need for stripping.
• the method for producing an olefin resin of the present invention preferably further includes a step of hydrogenation.
• the alicyclic olefin (A) as a raw material has two or more unsaturated bonds, or a monomer having two or more unsaturated bonds other than the alicyclic olefin (A) and the ⁇ -olefin (B)
• This step is more preferably a step of hydrogenating at 100 to 300 ° C. in the presence of a catalyst.
• the catalyst used in this hydrogenation step is preferably a metal catalyst, and examples thereof include a palladium catalyst, a nickel catalyst, a platinum catalyst, a ruthenium catalyst, a renium catalyst, a copper catalyst, and a rhodium catalyst.
• the palladium catalyst include palladium carbon, palladium alumina, palladium silica, palladium silica alumina, and zeolite-supported palladium.
• the nickel catalyst include nickel diatomaceous earth, sponge nickel, nickel alumina, nickel silica, nickel carbon and the like.
• the platinum catalyst include platinum silica, platinum silica alumina, and zeolite-supported platinum.
• the ruthenium catalyst examples include ruthenium carbon, ruthenium alumina, ruthenium silica, ruthenium silica alumina, and zeolite-supported ruthenium.
• the amount of the hydrogenation catalyst is preferably 1 to 40 parts by mass, more preferably 5 to 35 parts by mass with respect to 100 parts by mass of the olefin resin.
• the hydrogenation reaction temperature in this step is preferably 30 to 300 ° C., more preferably 60 to 300 ° C., further preferably 100 to 300 ° C., still more preferably 100 to 250 ° C.
• the hydrogen pressure in this step is preferably 1 to 20 MPa, more preferably 2 to 15 MPa, still more preferably 3 to 10 MPa.
• the hot melt adhesive of the present disclosure contains the olefin resin. That is, the hot melt adhesive of the present disclosure contains a structural unit derived from the alicyclic olefin (A), has a structural unit derived from an aromatic monomer of 1 mol% or less, and has a volatile component of 10 ppm or less. Contains certain olefinic resins. By adjusting the molecular weight, molecular weight distribution, glass transition temperature, etc.
• a component having the property of a tackifier among the components constituting the hot melt adhesive, a component having the property of a tackifier, a component having the property of a base polymer, or a component having the property of a base polymer, or It can be used as a component having both the properties of a tackifier and a base polymer.
• the olefin-based resin of the present disclosure can be used as a component having both the properties of a tackifier and a base polymer, a hot melt having less odor and excellent tackiness even when a separate tackifier and base polymer are not contained. An adhesive is obtained.
• the olefin-based resin of the present disclosure is used. Has excellent affinity with other materials, so that a good hot melt adhesive can be obtained.
• the effect of the present disclosure technology of having less odor and excellent affinity with other materials can be exhibited, the adhesiveness of the obtained hot melt adhesive is improved, and the odor is also reduced. It can be suppressed.
• the hot melt adhesive of the present disclosure may contain a base polymer, a tackifier, a plasticizer, and an additive in addition to the olefin resin.
• the hot melt adhesive of the present disclosure preferably further contains a base polymer.
• a base polymer When the olefin resin is used as a component having the properties of a base polymer or a component having both the properties of a tackifier and a base polymer, a good hot melt adhesive can be obtained even if the base polymer is not contained, but in particular.
• the olefin resin When the olefin resin is used as a component having the properties of a tackifier, it preferably contains a base polymer.
• the base polymer examples include natural rubber, olefin-based elastomer, styrene-based elastomer, and the like, and olefin-based elastomer and styrene-based elastomer are preferable. These may be used individually by 1 type, and may be used in combination of 2 or more type.
• olefin-based elastomer examples include ethylene-based olefin polymers, amorphous olefin polymers, propylene-based elastomers, ethylene-vinyl acetate copolymers, and ethylene-acrylic acid ester copolymers.
• the ethylene-based olefin polymer examples include polyethylene and a copolymer of ethylene and an olefin having 3 to 10 carbon atoms. It is not particularly limited as long as it can be used as a base polymer of a hot melt adhesive, but from the viewpoint of the adhesiveness of the hot melt adhesive, an ethylene- ⁇ -olefin copolymer is preferable.
• the ⁇ -olefin include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and 1-hexadecene.
• 1-octene is preferable. From the viewpoint of the adhesiveness of the hot melt adhesive, it is more preferably an ethylene-1-octene copolymer, and more preferably an ethylene-1-octene copolymer containing 5 to 50% by mass of a 1-octene-derived structural unit. It is a coalescence.
