KR20220070214A - Olefin-based resins and hot melt adhesives - Google Patents

Abstract

An olefin resin comprising a structural unit derived from an alicyclic olefin (A), an aromatic moiety of 1% or less, and a linearity of 70% or more.

Description

Olefin-based resins and hot melt adhesives

The present invention relates to an olefin-based resin and a hot melt adhesive.

A hot melt adhesive is a solvent-free adhesive agent, and after coating to a to-be-adhered body by heat-melting, it solidifies by cooling, and expresses adhesiveness. In recent years, since hot melt adhesives are excellent in high-speed coating properties, rapid curing properties, solvent-free properties, barrier properties, energy saving properties, economical efficiency, and the like, their use is expanding in various fields.

Since hot melt adhesives do not use a solvent, there is no solvent volatilization, but since petroleum products are used as raw materials, volatile organic compounds derived therefrom are contained in trace amounts. In particular, when hot-melt adhesives are used for hygiene products or members used indoors such as automobiles and houses, there is a possibility that volatile organic compounds contained in the product may adversely affect health or cause discomfort due to odor. Therefore, examination to reduce them is made (for example, refer patent documents 1 and 2).

Japanese Patent Laid-Open No. 2007-204519 Japanese Patent Laid-Open No. 2013-064056

As described above, since hot melt adhesives do not require solvents, although they have little effect on the environment or health, odor derived from volatile organic compounds contained in low molecular weight substances such as styrene-based elastomers and tackifiers, which are raw materials has become a problem, and it is calculated|required about the use of daily necessities, such as sanitary materials, such as a paper diaper and a mask, and a cleaning tool, to especially reduce an odor more.

On the other hand, in order to reduce odor, when low molecular weight substances such as the above-mentioned styrene-based elastomer or tackifier are not blended, the adhesion performance and miscibility with other raw materials are inferior, and the basic performance of the hot melt adhesive is reduced. may be lowered.

Accordingly, the problem to be solved by the technology of the present disclosure is to provide an olefin-based resin that has little odor, has excellent affinity with other materials when used as a raw material of a hot melt adhesive, and can also improve adhesion.

As a result of repeated intensive studies, the present inventors have included a structural unit derived from an alicyclic olefin of an olefin-based resin, and further made the aromatic moiety to a certain amount or less, and improved the linearity of the structure, thereby solving the above problems found that

That is, according to one aspect of the present disclosure, it is possible to provide a technology related to an olefin-based resin that includes a structural unit derived from an alicyclic olefin (A) and satisfies the following (a) and (b).

(a) 1% or less of aromatic moieties

(b) 70% or more linearity

The olefinic resin of the present disclosure has little odor, and when used as a raw material of a hot melt adhesive, it is excellent in compatibility with other materials and can also improve adhesiveness.

[Olefin resin]

The olefinic resin of the present disclosure contains the structural unit derived from the alicyclic olefin (A), and the aromatic moiety is 1% or less, and the linearity is 70% or more.

<alicyclic olefin (A)>

The olefin-based resin of the present disclosure includes a structural unit derived from an alicyclic olefin (A).

Examples of the alicyclic olefin (A) include monocyclic olefins and polycyclic olefins, and polycyclic olefins are preferable.

4-12 are preferable, as for carbon number of an alicyclic olefin (A), 6-10 are more preferable, and 7-10 are still more preferable.

Specific examples of the alicyclic olefin (A) include dicyclopentadiene, cyclopentene, cyclohexene, norbornene and derivatives thereof, and dicyclopentadiene, cyclopentene, cyclohexene, norbornene and these at least one selected from derivatives of, more preferably at least one selected from dicyclopentadiene, norbornene, and derivatives thereof, when the olefinic resin of the present disclosure is used as a tackifier, Dicyclopentadiene is more preferable, and when the olefinic resin of the present disclosure is used as the base polymer, norbornene is even more preferable. Since a resin having a low molecular weight but high glass transition temperature can be obtained by using dicyclopentadiene, the obtained resin is suitable as a tackifier, has high reactivity, and is excellent in the linearity of the obtained resin. Since it is possible to obtain a resin having a high molecular weight and a high glass transition temperature, it is considered that the obtained resin is suitable as a base polymer.

Examples of the derivative include 5-ethylidene-2-norbornene, 5-ethyl-2-norbornene, 5,6-dihydrodicyclopentadiene, tricyclopentadiene, and tetracyclopentadiene. and the like.

By using the alicyclic olefin (A) in the olefinic resin of the present disclosure, compared to resins using other monomers, there is less odor, and when used as a raw material for a hot melt adhesive, compatibility with other materials is excellent.

<α-olefin (B)>

In addition to the structural unit derived from the alicyclic olefin (A), the olefinic resin of the present disclosure preferably further includes a structural unit derived from the α-olefin (B).

By including the α-olefin (B) in the olefin-based resin of the present disclosure, compatibility and adhesion with other materials can be further improved when used as a raw material for a hot melt adhesive.

It is preferable that it is 2-10, and, as for carbon number of (alpha)-olefin (B), it is more preferable that it is 2-8.

The α-olefin (B) is preferably at least one selected from linear α-olefins and branched α-olefins.

As carbon number of a linear alpha-olefin, it is preferable that it is 2-6, 2-4 are more preferable, As carbon number of a branched alpha-olefin, 5-8 are preferable and 5-6 are more preferable.

Specific α-olefin (B) is preferably at least one selected from ethylene, propylene, butene, 3-methyl-1-butene, 4-methyl-1-pentene and 2-ethyl-1-hexene, ethylene, It is preferably at least one selected from propylene and 4-methyl-1-pentene.

In particular, when using an olefin resin as a tackifier, it is important that it is amorphous, low molecular weight, and high dielectric transition temperature (Tg), and as alpha-olefin (B), propylene and 4-methyl-1- pentene are more preferable. do. When an olefin resin is used as the base polymer, it is important to have a high molecular weight and a relatively high glass transition temperature (Tg), and as the α-olefin (B), ethylene and propylene are more preferable.

Moreover, when dicyclopentadiene and its derivative(s) are used as the alicyclic olefin (A), at least one selected from propylene and 4-methyl-1-pentene is preferable, and as the alicyclic olefin (A), When norbornene and its derivatives are used, at least one selected from ethylene and propylene is preferable, and in particular, propylene is more preferable from the viewpoint of compatibility.

<Composition and characteristics of olefin resin>

Although the olefinic resin of this indication contains the structural unit originating in an alicyclic olefin (A), when using as a tackifier, content of the structural unit originating in this alicyclic olefin (A) is 50 mol% or more is preferable, 60 mol% or more is more preferable, 70 mol% or more is more preferable, and 80 mol% or more is even more preferable. The upper limit may be 100 mol%, and when the structural unit derived from α-olefin (B) is included, 90 mol% or less is preferable, and 85 mol% or less is more preferable.

Further, when used as a base polymer, 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 still more preferably 3 mol% or more. and 4 mol% or more is more preferable. Moreover, 40 mol% or less is preferable, 38 mol% or less is more preferable, 35 mol% or less is still more preferable, and 30 mol% or less is still more preferable. On the other hand, 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.

3-50 mol% is preferable, as for content of the structural unit which has the origin of the alpha-olefin (B) of the olefin resin of this indication, 10-40 mol% is more preferable, 15-30 mol% is still more preferable. and 15 to 20 mol% is more preferable. The said range is favorable especially when it uses as a tackifier.

On the other hand, when using as a base polymer, 60-99 mol% is preferable, as for content of the structural unit originating in alpha-olefin (B), 62-98 mol% is more preferable, 65-97 mol% is More preferably, 70-96 mol% is still more preferable. On the other hand, from the viewpoint of compatibility, the content of the structural unit derived from the α-olefin (B) is preferably 60 to 95 mol%, more preferably 62 to 90 mol%, and still more preferably 62 to 85 mol%. and 62 to 80 mol% is more preferable. By including the α-olefin (B) in the above ratio, when it is used as a raw material of a hot melt adhesive, compatibility with other materials and adhesiveness can be further improved.

When the molar ratio [(A)/(B)] of the alicyclic olefin (A) to the α-olefin (B) is used as a tackifier, it is preferably 40/60 to 100/0, and 50/50 to It is more preferable that it is 100/0, It is more preferable that it is 60/40-100/0, It is still more preferable that it is 70/30-95/5, It is still more preferable that it is 80/60-95/5. Further, when used as a component having properties of a base polymer, the molar ratio [(A)/(B)] of the alicyclic olefin (A) to the α-olefin (B) is preferably 1/99 to 40/60. . In particular, from a compatible viewpoint, it is preferable that it is 10/90-40/60, It is more preferable that it is 15/85-40/60, It is more preferable that it is 20/80-40/60.

Especially, when using as a base polymer, it is preferable that it is 1/99-30/70, When using as a component which has the property of a base polymer and a tackifier, it is preferable that it is 5/95-40/60. .

The olefinic resin of the present disclosure has an aromatic moiety of 1% or less, preferably 0.5% or less, more preferably 0.1% or less, still more preferably 0.05% or less, and still more preferably 0%.

As for an aromatic part, content of the aromatic part of the whole olefinic resin can be estimated by measuring aromatic hydrogen.

Aromatic hydrogen can be calculated|required from the ratio of the peak area integral with respect to the proton couple|bonded with unsaturated carbon in < ¹ >H-NMR measurement of the resin after hydrogenation, Specifically, it can obtain|require by the method described in the Example. .

Therefore, the aromatic moiety in the olefinic resin of the present disclosure is in the range where aromatic hydrogen is 1% or less, preferably in the range of 0.5% or less, more preferably in the range of 0.1% or less, and 0.05 % or less is more preferable, and the range in which aromatic hydrogen is 0% is even more preferable.

As for the aromatic moiety in the olefinic resin of the present disclosure, a moiety derived from an aromatic monomer, a moiety having aromaticity by modifying a monomer having no aromaticity, a decomposition product of the resin after polymerization, and the like can be considered.

By making an aromatic part into said range, an odor can be reduced more. Especially, when it uses for a sanitary material, it becomes possible to reduce efficiently the odor of the aromatic type which reduces the quality of a product. Although the reason for this is not certain, when a hot melt adhesive containing an olefinic resin is used, the aromatic part tends to generate a component causing odor in a small amount, so the ratio of the aromatic part in the olefinic resin is small. It is thought that the reduction effect of an odor is achieved by setting it as.

In addition, the volatile component contained in the olefinic resin of the present disclosure is preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 3 ppm or less, still more preferably 2 ppm or less, and even more preferably 1 ppm or less. .

