WO2021060551A1

WO2021060551A1 - Olefin-based resin and hot-melt adhesive

Info

Publication number: WO2021060551A1
Application number: PCT/JP2020/036501
Authority: WO
Inventors: 省二朗棚瀬; 俊希長町; 南　裕
Original assignee: 出光興産株式会社
Priority date: 2019-09-27
Filing date: 2020-09-28
Publication date: 2021-04-01
Also published as: KR20220070214A; JPWO2021060551A1; DE112020004613T5

Abstract

This olefin-based resin contains a structural unit derived from an alicyclic olefin (A), and has 1% or less of an aromatic moiety and 70% or more of a straight-chain moiety.

Description

Olefin resin and hot melt adhesive

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

The hot melt adhesive is a solvent-free adhesive, which is applied to the adherend by heating and melting, and then solidified by cooling to develop adhesiveness. In recent years, hot melt adhesives have been widely used in various fields because they are excellent in high-speed coating property, quick-curing property, solvent-free property, barrier property, energy saving property, economy, and the like.

Since the hot melt adhesive does not use a solvent, the solvent does not volatilize, but since it is made from petroleum products, it contains a small amount of volatile organic compounds derived from them. In particular, when hot melt adhesives are used for hygiene products and indoor parts such as automobiles and houses, the volatile organic compounds contained in the products can cause adverse health effects and discomfort due to odors. Due to their nature, studies have been made to reduce them (see, for example, Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 2007-204519 Japanese Unexamined Patent Publication No. 2013-064056

As described above, since the hot melt adhesive does not require a solvent, it has little effect on the environment and health, but it is derived from a volatile organic compound contained in a low molecular weight substance such as a styrene elastomer or a tackifier as a raw material. Odor is a problem, and it is required to further reduce the odor especially for sanitary materials such as paper diapers and masks and daily necessities such as cleaning tools.
On the other hand, if low molecular weight substances such as the above-mentioned styrene-based elastomer and tackifier are not blended in order to reduce the odor, the adhesive performance and miscibility with other raw materials will be inferior, which is the basis of hot melt adhesives. Performance may be reduced.
Therefore, the problem to be solved by the technique of the present disclosure is to provide an olefin-based resin that has less odor, has excellent affinity with other materials when used as a raw material for a hot melt adhesive, and can improve adhesiveness. There is.

As a result of diligent studies, the present inventors have found that the olefin resin contains a constituent unit derived from an alicyclic olefin, and the aromatic portion is reduced to a certain amount or less to enhance the linearity of the structure. We have found that the above problems can be solved.

That is, according to one aspect of the present disclosure, it is possible to provide a technique relating to an olefin resin containing a structural unit derived from an alicyclic olefin (A) and satisfying the following (a) and (b).
(A) Aromatic part is 1% or less (b) Linearity is 70% or more

The olefin-based resin of the present disclosure has little odor, and when used as a raw material for a hot melt adhesive, it has excellent compatibility with other materials and can improve adhesiveness.

[Olefin resin]
The olefin-based resin of the present disclosure contains a structural unit derived from the alicyclic olefin (A), has an aromatic portion of 1% or less, and has a linearity of 70% or more.

<Alicyclic olefin (A)>
The olefin-based resin of the present disclosure contains a structural unit derived from the alicyclic olefin (A).
Examples of the alicyclic olefin (A) include monocyclic olefins and polycyclic olefins, and polycyclic olefins are preferable.
The alicyclic olefin (A) preferably has 4 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, and even more preferably 7 to 10 carbon atoms.
Specific examples of the alicyclic olefin (A) include dicyclopentadiene, cyclopentene, cyclohexene, norbornene and derivatives thereof, and one or more selected from dicyclopentadiene, cyclopentene, cyclohexene, norbornene and derivatives thereof. Is preferable, and one or more selected from dicyclopentadiene, norbornene and derivatives thereof is more preferable, and when the olefin-based resin of the present disclosure is used as a tackifier, dicyclopentadiene is further preferable, and the olefin-based resin of the present disclosure is used. Norbornene is even more preferred when the resin is used as the base polymer. By using dicyclopentadiene, a resin having a low molecular weight but a high glass transition temperature can be obtained. Therefore, the obtained resin is suitable as a tackifier, has high reactivity, and is a straight chain of the obtained resin. Since a resin having a high molecular weight and a high glass transition temperature can be obtained by using norbornene having excellent properties, it is considered that the obtained resin is suitable as a base polymer.
Examples of the derivative include 5-ethylidene-2-norbornene, 5-ethyl-2-norbornene, 5,6-dihydrodicyclopentadiene, tricyclopentadiene, tetracyclopentadiene and the like.
By using the alicyclic olefin (A) in the olefin resin of the present disclosure, the odor is less than that of the resin using other monomers, and when it is used as a raw material of a hot melt adhesive, it can be used with other materials. It has excellent compatibility with.

<Α-olefin (B)>
The olefin-based resin of the present disclosure preferably contains a structural unit derived from an α-olefin (B) in addition to a structural unit derived from the alicyclic olefin (A).
By containing the α-olefin (B) in the olefin-based resin of the present disclosure, when used as a raw material for a hot melt adhesive, compatibility with other materials and adhesiveness can be further improved.
The carbon number of the α-olefin (B) is preferably 2 to 10, and more preferably 2 to 8.
The α-olefin (B) is preferably one or more selected from linear α-olefins and branched α-olefins.
The number of carbon atoms of the linear α-olefin is preferably 2 to 6, more preferably 2 to 4, and the number of carbon atoms of the branched α-olefin is preferably 5 to 8 and more preferably 5 to 6. preferable.
The specific α-olefin (B) shall be one or more selected from ethylene, propylene, butene, 3-methyl-1-butene, 4-methyl-1-pentene and 2-ethyl-1-hexene. Is preferable, and one or more selected from ethylene, propylene and 4-methyl-1-pentene is preferable.
In particular, when an olefin resin is used as a tackifier, it is important that it is amorphous, has a low molecular weight, and has a high glass transition temperature (Tg), and the α-olefin (B) is propylene or 4-methyl-1. -Pentene is more preferred. When an olefin resin is used as a base polymer, it is important to have a high molecular weight and a relatively high glass transition temperature (Tg), and ethylene and propylene are more preferable as the α-olefin (B).
Further, when dicyclopentadiene or a derivative thereof is used as the alicyclic olefin (A), it is preferably one or more selected from propylene and 4-methyl-1-pentene, and the alicyclic olefin (A) When norbornene and its derivatives are used as A), it is preferably one or more selected from ethylene and propylene, and more preferably propylene from the viewpoint of compatibility.

<Composition and characteristics of olefin resin>
The olefin-based resin of the present disclosure contains a structural unit derived from the alicyclic olefin (A), but when used as a tackifier, it contains a structural unit derived from the alicyclic olefin (A). The amount is preferably 50 mol% or more, more preferably 60 mol% or more, further preferably 70 mol% or more, still more preferably 80 mol% or more. The upper limit may be 100 mol%, and when a structural unit derived from α-olefin (B) is contained, 90 mol% or less is preferable, and 85 mol% or less is more preferable.
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 further preferably 3 mol% or more. Preferably, 4 mol% or more is even more preferable. Further, 40 mol% or less is preferable, 38 mol% or less is more preferable, 35 mol% or less is further preferable, and 30 mol% or less is further preferable. From the viewpoint of compatibility, the content of the structural unit derived from the alicyclic olefin (A) is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 15 mol% or more. , 20 mol% or more is even more preferable.

The content of the constituent unit derived from the α-olefin (B) of the olefin resin of the present disclosure is preferably 3 to 50 mol%, more preferably 10 to 40 mol%, still more preferably 15 to 30 mol%. 15 to 20 mol% is even more preferable. The range is particularly good when used as a tackifier.
On the other hand, when used as a base polymer, the content of the structural unit derived from α-olefin (B) is preferably 60 to 99 mol%, more preferably 62 to 98 mol%, and 65 to 97 mol%. Even more preferably, 70 to 96 mol% is even more preferable. 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 further preferably 62 to 85 mol%. Preferably, 62-80 mol% is even more preferred. By containing α-olefin (B) in the above ratio, compatibility with other materials and adhesiveness can be further improved when used as a raw material for a hot melt adhesive.