• the melting point of the ethylene-based olefin polymer is preferably 60 to 120 ° C., more preferably 60 to 90 ° C. from the viewpoint of heat-resistant creep property. The melting point of the ethylene-based olefin polymer can be measured by differential scanning calorimetry.
• amorphous ones belong to the amorphous olefin polymers described later.
• the amorphous olefin polymer is one or more homopolymers or copolymers selected from the group consisting of linear or branched ⁇ -olefins or dienes having 2 to 24 carbon atoms, and is not particularly limited. , Polybutene, polybutadiene, polyisoprene, and amorphous polyalphaolefins.
• polybutene include isobutene and normal butene alone or copolymers and hydrogenated products thereof.
• polybutadiene include 1,2-butadiene and 1,4-butadiene alone or copolymers and hydrogenated products thereof, and may have a hydroxyl group at the terminal.
• polyisoprene examples include homopolymers or copolymers of isoprene and hydrogenated products thereof, and may have a hydroxyl group at the terminal.
• amorphous polyalphaolefin examples include homopolymerizations and copolymers of olefins having 2 to 6 carbon atoms.
• propylene-based elastomer examples include elastomers having a propylene unit as a main constituent unit, such as low melting point polypropylene.
• the elastomer is not limited by the density as long as it has rubber elastic properties, and may be chemically crosslinked or not chemically crosslinked.
• the vinyl acetate content of the ethylene-vinyl acetate copolymer is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.
• styrene-based elastomer a styrene-based block copolymer is preferable.
• the styrene-based block copolymer is a copolymer in which a styrene-based compound and a conjugated diene compound are block-copolymerized, and usually has a styrene-based compound block and a conjugated diene compound block.
• examples of the "styrene-based compound” include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, ⁇ -methylstyrene, vinylnaphthalene, vinylanthracene and the like. it can. Styrene is particularly preferable. These styrene compounds can be used alone or in combination.
• conjugated diene compound is meant a diolefin compound having at least a pair of conjugated double bonds.
• conjugated diene compound examples include 1,3-butadiene, 2-methyl-1,3-butadiene (or isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and the like.
• 1,3-Hexadiene can be exemplified.
• 1,3-butadiene and 2-methyl-1,3-butadiene are particularly preferable.
• These conjugated diene compounds can be used alone or in combination.
• the styrene-based block copolymer may be an unhydrogenated additive or a hydrogenated additive.
• the "non-hydrogenated styrene block copolymer” can be specifically exemplified by a block based on a conjugated diene compound to which no hydrogenation has been added.
• the "hydrogenated styrene-based block copolymer” can be specifically exemplified by a block copolymer in which all or part of a block based on a conjugated diene compound is hydrogenated.
• the hydrogenated ratio of the "hydrogenated styrene block copolymer" can be indicated by the "hydrogenation rate".
• the “hydrogenation rate” of the “hydrogenation of styrene-based block copolymer” is based on the total aliphatic double bond contained in the block based on the conjugated diene compound, in which hydrogenation is performed and saturated hydrocarbonation is performed. The ratio of double bonds converted to hydrogen bonds. This "hydrogenation rate” can be measured by an infrared spectrophotometer, a magnetic resonance imaging device, or the like.
• non-hydrogenated styrene block copolymer examples include styrene-isoprene-styrene block copolymer (also referred to as "SIS”) and styrene-butadiene-styrene block copolymer (also referred to as "SBS”).
• SIS styrene-isoprene-styrene block copolymer
• SBS styrene-butadiene-styrene block copolymer
• SEBS hydrogenated styrene-butadiene-styrene block copolymers
• the styrene block copolymer preferably has a styrene block ratio (styrene content) contained in the styrene block copolymer of 5 to 50% by mass, more preferably 10. ⁇ 40% by mass.
• the difference between the Hansen solubility parameter of the base polymer used in the hot melt adhesive of the present disclosure and the Hansen solubility parameter of the olefin resin is preferably 5 or less, more preferably 4 or less, still more preferably 3 or less. 2, 2 or less is more preferable, and 1 or less is even more preferable.
• the difference in the Hansen solubility parameter referred to here means the Ra value obtained by the following formula.