Among the volatile components, the component of the compound having 10 or less carbon atoms contained in the olefinic resin of the present disclosure is preferably 2 ppm or less, more preferably 1 ppm or less, still more preferably 0.5 ppm or less, and still more preferably 0.3 ppm or less. and 0.1 ppm or less is more preferable.

By making the quantity of the volatile component contained in resin into said range, an odor can be reduced more.

Hydrogenated hydrogenated olefin resin may be sufficient as the olefin resin of this indication.

When the raw material alicyclic olefin (A) has two or more unsaturated bonds, or when a monomer having two or more unsaturated bonds other than the alicyclic olefin (A) and α-olefin (B) is used, hydrogenated olefin resin It is preferable to

Hydrogenated olefin resin improves chemical stability and thermal stability more, and also reduces an odor. Especially, the odor of an aromatic type is reduced.

The glass transition temperature of the olefin-based resin of the present disclosure is preferably -40 to 120°C. When using as a component which has the property of the tackifier of a hot melt adhesive, 20-120 degreeC is preferable, 30-100 degreeC is more preferable, 50-80 degreeC is still more preferable, 50-70 degreeC is still more preferable. . Further, when used as a component having the properties of a base polymer of a hot melt adhesive, -40 to 80° C. is preferable, -40 to 60° C. is more preferable, -40 to 50° C. is still more preferable, and -40 to 20° C. is more preferable than When using as a component which has the property of a base polymer and a tackifier, it is preferable that it is -40-100 degreeC, It is more preferable that it is -20-100 degreeC, It is still more preferable that it is -20-80 degreeC, - It is more preferable that it is 20-60 degreeC, and it is still more preferable that it is -20-40 degreeC.

As for the number average molecular weight (Mn) of the olefin resin of this indication, 100-100,000 are preferable. Especially, when using as a component which has the property as a tackifier, 100-2,000 are more preferable, 200-1,000 are more preferable, and 200-500 are still more preferable. Moreover, when using as a component which has the property of the base polymer of a hot melt adhesive, 1,000-100,000 are more preferable.

As for the weight average molecular weight (Mw) of the olefin resin of this indication, 300-200,000 are preferable. Especially, when using as a component which has the property as a tackifier, 300-5,000 are more preferable, 500-3,000 are more preferable, 600-2,000 are still more preferable, and 600-1,200 are still more preferable. In addition, when used as a component having the properties of a base polymer of a hot melt adhesive, 5,000 to 200,000 are more preferable, and when used as a base polymer, 20,000 to 200,000 are more preferable, and 20,000 to 40,000 are still more preferable, the base polymer When using as a component which has both and the property of a tackifier, 5,000-100,000 are more preferable.

As for Z average molecular weight (Mz) of the olefin resin of this indication, 500-500,000 are preferable. Especially, when using as a component which has the property as a tackifier, 700-20,000 are more preferable, 1,000-7,000 are more preferable, 1,200-4,000 are still more preferable. Moreover, when using as a component which has the property of the base polymer of a hot melt adhesive, 10,000-500,000 are more preferable.

It is preferable that it is 2.5 or more, and, as for the molecular weight distribution (Mw/Mn) of the olefin resin of this indication, it is more preferable that it is 3.0 or more.

Moreover, it is preferable that molecular weight distribution (Mz/Mw) is 1.5 or more, It is more preferable that it is 2.0 or more, It is more preferable that it is more than 2.5, It is still more preferable that it is 3.0 or more.

When the molecular weight distribution is within the above range, when used as a raw material of a hot melt adhesive, compatibility with other materials and adhesiveness can be further improved. Specifically, for example, by making Mw/Mn within the above range, it becomes possible to express the tack of the hot melt adhesive, and by making Mz/Mw within the above range, it becomes possible to express the holding power of the hot melt adhesive.

It is preferable that the olefin resin of this indication has a linearity of 70 % or more, and 80 % or more.

Linearity is a ratio in which alicyclic monomers are polymerized with 1,2-bonds, and when one alicyclic monomer unit has two or more unsaturated bonds, the total number of carbon atoms in the alicyclic monomer is x, the number of unsaturated carbon bonds is y, If the integral of the peak area with respect to the structural unit derived from the alicyclic monomer obtained by ¹³ C-NMR measurement is S _Alicyclic , among them, the integral of the peak area derived from the unsaturated carbon is S _CH=CH ,

Linearity (%) = (x/2 (y-1)) × S _{CH =CH} /S _Alicyclic × 100

can be expressed as This is a monomer that is not involved in the formation of a branched structure in which both double bonds of the alicyclic monomer contribute to the polymerization reaction, and a monomer that is not involved in ring formation (reaction to increase the ring size) by Diels-Alder reaction, etc. ratio is shown.

On the other hand, in the case of having one unsaturated bond in one alicyclic monomer unit, x is the total number of carbon bonds in the alicyclic monomer, y is the number of unsaturated carbon bonds, and ¹³ C-NMR measurement with respect to the structural unit derived from the alicyclic monomer obtained by C-NMR measurement. If the integral of the peak area is S _Alicyclic , among them, the integral of the peak area with respect to saturated carbon derived from the 1,2-bond is S _CH-CH ,

Linearity (%) = (x/2y) × S _{CH -CH} /S _Alicyclic × 100

can be expressed as

When the linearity is within the above range, when used as a raw material of a hot melt adhesive, the viscosity at the time of heating is reduced and the cohesive force at the time of cooling is excellent, so that the adhesiveness can be further improved. Moreover, since linearity is high, it is hard to produce decomposition|disassembly also at the time of heating, and it is thought that the olefin resin of this indication has little odor.

<Method for producing olefin-based resin>

The olefinic resin of this indication is obtained by superposing|polymerizing the monomer containing an alicyclic olefin (A). In the polymerization reaction, it is preferable to use a metallocene catalyst. That is, it is preferable to have the process of superposing|polymerizing the monomer component containing an alicyclic olefin (A) at 0-240 degreeC in presence of a metallocene catalyst.

The metallocene catalyst used in this step is a catalyst comprising a metallocene-based transition metal complex as a main catalyst and a cocatalyst, and may use a scavenger or may be supported on an inorganic material or the like.

Examples of the metallocene-based transition metal complex include a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and a tetrahydroindenyl group to a transition metal selected from Group 4 (titanium, zirconium, hafnium). , a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group is coordinated as a ligand in one or two, or two of these groups are coordinated by a covalent bond, and other hydrogen atoms, oxygen and those having a ligand such as an 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 cocatalyst include an alkylaluminoxane compound, a boron compound, and the like.

Examples of the alkyl aluminoxane compound include methyl aluminoxane, ethyl aluminoxane, propyl aluminoxane, butyl aluminoxane, isobutyl aluminoxane, 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, 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-trifluoro) Rophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate, tetrakis (3,5-bistrifluoromethylphenyl) borate, etc. are mentioned. .

Moreover, as a scavenger, an alkyl aluminum compound is mentioned, Specifically, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tributyl aluminum, triisobutyl aluminum, etc. are mentioned.

0.1-50 mol% is preferable with respect to all the monomer components containing an alicyclic olefin (A), and, as for the quantity of a metallocene-type transition metal complex, 1-20 mol% is more preferable.

Moreover, 0.2-60 mol% is preferable with respect to all the monomer components containing an alicyclic olefin (A), and, as for the quantity of a promoter, 2-30 mol% is more preferable.

In this process, 2 or more types of metallocene catalysts may be used, and it is preferable to use 2 or more types together. By using a some catalyst together, molecular weight distribution of the olefin resin obtained can be adjusted, and it becomes possible to improve adhesiveness, suppressing an odor.

0-240 degreeC is preferable, as for the polymerization temperature in this process, 20-220 degreeC is more preferable, and its 40-200 degreeC is still more preferable.

It is preferable that the manufacturing method of the olefin resin of this invention includes the process of stripping. The stripping process which is this process may be performed after superposition|polymerization of an olefin resin, and may be performed after the hydrogenation process demonstrated next.

It is preferable to use inert gas, such as nitrogen and argon gas, as a medium, and, as for stripping, it is more preferable to use nitrogen. Specifically, in a state in which the resin is heated and melted in a container, the interface between the gas in the container and the resin is updated by stirring or the like, and the gas in the container is further updated with an inert gas medium to remove volatile impurities. For example, the stripping process can be performed with nitrogen-containing inert gas as a medium at 150-300 degreeC, 0.5-5 hours, and nitrogen 1-1000 L/min flow volume with respect to 100 g of olefin resins.

Here, each parameter of the stripping process mentioned above is not limited to this, For example, 100-300 degreeC is preferable, 150-300 degreeC is more preferable, and, as for the temperature of stripping, 150-250 degreeC is still more preferable.

In addition, for example, the time for stripping may be selected according to the amount of resin or the size of the container to be used, but is preferably 0.1 to 20 hours, more preferably 0.5 to 10 hours, and 0.5 to 5 hours. Time is more preferable.

In addition, the flow rate of nitrogen at the time of stripping using nitrogen should just select an optimal flow volume according to the size of the container used, 0.1-20 L/min is preferable with respect to 100 g of olefin resin amount, and 1 to 10 L/min is more preferable.

By performing stripping under each condition of the said temperature, the said time, and the said nitrogen flow rate, there is little odor, and an olefin resin can be efficiently obtained suitable for the raw material of a hot melt adhesive. The method for producing an olefin-based resin of the present invention, that is, an olefin-based resin obtained by polymerization of a monomer component containing an alicyclic olefin (A) at 0 to 240°C in the presence of a metallocene catalyst, is the obtained resin itself Since there is little odor, the condition of excessive stripping is not required. Moreover, when the olefinic resin obtained in the said polymerization process satisfies the conditions that an aromatic part is 1 % or less and linearity is 70 % or more, since the resin itself has less odor, excessive stripping becomes unnecessary.

It is preferable that the manufacturing method of the olefin resin of this invention further includes the process of hydrogenating.

When the raw material alicyclic olefin (A) has two or more unsaturated bonds, or when a monomer having two or more unsaturated bonds other than the alicyclic olefin (A) and α-olefin (B) is used, the hydrogenation step is It is more preferable to include

It is more preferable that this process is a process of hydrogenating at 100-300 degreeC in presence of a catalyst. By hydrogenating the olefin resin obtained in the said polymerization process, chemical stability and thermal stability can improve, and an odor can also be reduced further. Especially, it becomes possible to reduce the odor of an aromatic type.

A metal catalyst is preferable and, as for the catalyst used in this hydrogenation process, a palladium catalyst, a nickel catalyst, a platinum catalyst, a ruthenium catalyst, a rhenium catalyst, a copper catalyst, a rhodium catalyst, etc. are mentioned.