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

The olefin resin of the present disclosure has an aromatic portion of 1% or less, preferably 0.5% or less, more preferably 0.1% or less, further preferably 0.05% or less, and 0%. Is even more preferable.
For the aromatic moiety, the content of the aromatic moiety in the entire olefin resin can be estimated by measuring the aromatic hydrogen.
Aromatic hydrogen can be obtained from the ratio of the peak area integrated value to the proton bonded to unsaturated carbon in ¹ H-NMR measurement of the resin after the hydrogenation reaction, and specifically, the method described in Examples. Can be obtained by
Therefore, the aromatic portion of the olefin-based resin of the present disclosure is in the range where the aromatic hydrogen is 1% or less, preferably in the range of 0.5% or less, and more preferably in the range of 0.1% or less. The range of 0.05% or less is more preferable, and the range of aromatic hydrogen of 0% is even more preferable.
The aromatic portion of the olefin-based resin of the present disclosure may be a portion derived from an aromatic monomer, a portion obtained by modifying a non-aromatic monomer to have aromaticity, a decomposition product of the resin after polymerization, or the like. Be done.
By setting the aromatic portion in the above range, the odor can be further reduced. In particular, it is possible to efficiently reduce aromatic odors that deteriorate the quality of products when used as sanitary materials. The reason for this is not clear, but when a hot melt adhesive containing an olefin resin is used, the aromatic portion tends to generate odor-causing components in a small amount, so that the aromatic portion in the olefin resin is likely to be generated. It is considered that the effect of reducing the odor is achieved by setting the ratio of the above to a small range.

The volatile component contained in the olefin resin of the present disclosure is preferably 10 ppm or less, more preferably 5 ppm or less, further preferably 3 ppm or less, further preferably 2 ppm or less, still more preferably 1 ppm or less.
Among the volatile components, the component of the compound having 10 or less carbon atoms contained in the olefin resin of the present disclosure is preferably 2 ppm or less, more preferably 1 ppm or less, further preferably 0.5 ppm or less, and even more preferably 0.3 ppm. The following is even more preferable, and 0.1 ppm or less is even more preferable.
By setting the amount of the volatile component contained in the resin within the above range, the odor can be further reduced.

The olefin-based resin of the present disclosure may be a hydrogenated olefin-based resin.
When the alicyclic olefin (A) as a raw material has two or more unsaturated bonds, or a monomer having two or more unsaturated bonds other than the alicyclic olefin (A) and the α-olefin (B) When used, it is preferably a hydrogenated olefin resin.
The hydrogenated olefin-based resin has further improved chemical stability and thermal stability, and further reduces odor. In particular, aromatic odors are reduced.

The glass transition temperature of the olefin resin of the present disclosure is preferably −40 to 120 ° C. When used as a component having the properties of a tackifier for hot melt adhesives, 20 to 120 ° C. is preferable, 30 to 100 ° C. is more preferable, 50 to 80 ° C. is even more preferable, and 50 to 70 ° C. is even more preferable. 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 further preferable, and -40 to 20 ° C is preferable. Even more preferable. When used as a component having both the properties of a base polymer and a tackifier, the temperature is preferably -40 to 100 ° C, more preferably -20 to 100 ° C, and further preferably -20 to 80 ° C. It is more preferably −20 to 60 ° C., even more preferably −20 to 40 ° C.

The number average molecular weight (Mn) of the olefin resin of the present disclosure is preferably 100 to 100,000. Among them, when used as a component having properties as a tackifier, 100 to 2,000 is more preferable, 200 to 1,000 is more preferable, and 200 to 500 is even more preferable. Further, when used as a component having the properties of a base polymer of a hot melt adhesive, 1,000 to 100,000 is more preferable.
The weight average molecular weight (Mw) of the olefin resin of the present disclosure is preferably 300 to 200,000. Among them, when used as a component having properties as a tackifier, 300 to 5,000 is more preferable, 500 to 3,000 is more preferable, 600 to 2,000 is even more preferable, and 600 to 1, 200 is even more preferred. Further, when used as a component having the properties of a base polymer of a hot melt adhesive, 5,000 to 200,000 is more preferable, and when used as a base polymer, 20,000 to 200,000 is further preferable. More preferably 000 to 40,000, and even more preferably 5,000 to 100,000 when used as a component having both the properties of a base polymer and a tackifier.
The Z average molecular weight (Mz) of the olefin resin of the present disclosure is preferably 500 to 500,000. Among them, when used as a component having properties as a tackifier, 700 to 20,000 is more preferable, 1,000 to 7,000 is more preferable, and 1,200 to 4,000 is even more preferable. Further, when used as a component having the properties of a base polymer of a hot melt adhesive, 10,000 to 500,000 is more preferable.

The molecular weight distribution (Mw / Mn) of the olefin resin of the present disclosure is preferably 2.5 or more, and more preferably 3.0 or more.
The molecular weight distribution (Mz / Mw) is preferably 1.5 or more, more preferably 2.0 or more, further preferably more than 2.5, and more than 3.0. Is even more preferable.
When the molecular weight distribution is in the above range, the compatibility and adhesiveness with other materials can be further improved when used as a raw material for a hot melt adhesive. Specifically, for example, by setting Mw / Mn in the above range, it is possible to develop the tack of the hot melt adhesive, and by setting Mz / Mw in the above range, the holding power of the hot melt adhesive Can be expressed.

The olefin-based resin of the present disclosure has a linearity of 70% or more, preferably 80% or more.
Linearity is the ratio of alicyclic monomers polymerized in 1,2-bonds, and when one alicyclic monomer unit has two or more unsaturated bonds, the total number of carbon atoms of the alicyclic monomer is X, the number of unsaturated carbon bonds is y, ¹³ The integrated value of the peak area with respect to the alicyclic monomer-derived structural unit obtained by C-NMR measurement is S _Alicyclic , of which the integral of the peak area derived from unsaturated carbon If the value is S _{CH = CH}
_Linearity (%) = (x / 2 (y-1)) x S _{CH = CH} / S Alicyclic x 100
Can be shown. This is because both of the two double bonds of the alicyclic monomer are not involved in the formation of a branched structure that contributed to the polymerization reaction, and are not involved in the ring formation (reaction that increases the ring size) by the Diels-Alder reaction or the like. It shows the ratio of monomers.
On the other hand, when one alicyclic monomer unit has one unsaturated bond, the total number of carbon atoms of the alicyclic monomer is x, the number of unsaturated carbon bonds is y, and ¹³ the alicyclic compound obtained by C-NMR measurement. _{Let S Alicyclic be} the integrated value of the peak area for the _{building blocks derived from the monomer, and S CH-CH} be the integrated value of the peak area for the saturated carbon derived from the 1,2-bond.
_Linearity (%) = (x / 2y) x S _CH-CH / S Alicyclic x 100
Can be shown.
When the linearity is in the above range, when used as a raw material for 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. Further, since it has high linearity, decomposition is unlikely to occur even during heating, and it is considered that the olefin-based resin of the present disclosure has little odor.

<Manufacturing method of olefin resin>
The olefin-based resin of the present disclosure is obtained by polymerizing a 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 a step of polymerizing the monomer component containing the alicyclic olefin (A) at 0 to 240 ° C. in the presence of a metallocene catalyst.

The metallocene catalyst used in this step is a catalyst composed of a metallocene-based transition metal complex as a main catalyst and a co-catalyst, and a scavenger may be used, or the metallocene catalyst may be supported on an inorganic substance or the like.
As the metallocene-based transition metal complex, a transition metal (titanium, zirconium, hafnium) selected from Group 4 contains a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, and the like. A substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group is coordinated as one or two ligands, or two of these groups are coordinated by a covalent bond. Other examples include those having a ligand such as a hydrogen atom, an oxygen atom, a nitrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an acetylacetonate group, and an amide group.

Examples of the co-catalyst include alkylaluminoxane compounds and boron compounds.
Examples of the alkylaluminoxane compound include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane and the like.
Examples of the boron compound include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane, and tris (3,4). , 5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6- Tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, Phenylbis (pentafluorophenyl) borate, tetrakis (3,5-bistrifluoromethylphenyl) borate and the like can be mentioned.
Examples of the scavenger include alkylaluminum compounds, and specific examples thereof include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, and triisobutylaluminum.

The amount of the metallocene-based transition metal complex is preferably 0.1 to 50 mol%, more preferably 1 to 20 mol%, based on all the monomer components including the alicyclic olefin (A).
The amount of the co-catalyst is preferably 0.2 to 60 mol%, more preferably 2 to 30 mol%, based on all the monomer components including the alicyclic olefin (A).
In this step, two or more kinds of metallocene catalysts may be used, and it is preferable to use two or more kinds in combination. By using a plurality of catalysts in combination, the molecular weight distribution of the obtained olefin resin can be adjusted, and the adhesiveness can be improved while suppressing the odor.
The polymerization temperature in this step is preferably 0 to 240 ° C., more preferably 20 to 220 ° C., and even more preferably 40 to 200 ° C.