• Ra [4 ( ⁇ d2- ⁇ d1 ) 2 + ( ⁇ p2- ⁇ p1 ) 2 + ( ⁇ h2- ⁇ h1 ) 2 ] 1/2
• ⁇ d is the dispersive force
• ⁇ p is the polarization force
• ⁇ h is the solubility parameter based on the hydrogen bonding force
• ⁇ d1 , ⁇ p1 , and ⁇ h1 are the solubility parameters of the olefin resin
• ⁇ d2 , ⁇ p2 and ⁇ h2 are solubility parameters of the base polymer.
• the content of the base polymer is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, still more preferably 30 parts by mass, based on 100 parts by mass of the hot melt adhesive. It is more than parts, and preferably 80 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less. That is, in the hot melt adhesive, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, still more preferably 30% by mass or more, and preferably 80% by mass or less.
• the glass transition temperature of the base polymer is preferably ⁇ 20 to 100 ° C., more preferably ⁇ 20 to 60 ° C.
• the olefin resin may contain a second base polymer even when it is used as a component having the properties of a base polymer or a component having both the properties of a tackifier and the base polymer.
• the second base polymer the olefin resin of the present disclosure, that is, the olefin resin described in the section of the [olefin resin], or the olefin elastomer is preferably used.
• the melting point of the second base polymer is preferably 60 to 120 ° C., more preferably 60 to 110 ° C., and even more preferably 70 to 100 ° C.
• the hot melt adhesive of the present disclosure preferably further contains a tackifier.
• a tackifier When the olefin resin is used as a component having the properties of a tackifier or a component having both the properties of a tackifier and a base polymer, a good hot melt adhesive can be obtained even if the tackifier is not contained.
• the olefin resin when used as a component having the properties of a base polymer, it preferably contains a tackifier.
• the olefin resin preferably has the properties of a base polymer.
• tackifier examples include hydrogenated derivatives of aliphatic hydrocarbon petroleum resins, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, and the like, which are solid, semi-solid, or liquid at room temperature. be able to.
• the content of the tackifier is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, still more preferably 20 parts by mass or more, based on 100 parts by mass of the hot melt adhesive. It is 30 parts by mass or more, and preferably 80 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less. That is, in the hot melt adhesive, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, and preferably 80% by mass or less. It is more preferably 70% by mass or less, further preferably 60% by mass or less, still more preferably 50% by mass or less.
• the softening point of the tackifier is preferably ⁇ 20 ° C. or higher, more preferably ⁇ 15 ° C. or higher, further preferably ⁇ 10 ° C. or higher, and preferably 180 ° C. or lower, more preferably 170 ° C. or lower, further preferably. Is 160 ° C or lower.
• the hot melt adhesive of the present disclosure preferably further contains a plasticizer.
• the plasticizer is not particularly limited, but those used for hot melt adhesives are preferable, and oils or waxes are more preferable. Further, as the plasticizer, phthalates, adipates, fatty acid esters, glycols, epoxy-based polymer plasticizers and the like can also be used.
• oil examples include paraffinic process oil, naphthenic process oil, and isoparaffinic oil.
• paraffin-based process oils include "Diana Process Oil PW-32", “Diana Process Oil PW-90”, “Diana Process Oil PW-150”, and “Diana Process Oil PS-32” manufactured by Idemitsu Kosan Co., Ltd. , “Diana Process Oil PS-90”, “Diana Process Oil PS-430”; “Kaydol Oil”, “ParaLux Oil” manufactured by Chevron USA, etc. (all are trade names).
• isoparaffin oils include “IP Solvent 1016”, “IP Solvent 1620”, “IP Solvent 2028”, “IP Solvent 2835”, and “IP Clean LX” manufactured by Idemitsu Kosan Co., Ltd .; “NA Solvent” series, etc. (both are product names).
• waxes examples include animal wax, vegetable wax, carnauba wax, candelilla wax, wood wax, beeswax, mineral wax, petroleum wax, paraffin wax, microcrystallin wax, petroleum, higher fatty acid wax, higher fatty acid ester wax, and Fisher. Tropsch wax and the like can be exemplified.
• the content of the plasticizer in the hot melt adhesive of the present disclosure is 2 parts by mass or more, preferably 5 parts by mass or more, out of 100 parts by mass of the hot melt adhesive from the viewpoint of improving the adhesiveness and the coatability. , More preferably 10 parts by mass or more, and 60 parts by mass or less, preferably 40 parts by mass or less, more preferably 30 parts by mass or less. That is, in the hot melt adhesive, 2% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and 60% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less. It is mass% or less.
• the resin composition of the present disclosure further contains an inorganic filler, an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant and other arbitrary additives as necessary, as long as the object of the disclosed technology is not impaired. May be good.