Examples of the palladium catalyst include palladium carbon, palladium alumina, palladium silica, palladium silica alumina, zeolite-supported palladium, and the like.

Examples of the nickel catalyst include nickel diatomaceous earth, sponge nickel, nickel alumina, nickel silica, nickel carbon, and the like.

Examples of the platinum catalyst include platinum silica, platinum silica alumina, and zeolite-supported platinum.

Examples of the ruthenium catalyst include ruthenium carbon, ruthenium alumina, ruthenium silica, ruthenium silica alumina, and zeolite-supported ruthenium.

1-40 mass parts is preferable with respect to 100 mass parts of olefin resin, and, as for the quantity of a hydrogenation catalyst, 5-35 mass parts is more preferable.

30-300 degreeC is preferable, as for the hydrogenation reaction temperature in this process, 60-300 degreeC is more preferable, 100-300 degreeC is still more preferable, and its 100-250 degreeC is still more preferable.

1-20 MPa is preferable, as for the hydrogen pressure in this process, 2-15 MPa is more preferable, and its 3-10 MPa is still more preferable.

[Hot Melt Adhesive]

The hot-melt adhesive of the present disclosure includes the olefin-based resin.

That is, the hot melt adhesive of the present disclosure contains a structural unit derived from an alicyclic olefin (A), a structural unit derived from an aromatic monomer is 1 mol% or less, and a volatile component is 10 ppm or less It contains an olefinic resin do.

The olefin resin, by controlling its molecular weight, molecular weight distribution, glass transition temperature, etc., among components constituting the hot melt adhesive, a component having a property of a tackifier, a component having a property of a base polymer, or a tackifier and base polymer properties.

In particular, since the olefin-based resin of the present disclosure can be used as a component having both properties of a tackifier and a base polymer, even when a tackifier or a base polymer is not separately included, the hot melt adhesive has little odor and excellent adhesion. is obtained On the other hand, when used as a component having properties of a tackifier or a component having properties of a base polymer, it is preferable to separately include a base polymer or a tackifier, but even in this case, the olefinic resin of the present disclosure is Since the affinity with other materials is excellent, a good hot melt adhesive can be obtained.

Even when it is used as any component, the effect of the presently disclosed technique that there is little odor and excellent affinity with other materials can be exhibited, the adhesiveness of the obtained hot melt adhesive can be improved, and an odor can also be suppressed.

The hot melt adhesive of the present disclosure may include, in addition to the olefin-based resin, a base polymer, a tackifier, a plasticizer, and an additive.

<Base Polymer>

The hot melt adhesive of the present disclosure preferably further contains a base polymer.

When the olefin resin is used as a component having properties of a base polymer or a component having both properties of a tackifier and a base polymer, a good hot melt adhesive can be obtained even without a base polymer. When used as a component having the properties of a tackifier, it is preferable to include a base polymer.

Specific examples of the base polymer include natural rubber, olefin-based elastomer, and styrene-based elastomer, 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.

Examples of the olefin-based elastomer include an ethylene-based olefin polymer, an amorphous olefin polymer, a propylene-based elastomer, an ethylene-vinyl acetate copolymer, and an ethylene-acrylic acid ester copolymer.

Specific examples of the ethylene-based olefin polymer include polyethylene and a copolymer of ethylene and an olefin having 3 to 10 carbon atoms. Although it will not specifically limit as long as it can be used as a base polymer of a hot melt adhesive, From a viewpoint of the adhesiveness of a hot melt adhesive, Preferably, it is an ethylene-alpha-olefin copolymer. Specific examples of the α-olefin include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and 1-hexa decene, 1-octadecene, 1-eicocene, etc. are mentioned, Among these, 1 type, or 2 or more types can be used. Among these ?-olefins, 1-octene is preferable. From the viewpoint of the tackiness of the hot melt adhesive, more preferably an ethylene-1-octene copolymer, and still more preferably an ethylene-1-octene copolymer containing 5 to 50% by mass of 1-octene-derived structural units.

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 thermal creep resistance. The melting point of the ethylene-based olefin polymer can be measured by differential scanning calorimetry. On the other hand, among the ethylene-based olefin polymers, those that are amorphous belong to the amorphous olefin polymers described later.

The amorphous olefin polymer is at least one homopolymer or copolymer selected from the group consisting of a linear or branched α-olefin having 2 to 24 carbon atoms or diene, and is not particularly limited, but polybutene and polybutadiene , polyisoprene, and amorphous polyalphaolefin.

As polybutene, each individual or copolymer of isobutene and normal butene, and its hydrogenated product are mentioned.

As polybutadiene, the homo or copolymer of 1,2-butadiene and 1, 4- butadiene, and its hydrogenated body are mentioned, and it may have a hydroxyl group at the terminal.

Examples of the polyisoprene include a homopolymer or copolymer of isoprene and a hydrogenated product thereof, and may have a hydroxyl group at the terminal.

Examples of the amorphous polyalphaolefin include homopolymers or copolymers of olefins having 2 to 6 carbon atoms.

The propylene-based elastomer is an elastomer having a propylene unit as a main structural unit, and includes a low-melting-point polypropylene and the like. The elastomer is not limited by its density as long as it has rubber-elastic properties, and may be chemically crosslinked or not chemically crosslinked.

5-50 mass % is preferable and, as for the vinyl acetate content rate of an ethylene- vinyl acetate copolymer, 10-40 mass % is more preferable.

As the styrene-based elastomer, a styrene-based block copolymer is preferable.

The styrene-based block copolymer is a copolymer obtained by block copolymerization of a styrene-based compound and a conjugated diene compound, and usually has a styrene-based compound block and a conjugated diene compound block.

Here, as the "styrene-based compound", styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene and vinylanthracene. In particular, styrene is preferable. These styrene-type compounds can be used individually or in combination.

A "conjugated diene compound" means a diolefin compound having at least one pair of conjugated double bonds. As a "conjugated diene compound", specifically, 1,3-butadiene, 2-methyl-1,3-butadiene (or isoprene), 2,3-dimethyl-1,3-butada ene, 1,3-pentadiene, and 1,3-hexadiene can be exemplified. Particular preference is given to 1,3-butadiene, 2-methyl-1,3-butadiene. These conjugated diene compounds can be used individually or in combination.

A non-hydrogenated substance or a hydrogenated substance may be sufficient as a styrene-type block copolymer. Specifically, the "unhydrogenated substance of a styrene-type block copolymer" can illustrate that the block based on the conjugated diene compound is not hydrogenated. In addition, specifically, "a hydrogenated substance of a styrene-type block copolymer" can illustrate the block copolymer to which all or part of the block based on a conjugated diene compound was hydrogenated.

The hydrogenated ratio of "the hydrogenated substance of a styrene-type block copolymer" can be expressed as a "hydrogenation rate." The "hydrogenation rate" of the "hydrogenated product of a styrene-based block copolymer" is based on all aliphatic double bonds contained in the block based on the conjugated diene compound, among them, hydrogenated doubles converted to saturated hydrocarbon bonds refers to the ratio of bonding. This "hydrogenation rate" can be measured with an infrared spectrophotometer, a nuclear magnetic resonance apparatus, or the like.

As "a non-hydrogenated additive of a styrene-based block copolymer", specifically, for example, a styrene-isoprene-styrene block copolymer (also referred to as "SIS"), a styrene-butadiene-styrene block copolymer, A polymer (it is also called "SBS") can be illustrated. As a "hydrogenated product of a styrene-based block copolymer", specifically, for example, a hydrogenated styrene-isoprene-styrene block copolymer (also referred to as "SEPS") and a hydrogenated styrene-butadiene -Styrene block copolymer (also called "SEBS") can be illustrated.

A styrene-type block copolymer can be used individually or in combination.

In the styrene-based block copolymer, from the viewpoint of the adhesive strength of the hot-melt adhesive, the ratio of the styrene block contained in the styrene-based block copolymer (styrene content) is preferably 5 to 50% by mass, more preferably 10 to 40 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 olefinic resin is preferably 5 or less, more preferably 4 or less, still more preferably 3 or less, and 2 or less. more preferably, and even more preferably 1 or less.

The difference in Hansen solubility parameters here means the Ra value calculated|required by the following formula|equation.

Ra=[4(δ _d2- δ _d1 ) ² +(δ _p2 -δ _p1 ) ² +(δ _h2 -δ _h1 ) ² ] ^1/2

(Wherein, δ _d is a dispersing force, δ _p is a polarization force, δ _h is a solubility parameter based on hydrogen bonding strength, δ _d1 , δ _p1 , δ _h1 is a solubility parameter of an olefinic resin, δ _d2 , δ _p2 , δ _h2 is the solubility parameter of the base polymer.)

The content of the base polymer is, from the viewpoint of cohesiveness, 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 in 100 parts by mass of the hot melt adhesive. It is more than part, Preferably it is 80 mass parts or less, More preferably, it is 70 mass parts or less, More preferably, it is 60 mass parts or less, More preferably, it is 50 mass parts or less. That is, in the hot melt adhesive, preferably 5 mass % or more, more preferably 10 mass % or more, still more preferably 20 mass % or more, still more preferably 30 mass % or more, and preferably 80 mass % or more. Hereinafter, more preferably, it is 70 mass % or less, More preferably, it is 60 mass % or less, More preferably, it is 50 mass % or less.

-20-100 degreeC is preferable and, as for the glass transition temperature of a base polymer, -20-60 degreeC is more preferable.

Even when the said olefin resin is used as a component which has the property of a base polymer, or a component which has both a tackifier and the property of a base polymer, a 2nd base polymer may be included.

As the second base polymer, the olefin resin of the present disclosure, that is, the olefin resin described in the section of the [olefin-based resin], or the olefin-based elastomer is preferably used.

It is preferable that it is 60-120 degreeC, as for melting|fusing point of a 2nd base polymer, it is more preferable that it is 60-110 degreeC, It is more preferable that it is 70-100 degreeC.

<Tackifier>

The hot melt adhesive of the present disclosure preferably further contains a tackifier.

When the olefin resin is used as a component having the properties of a tackifier or a component having both properties of a tackifier and a base polymer, a good hot melt adhesive can be obtained even without a tackifier, but in particular, the olefin resin It is preferable to include a tackifier when it is used as a component having properties of a base polymer.

When the hot-melt adhesive of the present disclosure contains a tackifier, it is preferable that the olefin-based resin has properties of a base polymer.