The method for producing an olefin resin of the present invention preferably includes a step of stripping. The stripping step, which is the main step, may be carried out after the polymerization of the olefin resin, or may be carried out after the hydrogenation step described below.
For stripping, it is preferable to use an inert gas such as nitrogen or argon gas as a medium, and it is more preferable to use nitrogen. Specifically, in a state where the resin is heated and melted in the container, the interface between the gas and the resin in the container is renewed by stirring or the like, and the gas in the container is renewed with an inert gas medium to make the resin volatile. Remove impurities. For example, using an inert gas containing nitrogen as a medium, stripping treatment can be performed at 150 to 300 ° C. for 0.5 to 5 hours at a flow rate of 1 to 1000 L / min of nitrogen with respect to 100 g of the olefin resin.
Here, each parameter of the stripping treatment described above is not limited to this, and for example, the stripping temperature is preferably 100 to 300 ° C, more preferably 150 to 300 ° C, and even more preferably 150 to 250 ° C.
Further, for example, the time for stripping may be selected optimally depending on the amount of resin and the size of the container used, but is preferably 0.1 to 20 hours, more preferably 0.5 to 10 hours, and 0. .5-5 hours is more preferred.
The optimum flow rate of nitrogen when stripping with nitrogen may be selected according to the size of the container used, but 0.1 to 20 L / min is used for 100 g of the olefin resin. Preferably, 1 to 10 L / min is more preferable.
By performing stripping under the respective conditions of the above temperature, the above time, and the flow rate of nitrogen, an olefin resin having less odor and suitable as a raw material for a hot melt adhesive can be efficiently obtained. The method for producing an olefin-based resin of the present invention, that is, the olefin-based resin obtained by polymerizing a monomer component containing an alicyclic olefin (A) at 0 to 240 ° C. in the presence of a metallocene catalyst is the obtained resin. Since it has little odor by itself, it does not require excessive stripping conditions. Further, when the olefin resin obtained in the polymerization step satisfies the condition that the aromatic portion is 1% or less and the linearity is 70% or more, the odor of the resin itself is further reduced, which is excessive. No need for stripping.

The method for producing an olefin resin of the present invention preferably further includes a step of hydrogenation.
When the alicyclic olefin (A) as a raw material has two or more unsaturated bonds, or a monomer having two or more unsaturated bonds other than the alicyclic olefin (A) and the α-olefin (B) When used, it is more preferred to include a step of hydrogenation.
This step is more preferably a step of hydrogenating at 100 to 300 ° C. in the presence of a catalyst. By hydrogenating the olefin-based resin obtained in the above polymerization step, chemical stability and thermal stability can be improved, and odor can also be reduced. In particular, it is possible to reduce aromatic odors.
The catalyst used in this hydrogenation step is preferably a metal catalyst, and examples thereof include a palladium catalyst, a nickel catalyst, a platinum catalyst, a ruthenium catalyst, a renium catalyst, a copper catalyst, and a rhodium catalyst.
Examples of the palladium catalyst include palladium carbon, palladium alumina, palladium silica, palladium silica alumina, and zeolite-supported palladium.
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.
The amount of the hydrogenation catalyst is preferably 1 to 40 parts by mass, more preferably 5 to 35 parts by mass with respect to 100 parts by mass of the olefin resin.
The hydrogenation reaction temperature in this step is preferably 30 to 300 ° C., more preferably 60 to 300 ° C., further preferably 100 to 300 ° C., still more preferably 100 to 250 ° C.
The hydrogen pressure in this step is preferably 1 to 20 MPa, more preferably 2 to 15 MPa, still more preferably 3 to 10 MPa.

[Hot melt adhesive]
The hot melt adhesive of the present disclosure contains the olefin resin.
That is, the hot melt adhesive of the present disclosure contains a structural unit derived from the alicyclic olefin (A), has a structural unit derived from an aromatic monomer of 1 mol% or less, and has a volatile component of 10 ppm or less. Contains certain olefinic resins.
By adjusting the molecular weight, molecular weight distribution, glass transition temperature, etc. of the olefin resin, among the components constituting the hot melt adhesive, a component having the property of a tackifier, a component having the property of a base polymer, or a component having the property of a base polymer, or It can be used as a component having both the properties of a tackifier and a base polymer.
In particular, since the olefin-based resin of the present disclosure can be used as a component having both the properties of a tackifier and a base polymer, a hot melt having less odor and excellent tackiness even when a separate tackifier and base polymer are not contained. An adhesive is obtained. On the other hand, when used as a component having the properties of a tackifier or a component having the properties of a base polymer, it is preferable to separately contain a base polymer and a tackifier, respectively. In this case as well, the olefin-based resin of the present disclosure is used. Has excellent affinity with other materials, so that a good hot melt adhesive can be obtained.
When used as any of the components, the effect of the present disclosure technology of having less odor and excellent affinity with other materials can be exhibited, the adhesiveness of the obtained hot melt adhesive is improved, and the odor is also reduced. It can be suppressed.

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

<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 the properties of a base polymer or a component having both the properties of a tackifier and a base polymer, a good hot melt adhesive can be obtained even if the base polymer is not contained, but in particular. When the olefin resin is used as a component having the properties of a tackifier, it preferably contains a base polymer.
Specific examples of the base polymer include natural rubber, olefin-based elastomer, styrene-based elastomer, and the like, and olefin-based elastomer and styrene-based elastomer are preferable.
These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the olefin-based elastomer include ethylene-based olefin polymers, amorphous olefin polymers, propylene-based elastomers, ethylene-vinyl acetate copolymers, and ethylene-acrylic acid ester copolymers.

Specific examples of the ethylene-based olefin polymer include polyethylene and a copolymer of ethylene and an olefin having 3 to 10 carbon atoms. It is not particularly limited as long as it can be used as a base polymer of a hot melt adhesive, but from the viewpoint of the adhesiveness of the hot melt adhesive, an ethylene-α-olefin copolymer is preferable. 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-hexadecene. , 1-Octadecene, 1-Eikosen and the like, and one or more of these can be used. Among these α-olefins, 1-octene is preferable. From the viewpoint of the adhesiveness of the hot melt adhesive, it is more preferably an ethylene-1-octene copolymer, and more preferably an ethylene-1-octene copolymer containing 5 to 50% by mass of a 1-octene-derived structural unit. It is a coalescence.
The melting point of the ethylene-based olefin polymer is preferably 60 to 120 ° C., more preferably 60 to 90 ° C. from the viewpoint of heat-resistant creep property. The melting point of the ethylene-based olefin polymer can be measured by differential scanning calorimetry. Of the ethylene-based olefin polymers, amorphous ones belong to the amorphous olefin polymers described later.

The amorphous olefin polymer is one or more homopolymers or copolymers selected from the group consisting of linear or branched α-olefins or dienes having 2 to 24 carbon atoms, and is not particularly limited. , Polybutene, polybutadiene, polyisoprene, and amorphous polyalphaolefins.
Examples of polybutene include isobutene and normal butene alone or copolymers and hydrogenated products thereof.
Examples of polybutadiene include 1,2-butadiene and 1,4-butadiene alone or copolymers and hydrogenated products thereof, and may have a hydroxyl group at the terminal.
Examples of polyisoprene include homopolymers or copolymers of isoprene and hydrogenated products thereof, and may have a hydroxyl group at the terminal.
Examples of the amorphous polyalphaolefin include homopolymerizations and copolymers of olefins having 2 to 6 carbon atoms.

Examples of the propylene-based elastomer include elastomers having a propylene unit as a main constituent unit, such as low melting point polypropylene. The elastomer is not limited by the density as long as it has rubber elastic properties, and may be chemically crosslinked or not chemically crosslinked.

The vinyl acetate content of the ethylene-vinyl acetate copolymer is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.

As the styrene-based elastomer, a styrene-based block copolymer is preferable.
The styrene-based block copolymer is a copolymer in which a styrene-based compound and a conjugated diene compound are block-copolymerized, and usually has a styrene-based compound block and a conjugated diene compound block.

Here, examples of the "styrene-based compound" include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene and the like. it can. Styrene is particularly preferable. These styrene compounds can be used alone or in combination.
By "conjugated diene compound" is meant a diolefin compound having at least a pair of conjugated double bonds. Specific examples of the "conjugated diene compound" include 1,3-butadiene, 2-methyl-1,3-butadiene (or isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and the like. 1,3-Hexadiene can be exemplified. 1,3-butadiene and 2-methyl-1,3-butadiene are particularly preferable. These conjugated diene compounds can be used alone or in combination.

The styrene-based block copolymer may be an unhydrogenated additive or a hydrogenated additive. The "non-hydrogenated styrene block copolymer" can be specifically exemplified by a block based on a conjugated diene compound to which no hydrogenation has been added. Further, the "hydrogenated styrene-based block copolymer" can be specifically exemplified by a block copolymer in which all or part of a block based on a conjugated diene compound is hydrogenated.
The hydrogenated ratio of the "hydrogenated styrene block copolymer" can be indicated by the "hydrogenation rate". The "hydrogenation rate" of the "hydrogenation of styrene-based block copolymer" is based on the total aliphatic double bond contained in the block based on the conjugated diene compound, in which hydrogenation is performed and saturated hydrocarbonation is performed. The ratio of double bonds converted to hydrogen bonds. This "hydrogenation rate" can be measured by an infrared spectrophotometer, a magnetic resonance imaging device, or the like.