• Inorganic fillers include talc, calcium carbonate, barium carbonate, wollastonite, silica, clay, mica, kaolin, titanium oxide, silica soil, urea resin, styrene beads, starch, barium sulfate, calcium sulfate, magnesium silicate, Examples thereof include magnesium carbonate, alumina, and quartz powder.
• Antioxidants include trisnonylphenylphosphite, distearylpentaerythritol diphosphite, "Adecastab 1178" (manufactured by ADEKA Co., Ltd.), “Stamylizer TNP” (manufactured by Sumitomo Chemical Co., Ltd.), “Irgafos 168" (BASF , “Sandstab P-EPQ” (manufactured by Sand), phosphorus-based antioxidants, 2,6-di-t-butyl-4-methylphenol, n-octadecil-3- (3', 5'- Di-t-butyl-4'-hydroxyphenyl) propionate, phenolic antioxidants such as “Smilizer BHT” (manufactured by Sumitomo Chemical Co., Ltd.), “Irganox 1010” (manufactured by BASF), dilauryl-3,3' -Thiodiprop
• a base polymer, a tackifier, a plasticizer and an additive are dry-blended using a Henschel mixer or the like, and uniaxial or biaxial extrusion is performed. It can be manufactured by melt-kneading with a machine, a plastic mill, a Banbury mixer, or the like.
• the hot melt adhesives of the present disclosure have excellent adhesiveness and low odor, and therefore, for example, for sanitary materials, packaging, bookbinding, textiles, woodworking, electrical materials, can making, construction, filters. It can be suitably used for low-pressure molding, bag making, and the like.
• an adhesive for sanitary products such as disposable diapers and sanitary napkins represented by fixing non-woven fabrics or super absorbent polymers (SAPs)
• SAPs super absorbent polymers
• assemblies represented by automobile floor mats It can be preferably used, and it can be suitably used as an adhesive for sanitary products because it has a particularly low odor.
• Aromatic components (benzene, toluene, xylene, styrene, etc.) that generate a gas component using a headspace gas chromatograph (device name: Agent7697A / Agent7890B) and have a retention time of less than 10 minutes when measured under the following conditions. ) was defined as the amount of aromatic volatile components (aroma). Further, the amount of components having a retention time of less than 13 minutes (generally below the boiling point of a compound having 10 or less carbon atoms) is defined as the amount of volatile components (VOC), and the amount of components having a retention time of less than 40 minutes for all volatile components to be desorbed.
• VOC volatile components
• HSP Hansen solubility parameter
• olefin resins HP1 and HP2 are used using 20 kinds of solvents having known solubility parameters (dispersion force: ⁇ d , polarization force: ⁇ p , hydrogen bond force: ⁇ h).
• HP5, HP6 and HP8 to HP11 evaluate the solubility, plot the solvent value on a three-dimensional plot, create the smallest sphere with the good solvent on the inside and the poor solvent on the outside, and create a sphere.
• the coordinate at the center of was used as the solubility parameter of the olefin resin.
• Reference 1 Hildebrand JH, Scott RL.
• Low melting point polypropylene which is an olefin elastomer (manufactured by Idemitsu Kosan Co., Ltd., trade name: L-MODU S400, Mw: 45,000, melt viscosity (B viscosity) (190 ° C., ASTM D 3236): 8500 mPa.
• Amorphous polyalphaolefin (manufactured by Evonik Industries AG, which is an olefin-based elastomer, trade name: VESTOPLAST (registered trademark) 708, melt viscosity (190 ° C., DIN 53 019): 8000 mPa ⁇ s, softening point (R & B) , DIN EN 1427): 108 ° C.) Styrene-isoprene-styrene block copolymer (SIS) (manufactured by Kraton Corporation, trade name: KRATON® D1161, MFR (190 ° C., 2.16 kg, ISO 1133): 1.3 to 3.
• APAO Amorphous polyalphaolefin
• Ra value which is an index of affinity, was calculated by the following formula. The smaller the Ra value, the better the affinity. Further, in the following formula, ⁇ d1 , ⁇ p1 , and ⁇ h1 are solubility parameters of the olefin resin, and ⁇ d2 , ⁇ p2 , and ⁇ h2 are solubility parameters of each of the elastomers.