Examples of the tackifier 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. Specifically, natural rosin, modified rosin, hydrogenated rosin, glycerol ester of natural rosin, glycerol ester of modified rosin, pentaerythritol ester of natural rosin, pentaerythritol ester of modified rosin, pentaerythritol ester of hydrogenated rosin, natural rosin Terpene copolymer, natural terpene three-dimensional polymer, hydrogenated terpene copolymer, hydrogenated derivative, polyterpene resin, phenol-modified terpene resin hydrogenated derivative, aliphatic petroleum hydrocarbon resin, aliphatic petroleum hydrocarbon resin hydrogenated derivative, aromatic petroleum hydrocarbon Resin, hydrogenated derivatives of aromatic petroleum hydrocarbon resins, cyclic aliphatic petroleum hydrocarbon resins, and hydrogenated derivatives of cyclic aliphatic petroleum hydrocarbon resins can be exemplified. These may be used individually or in combination of 2 or more types.

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 in 100 parts by mass of the hot-melt adhesive from the viewpoint of improving the tackiness. It is 30 mass parts or more, Preferably it is 80 mass parts or less, More preferably, it is 70 mass parts or less, More preferably, it is 60 mass parts or less, More preferably, it is 50 mass parts or less. That is, in the hot melt adhesive, preferably 5 mass % or more, more preferably 10 mass % or more, still more preferably 20 mass % or more, still more preferably 30 mass % or more, and preferably 80 mass % or more. Hereinafter, more preferably, it is 70 mass % or less, More preferably, it is 60 mass % or less, More preferably, it is 50 mass % or less.

The softening point of the tackifier is preferably -20°C or higher, more preferably -15°C or higher, still more preferably -10°C or higher, and preferably 180°C or lower, more preferably 170°C or lower. , more preferably 160°C or less.

<Plasticizer>

The hot melt adhesive of the present disclosure preferably further contains a plasticizer.

Although it does not specifically limit as a plasticizer, It is preferable to use for a hot melt adhesive, More preferably, it is oil or wax. Moreover, as a plasticizer, phthalic acid esters, adipic acid esters, fatty acid esters, glycols, epoxy polymer plasticizers, etc. can also be used.

Examples of the oil include paraffinic process oil, naphthenic process oil, isoparaffinic oil, and the like.

Commercial products of paraffinic process oil include "Diana Process Oil PW-32", "Diana Process Oil PW-90", "Diana Process Oil PW-150", "Diana Process Oil PS-32" manufactured by Idemitsu Kosan Co., Ltd. "Diana Process Oil PS-90", "Diana Process Oil PS-430"; "Kaydol oil" made by Chevron USA company, "ParaLux oil", etc. are mentioned (all are brand names).

Examples of commercially available isoparaffinic oils include "IP Solvent 1016", "IP Solvent 1620", "IP Solvent 2028", "IP Solvent 2835", and "IP Clean LX" manufactured by Idemitsu Kosan Co., Ltd.; Nichiyu Co., Ltd. "NA Solvent" series, etc. are mentioned (all are brand names).

Examples of the wax include animal wax, plant wax, carnauba wax, candelilla wax, wood wax, beeswax, mineral wax, petroleum wax, paraffin wax, microcrystalline wax, petrolatam, higher fatty acid wax, higher fatty acid ester Wax, Fischer-Tropsch wax, etc. can be illustrated.

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, in 100 parts by mass of the hot-melt adhesive from the viewpoint of improving the adhesion and improving the applicability, more preferably It is 10 mass parts or more, and is 60 mass parts or less, Preferably it is 40 mass parts or less, More preferably, it is 30 mass parts or less. That is, in the hot melt adhesive, 2 mass% or more, preferably 5 mass% or more, more preferably 10 mass% or more, and 60 mass% or less, preferably 40 mass% or less, more preferably 30 mass% or less.

<Other additives>

The resin composition of this indication may contain arbitrary additives, such as an inorganic filler, antioxidant, a ultraviolet absorber, a light stabilizer, and a lubricating agent, further as needed in the range which does not impair the objective of this indication technology.

Examples of the inorganic filler include talc, calcium carbonate, barium carbonate, wollastonite, silica, clay, mica, kaolin, titanium oxide, diatomaceous earth, urea resin, styrene bead, starch, barium sulfate, calcium sulfate, magnesium silicate, magnesium carbonate. , alumina, quartz powder, and the like can be exemplified.

As antioxidants, trisnonylphenyl phosphite, distearyl pentaerythritol diphosphite, "adecastap 1178" (made by ADEKA Corporation), "stamilizer TNP" (manufactured by Sumitomo Chemical Co., Ltd.), "ilgafoss 168" ' (manufactured by BASF), phosphorus-based antioxidants such as "SandstabP-EPQ" (manufactured by Sando Corporation), 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3-(3',5'- Phenolic antioxidants, such as di-t-butyl-4'-hydroxyphenyl) propionate, "Smilizer BHT" (made by Sumitomo Chemical Co., Ltd.), "Ilganox 1010" (made by BASF), dilauryl-3 ,3'-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), "Smilizer TPL" (manufactured by Sumitomo Chemical Co., Ltd.), "DLTP "Yoshitomi" (Mitsubishi Chemical Co., Ltd.) ) and sulfur-based antioxidants such as “Antiox L” (manufactured by Nichiyu Corporation).

<Manufacturing method and use of hot melt adhesive>

The hot melt adhesive of the present disclosure, in addition to the olefinic resin, if necessary, dry blending a base polymer, tackifier, plasticizer and additive using a Henschel mixer, etc., single or twin screw extruder, plastomer or It can manufacture by melt-kneading with a Banbury mixer etc.

Since the hot melt adhesive of the present disclosure has excellent adhesiveness and low odor, for example, sanitary materials, packaging, bookbinding, textiles, woodworking, electrical materials, pipe making, construction, filters It can be used suitably for manufacturing, low-pressure molding, and sacking.

Specifically, it can be preferably used as an adhesive for hygiene products such as paper diapers and sanitary products, typified by fixing of nonwoven fabric or superabsorbent polymer (SAP), and as an adhesive for assembly typified by automobile floor mats, particularly Since there is little odor, it can use suitably as adhesive agents for hygiene products.

Example

Next, an aspect of the present disclosure technology will be described in more detail by way of examples, but the present disclosure technology is not limited by these examples at all.

[Analysis and evaluation of olefin resin]

〔One. Composition of Copolymer]

For the resins HP1 to HP11 described later, a nuclear magnetic resonance (NMR) apparatus ( ^ECA500 , manufactured by Nippon Denshi Corporation, 1H resonance frequency: 500 MHz) was used, and the solvent was deuterated chloroform (chloroform-d), the number of integrations. ¹³ C-NMR measurement was performed 10,000 times under the condition of a temperature of 25 ° C., and the composition of the copolymer (mol%) from the ratio of the integral of the peak area for each monomer component (structural unit) to the integral of the total peak area saved Specifically, the integral of the peak area for each monomer component (structural unit) was divided by the number of carbon atoms of the monomer constituting the integral value, and the composition (mol%) of the copolymer was obtained from the ratio. A result is shown in Table 1 and Table 2.

For the resins BP1 to BP10 and BP12 to BP16 described later, compositions were measured in the same manner as above except that deuterated 1,2-tetrachloroethane was used as a solvent and the temperature was 120°C. A result is shown in Table 5, Table 6, and Table 10.

〔2. Aromatic hydrogen content %]

For the resins HP1 to HP11 described later, a nuclear magnetic resonance (NMR) apparatus ( ^ECA500 , manufactured by Nippon Denshi Corporation, 1H resonance frequency: 500 MHz) is used, and the solvent is deuterated chloroform, the number of times of integration is 256 times, and the temperature is 25°C. ¹ H-NMR measurement of the resin after hydrogenation obtained in Examples and Comparative Examples under the conditions of The amount of aromatic hydrogen was calculated from A result is shown in Table 1 and Table 2.

The detection limit is less than 0.1%. In Tables 1 and 2, "n.d." represents less than the detection limit.

For the resins BP1 to BP12 described later, the amount of aromatic hydrogen was measured in the same manner as above, except that deuterated 1,2-tetrachloroethane was used as a solvent. The results are shown in Tables 5 and 6.

[3. average molecular weight]

About the resins HP1-HP11 mentioned later, the average molecular weight was measured by the gel permeation chromatography (GPC) method. For the measurement, a GPC measuring device (HLC8220, detector: RI, column: TSK-GEL GHXL-L, G4000HXL, G2000HXL (all manufactured by Tosoh Corporation)) was used, and tetrahydrofuran was used as the eluent, and the oven temperature was 40°C. As such, polystyrene conversion number average molecular weight (Mn), weight average molecular weight (Mw), and Z average molecular weight (Mz) were obtained. A result is shown in Table 1 and Table 2.

For the resins BP1 to BP16 to be described later, a GPC measuring device (HLC8321GPC/HT, detector: RI, column: TSK-GEL GMHHR-H(S)HT two (both manufactured by Tosoh Corporation)) was used, and as the eluent Using 1,2,4-trichlorobenzene, the average molecular weight was measured by the method similar to the above except having set it as the oven temperature of 145 degreeC. A result is shown in Table 5, Table 6, and Table 10.

〔4. glass transition temperature]

For the resins HP1 to HP11, which will be described later, glass transition temperatures were measured using a differential scanning calorimeter (DSC8500, manufactured by Parkin Elmer) with a temperature program of -40°C to 220°C and temperature increase at 10°C/min. A result is shown in Table 1 and Table 2.

For the resins BP1 to BP10 and BP12 to BP16, which will be described later, dynamic viscoelasticity measurement (rheometer, manufactured by Anton Paar, MCR302) is performed in shear mode while the temperature is raised from -30°C to 150°C at 5°C/min, and tanδ The glass transition temperature was obtained from the peak value of The glass transition temperature of BP11 is a literature value, and the butadiene chain is -100°C and the styrene chain is 100°C. A result is shown in Table 5, Table 6, and Table 10.

[5. linearity]

The ¹³ C-NMR measurement of the resin before the hydrogenation reaction was performed in the above [1. composition of the copolymer].

For the resins HP1 to HP10 described later, in the case of a straight chain, one of the two dicyclopentadiene monomers used does not consume an unsaturated bond, so one dicyclopentadiene-derived structural unit includes: Total carbon number is 10, unsaturated carbon number is 2. Then, the integral of the peak area with respect to the structural unit derived from dicyclopentadiene is S _DCPD , among them, the integral of the peak area derived from the unsaturated carbon is S _{CH = CH} , and the linearity (%) by the following formula saved A result is shown in Table 1 and Table 2.