Specific examples of the "non-hydrogenated styrene block copolymer" include styrene-isoprene-styrene block copolymer (also referred to as "SIS") and styrene-butadiene-styrene block copolymer (also referred to as "SBS"). Can be exemplified. Specific examples of "hydrogenated styrene block copolymers" include hydrogenated styrene-isoprene-styrene block copolymers (also referred to as "SEPS") and hydrogenated styrene-butadiene-styrene block copolymers. (Also referred to as "SEBS") can be exemplified.
Styrene-based block copolymers can be used alone or in combination.

From the viewpoint of the adhesive strength of the hot melt adhesive, the styrene block copolymer preferably has a styrene block ratio (styrene content) contained in the styrene block copolymer of 5 to 50% by mass, more preferably 10. ~ 40% by mass.

The difference between the Hansen solubility parameter of the base polymer used in the hot melt adhesive of the present disclosure and the Hansen solubility parameter of the olefin resin is preferably 5 or less, more preferably 4 or less, still more preferably 3 or less. 2, 2 or less is more preferable, and 1 or less is even more preferable.
The difference in the Hansen solubility parameter referred to here means the Ra value obtained by the following formula.
Ra = [4 (δ _d2- δ _d1 ) ² + (δ _p2- δ _p1 ) ² + (δ _h2- δ _h1 ) ² ] ^1/2
(In the equation, δ _d is the dispersive force, δ _p is the polarization force, δ _h is the solubility parameter based on the hydrogen bonding force, and δ _d1 , δ _p1 , and δ _h1 are the solubility parameters of the olefin resin, and δ _d2 , δ _p2 and δ _h2 are solubility parameters of the base polymer.)

From the viewpoint of cohesiveness, the content of the base polymer is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, still more preferably 30 parts by mass, based on 100 parts by mass of the hot melt adhesive. It is more than parts, and preferably 80 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less. That is, in the hot melt adhesive, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, still more preferably 30% by mass or more, and preferably 80% by mass or less. It is more preferably 70% by mass or less, further preferably 60% by mass or less, still more preferably 50% by mass or less.
The glass transition temperature of the base polymer is preferably −20 to 100 ° C., more preferably −20 to 60 ° C.

The olefin resin may contain a second base polymer even when it is used as a component having the properties of a base polymer or a component having both the properties of a tackifier and the base polymer.
As the second base polymer, the olefin resin of the present disclosure, that is, the olefin resin described in the section of the [olefin resin], or the olefin elastomer is preferably used.
The melting point of the second base polymer is preferably 60 to 120 ° C., more preferably 60 to 110 ° C., and even more preferably 70 to 100 ° C.

<Adhesive imparting agent>
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 the properties of a tackifier and a base polymer, a good hot melt adhesive can be obtained even if the tackifier is not contained. In particular, when the olefin resin is used as a component having the properties of a base polymer, it preferably contains a tackifier.
When the hot melt adhesive of the present disclosure contains a tackifier, the olefin resin preferably has the 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. be able to. Specifically, natural rosin, modified rosin, hydrocarbon 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 Terpene copolymers, natural terpene three-dimensional polymers, hydrogenated terpene copolymer hydride derivatives, polyterpene resins, phenolic modified terpene resin hydride derivatives, aliphatic petroleum hydrocarbon resins, aliphatic petroleum hydrocarbon resin hydrides Examples thereof include derivatives, aromatic petroleum hydrocarbon resins, hydrides of aromatic petroleum hydrocarbon resins, cyclic aliphatic petroleum hydrocarbon resins, and hydrides of cyclic aliphatic petroleum hydrocarbon resins. These may be used alone or in combination of two or more.

From the viewpoint of improving the tackiness, the content of the tackifier is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, still more preferably 20 parts by mass or more, based on 100 parts by mass of the hot melt adhesive. It is 30 parts by mass or more, and preferably 80 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less. That is, in the hot melt adhesive, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, and preferably 80% by mass or less. It is more preferably 70% by mass or less, further preferably 60% by mass or less, still more preferably 50% by mass or less.

The softening point of the tackifier is preferably −20 ° C. or higher, more preferably −15 ° C. or higher, further preferably −10 ° C. or higher, and preferably 180 ° C. or lower, more preferably 170 ° C. or lower, further preferably. Is 160 ° C or lower.

<Plasticizer>
The hot melt adhesive of the present disclosure preferably further contains a plasticizer.
The plasticizer is not particularly limited, but those used for hot melt adhesives are preferable, and oils or waxes are more preferable. Further, as the plasticizer, phthalates, adipates, fatty acid esters, glycols, epoxy-based polymer plasticizers and the like can also be used.

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

Commercially available paraffin-based process oils include "Diana Process Oil PW-32", "Diana Process Oil PW-90", "Diana Process Oil PW-150", and "Diana Process Oil PS-32" manufactured by Idemitsu Kosan Co., Ltd. , "Diana Process Oil PS-90", "Diana Process Oil PS-430"; "Kaydol Oil", "ParaLux Oil" manufactured by Chevron USA, etc. (all are trade names).

Commercially available isoparaffin oils include "IP Solvent 1016", "IP Solvent 1620", "IP Solvent 2028", "IP Solvent 2835", and "IP Clean LX" manufactured by Idemitsu Kosan Co., Ltd .; "NA Solvent" series, etc. (both are product names).

Examples of waxes include animal wax, vegetable wax, carnauba wax, candelilla wax, wood wax, beeswax, mineral wax, petroleum wax, paraffin wax, microcrystallin wax, petroleum, higher fatty acid wax, higher fatty acid ester wax, and Fisher. Tropsch wax and the like can be exemplified.

The content of the plasticizer in the hot melt adhesive of the present disclosure is 2 parts by mass or more, preferably 5 parts by mass or more, out of 100 parts by mass of the hot melt adhesive from the viewpoint of improving the adhesiveness and the coatability. , More preferably 10 parts by mass or more, and 60 parts by mass or less, preferably 40 parts by mass or less, more preferably 30 parts by mass or less. That is, in the hot melt adhesive, 2% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and 60% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less. It is mass% or less.

<Other additives>
The resin composition of the present disclosure further contains an inorganic filler, an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant and other arbitrary additives as necessary, as long as the object of the disclosed technology is not impaired. May be good.

Inorganic fillers include talc, calcium carbonate, barium carbonate, wollastonite, silica, clay, mica, kaolin, titanium oxide, silica soil, urea resin, styrene beads, starch, barium sulfate, calcium sulfate, magnesium silicate, Examples thereof include magnesium carbonate, alumina, and quartz powder.

Antioxidants include trisnonylphenylphosphite, distearylpentaerythritol diphosphite, "Adecastab 1178" (manufactured by ADEKA Co., Ltd.), "Stamylizer TNP" (manufactured by Sumitomo Chemical Co., Ltd.), "Irgafos 168" (BASF , "Sandstab P-EPQ" (manufactured by Sand), phosphorus-based antioxidants, 2,6-di-t-butyl-4-methylphenol, n-octadecil-3- (3', 5'- Di-t-butyl-4'-hydroxyphenyl) propionate, phenolic antioxidants such as "Smilizer BHT" (manufactured by Sumitomo Chemical Co., Ltd.), "Irganox 1010" (manufactured by BASF), dilauryl-3,3' -Thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), "Smilizer TPL" (manufactured by Sumitomo Chemical Co., Ltd.), "DLTP" Yoshitomi "(manufactured by Mitsubishi Chemical Co., Ltd.)," Antiox L " Examples thereof include sulfur-based antioxidants (manufactured by Nichiyu Co., Ltd.).

<Manufacturing method and application of hot melt adhesive>
In the hot melt adhesive of the present disclosure, in addition to the olefin resin, if necessary, a base polymer, a tackifier, a plasticizer and an additive are dry-blended using a Henschel mixer or the like, and uniaxial or biaxial extrusion is performed. It can be manufactured by melt-kneading with a machine, a plastic mill, a Banbury mixer, or the like.

The hot melt adhesives of the present disclosure have excellent adhesiveness and low odor, and therefore, for example, for sanitary materials, packaging, bookbinding, textiles, woodworking, electrical materials, can making, construction, filters. It can be suitably used for low-pressure molding, bag making, and the like.
Specifically, as an adhesive for sanitary products such as disposable diapers and sanitary napkins represented by fixing non-woven fabrics or super absorbent polymers (SAPs), and as an adhesive for assemblies represented by automobile floor mats. It can be preferably used, and it can be suitably used as an adhesive for sanitary products because it has a particularly low odor.

Next, one aspect of the disclosed technology will be described in more detail with reference to Examples, but the disclosed technology is not limited to these examples.