• Ra [4 ( ⁇ d2- ⁇ d1 ) 2 + ( ⁇ p2- ⁇ p1 ) 2 + ( ⁇ h2- ⁇ h1 ) 2 ] 1/2
• ⁇ Ra value ⁇ 1.5 ⁇ : 1.5 ⁇ Ra value ⁇ 3.0 ⁇ : 3.0 ⁇ Ra value ⁇ 5.0 X: 5.0 ⁇ Ra value
• Dispersibility was evaluated as follows. The olefin resin and the base polymer (elastomer) were placed in a container at a mass ratio of 1: 1 and stirred at 180 ° C. for 1 hour, then allowed to stand to cool to room temperature, and after 1 day, the visually obtained mixture was obtained. Dispersibility was evaluated. ⁇ : Transparent ⁇ : Almost transparent (slightly cloudy) ⁇ : White turbidity (slightly transparent) ⁇ : Milky white
• Tg change rate The rate of change in the glass transition temperature (Tg) before and after mixing was evaluated by the following method. It is presumed that the larger the Tg change rate, the higher the affinity between the two. Elastomer alone, olefin resin and elastomer are mixed at a mass ratio of 1: 1 and a strip-shaped test piece cut out from a sheet (1 mm thick) obtained by press molding is used, and the temperature is -150 ° C to 230 ° C (test piece is While raising the temperature at 2 ° C./min to the breaking temperature), perform dynamic viscoelasticity measurement (using a rheometer, manufactured by Hitachi High-Tech Science Co., Ltd., DMS6100) in the tensile test mode, and calculate Tg from the peak value of tan ⁇ .
• Tg derived from the olefin-based elastomer low melting point polypropylene (PP) (L-MODU S-400): Tg-3 ° C., amorphous polyalphaolefin (APAO) (VESTOPLAST 708): Tg-35 ° C.
• APAO amorphous polyalphaolefin
• Tg shifts to the high temperature side.
• the rate of change in Tg was evaluated according to the following criteria.
• HMA styrene-based hot melt adhesive
• SIS Styrene-isoprene-styrene block copolymer
• Plasticizer Paraffin oil (Diana Process Oil PS-32, manufactured by Idemitsu Kosan Co., Ltd.)
• Antioxidant Irganox 1010 (manufactured by BASF Japan Ltd.) ⁇ Adhesive strength> Measured according to JIS Z0237 (23 ° C
• HMA polyolefin hot melt adhesive
• HMA hot melt adhesive
• Adhesive agent ⁇ Escorez5300 (DCPD system) ⁇ Escorez5600 (C9 aroma / C5 series) -Plasticizer: Paraffin oil (PW-90) -Antioxidant: Irganox 1010 (manufactured by BASF Japan Ltd.)
• Adhesive> When the HMA sample was lightly tapped with a finger, the degree of adhesion to the finger was evaluated. The criteria were set so that the obtained evaluation results were generally correlated with the loop tack values in Table 3. ⁇ : Strongly adheres and follows ⁇ : Slightly strongly adheres ⁇ : Slightly weakly adheres ⁇ : Almost no adhesion
• the obtained resin heptane solution was filtered to remove the catalyst residue, 20 mg of Irganox 1010 (antioxidant, manufactured by BASF Japan Co., Ltd.) was added, and heptane was retained at 70 ° C. and 100 hPa using an evaporator. After the removal, unreacted DCPD was distilled off at 160 ° C. and 25 hPa to obtain 12.2 g of an olefin resin (P1) (Mw: 321 and DCPD content: 100 mol%).
• P1 an olefin resin
• ⁇ Hydrogenation reaction process 1 g of nickel diatomaceous earth catalyst, 10.0 g of the olefin resin (P1), and 391 mL of heptane were placed in a stainless steel 1 L autoclave to replace nitrogen, and then hydrogen gas was introduced at room temperature until it reached 5 MPa while stirring at 500 rpm. Then, the temperature was raised and maintained at 230 ° C. for 30 minutes to carry out a hydrogenation reaction. The unreacted hydrogen gas was removed, the obtained resin heptane solution was hot-filtered to remove the catalyst residue, irganox 1010: 40 mg was added, and heptane was added at 70 ° C. and 25 hPa using an evaporator. Distilled away.
• Production Example 3 (Production of hydrogenated olefin resin (HP3)) ⁇ Polymerization reaction process> The polymerization reaction was carried out under the same conditions as in Example 2 except that the pressure of the hydrogen gas was 0.02 MPa and the polymerization temperature was 90 ° C. to obtain 9.9 g of an olefin resin (P3). (Mw: 1,785, DCPD content: 100 mol%) ⁇ Hydrogenation reaction process / stripping process> Hydrogenated olefins by performing a hydrogenation reaction / stripping step under the same conditions as in Production Example 1 except that 9.0 g of olefin resin (P3), 392 mL of heptane, and 36 mg of Irganox 1010 were used. 7.2 g of resin (HP3) (Mw: 1,785, DCPD content: 100 mol%) was obtained.