Linearity (%) = 5S _{CH =CH} /S _DCPD × 100

About resins BP1-BP10 mentioned later, total carbon number is 7 and unsaturated carbon number 2 in the structural unit of the norbornene monomer used. Therefore, the integral of the peak area with respect to the structural unit derived from norbornene is S _NB , and among them, the integral of the peak area derived from the saturated carbon having a 1,2-bond form is S _{CH -CH} , by the following formula The linearity (%) was calculated|required. The results are shown in Tables 5 and 6.

Linearity (%) = 3.5S _{CH -CH} /S _NB × 100

[6. Amount of Volatile Components and Amount of Volatile Aromatic Components]

Aromatic components (benzene, toluene, xylene, styrene, etc.) whose holding time is less than 10 minutes when a gas component is generated using headspace gas chromatography (device name: Agilent7697A/Agilent7890B) and measured under the following conditions was taken as the amount of aromatic volatile components (aroma). In addition, the amount of the component having a holding time of less than 13 minutes (about 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 holding time of less than 40 minutes from which all volatile components are desorbed is the total amount of volatile components (TVOC).

A result is shown in Table 1, Table 2, Table 5, and Table 6.

In addition, in Table 1, Table 2, Table 5, and Table 6, it showed as toluene conversion mass (ppm) of the aromatic volatile component with respect to the mass of an olefin resin, a volatile component, and a total volatile component. On the other hand, the detection limit is about 1 ppb.

(Measurement conditions: sample heat treatment: 150°C, 20min, column: BPX5 30m×0.32m i.d.×1.0μm, inlet: 300°C, temperature program: 50°C to 300°C, 10°C/min, temperature rise)

[7. Hansen solubility parameter (HSP) value]

According to the method of Documents 1 to 3 shown below, olefinic _{resins HP1} , _HP2 , Evaluate the solubility with HP5, HP6, and HP8 to HP11, plot the value of the solvent on a three-dimensional plot, create a minimum sphere with a good solvent on the inside and a poor solvent on the outside, and determine the coordinates at the center of the sphere It was set as the solubility parameter of olefin resin. A result is shown in Table 1 and Table 2.

Literature 1: Hildebrand JH, Scott RL. The solubility of nonelectrolytes, 3 rd ed. New York, NY: Dover Publications; 1964

Document 2: C. M. Hansen et al., Carbon, 42, 1591-1597, 2004

Document 3: Masato Morimoto et al., Energy Fuels, 32, 11296-11303, 2018

〔8. Affinity]

[7. Hansen solubility parameter (HSP) value], the same evaluation was performed about the following three types of elastomers used for a hot melt adhesive, and affinity was evaluated. Specifically, the solubility of various solvents was evaluated for each elastomer, the solubility parameter of the elastomer was determined, and the affinity between the olefin resin and each elastomer was evaluated by the following Ra value. In addition, affinity was evaluated also by dispersibility and Tg change rate. A result is shown in Table 1 and Table 2.

<Elastomer>

· Low melting point polypropylene (PP), an olefinic elastomer (manufactured by Idemitsu Kosan Co., Ltd., trade name: L-MODU S400, Mw: 45,000, melt viscosity (viscosity B) (190°C, ASTM D 3236): 8500 mPa·s, softening point (R&B, ISO4635): 93℃)

Amorphous polyalphaolefin (APAO), an olefinic elastomer (manufactured by Evonik Industries AG, trade name: VESTOPLAST (registered trademark) 708, melt viscosity (190°C, DIN 53 019): 8000 mPa·s, softening point (R&B, DIN EN 1427) ): 108℃)

Styrene-isoprene-styrene block copolymer (SIS), a styrene-based elastomer (manufactured by Kraton Corporation, trade name: KRATON (registered trademark) D1161, MFR (190°C, 2.16 kg, ISO 1133): 1.3 to 3.7 g/ 10min, styrene content: 15wt%)

<Ra Chi>

The Ra value which is an index|index of affinity was computed by the following formula. On the other hand, the smaller the Ra value, the better the affinity. In addition, in the following formulas, δ _d1 , δ _p1 , and δ _h1 are solubility parameters of the olefin-based resin, and δ _d2 , δ _p2 , and δ _h2 are solubility parameters of each of the elastomers.

Ra=[4(δ _d2- δ _d1 ) ² +(δ _p2 -δ _p1 ) ² +(δ _h2 -δ _h1 ) ² ] ^1/2

Here, it has shown that it is excellent in compatibility, so that Ra value is small, and the following criteria evaluated it.

◎: Ra value ≤ 1.5

○: 1.5<Ra value ≤3.0

△: 3.0 < Ra value ≤ 5.0

×: 5.0 <Ra level

<Dispersibility>

Dispersibility was evaluated as follows.

The olefin-based resin and the base polymer (elastomer) were put in a container at a mass ratio of 1:1, stirred at 180° C. for 1 hour, left still to cool to room temperature, and after 1 day, visually evaluate the dispersibility of the obtained mixture. did.

◎: Transparent

○: About transparent (slightly cloudy)

△: Cloudy (slightly transparent)

×: milky white

<Tg change rate>

The rate of change of the glass transition temperature (Tg) before and after mixing was evaluated by the following method. On the other hand, it is estimated that the affinity between the two is high, so that the Tg change rate is large.

Using a single piece of elastomer, a strip-shaped test piece cut out from a sheet (1 mm thick) obtained by mixing an olefin resin and an elastomer in a mass ratio of 1:1 and press-molding, -150°C to 230°C (the test piece breaks temperature), dynamic viscoelasticity measurement (Rheometer, Hitachi High-Tech Sciences Co., Ltd., DMS6100) was performed in tensile test mode while heating at 2°C/min), and Tg was determined from the peak value of tanδ. Tg (low melting point polypropylene (PP) (L-MODU S-400): Tg -3 ° C., amorphous polyalpha olefin (APAO) (VESTOPLAST 708): Tg -35 ° C.) derived from the olefinic elastomer is an olefin Tg shifts to the high temperature side with mixing|blending of a system resin (Tg 36 degreeC or more). The Tg change rate was evaluated based on the following criteria. On the other hand, the case where there was no change from the Tg derived from the olefin-based elastomer was 0%, and the case where the Tg changed to the same Tg as that of the olefin-based resin was 100%.

◎: 80% or more

○: 60% or more and less than 80%

△: 40% or more and less than 60%

×: less than 40%

<Comprehensive evaluation of affinity>

Comprehensive evaluation of affinity was performed on the basis of the following criteria. For the three evaluation results of the aforementioned Ra value (HSP), dispersibility, and Tg change rate, an average value was calculated by taking ◎ as 4 points, ○ as 3 points, △ as 2 points, and × as 1 point, respectively, and the average value obtained It was set as the comprehensive evaluation by rounding off, and it showed with the said symbol.

[9. Evaluation of adhesion properties in styrene-based hot melt adhesive (HMA) (pressure-sensitive adhesive)]

At the compounding ratio shown in Table 3, each raw material was extract|collected to the sample bottle, toluene solvent was added, it stirred and melt|dissolved, and HMA solution was prepared. The HMA solution was apply|coated to the PET (polyethylene terephthalate) film, the toluene solvent was volatilized, and the HMA sample was prepared. A SUS plate was used as the adherend, and the adhesion tri-physical properties were evaluated by the following test method. In addition, in this evaluation, resin HP2, HP4, and HP7-HP11 were used as a tackifier.

<Raw material>

Base polymer: styrene-isoprene-styrene block copolymer (SIS) (manufactured by Kraton Corporation, trade name: KRATON (registered trademark) D1161)

Plasticizer: Paraffin-based oil (Diana Process Oil PS-32, manufactured by Idemitsu Kosan Co., Ltd.)

・Antioxidant: Ilganox 1010 (manufactured by BASF Japan Co., Ltd.)

<Adhesiveness>

It measured according to JIS Z0237 (23 degreeC, 180 degree peel).

◎: 10N/cm or more

○: 6N/cm or more and less than 10N/cm

△: 3N/cm or more and less than 6N/cm

×: less than 3N/cm

<loop tag>

It measured according to JIS Z0237, FINAT test standard (23 degreeC, 2 second contact).

◎: 10N/cm or more

○: 6N/cm or more and less than 10N/cm

△: 3N/cm or more and less than 6N/cm

×: less than 3N/cm

<Maintaining Power>

It measured according to JIS Z0237 (50 degreeC, 1 kg load creep).

◎: 500min or more

○: 300min or more and less than 500min

△: 100 min or more and less than 300 min

×: less than 100 min

<Comprehensive evaluation of adhesiveness>

Comprehensive evaluation of adhesiveness was performed on the following reference|standard. For the three evaluation results of adhesive force, loop tack, and holding force described above, ◎ is 4 points, ○ is 3 points, △ is 2 points, and × is 1 point, the average value is calculated, and the obtained average value is rounded up for comprehensive evaluation and was represented by the above symbol.

[10. Evaluation of compoundability in polyolefin-based hot melt adhesive (HMA)]

At the blending ratio shown in Table 4, each raw material was collected in a sample bottle, melted and stirred at 140° C. for 30 minutes, then the contents were transferred onto a PET film and allowed to cool at room temperature to prepare an HMA sample. The following method evaluated the adhesive force (adhesiveness) of the obtained HMA sample. In addition, in this evaluation, resin HP5, HP7, and HP10 were used as a tackifier.

<Raw material>

· Tackifier: terpene resin, manufactured by Yasuhara Chemical Co., Ltd., YS resin PX300N (softening point: 30°C, liquid at room temperature)

Base polymer: low-melting polypropylene (L-MODUS400, manufactured by Idemitsu Kosan Co., Ltd.)

Plasticizer: Paraffinic oil (Diana Process Oil PS-32, manufactured by Idemitsu Kosan Co., Ltd.), polyisobutene (manufactured by INEOS Oligomers, Indopol (registered trademark) H-18000, Mw: 6,000, Viscosity (100°C): 40,500 cSt )

・Antioxidant: Ilganox 1010 (manufactured by BASF Japan Co., Ltd.)

<Adhesiveness>

When the HMA sample was lightly tapped with a finger, the degree of adhesion to the finger was evaluated. The evaluation result obtained was set as a reference|standard so that it might correlate substantially with the value of the loop tack of Table 3.

◎: strongly attached and followed

○: Slightly strongly adhered

△: slightly weakly adhered

x: hardly adhered

[11. melting point]

For the resins BP1 to BP10 and BP12 to BP16 to be described later, while the temperature is increased from -30°C to 150°C at 5°C/min, dynamic viscoelasticity measurement in shear mode (using a rheometer, manufactured by Anton Parsa, MCR302) is performed and stored The temperature at which the values of the elastic modulus G' and the loss elastic modulus G" became the same was calculated|required as melting|fusing point. The result is shown in Table 5, Table 6, and Table 10.