[Analysis and evaluation of olefin resins]
[1. Copolymer composition]
The resin HP1 ~ HP11 below, nuclear magnetic resonance (NMR) apparatus (ECA500, manufactured by JEOL Ltd., ¹ H resonance frequency: 500 MHz) used, the solvent is deuterated chloroform (chloroform -d), accumulated number 10 ¹³ C-NMR measurements were performed 000 times under the condition of a temperature of 25 ° C., and the composition of the copolymer (mol%) was obtained from the ratio of the integrated value of the peak area to each monomer component (constituent unit) to the integrated value of the total peak area. ) Was asked. Specifically, the integral value of the peak area for each monomer component (constituent unit) was divided by the number of carbon atoms of the monomer, and the composition (mol%) of the copolymer was obtained from the ratio. The results are shown in Tables 1 and 2.
The compositions of the resins BP1 to BP10 and BP12 to BP16, which will be described later, were measured by the same method as above except that deuterated 1,2-tetrachloroethane was used as a solvent and the temperature was set to 120 ° C. The results are shown in Tables 5, 6 and 10.

[2. Aromatic hydrogen content%]
The resin HP1 ~ HP11 below, nuclear magnetic resonance (NMR) apparatus (ECA500, manufactured by JEOL Ltd., ¹ H resonance frequency: 500 MHz) was used, the solvent is deuterated chloroform, integration 256 times, temperature 25 ° C. ^{Under the conditions of, 1} H-NMR measurement of the resin after the hydrogenation reaction obtained in Examples and Comparative Examples was performed, and the peak for the proton (6 to 8 ppm) bonded to the unsaturated carbon with respect to the integrated value of the total peak area. The amount of aromatic hydrogen was determined from the ratio of the area integrated values. The results are shown in Tables 1 and 2.
The detection limit is 0.1% or less. In Tables 1 and 2, "nd" indicates that it is below the detection limit.
For the resins BP1 to BP12 described later, the amount of aromatic hydrogen was measured by the same method as above except that deuterated 1,2-tetrachloroethane was used as the solvent. The results are shown in Tables 5 and 6.

[3. Average molecular weight]
For the resins HP1 to HP11 described later, the average molecular weight was measured by the gel permeation chromatography (GPC) method. A GPC measuring device (HLC8220, detector: RI, column: TSK-GEL GHXL-L, G4000HXL, G2000HXL (all manufactured by Toso Co., Ltd.)) was used for the measurement, and tetrahydrofuran was used as the eluent, and the oven temperature was used. At 40 ° C., polystyrene-equivalent number average molecular weight (Mn), weight average molecular weight (Mw) and Z average molecular weight (Mz) were obtained. The results are shown in Tables 1 and 2.
For the resins BP1 to BP16 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. 1,2,4-Trichlorobenzene was used as the eluent, and the average molecular weight was measured by the same method as above except that the oven temperature was 145 ° C. The results are shown in Tables 5, 6 and 10.

[4. Glass-transition temperature〕
For the resins HP1 to HP11 described later, the glass transition temperature was measured by using a differential scanning calorimeter (DSC8500, manufactured by PerkinElmer) and setting the temperature program to -40 ° C to 220 ° C and 10 ° C / min. did. The results are shown in Tables 1 and 2.
For the resins BP1 to BP10 and BP12 to BP16 described later, dynamic viscoelasticity measurement (rheometer, manufactured by Antonio Par, MCR302) was performed in a shear shear mode while raising the temperature from -30 ° C to 150 ° C at 5 ° C / min. Was used), and the glass transition temperature was determined from the peak value of tan δ. The glass transition temperature of BP11 is a literature value, and is -100 ° C for the butadiene chain and 100 ° C for the styrene chain. The results are shown in Tables 5, 6 and 10.

[5. Linearity]
^{The 13} C-NMR measurement of the resin before the hydrogenation reaction was carried out in the above [1. The composition of the copolymer] was the same as that of the above.
Regarding 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 that one dicyclopentadiene-derived structural unit includes all. It has 10 carbon atoms and 2 unsaturated carbon atoms. Therefore, the integral value of the peak area with respect to the constituent unit derived from dicyclopentadiene is S _DCPD , and the integral value of the peak area derived from unsaturated carbon is S _{CH = CH} , and the linearity (%) is calculated by the following formula. It was. The results are shown in Tables 1 and 2.
Linearity (%) = 5S _{CH = CH} / S _DCPD x 100
Regarding the resins BP1 to BP10 described later, the structural unit of the norbornene monomer used has a total carbon number of 7 and an unsaturated carbon number of 2. Therefore, the integral value of the peak area with respect to the constituent unit derived from norbornene is S _NB , and the integral value of the peak area derived from saturated carbon having a 1,2-bonded form is S _CH-CH . (%) Was calculated. The results are shown in Tables 5 and 6.
Linearity (%) = 3.5S _CH-CH / S _NB x 100

[6. Amount of volatile components and amount of aromatic volatile components]
Aromatic components (benzene, toluene, xylene, styrene, etc.) that generate a gas component using a headspace gas chromatograph (device name: Agent7697A / Agent7890B) and have a retention time of less than 10 minutes when measured under the following conditions. ) Was defined as the amount of aromatic volatile components (aroma). Further, the amount of components having a retention time of less than 13 minutes (generally below the boiling point of a compound having 10 or less carbon atoms) is defined as the amount of volatile components (VOC), and the amount of components having a retention time of less than 40 minutes for all volatile components to be desorbed. Was defined as the total amount of volatile components (TVOC).
The results are shown in Table 1, Table 2, Table 5 and Table 6.
In Tables 1, 2, 5, and 6, the aromatic volatile components, the volatile components, and the total volatile components are represented as toluene-equivalent mass (ppm) with respect to the mass of the olefin resin. The detection limit is about 1 ppb.
(Measurement conditions: sample heat treatment: 150 ° C., 20 min, column: BPX5 30 m × 0.32 m id × 1.0 μm, injection port: 300 ° C., temperature program: 50 ° C. to 300 ° C., 10 ° C./min, rise Warm)

[7. Hansen solubility parameter (HSP) value]
According to the methods of Documents 1 to 3 shown below, olefin resins HP1 and HP2 are used using 20 kinds of solvents having known _{solubility parameters (dispersion force: δ d} , polarization force: δ _p , hydrogen bond force: δ _h). , HP5, HP6 and HP8 to HP11, evaluate the solubility, plot the solvent value on a three-dimensional plot, create the smallest sphere with the good solvent on the inside and the poor solvent on the outside, and create a sphere. The coordinate at the center of was used as the solubility parameter of the olefin resin. The results are shown in Tables 1 and 2.
Reference 1: Hildebrand JH, Scott RL. The Solubility of non-conductorrytes, 3rd ed. New York, NY: Dover Publications; 1964
Reference 2: C.I. M. Hansen et al. , Carbon, 42, 1591-1597, 2004
Reference 3: Masato Morimoto et al. , Energy Fuels, 32, 11296-11303, 2018

[8. Affinity〕
[7. The same evaluation as the Hansen solubility parameter (HSP) value] was performed on the following three types of elastomers used in hot melt adhesives to evaluate the affinity. 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. The affinity was also evaluated by the dispersibility and the rate of change in Tg. The results are shown in Tables 1 and 2.
<Elastomer>
Low melting point polypropylene (PP), which is an olefin elastomer (manufactured by Idemitsu Kosan Co., Ltd., trade name: L-MODU S400, Mw: 45,000, melt viscosity (B viscosity) (190 ° C., ASTM D 3236): 8500 mPa. s, softening point (R & B, ISO4635): 93 ° C.)
Amorphous polyalphaolefin (APAO) (manufactured by Evonik Industries AG, which is an olefin-based elastomer, trade name: VESTOPLAST (registered trademark) 708, melt viscosity (190 ° C., DIN 53 019): 8000 mPa · s, softening point (R & B) , DIN EN 1427): 108 ° C.)
Styrene-isoprene-styrene block copolymer (SIS) (manufactured by Kraton Corporation, trade name: KRATON® D1161, MFR (190 ° C., 2.16 kg, ISO 1133): 1.3 to 3. 7g / 10min, styrene content: 15wt%)
<Ra value>
The Ra value, which is an index of affinity, was calculated by the following formula. The smaller the Ra value, the better the affinity. Further, in the following formula, δ _d1 , δ _p1 , and δ _h1 are solubility parameters of the olefin 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, the smaller the Ra value, the better the compatibility, and the evaluation was made according to the following criteria.
⊚: Ra value ≤ 1.5
〇: 1.5 <Ra value ≤ 3.0
Δ: 3.0 <Ra value ≤ 5.0
X: 5.0 <Ra value

<Dispersibility>
The dispersibility was evaluated as follows.
The olefin resin and the base polymer (elastomer) were placed in a container at a mass ratio of 1: 1 and stirred at 180 ° C. for 1 hour, then allowed to stand to cool to room temperature, and after 1 day, the visually obtained mixture was obtained. Dispersibility was evaluated.
◎: Transparent 〇: Almost transparent (slightly cloudy)
Δ: White turbidity (slightly transparent)
×: Milky white