• Production Example 4 (Production of hydrogenated olefin resin (HP4)) ⁇ Polymerization reaction step 1> To a 1 L autoclave made of stainless steel, add 400 mL (2.73 mol) of a heptane solution of DCPD as a monomer at room temperature under a nitrogen atmosphere, and while stirring at 100 rpm, use TIBA (4 mmol) as a scavenger and Borate (300 ⁇ mol) as a cocatalyst.
• TIBA 4 mmol
• Borate 300 ⁇ mol
• ⁇ Polymerization reaction step 2> Bis (dimethylsilylene) -bis (cyclopentadienyl) zirconium dichloride ((Me 2 )) as the second main catalyst while stirring the reaction solution obtained in the above ⁇ polymerization reaction step 1> in a nitrogen atmosphere at 100 rpm. Si) 2 Cp 2 ZrCl 2 ) (50 ⁇ mol) was further added, the stirring speed was increased to 400 rpm, and then 0.02 MPa of hydrogen gas, which is a chain transfer agent, was introduced. Subsequently, the internal temperature was raised to 90 ° C. and polymerization was carried out for 1 hour, and then unreacted hydrogen gas was depressurized and removed.
• ⁇ Hydrogenation reaction process / stripping process Perform the hydrogenation reaction step and stripping step under the same conditions as in Production Example 1 except that 3 g of nickel diatomaceous earth catalyst, 30.0 g of olefin resin (P4), 373 mL of heptane, and 120 mg of irganox 1010 were used. Obtained 27.8 g of a hydrogenated olefin resin (HP4) (Mw: 1,050, DCPD content: 100 mol%).
• HP4 hydrogenated olefin resin
• Production Example 5 (Production of hydrogenated olefin resin (HP5)) ⁇ Polymerization reaction process> A heptane solution of DCPD with a solvent of 80 mL as a solvent and a concentration of 95% by volume as the first monomer in a stainless steel 1 L autoclave under a nitrogen atmosphere (primary reagent, stabilizer and polar impurities have been removed with alumina).
• Production Example 6 (Production of hydrogenated olefin resin (HP6)) ⁇ Polymerization reaction process> 283 mL of heptane as a solvent, 117 mL (0.80 mol) of a heptane solution of DCPD as the first monomer, Borate (60 ⁇ mol) as a co-catalyst, bis (dimethylsilylene) -bis (cyclopentadienyl) zirconium dichloride ((Me) 2 Si) 2 Cp 2 ZrCl 2 ) (40 ⁇ mol), olefin-based by carrying out the polymerization reaction under the same conditions as in Production Example 5 except that the pressure of hydrogen gas was 0.03 MPa and the total pressure was 0.8 MPa. 19.7 g of a resin (P6) (Mw: 1,728, DCPD content: 76 mol%) was obtained.
• Production Example 7 (Production of hydrogenated olefin resin (HP7)) ⁇ Polymerization reaction step 1> Add 283 mL of heptane as a solvent and 117 mL (0.80 mol) of a heptane solution of DCPD as the first monomer to a stainless steel 1 L autoclave under a nitrogen atmosphere at room temperature, and while stirring at 100 rpm, use TIBA (2 mmol) as a scavenger.
• ⁇ Polymerization reaction step 2> 70 mL of heptane as a solvent and 330 mL (2.25 mol) of a heptane solution of DCPD as the first monomer were added to the same stainless steel 1 L autoclave used in the above ⁇ polymerization reaction step 1> under a nitrogen atmosphere at room temperature.
• TIBA 2 mmol
• Borate 60 ⁇ mol
• bis (dimethylsilylene) -bis (cyclopentadienyl) zirconium dichloride (Me 2 Si) 2 Cp 2 ZrCl)
• ⁇ Hydrogenation reaction process / stripping process Perform the hydrogenation reaction step and stripping step under the same conditions as in Production Example 1 except that 4 g of nickel diatomaceous earth catalyst, 60.0 g of olefin resin (P7), 346 mL of heptane, and 240 mg of irganox 1010 were used. Obtained 57.0 g of a hydrogenated olefin resin (HP7) (Mw: 1,104, DCPD content: 83 mol%).