On the other hand, using a differential scanning calorimeter (DSC8500, manufactured by Parkin Elmer), the temperature program is increased to -40°C to 220°C, 10°C/min. Since it corresponds to the softening point of an amorphous polymer, it showed as "n.d." in Tables 5 and 6.

[12. Oil compatibility]

Resins BP1 to BP12 described later and paraffinic oil (Diana Process Oil PW-90, manufactured by Idemitsu Kosan Co., Ltd.) were placed in a container at a mass ratio of 3:1, stirred at 180° C. for 1 hour, and then left at the same temperature for 5 minutes. Then, the dispersibility of the obtained mixture was evaluated visually. The results are shown in Tables 5 and 6.

◎: Transparent (uniform)

○: Approximately transparent (with diffuse reflection)

△: some lumps (with swelling)

×: lump (swelling)

[13. TF compatibility]

Resins BP1 to BP10 and BP12 described later, and a DCPD-based tackifier (Escorez5300, manufactured by Exxon Mobil) are placed in a container at a mass ratio of 2:1, stirred at 180° C. for 1 hour, then left standing to cool to room temperature, and allowed to cool to room temperature for 1 week After progress, the dispersibility of the obtained mixture was evaluated visually.

In addition, BP11 resin and C9 aroma/C5 tackifier (Escorez5600, manufactured by Exxon Mobil) were put in a container at a mass ratio of 2:1, stirred at 180° C. for 1 hour, left standing to cool to room temperature, and after 1 week Then, the dispersibility of the obtained mixture was evaluated visually. The results are shown in Tables 5 and 6.

◎: Transparent

○: About transparent (slightly cloudy)

△: Cloudy (slightly transparent)

×: milky white

[14. Tackiness evaluation of hot melt adhesive (HMA)]

At the compounding ratios shown in Tables 7, 8, 9 and 10, each raw material is collected in a sample bottle, melted and stirred at 180° C. for 30 minutes, and then the contents are transferred onto a PET film and left to cool at room temperature, HMA Samples were prepared. The following method evaluated the adhesiveness of the obtained HMA sample. In addition, in this evaluation, resin BP1-BP3, BP5, and BP8-BP16 were used. These resins were used as a component which serves also as a base polymer or a base polymer and a tackifier.

<Raw material>

· Tackifier:

· Escorez 5300 (DCPD system)

· Escorez 5600 (C9 Aroma/C5 series)

Plasticizer: Paraffinic oil (PW-90)

・Antioxidant: Ilganox 1010 (manufactured by BASF Japan Co., Ltd.)

<Adhesiveness>

When the HMA sample was lightly tapped with a finger, the degree of adhesion to the finger was evaluated. The evaluation result obtained was set as a reference|standard so that it might correlate substantially with the value of the loop tack of Table 3.

◎: strongly attached and followed

○: Slightly strongly adhered

△: slightly weakly adhered

x: hardly adhered

[Production of olefin resin]

Production Example 1 (Preparation of hydrogenated olefin resin (HP1))

<Polymerization reaction process>

400 mL of a heptane solution of dicyclopentadiene (DCPD) with a concentration of 95% by volume as a monomer (reagent 1st grade, stabilizer and polar impurities removed with alumina) in a 1L stainless steel autoclave at room temperature under nitrogen atmosphere ( 2.73 mol) and stirring at 100 rpm, 1.0 mL of a 2M heptane solution of triisobutylaluminum (TIBA) as a scavenger, and dimethylanilinium tetrakis (pentafluorophenyl) at a concentration of 20 mM as a cocatalyst 6.0 mL (120 mmol) of a heptane solution of borate, 4.0 mL (80 mmol) of a heptane solution of bis (cyclopentadienyl) zirconium dichloride (Cp ₂ ZrCl ₂ ) as a main catalyst were added, and the stirring water was stirred at 400 rpm After raising to , hydrogen gas as a chain transfer agent was introduced at a pressure of 0.05 MPa.

Subsequently, the internal temperature was raised to 80° C. and polymerization was performed for 1 hour. After depressurizing unreacted hydrogen gas, a small amount of ethanol was added to stop polymerization.

The heptane solution of the obtained resin was filtered to remove the catalyst residue, 20 mg of Ilganox 1010 (antioxidant, manufactured by BASF Japan Co., Ltd.) was added, and the heptane was distilled off at 70°C and 100 hPa using an evaporator, 160 By distilling off unreacted DCPD at °C and 25 hPa, 12.2 g of olefin resin (P1) (Mw: 321, DCPD content: 100 mol%) was obtained.

<Hydrogenation reaction process>

In a stainless steel 1L autoclave, 1 g of nickel diatomaceous earth catalyst, 10.0 g of the above olefinic resin (P1), and 391 mL of heptane were added, replaced with nitrogen, and hydrogen gas was introduced at room temperature until 5 MPa while stirring at 500 rpm. Then, the temperature was raised and held at 230°C for 30 minutes to perform a hydrogenation reaction.

The unreacted hydrogen gas was removed, and the heptane solution of the obtained resin was subjected to thermal filtration to remove the catalyst residue, Ilganox 1010: 40 mg was added, and the heptane was distilled off at 70°C and 25 hPa using an evaporator.

<Stripping process>

Furthermore, nitrogen stripping was performed by putting the said sample whole quantity into a 1 L flask, and heating to 200 degreeC, rotating using an evaporator, and nitrogen blowing at a flow rate of 1500 mL/min for 120 minutes, hydrogenated olefin resin 8.0 g of (HP1) (Mw: 338, DCPD content: 100 mol%) was obtained.

Production Example 2 (Preparation of hydrogenated olefin-based resin (HP2))

<Polymerization reaction process>

As a main catalyst, instead of bis(cyclopentadienyl)zirconium dichloride (Cp ₂ ZrCl ₂ ), bis(dimethylsilylene)-bis(cyclopentadienyl)zirconium dichloride ((Me ₂ Si) ₂ Except having used Cp ₂ ZrCl ₂ ), polymerization reaction was performed under the same conditions as in Production Example 1 to obtain 9.2 g of an olefin-based resin (P2). (Mw: 623, DCPD content: 100 mol%)

<Hydrogenation reaction process/stripping process>

Olefin resin (HP2) hydrogenated by performing a hydrogenation reaction step and a stripping step under the same conditions as in Example 1 except that 8.0 g of olefin resin (P2), 393 mL of heptane, and 32 mg of Ilganox 1010 were used. (Mw: 645, DCPD content: 100 mol%) 6.4 g was obtained.

Production Example 3 (Preparation of hydrogenated olefin-based resin (HP3))

<Polymerization reaction process>

9.9 g of olefin resin (P3) was obtained by performing polymerization reaction on the conditions similar to Example 2 except having made the pressure of hydrogen gas into 0.02 MPa, and having set the polymerization temperature to 90 degreeC. (Mw: 1,785, DCPD content: 100 mol%)

<Hydrogenation reaction process/stripping process>

Hydrogenated olefinic resin (HP3) ( Mw: 1,785, DCPD content: 100 mol%) 7.2 g was obtained.

Production Example 4 (Preparation of hydrogenated olefin-based resin (HP4))

<Polymerization reaction step 1>

400 mL (2.73 mol) of a DCPD heptane solution as a monomer was added to a 1 L stainless steel autoclave under nitrogen atmosphere at room temperature, and while stirring at 100 rpm, TIBA (4 mmol) as a scavenger and Borate (300 μmol) as a co-catalyst , bis(cyclopentadienyl)zirconium dichloride (Cp ₂ ZrCl ₂ ) (75 μmol) as the first main catalyst, bis(dimethylsilylene)-bis(cyclopentadienyl)zirconium die as the second main catalyst Chloride ((Me ₂ Si) ₂ Cp ₂ ZrCl ₂ ) (75 μmol) was added, the stirring water was raised to 400 rpm, and then hydrogen gas as a chain transfer agent was introduced at a pressure of 0.10 MPa.

Then, the internal temperature was raised to 80 degreeC, and after superposition|polymerization for 2 hours, unreacted hydrogen gas was depressurized and removed.

<Polymerization reaction step 2>

Bis(dimethylsilylene)-bis(cyclopentadienyl)zirconium dichloride ((Me ₂ ) as a second main catalyst while stirring the reaction solution obtained in <Polymerization reaction step 1> at 100 rpm under a nitrogen atmosphere. Si) ₂ Cp ₂ ZrCl ₂ ) (50 μmol) was further added, the stirring water was increased to 400 rpm, and then 0.02 MPa of hydrogen gas as a chain transfer agent was introduced.

Subsequently, the internal temperature was raised to 90°C and polymerization was performed for 1 hour, and then unreacted hydrogen gas was depressurized.

The heptane solution of the obtained resin was filtered to remove the catalyst residue, and 20 mg of Ilganox 1010 was added using an evaporator, and the heptane was distilled off at 70°C and 100 hPa, and then unreacted DCPD was distilled at 160°C and 25 hPa. By removing, 34.2 g of olefin resin (P4) (Mw: 1,005, DCPD content: 100 mol%) was obtained.

<Hydrogenation reaction process/stripping process>

3 g of nickel diatomaceous earth catalyst, 30.0 g of olefin-based resin (P4), 373 mL of heptane, and 120 mg of Ilganox 1010 were used. 27.8 g of an olefin-based resin (HP4) (Mw: 1,050, DCPD content: 100 mol%) was obtained.

Production Example 5 (Preparation of hydrogenated olefin resin (HP5))

<Polymerization reaction process>

In a stainless steel 1L autoclave, at room temperature under nitrogen atmosphere, 80 mL of heptane as a solvent, and a heptane solution of DCPD with a concentration of 95% by volume as the first monomer (reagent 1st grade, stabilizer and polar impurities removed with alumina) 320 mL (2.19 mol) was added, and while stirring at 100 rpm, 1.0 mL (2 mmol) of a 2M heptane solution of TIBA as a scavenger, 6.0 mL (120 μmol) of a 20 mM heptane solution of borate as a co-catalyst, as a main catalyst 4.0 mL (80 μmol) of a heptane solution of bis(cyclopentadienyl)zirconium dichloride (Cp ₂ ZrCl ₂ ) having a concentration of 20 mM was added, the stirring water was raised to 400 rpm, and hydrogen gas as a chain transfer agent was applied at a pressure of 0.10 MPa. introduced

Subsequently, while introducing propylene gas as the second monomer, the internal temperature is raised to 80° C. and the total pressure is raised to 0.45 MPa, and after polymerization for 1 hour, unreacted propylene gas and hydrogen gas are depressurized, and a small amount of ethanol is added. to stop polymerization.