<Tg change rate>
The rate of change in the glass transition temperature (Tg) before and after mixing was evaluated by the following method. It is presumed that the larger the Tg change rate, the higher the affinity between the two.
Elastomer alone, olefin resin and elastomer are mixed at a mass ratio of 1: 1 and a strip-shaped test piece cut out from a sheet (1 mm thick) obtained by press molding is used, and the temperature is -150 ° C to 230 ° C (test piece is While raising the temperature at 2 ° C./min to the breaking temperature), perform dynamic viscoelasticity measurement (using a rheometer, manufactured by Hitachi High-Tech Science Co., Ltd., DMS6100) in the tensile test mode, and calculate Tg from the peak value of tan δ. I asked. Tg derived from the olefin-based elastomer (low melting point polypropylene (PP) (L-MODU S-400): Tg-3 ° C., amorphous polyalphaolefin (APAO) (VESTOPLAST 708): Tg-35 ° C.) is an olefin. With the blending of the based resin (Tg 36 ° C. or higher), Tg shifts to the high temperature side. The rate of change in Tg was evaluated according to the following criteria. The case where there was no change from the Tg derived from the olefin elastomer was defined as 0%, and the case where the Tg was changed to the same Tg as the olefin resin was defined as 100%.
⊚: 80% or more 〇: 60% or more and less than 80% Δ: 40% or more and less than 60% ×: less than 40% <Comprehensive evaluation of affinity>
The comprehensive evaluation of affinity was performed according to the following criteria. For the above three evaluation results of Ra value (HSP), dispersibility and Tg change rate, the average value was calculated with ◎ as 4 points, 〇 as 3 points, △ as 2 points, and × as 1 point, respectively. The average value was rounded off to obtain a comprehensive evaluation, which is indicated by the above symbol.

[9. Evaluation of three adhesive properties of styrene-based hot melt adhesive (HMA) (pressure sensitive adhesive)]
Each raw material was collected in a sample bottle at the compounding ratio shown in Table 3, and a toluene solvent was added and stirred / dissolved to prepare an HMA solution. An HMA solution was applied to a PET (polyethylene terephthalate) film to volatilize the toluene solvent to prepare an HMA sample. A SUS plate was used as the adherend, and the three physical characteristics of the adhesive were evaluated by the following test method. In this evaluation, resins HP2, HP4 and HP7 to HP11 were used as tackifiers.
<Raw materials>
-Base polymer: Styrene-isoprene-styrene block copolymer (SIS) (manufactured by Kraton Corporation, trade name: KRATON® D1161)
-Plasticizer: Paraffin oil (Diana Process Oil PS-32, manufactured by Idemitsu Kosan Co., Ltd.)
-Antioxidant: Irganox 1010 (manufactured by BASF Japan Ltd.)
<Adhesive strength>
Measured according to JIS Z0237 (23 ° C, 180 ° peel).
⊚: 10 N / cm or more 〇: 6 N / cm or more and less than 10 N / cm Δ: 3 N / cm or more and less than 6 N / cm ×: 3 N / cm or less <loop tack>
Measured according to JIS Z0237, FINAT test standard (23 ° C, contact for 2 seconds).
⊚: 10 N / cm or more 〇: 6 N / cm or more and less than 10 N / cm Δ: 3 N / cm or more and less than 6 N / cm ×: 3 N / cm or less <holding power>
Measured according to JIS Z0237 (50 ° C, 1 kg load creep).
⊚: 500 min or more 〇: 300 min or more and less than 500 min Δ: 100 min or more and less than 300 min ×: less than 100 min <Comprehensive evaluation of adhesiveness>
The comprehensive evaluation of adhesiveness was performed according to the following criteria. For the above-mentioned three evaluation results of adhesive strength, loop tack, and holding power, the average value was calculated with ◎ as 4 points, 〇 as 3 points, △ as 2 points, and × as 1 point, and the obtained average value was calculated. Rounded off to give a comprehensive evaluation, indicated by the above symbols.

[10. Evaluation of compoundability in polyolefin hot melt adhesive (HMA)]
Each raw material was collected in a sample bottle at the compounding ratio shown in Table 4, melted and stirred at 140 ° C. for 30 minutes, and then the contents were transferred onto a PET film and allowed to cool at room temperature to prepare an HMA sample. Prepared. The adhesive strength (adhesiveness) of the obtained HMA sample was evaluated by the following method. In this evaluation, resins HP5, HP7 and HP10 were used as tackifiers.
<Raw materials>
-Adhesive imparting agent: Terpene resin, manufactured by Yasuhara Chemical Co., Ltd., YS resin PX300N (softening point: 30 ° C, liquid at room temperature)
-Base polymer: Low melting point polypropylene (L-MODU S400, manufactured by Idemitsu Kosan Co., Ltd.)
-Plasticizer: Paraffin-based 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 , 500cSt)
-Antioxidant: Irganox 1010 (manufactured by BASF Japan Ltd.)
<Adhesive>
When the HMA sample was lightly tapped with a finger, the degree of adhesion to the finger was evaluated. The criteria were set so that the obtained evaluation results were generally correlated with the loop tack values in Table 3.
◎: Strongly adheres and follows 〇: Slightly strongly adheres △: Slightly weakly adheres ×: Almost no adhesion

[11. Melting point]
For the resins BP1 to BP10 and BP12 to BP16 described later, dynamic viscoelasticity measurement (rheometer, manufactured by Anton Pearl Co., Ltd., MCR302) was performed in a shear shear mode while raising the temperature from -30 ° C to 150 ° C at 5 ° C / min. The temperature at which the values of the storage elastic modulus G'and the loss elastic modulus G'are the same was determined as the melting point. The results are shown in Tables 5, 6 and 10.
If the temperature program is heated at -40 ° C to 220 ° C and 10 ° C / min using a differential scanning calorimeter (DSC8500, manufactured by PerkinElmer) and the melting point is not observed, the above-mentioned Leo Since the value on the meter corresponds to the softening point of the amorphous polymer, it is shown as "nd" in Tables 5 and 6.

[12. Oil compatibility]
Resins BP1 to BP12 and paraffin oil (Diana Process Oil PW-90, manufactured by Idemitsu Kosan Co., Ltd.), which will be described later, are placed in a container at a mass ratio of 3: 1 and stirred at 180 ° C. for 1 hour, and then kept at the same temperature for 5 minutes. After standing, the dispersibility of the obtained mixture was evaluated visually. The results are shown in Tables 5 and 6.
⊚: Transparent (uniform)
〇: Almost transparent (with diffuse reflection)
Δ: Partially lumpy (with swelling)
×: Massive (swelling)

[13. TF compatibility]
Resins BP1 to BP10 and BP12, which will be described later, and a DCPD-based tackifier (Escorez5300, manufactured by ExxonMobil) are placed in a container at a mass ratio of 2: 1, stirred at 180 ° C. for 1 hour, and then allowed to stand to cool to room temperature. After 1 week, the dispersibility of the obtained mixture was evaluated visually.
Further, the resin of BP11 and the C9 aroma / C5 adhesive (Escorez5600, manufactured by ExxonMobil) were placed in a container at a mass ratio of 2: 1 and stirred at 180 ° C. for 1 hour, then allowed to stand and allowed to cool to room temperature. After 1 week, the dispersibility of the obtained mixture was evaluated visually. The results are shown in Tables 5 and 6.
◎: Transparent 〇: Almost transparent (slightly cloudy)
Δ: White turbidity (slightly transparent)
×: Milky white

[14. Adhesiveness evaluation of hot melt adhesive (HMA)]
Each raw material was collected in a sample bottle at the compounding ratios shown in Tables 7, 8, 9 and 10, melted and stirred at 180 ° C. for 30 minutes, and then the contents were transferred onto a PET film at room temperature. The HMA sample was prepared by allowing to cool in. The adhesiveness of the obtained HMA sample was evaluated by the following method. In this evaluation, resins BP1 to BP3, BP5, and BP8 to BP16 were used. These resins were used as a base polymer or a component that also serves as a base polymer and a tackifier.
<Raw materials>
・ Adhesive agent:
・ Escorez5300 (DCPD system)
・ Escorez5600 (C9 aroma / C5 series)
-Plasticizer: Paraffin oil (PW-90)
-Antioxidant: Irganox 1010 (manufactured by BASF Japan Ltd.)
<Adhesive>
When the HMA sample was lightly tapped with a finger, the degree of adhesion to the finger was evaluated. The criteria were set so that the obtained evaluation results were generally correlated with the loop tack values in Table 3.
◎: Strongly adheres and follows 〇: Slightly strongly adheres △: Slightly weakly adheres ×: Almost no adhesion

[Manufacturing of olefin resin]
Production Example 1 (Production of hydrogenated olefin resin (HP1))
<Polymerization reaction process>
A heptane solution of dicyclopentadiene (DCPD) having a concentration of 95% by volume as a monomer in a stainless steel 1L autoclave under a nitrogen atmosphere at room temperature (first-class reagent, stabilizers and polar impurities removed with alumina) 400 mL ( 2.73 mol) was added, and while stirring at 100 rpm, 1.0 mL of a heptane solution of triisobutylaluminum (TIBA) having a concentration of 2 M as a scavenger and a dimethylanilinium tetrakis (pentafluorophenyl) borate (Borate) having a concentration of 20 mM as a co-catalyst. Add 6.0 mL (120 mmol) of the heptane solution of Heptane and 4.0 mL ( _{80 mmol) of the heptane solution of bis (cyclopentadienyl) zirconium dichloride (Cp 2} ZrCl ₂ ) as the main catalyst, increase the stirring rate to 400 rpm, and then chain. Hydrogen gas, which is a transfer agent, was introduced at a pressure of 0.05 MPa.
Subsequently, the internal temperature was raised to 80 ° C. and polymerization was carried out for 1 hour, then unreacted hydrogen gas was depressurized and removed, and a small amount of ethanol was added to stop the polymerization.
The obtained resin heptane solution was filtered to remove the catalyst residue, 20 mg of Irganox 1010 (antioxidant, manufactured by BASF Japan Co., Ltd.) was added, and heptane was retained at 70 ° C. and 100 hPa using an evaporator. After the removal, unreacted DCPD was distilled off at 160 ° C. and 25 hPa to obtain 12.2 g of an olefin resin (P1) (Mw: 321 and DCPD content: 100 mol%).