• HP7 hydrogenated olefin resin
• Production Example 8 (Production of hydrogenated olefin resin (HP8)) ⁇ Polymerization reaction process> A heptane solution of DCPD having a concentration of 95% by volume as the first monomer in a stainless steel 1L autoclave under a nitrogen atmosphere at room temperature (primary reagent, stabilizers and polar impurities have been removed with alumina) 264 mL (1. 90 mol), 120 mL (0.95 mol) of 4-methyl-1-pentene (4M1P) (polar impurities have been removed with alumina) as the second monomer, and while stirring at 100 rpm, as a scavenger of TIBA having a concentration of 2 M.
• 4M1P 4-methyl-1-pentene
• ⁇ Hydrogenation reaction process / stripping process Perform the hydrogenation reaction step and stripping step under the same conditions as in Production Example 5, except that 3 g of nickel diatomaceous earth catalyst, 30.0 g of olefin resin (P8), 373 mL of heptane, and 120 mg of irganox 1010 were used. Obtained 28.0 g of a hydrogenated olefin resin (HP8) (Mw: 613, DCPD content: 83 mol%).
• HP8 hydrogenated olefin resin
• Production Example 9 (Production of hydrogenated olefin resin (HP9)) ⁇ Polymerization reaction process> The polymerization reaction was carried out under the same conditions as in Production Example 8 except that 167 mL (1.14 mol) of a heptane solution of DCPD was used as the first monomer and 220 mL (1.74 mol) of 4M1P was used as the second monomer. 57.1 g of a resin (P9) (Mw: 762, DCPD content: 65 mol%) was obtained.
• Hydrogenation is performed by performing a hydrogenation reaction step and a stripping step under the same conditions as in Production Example 8 except that an olefin resin (P9) is used instead of the olefin resin (P8) as the olefin resin. 28.5 g of the olefin resin (HP9) (Mw: 801 and DCPD content: 65 mol%) was obtained.
• Comparative production example 2 (Production of hydrogenated petroleum resin (HP11)) Dicyclopentadiene (DCPD) and styrene were used as raw material monomers in the ratio shown in Table 1 according to Example 1 of International Publication No. 2004/056882, and dicyclopentadiene (DCPD) and styrene were combined by a thermal polymerization method. After obtaining the copolymer, partial hydrogenation using a nickel catalyst was carried out to obtain a hydrogenated petroleum resin (HP11).
• DCPD dicyclopentadiene
• styrene were combined by a thermal polymerization method. After obtaining the copolymer, partial hydrogenation using a nickel catalyst was carried out to obtain a hydrogenated petroleum resin (HP11).
• Production Example 10 (Production of olefin resin (BP1)) In a stainless steel 1L autoclave, under a nitrogen atmosphere, at room temperature, 327 mL of toluene as a solvent and 73 mL (0.60 mol) of a toluene solution of norbornene (NB) having a concentration of 80% by weight as a monomer (first-class reagent, alumina-treated).
• NB norbornene
• the toluene solution of the olefin resin obtained by the above polymerization is added dropwise to a large amount of stirred ethanol, the polymer is reprecipitated, washed and filtered with ethanol several times, and then vacuum dried at 190 ° C. for 6 hours. Obtained 39 g of an olefin resin (BP1) (Mw: 33,000, NB content: 14 mol%).
• Production Example 11 (Production of olefin resin (BP2)) Olefin resin (BP2) (Mw) was subjected to polymerization reaction, reprecipitation, washing, and drying under the same conditions as in Production Example 10 except that the pressure of hydrogen gas, which is a chain transfer agent, was changed to 0.01 MPa. : 50,000, NB content: 14 mol%) 75 g was obtained.
• BP2 olefin resin
• Mw Olefin resin
• Production Example 12 (Production of olefin resin (BP3)) Olefin resin (BP3) (Mw: 91,000) was subjected to polymerization reaction, reprecipitation, washing, and drying under the same conditions as in Production Example 10 except that hydrogen gas, which is a chain transfer agent, was not used. , NB content: 14 mol%) 109 g was obtained.
• Production Example 14 (Production of olefin resin (BP5)) Polymerization reaction, reprecipitation, washing, and drying were carried out under the same conditions as in Production Example 13 except that the amount of toluene was changed to 305 mL and the amount of norbornene (NB) in a toluene solution was changed to 95 mL (0.80 mol). By doing so, 30 g of an olefin resin (BP5) (Mw: 28,000, NB content: 21 mol%) was obtained.