The heptane solution of the obtained resin is filtered to remove the catalyst residue, and the heptane is distilled off at 70° C. and 100 hPa using an evaporator, and then unreacted DCPD is distilled off at 160° C. and 25 hPa. (P5) (Mw: 749, DCPD content: 96 mol%) 30.4 g was obtained.

<Hydrogenation reaction process/stripping process>

Hydrogenated olefinic resin (HP5) by performing a hydrogenation reaction step and a stripping step under the same conditions as in Production Example 1, except that 2 g of nickel diatomaceous earth catalyst, 20.0 g of olefinic resin (P5), and 382 mL of heptane were used. (Mw: 813, DCPD content: 96 mol%) 19.0 g was obtained.

Production Example 6 (Preparation of hydrogenated olefin-based resin (HP6))

<Polymerization reaction process>

283 mL of heptane as a solvent, 117 mL (0.80 mol) of a heptane solution of DCPD as a first monomer, Borate (60 μmol) as a cocatalyst, bis(dimethylsilylene)-bis(cyclopentadienyl)zirconium di Chloride ((Me ₂ Si) ₂ Cp ₂ ZrCl ₂ ) (40 μmol), the hydrogen gas pressure was 0.03 MPa, and the total pressure was 0.8 MPa, except that the polymerization reaction was carried out under the same conditions as in Production Example 5. 19.7 g of a system resin (P6) (Mw: 1,728, DCPD content: 76 mol%) was obtained.

<Hydrogenation reaction process/stripping process>

Olefin resin (P6) 16.0 g, heptane 386 mL, Ilganox 1010: 64 mg, hydrogenated olefin resin (HP6) ( Mw: 1,751, DCPD content: 76 mol%) 14.5 g was obtained.

Production Example 7 (Preparation of hydrogenated olefin resin (HP7))

<Polymerization reaction step 1>

To a stainless steel 1L autoclave under nitrogen atmosphere, at room temperature, 283 mL of heptane as a solvent and 117 mL (0.80 mol) of a heptane solution of DCPD as a first monomer were added, and TIBA (2 mmol) as a scavenger while stirring at 100 rpm. , Borate (180 μmol) as a cocatalyst, Bis (cyclopentadienyl) zirconium dichloride (Cp ₂ ZrCl ₂ ) (80 μmol) as a first main catalyst, Bis (dimethylsilylene) -bis ( Cyclopentadienyl)zirconium dichloride ((Me ₂ Si) ₂ Cp ₂ ZrCl ₂ ) (40 μmol) was added, the stirring water was increased to 400 rpm, and then 0.05 MPa of hydrogen gas as a chain transfer agent was introduced.

Then, while introducing propylene gas as the second monomer, the internal temperature was raised to 80° C. and the total pressure was raised to 0.80 MPa, polymerization was performed for 1 hour, and then unreacted propylene gas and hydrogen gas were depressurized. The polymerization solution was transferred to a 5L flask together with washed heptane in the 1L autoclave, a small amount of ethanol was added to deactivate the catalyst, and the 1L autoclave was vacuum dried at 80°C, followed by nitrogen purging.

<Polymerization reaction step 2>

70 mL of heptane as a solvent and 330 mL (2.25 mol) of a heptane solution of DCPD as a first monomer were added to a 1 L autoclave made of stainless steel identical to the one used in <Polymerization Step 1> above under nitrogen atmosphere at room temperature, 100 rpm TIBA (2mmol) as a scavenger, Borate (60μmol) as a co-catalyst, bis(dimethylsilylene)-bis(cyclopentadienyl)zirconium dichloride ((Me ₂ Si) ₂ as a main catalyst while stirring with Cp ₂ ZrCl ₂ ) (40 μmol) was added, the stirring water was raised to 400 rpm, and then hydrogen gas as a chain transfer agent was introduced at a pressure of 0.50 MPa.

Then, while introducing propylene gas as the second monomer, the internal temperature was raised to 80° C. and the total pressure was raised to 0.80 MPa, polymerization was performed for 1 hour, and then unreacted propylene gas and hydrogen gas were depressurized. All of the polymerization solution was transferred to the same 5L flask as used in the <Polymerization Reaction Step 1> above, together with the heptane washed in the 1L autoclave.

The heptane solution of the obtained resin was filtered to remove the catalyst residue, 20 mg of Ilganox 1010 was added, and the heptane was distilled off at 70° C. and 100 hPa using an evaporator, and then unreacted DCPD was distilled at 160° C. and 25 hPa. By removing, 102.0 g of olefin resin (P7) (Mw: 1,085, DCPD content: 83 mol%) was obtained.

<Hydrogenation reaction process/stripping process>

4 g of nickel diatomaceous earth catalyst, 60.0 g of olefin-based resin (P7), 346 mL of heptane, and 240 mg of Ilganox 1010 were hydrogenated by performing a hydrogenation reaction step and a stripping step under the same conditions as in Production Example 1 57.0 g of an olefin-based resin (HP7) (Mw: 1,104, DCPD content: 83 mol%) was obtained.

Production Example 8 (Preparation of hydrogenated olefin-based resin (HP8))

<Polymerization reaction process>

264 mL (1.90 mol) of a heptane solution of DCPD with a concentration of 95 vol% as the first monomer (reagent 1st grade, stabilizer and polar impurities removed with alumina) in a stainless steel 1L autoclave at room temperature under nitrogen atmosphere 2 As a monomer, 120 mL (0.95 mol) of 4-methyl-1-pentene (4M1P) (polar impurities have been removed with alumina) was added, and while stirring at 100 rpm, 1.0 mL of a 2M heptane solution of TIBA as a scavenger ( 2 mmol), 3.0 mL (60 μmol) of a heptane solution with a concentration of 20 mM as a cocatalyst, bis(dimethylsilylene)-bis(cyclopentadienyl) zirconium dichloride ((Me ₂ Si) at a concentration of 20 mM as a main catalyst ) ₂ Cp ₂ ZrCl ₂ ) 4.0 mL (40 µmol) of a heptane solution was added, the stirring water was raised to 400 rpm, and then hydrogen gas as a chain transfer agent was introduced at a pressure of 0.10 MPa.

Subsequently, the internal temperature was raised to 80° C. and polymerization was performed for 1 hour. After depressurizing unreacted hydrogen gas, a small amount of ethanol was added to stop polymerization.

After filtering the heptane solution of the obtained resin to remove the catalyst residue, air drying for a day and night, 20 mg of Ilganox 1010 was added, and the heptane was distilled off at 70 ° C. and 100 hPa using an evaporator, 160 By distilling off unreacted DCPD at °C and 25 hPa, 35.5 g of olefin resin (P8) (Mw: 555, DCPD content: 83 mol%) was obtained.

<Hydrogenation reaction process/stripping process>

3 g of nickel diatomaceous earth catalyst, 30.0 g of olefinic resin (P8), 373 mL of heptane, and 120 mg of Ilganox 1010 were used. 28.0 g of an olefin resin (HP8) (Mw: 613, DCPD content: 83 mol%) was obtained.

Production Example 9 (Preparation of hydrogenated olefin resin (HP9))

<Polymerization reaction process>

Olefin resin (P9) ( Mw: 762, DCPD content: 65 mol%) 57.1 g was obtained.

<Hydrogenation reaction process/stripping process>

As the olefin-based resin, hydrogenated olefin-based resin (HP9) by performing a hydrogenation reaction step and a stripping step under the same conditions as in Production Example 8, except that an olefin-based resin (P9) was used instead of the olefin-based resin (P8). ) (Mw: 801, DCPD content: 65 mol%) 28.5 g was obtained.

Comparative Preparation Example 1 (Production of Hydrogenated Petroleum Resin (HP10))

According to Example 1 of International Publication No. 2004/056882, a homopolymer of dicyclopentadiene (DCPD) by thermal polymerization (polymerization temperature: 260° C.) using only dicyclopentadiene (DCPD) as a raw material monomer. After obtaining , partial hydrogenation using a nickel catalyst was performed to obtain a hydrogenated petroleum resin (HP10).

Comparative Preparation Example 2 (Production of Hydrogenated Petroleum Resin (HP11))

According to Example 1 of International Publication No. 2004/056882, dicyclopentadiene (DCPD) and styrene as raw material monomers were used so as to be in the ratio of Table 1, and dicyclopentadiene (DCPD) and After obtaining the copolymer of styrene, partial hydrogenation using a nickel catalyst was performed, and the hydrogenated petroleum resin (HP11) was obtained.

Production Example 10 (Preparation of olefin-based resin (BP1))

In a stainless steel 1L autoclave, at room temperature under nitrogen atmosphere, 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 (reagent 1st grade, alumina treatment complete) was added , while stirring at 100 rpm, 1.0 mL of a heptane solution of 2M concentration of triisobutylaluminum (TIBA) as a scavenger, 5 mM of dimethylanilinium tetrakis (pentafluorophenyl) borate as a cocatalyst 2.0 mL (10 μmol) of a toluene solution, 1.0 mL (5 μmol) of a toluene solution of bis (cyclopentadienyl) zirconium dichloride (Cp ₂ ZrCl ₂ ) having a concentration of 5 mM as a main catalyst (5 μmol) was added, and the stirring water was raised to 400 rpm, Hydrogen gas as a chain transfer agent was introduced at a pressure of 0.05 MPa.

Subsequently, while introducing ethylene gas as the second monomer, the internal temperature is raised to 90° C. and the total pressure is raised to 0.70 MPa, and after polymerization for 1 hour, unreacted ethylene gas and hydrogen gas are depressurized and removed, and a small amount of ethanol is added. to stop polymerization.

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 several times with ethanol, and then vacuum-dried at 190°C for 6 hours. 39 g of (BP1) (Mw: 33,000, NB content: 14 mol%) was obtained.

Production Example 11 (Preparation of olefin-based resin (BP2))

Olefin resin (BP2) (Mw: 5.0 million, NB by performing polymerization reaction, reprecipitation, washing, and drying under the same conditions as in Production Example 10 except that the pressure of hydrogen gas serving as a chain transfer agent was changed to 0.01 MPa. Content: 14 mol%) to obtain 75 g.

Production Example 12 (Preparation of olefin-based resin (BP3))

Olefin resin (BP3) (Mw: 91,000, NB content: 14 mol%) by polymerization reaction, reprecipitation, washing, and drying under the same conditions as in Production Example 10 except that hydrogen gas as a chain transfer agent was not used. ) to obtain 109 g.