<Hydrogenation reaction process>
1 g of nickel diatomaceous earth catalyst, 10.0 g of the olefin resin (P1), and 391 mL of heptane were placed in a stainless steel 1 L autoclave to replace nitrogen, and then hydrogen gas was introduced at room temperature until it reached 5 MPa while stirring at 500 rpm. Then, the temperature was raised and maintained at 230 ° C. for 30 minutes to carry out a hydrogenation reaction.
The unreacted hydrogen gas was removed, the obtained resin heptane solution was hot-filtered to remove the catalyst residue, irganox 1010: 40 mg was added, and heptane was added at 70 ° C. and 25 hPa using an evaporator. Distilled away.

<Stripping process>
Further, the entire amount of the above sample was placed in a 1 L flask, heated to 200 ° C. while rotating using an evaporator, and nitrogen was blown at a flow rate of 1500 mL / min for 120 minutes to perform nitrogen stripping and hydrogenation. 8.0 g of an olefin resin (HP1) (Mw: 338, DCPD content: 100 mol%) was obtained.

Production Example 2 (Production of hydrogenated olefin resin (HP2))
<Polymerization reaction process>
As the main catalyst, instead of bis (cyclopentadienyl) zirconium dichloride (Cp ₂ ZrCl ₂ ), bis (dimethylsilylene) -bis (cyclopentadienyl) zirconium dichloride ((Me ₂ Si) ₂ Cp ₂ ZrCl ₂ ) The polymerization reaction was carried out under the same conditions as in Production Example 1 except that 9.2 g of an olefin resin (P2) was obtained. (Mw: 623, DCPD content: 100 mol%)
<Hydrogenation reaction process / stripping process>
Hydrogenated olefins by performing a hydrogenation reaction step and a stripping step under the same conditions as in Example 1 except that 8.0 g of an olefin resin (P2), 393 mL of heptane, and 32 mg of Irganox 1010 were used. 6.4 g of the system resin (HP2) (Mw: 645, DCPD content: 100 mol%) was obtained.

Production Example 3 (Production of hydrogenated olefin resin (HP3))
<Polymerization reaction process>
The polymerization reaction was carried out under the same conditions as in Example 2 except that the pressure of the hydrogen gas was 0.02 MPa and the polymerization temperature was 90 ° C. to obtain 9.9 g of an olefin resin (P3). (Mw: 1,785, DCPD content: 100 mol%)
<Hydrogenation reaction process / stripping process>
Hydrogenated olefins by performing a hydrogenation reaction / stripping step under the same conditions as in Production Example 1 except that 9.0 g of olefin resin (P3), 392 mL of heptane, and 36 mg of Irganox 1010 were used. 7.2 g of resin (HP3) (Mw: 1,785, DCPD content: 100 mol%) was obtained.

Production Example 4 (Production of hydrogenated olefin resin (HP4))
<Polymerization reaction step 1>
To a 1 L autoclave made of stainless steel, add 400 mL (2.73 mol) of a heptane solution of DCPD as a monomer at room temperature under a nitrogen atmosphere, and while stirring at 100 rpm, use TIBA (4 mmol) as a scavenger and Borate (300 μmol) as a cocatalyst. Bis (cyclopentadienyl) zirconium dichloride (Cp ₂ ZrCl ₂ ) (75 μmol) as the first main catalyst, bis (dimethylsilylene) -bis (cyclopentadienyl) zirconium dichloride ((Me _{2)) as the second main catalyst} Si) ₂ Cp ₂ ZrCl ₂ ) (75 μmol) was added, the stirring speed was increased 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 carried out for 2 hours, and then unreacted hydrogen gas was depressurized and removed.

<Polymerization reaction step 2>
_{Bis (dimethylsilylene) -bis (cyclopentadienyl) zirconium dichloride ((Me 2} )) as the second main catalyst while stirring the reaction solution obtained in the above <polymerization reaction step 1> in a nitrogen atmosphere at 100 rpm. Si) ₂ Cp ₂ ZrCl ₂ ) (50 μmol) was further added, the stirring speed was increased to 400 rpm, and then 0.02 MPa of hydrogen gas, which is a chain transfer agent, was introduced.
Subsequently, the internal temperature was raised to 90 ° C. and polymerization was carried out for 1 hour, and then unreacted hydrogen gas was depressurized and removed.
The obtained resin heptane solution was filtered to remove the catalyst residue, 20 mg of Irganox 1010 was added using an evaporator, heptane was distilled off at 70 ° C. and 100 hPa, and then not at 160 ° C. and 25 hPa. By distilling off the reaction DCPD, 34.2 g of an olefin resin (P4) (Mw: 1,005, DCPD content: 100 mol%) was obtained.

<Hydrogenation reaction process / stripping process>
Perform the hydrogenation reaction step and stripping step under the same conditions as in Production Example 1 except that 3 g of nickel diatomaceous earth catalyst, 30.0 g of olefin resin (P4), 373 mL of heptane, and 120 mg of irganox 1010 were used. Obtained 27.8 g of a hydrogenated olefin resin (HP4) (Mw: 1,050, DCPD content: 100 mol%).

Production Example 5 (Production of hydrogenated olefin resin (HP5))
<Polymerization reaction process>
A heptane solution of DCPD with a solvent of 80 mL as a solvent and a concentration of 95% by volume as the first monomer in a stainless steel 1 L autoclave under a nitrogen atmosphere (primary reagent, stabilizer and polar impurities have been removed with alumina). ) 320 mL (2.19 mol) is added, and while stirring at 100 rpm, 1.0 mL (2 mmol) of TIBA heptane solution having a concentration of 2 M as a scavenger and 6.0 mL (120 μmol) of Borate heptane solution having a concentration of 20 mM as a co-catalyst are mainly used. Add 4.0 mL (80 μmol) of a heptane solution of bis (cyclopentadienyl) zirconium dichloride (Cp ₂ ZrCl ₂ ) at a concentration of 20 mM as a catalyst, increase the stirring rate to 400 rpm, and then pressurize hydrogen gas, which is a chain transfer agent. It was introduced at 0.10 MPa.
Subsequently, while introducing propylene gas as the second monomer, the internal temperature was raised to 80 ° C. and the total pressure was raised to 0.45 MPa to polymerize for 1 hour, and then the unreacted propylene gas and hydrogen gas were depressurized. After removal, a small amount of ethanol was added to terminate the polymerization.
The obtained resin heptane solution was filtered to remove the catalyst residue, and heptane was distilled off at 70 ° C. and 100 hPa using an evaporator, and then unreacted DCPD was distilled off at 160 ° C. and 25 hPa. 30.4 g of an olefin resin (P5) (Mw: 749, DCPD content: 96 mol%) was obtained.

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

Production Example 6 (Production of hydrogenated olefin resin (HP6))
<Polymerization reaction process>
283 mL of heptane as a solvent, 117 mL (0.80 mol) of a heptane solution of DCPD as the first monomer, Borate (60 μmol) as a co-catalyst, bis (dimethylsilylene) -bis (cyclopentadienyl) zirconium dichloride ((Me) ₂ Si) ₂ Cp ₂ ZrCl ₂ ) (40 μmol), olefin-based by carrying out the polymerization reaction under the same conditions as in Production Example 5 except that the pressure of hydrogen gas was 0.03 MPa and the total pressure was 0.8 MPa. 19.7 g of a resin (P6) (Mw: 1,728, DCPD content: 76 mol%) was obtained.

<Hydrogenation reaction process / stripping process>
Hydrogenated olefins by performing a hydrogenation reaction step and a stripping step under the same conditions as in Production Example 5 except that 16.0 g of an olefin resin (P6), 386 mL of heptane, and 1010: 64 mg of Irganox were used. 14.5 g of a resin (HP6) (Mw: 1,751, DCPD content: 76 mol%) was obtained.