• Production Example 15 (Production of olefin resin (BP6)) Olefin resin (BP6) (Mw: 45,000, NB content: 24 mol) was subjected to polymerization reaction, reprecipitation, washing, and drying under the same conditions as in Production Example 13 except that the solvent was changed to cyclohexane. %) 50 g was obtained.
• BP6 Olefin resin (BP6) (Mw: 45,000, NB content: 24 mol) was subjected to polymerization reaction, reprecipitation, washing, and drying under the same conditions as in Production Example 13 except that the solvent was changed to cyclohexane. %) 50 g was obtained.
• Production Example 16 (Production of olefin resin (BP7)) In a stainless steel 1L autoclave, under a nitrogen atmosphere, at room temperature, 296 mL of toluene as a solvent and 104 mL (0.85 mol) of a toluene solution of norbornene (NB) having a concentration of 80% by weight as a monomer (first-class reagent, alumina-treated).
• NB norbornene
• Production Example 17 (Production of olefin resin (BP8)) The amount of toluene was changed to 272 mL, the amount of the toluene solution of norbornene (NB) was changed to 128 mL (1.05 mol), hydrogen gas as a chain transfer agent was introduced at a pressure of 0.10 MPa, and ethylene gas was introduced.
• the olefin resin (BP8) (Mw: 25,000,) was subjected to the polymerization reaction, reprecipitation, washing, and drying under the same conditions as in Production Example 16 except that the total pressure was 0.80 MPa.
• NB content 27 mol%) 53 g was obtained.
• Production Example 18 (Production of olefin resin (BP9))
• BP9 Mw:
• BP9 Mw:
• hydrogen gas which is a chain transfer agent
• Production Example 19 (Production of olefin resin (BP10)) Production Example 16 except that the amount of toluene was changed to 242 mL, the amount of norbornene (NB) in a toluene solution was changed to 158 mL (1.30 mol), and hydrogen gas, which is a chain transfer agent, was introduced at a pressure of 0.10 MPa.
• BP10 olefin resin
• the polymerization reaction, reprecipitation, washing, and drying were carried out under the same conditions as in Production Example 5, except that the hydrogenation reaction was carried out for 3 hours, and a part of the polymerization yield of 137 g was hydrogenated and stripped to form an olefin. 137 g of a resin (BP13) (Mw: 64,000, DCPD content: 6 mol%) was obtained.
• Production Example 21 (Production of olefin resin (BP14)) The polymerization reaction was carried out under the same conditions as in Production Example 20 except that the amount of heptane was 188 mL, the amount of the heptane solution of DCPD was 200 mL (1.42 mol), and the pressure of hydrogen gas was 0.30 MPa. 158 g of a resin (BP14) (Mw: 29000, DCPD content: 22 mol%) was obtained.
• Production Example 22 (Production of olefin resin (BP15)) By carrying out the polymerization reaction under the same conditions as in Production Example 21 except that the pressure of hydrogen gas was set to 0.05 MPa, 72 g of an olefin resin (BP15) (Mw: 48,000, DCPD content: 23 mol%) was obtained. Obtained.
• Production Example 23 (Production of olefin resin (BP16)) 188 mL of toluene as a solvent, 200 mL (1.42 mol) of a toluene solution of dicyclopentadiene (DCPD) (primary reagent, treated with alumina), 3.0 mL (60 ⁇ mol) of a toluene solution of Borate, and dimethylsilylene- (tetra) as the main catalyst. Except for 2.0 mL (40 ⁇ mol) of a toluene solution of methylcyclopentadiene (t-butylamide) titanium dichloride (Me 2 Si (Me 4 Cp) (t-BuN) Tycol 2) and propylene as the second monomer.
• BP16 dicyclopentadiene
• styrene elastomer styrene elastomer
• SBS Styrene-butadiene-styrene block copolymer
• BP12 olefin elastomer
• PP Low melting point polypropylene
• L-MODU S400 Low melting point polypropylene
• the olefin-based resin of the present disclosure has little odor and has an excellent affinity with other materials that are raw materials for hot melt adhesives.
• the olefin-based resin of the present disclosure has good adhesiveness when blended with a styrene-based elastomer and a polyolefin-based elastomer.
• the olefin-based resin of the present disclosure has little odor and has an excellent affinity with other materials that are raw materials for hot melt adhesives.
• the olefin-based resin of the present disclosure has good adhesiveness even when used as a base polymer.

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