Production Example 13 (Preparation of olefin-based resin (BP4))

The amount of the toluene solution of dimethylanilinium tetrakis(pentafluorophenyl)borate with a concentration of 5mM was changed to 0.40mL (2μmol), and bis(cyclopentadienyl)zirconium die with a concentration of 5mM as a main catalyst A solution of chloride (Cp ₂ ZrCl ₂ ) in toluene with a concentration of 5 mM dimethylsilylene-(tetramethylcyclopentadienyl)(t-butylamide)titanium dichloride (Me ₂ Si(Me ₄ Cp)(t-BuN) ) TiCl ₂ ) of toluene solution 0.20 mL (1 μmol), and after introduction of ethylene gas, polymerization reaction, reprecipitation, washing, and drying are performed under the same conditions as in Production Example 10, except that the internal temperature is 80 ° C. Thus, 111 g of olefin resin (BP4) (Mw: 84,000, NB content: 18 mol%) was obtained.

Production Example 14 (Preparation of olefin-based resin (BP5))

Polymerization reaction, reprecipitation, washing, and drying under the same conditions as in Production Example 13 except that the amount of toluene was changed to 305 mL and the amount of toluene solution of norbornene (NB) was changed to 95 mL (0.80 mol) Thus, 30 g of an olefin-based resin (BP5) (Mw: 28,000, NB content: 21 mol%) was obtained.

Production Example 15 (Preparation of olefin-based resin (BP6))

Olefin resin (BP6) (Mw: 45,000, NB content: 24 mol%) by performing 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 were obtained.

Production Example 16 (Preparation of olefin-based resin (BP7))

In a stainless steel 1L autoclave under 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 (reagent 1st grade, alumina treatment complete) was added , while stirring at 100 rpm, 1.0 mL of a heptane solution of 2M concentration of triisobutylaluminum (TIBA) as a scavenger, 20 mM of dimethylanilinium tetrakis (pentafluorophenyl) borate as a cocatalyst Toluene solution 1.5mL (30μmol), dimethylsilylene-(tetramethylcyclopentadienyl)(t-butylamide)titanium dichloride (Me ₂ Si(Me ₄ Cp) (t-BuN) at a concentration of 10 mM as a main catalyst ) TiCl ₂ ) 2.0 mL (20 μmol) of a toluene solution was added, the stirring water was increased to 400 rpm, and then hydrogen gas as a chain transfer agent was introduced at a pressure of 0.05 MPa.

Then, while introducing propylene gas as the second monomer, the internal temperature is raised to 80° C. and the total pressure is raised to 0.70 MPa, and after polymerization for 1 hour, unreacted propylene gas and hydrogen gas are depressurized, and a small amount of ethanol is added. to stop polymerization.

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 several times with ethanol, and then vacuum-dried at 190°C for 6 hours. 73 g of (BP7) (Mw: 43,000, NB content: 18 mol%) was obtained.

Production Example 17 (Preparation of olefin-based 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 the total pressure after introducing ethylene gas 53 g of olefinic resin (BP8) (Mw: 2.5 million, NB content: 27 mol%) was obtained by performing polymerization reaction, reprecipitation, washing and drying under the same conditions as in Production Example 16, except that .

Production Example 18 (Preparation of olefin-based resin (BP9))

Olefin resin (BP9) (Mw: 4.0 million, NB content) by polymerization reaction, reprecipitation, washing, and drying under the same conditions as in Production Example 17 except that hydrogen gas as a chain transfer agent was introduced at a pressure of 0.05 MPa : 27 mol%) to obtain 66 g.

Production Example 19 (Preparation of olefin-based resin (BP10))

The same conditions as in Production Example 16 except that the amount of toluene was changed to 242 mL, the amount of the toluene solution of norbornene (NB) was changed to 158 mL (1.30 mol), and hydrogen gas as a chain transfer agent was introduced at a pressure of 0.10 MPa. 27 g of an olefin-based resin (BP10) (Mw: 22,000, NB content: 32 mol%) was obtained by carrying out a polymerization reaction in

Production Example 20 (Preparation of olefin-based resin (BP13))

In <Polymerization reaction process>, the amount of heptane is 347 mL, dicyclopentadiene (DCPD) heptane solution (reagent 1st grade, alumina treatment complete) 50 mL (0.36 mol), borate heptane solution 3.0 mL ( 60 μmol), 2.0 mL (40 μmol) of a heptane solution of Cp ₂ ZrCl ₂ , and ethylene as the second monomer, the hydrogen gas pressure is 0.05 MPa and the total pressure is 0.80 MPa, in <hydrogenation step>, 150 Polymerization reaction, reprecipitation, washing and drying were performed under the same conditions as in Production Example 5, except that hydrogenation was performed at ° C. for 3 hours. By hydrogenating and stripping a part of the polymerization amount of 137 g, olefinic resin (BP13) (Mw : 64,000, DCPD content: 6 mol%) 137 g was obtained.

Production Example 21 (Preparation of olefin-based resin (BP14))

The olefin resin was polymerized 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 (BP14) (Mw: 29,000, DCPD content: 22 mol%) was obtained.

Production Example 22 (Preparation of olefin-based resin (BP15))

72 g of an olefin-based resin (BP15) (Mw: 48,000, DCPD content: 23 mol%) was obtained by performing a polymerization reaction under the same conditions as in Production Example 21, except that the hydrogen gas pressure was set to 0.05 MPa.

Production Example 23 (Preparation of olefin-based resin (BP16))

188 mL toluene as a solvent, 200 mL (1.42 mol) of toluene solution of dicyclopentadiene (DCPD) (reagent grade 1, alumina treatment complete), 3.0 mL (60 μmol) of toluene solution of borate, dimethylsilylene-( 2.0 mL (40 μmol) of a toluene solution of tetramethylcyclopentadienyl) (t-butylamide) titanium dichloride (Me ₂ Si(Me ₄ Cp)(t-BuN)TiCl ₂ ), the second monomer was propylene Except for that, by performing a polymerization reaction under the same conditions as in Production Example 20, 35 g of an olefin-based resin (BP16) (Mw: 24,000, DCPD content: 36 mol%) was obtained.

Other resin raw materials (styrene-based elastomer (BP11))

Styrene-butadiene-styrene block copolymer (SBS), a styrene-based elastomer (manufactured by Kraton Corporation, trade name: KRATON (D1102), MFR (200° C., 5 kg, ISO 1133): 6 g/10 min, styrene content: 30 wt%) was used as BP11 for evaluation as a base polymer.

Other resin raw materials (olefin-based elastomer (BP12))

Low-melting-point polypropylene (PP) (made by Idemitsu Kosan Co., Ltd., trade name: L-MODUS400) which is an olefin type elastomer was set as BP12, and it used for evaluation as a base polymer.

As is clear from the results of Tables 1 and 2, it is understood that the olefin-based resin of the present disclosure has little odor and is excellent in affinity with other materials that are raw materials for hot melt adhesives.

As indicated in Tables 3 and 4, it can be seen that the olefin-based resin of the present disclosure has good adhesion when blended with a styrene-based elastomer and a polyolefin-based elastomer.

As is clear from the results of Tables 5 and 6, it is understood that the olefin-based resin of the present disclosure has little odor and is excellent in affinity with other materials that are raw materials for hot-melt adhesives.

As indicated in Tables 7 to 10, it is understood that the olefin-based resin of the present disclosure has good adhesiveness even when used as a base polymer.

Claims (20)

An olefin-based resin comprising a structural unit derived from an alicyclic olefin (A) and satisfying the following (a) and (b).
(a) less than 1% aromatic moiety
(b) 70% or more linearity The method of claim 1,
The alicyclic olefin (A) is at least one selected from dicyclopentadiene, cyclopentene, cyclohexene, norbornene and derivatives thereof. 3. The method of claim 1 or 2,
An olefin-based resin further comprising a structural unit derived from α-olefin (B). 4. The method of claim 3,
The olefin resin having 2 to 10 carbon atoms in the α-olefin (B). 5. The method according to claim 3 or 4,
The olefin-based resin, wherein the α-olefin (B) is at least one selected from linear α-olefins and branched α-olefins. 6. The method according to any one of claims 3 to 5,
The olefin-based resin, wherein the α-olefin (B) is at least one selected from ethylene, propylene, butene, 3-methyl-1-butene, 4-methyl-1-pentene and 2-ethyl-1-hexene. 7. The method according to any one of claims 1 to 6,
Olefinic resin whose volatile component contained in olefinic resin is 10 ppm or less. 8. The method according to any one of claims 1 to 7,
The molecular weight distribution (Mw/Mn) is 2.5 or more, the olefin resin. 9. The method according to any one of claims 1 to 8,
An olefinic resin having a molecular weight distribution (Mz/Mw) greater than 2.5. 10. The method according to any one of claims 1 to 9,
The olefin resin having a weight average molecular weight of 5,000 to 200,000. 11. The method according to any one of claims 3 to 10,
The olefinic resin wherein the molar ratio [(A)/(B)] of the alicyclic olefin (A) to the α-olefin (B) is 40/60 to 100/0. 11. The method according to any one of claims 3 to 10,
The olefin resin, wherein the molar ratio [(A)/(B)] of the alicyclic olefin (A) to the α-olefin (B) is 1/99 to 40/60. A hot-melt adhesive comprising the olefin-based resin according to any one of claims 1 to 12. 14. The method of claim 13,
A hot melt adhesive further comprising a base polymer. 15. The method of claim 14,
The difference between the Hansen solubility parameter of the base polymer and the Hansen solubility parameter of the olefin-based resin is 5 or less. 16. The method according to any one of claims 13 to 15,
A hot melt adhesive further comprising a tackifying resin. A method for producing an olefin-based resin, comprising: a step of polymerizing a monomer component containing an alicyclic olefin (A) at 0 to 240°C in the presence of a metallocene catalyst; and a step of stripping. 18. The method of claim 17,
In the presence of a catalyst, the manufacturing method of the olefin resin further comprising the process of hydrogenating at 100-300 degreeC. 19. The method according to claim 17 or 18,
The process of stripping uses an inert gas as a medium, The manufacturing method of the olefin resin which performs a stripping process at 150-300 degreeC for 0.5 to 5 hours. 20. The method according to any one of claims 17 to 19,
In the above step of polymerizing a monomer component containing an alicyclic olefin (A) at 0 to 240° C. in the presence of a metallocene catalyst, polymerization is performed in the presence of two or more metallocene catalysts, production of an olefin-based resin Way.