Production Example 7 (Production of hydrogenated olefin resin (HP7))
<Polymerization reaction step 1>
Add 283 mL of heptane as a solvent and 117 mL (0.80 mol) of a heptane solution of DCPD as the first monomer to a stainless steel 1 L autoclave under a nitrogen atmosphere at room temperature, and while stirring at 100 rpm, use TIBA (2 mmol) as a scavenger. Borate (180 μmol) as a co-catalyst, bis (cyclopentadienyl) zirconium dichloride (Cp ₂ ZrCl ₂ ) (80 μmol) as the first main catalyst, and bis (dimethylsilylene) -bis (cyclopentadi) as the second main catalyst. Enyl) Zirconium dichloride ((Me ₂ Si) ₂ Cp ₂ ZrCl ₂ ) (40 μmol) was added, the stirring rate was increased to 400 rpm, and then a chain transfer agent, hydrogen gas 0.05 MPa, was introduced.
Subsequently, 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 to polymerize for 1 hour, and then the unreacted propylene gas and hydrogen gas were depressurized. Removed. The polymerization solution was completely transferred to a 5 L flask together with the washed heptane of the 1 L autoclave, and then a small amount of ethanol was added to inactivate the catalyst, and the 1 L autoclave was vacuum dried at 80 ° C. and then purged with nitrogen.

<Polymerization reaction step 2>
70 mL of heptane as a solvent and 330 mL (2.25 mol) of a heptane solution of DCPD as the first monomer were added to the same stainless steel 1 L autoclave used in the above <polymerization reaction step 1> under a nitrogen atmosphere at room temperature. , TIBA (2 mmol) as a scavenger, Borate (60 μmol) as a co-catalyst, and bis (dimethylsilylene) -bis (cyclopentadienyl) zirconium dichloride ((Me ₂ Si) ₂ Cp ₂ ZrCl) as a main catalyst while stirring at 100 rpm. ₂ ) (40 μmol) was added, the stirring speed was increased to 400 rpm, and then hydrogen gas as a chain transfer agent was introduced at a pressure of 0.50 MPa.
Subsequently, 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 to polymerize for 1 hour, and then the unreacted propylene gas and hydrogen gas were depressurized. Removed. The polymerization solution was completely transferred to the same 5L flask as that used in the above <polymerization reaction step 1> together with the washed heptane of the 1L autoclave.
The obtained resin heptane solution was filtered to remove the catalyst residue, 20 mg of Irganox 1010 was added, heptane was distilled off at 70 ° C. and 100 hPa using an evaporator, and then not at 160 ° C. and 25 hPa. By distilling off the reaction DCPD, 102.0 g of an olefin resin (P7) (Mw: 1,085, DCPD content: 83 mol%) was obtained.

<Hydrogenation reaction process / stripping process>
Perform the hydrogenation reaction step and stripping step under the same conditions as in Production Example 1 except that 4 g of nickel diatomaceous earth catalyst, 60.0 g of olefin resin (P7), 346 mL of heptane, and 240 mg of irganox 1010 were used. Obtained 57.0 g of a hydrogenated olefin resin (HP7) (Mw: 1,104, DCPD content: 83 mol%).

Production Example 8 (Production of hydrogenated olefin resin (HP8))
<Polymerization reaction process>
A heptane solution of DCPD having a concentration of 95% by volume as the first monomer in a stainless steel 1L autoclave under a nitrogen atmosphere at room temperature (primary reagent, stabilizers and polar impurities have been removed with alumina) 264 mL (1. 90 mol), 120 mL (0.95 mol) of 4-methyl-1-pentene (4M1P) (polar impurities have been removed with alumina) as the second monomer, and while stirring at 100 rpm, as a scavenger of TIBA having a concentration of 2 M. Heptan solution 1.0 mL (2 mmol), Borate heptane solution 3.0 mL (60 μmol) with a concentration of 20 mM as a co-catalyst, bis (dimethylsilylene) -bis (cyclopentadienyl) zirconium dichloride ((Me)) with a concentration of 20 mM as a main catalyst. ₂ Si) _{4.0 mL (40 μmol) of a heptane solution of 2} Cp ₂ ZrCl ₂ ) was added, the stirring rate was increased 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 carried out for 1 hour, then unreacted hydrogen gas was depressurized and removed, and a small amount of ethanol was added to stop the polymerization.
The obtained resin heptane solution was filtered to remove the catalyst residue, air-dried for a whole day and night, 20 mg of Irganox 1010 was added, and heptane was distilled off at 70 ° C. and 100 hPa using an evaporator, and then 160 ° C. , Unreacted DCPD was distilled off at 25 hPa to obtain 35.5 g of an olefin resin (P8) (Mw: 555, DCPD content: 83 mol%).

<Hydrogenation reaction process / stripping process>
Perform the hydrogenation reaction step and stripping step under the same conditions as in Production Example 5, except that 3 g of nickel diatomaceous earth catalyst, 30.0 g of olefin resin (P8), 373 mL of heptane, and 120 mg of irganox 1010 were used. Obtained 28.0 g of a hydrogenated olefin resin (HP8) (Mw: 613, DCPD content: 83 mol%).

Production Example 9 (Production of hydrogenated olefin resin (HP9))
<Polymerization reaction process>
The polymerization reaction was carried out under the same conditions as in Production Example 8 except that 167 mL (1.14 mol) of a heptane solution of DCPD was used as the first monomer and 220 mL (1.74 mol) of 4M1P was used as the second monomer. 57.1 g of a resin (P9) (Mw: 762, DCPD content: 65 mol%) was obtained.
<Hydrogenation reaction process / stripping process>
Hydrogenation is performed by performing a hydrogenation reaction step and a stripping step under the same conditions as in Production Example 8 except that an olefin resin (P9) is used instead of the olefin resin (P8) as the olefin resin. 28.5 g of the olefin resin (HP9) (Mw: 801 and DCPD content: 65 mol%) was obtained.

Comparative Production Example 1 (Production of Hydrogenated Petroleum Resin (HP10))
A homopolymer of dicyclopentadiene (DCPD) is obtained by a thermal polymerization method (polymerization temperature: 260 ° C.) using only dicyclopentadiene (DCPD) as a raw material monomer according to Example 1 of International Publication No. 2004/056882. After that, partial hydrogenation using a nickel catalyst was carried out to obtain a hydrogenated petroleum resin (HP10).

Comparative production example 2 (Production of hydrogenated petroleum resin (HP11))
Dicyclopentadiene (DCPD) and styrene were used as raw material monomers in the ratio shown in Table 1 according to Example 1 of International Publication No. 2004/056882, and dicyclopentadiene (DCPD) and styrene were combined by a thermal polymerization method. After obtaining the copolymer, partial hydrogenation using a nickel catalyst was carried out to obtain a hydrogenated petroleum resin (HP11).

Production Example 10 (Production of olefin resin (BP1))
In a stainless steel 1L autoclave, under a nitrogen atmosphere, at room temperature, 327 mL of toluene as a solvent and 73 mL (0.60 mol) of a toluene solution of norbornene (NB) having a concentration of 80% by weight as a monomer (first-class reagent, alumina-treated). In addition, while stirring at 100 rpm, 1.0 mL of a heptane solution of triisobutylaluminum (TIBA) having a concentration of 2 M as a scavenger and a toluene solution of dimethylanilinium tetrakis (pentafluorophenyl) borate (Borate) having a concentration of 5 mM as a co-catalyst 2. Add 1.0 mL (5 μmol) of a toluene solution of 0 mL (10 μmol) and a concentration of 5 mM bis (cyclopentadienyl) zirconium dichloride (Cp ₂ ZrCl ₂ ) as the main catalyst, increase the stirring rate to 400 rpm, and then the chain transfer agent. Hydrogen gas was introduced at a pressure of 0.05 MPa.
Subsequently, while introducing ethylene gas as the second monomer, the internal temperature was raised to 90 ° C. and the total pressure was raised to 0.70 MPa to polymerize for 1 hour, and then the unreacted ethylene gas and hydrogen gas were depressurized. After removal, a small amount of ethanol was added to terminate the 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 with ethanol several times, and then vacuum dried at 190 ° C. for 6 hours. Obtained 39 g of an olefin resin (BP1) (Mw: 33,000, NB content: 14 mol%).

Production Example 11 (Production of olefin resin (BP2))
Olefin resin (BP2) (Mw) was subjected to polymerization reaction, reprecipitation, washing, and drying under the same conditions as in Production Example 10 except that the pressure of hydrogen gas, which is a chain transfer agent, was changed to 0.01 MPa. : 50,000, NB content: 14 mol%) 75 g was obtained.

Production Example 12 (Production of olefin resin (BP3))
Olefin resin (BP3) (Mw: 91,000) was subjected to polymerization reaction, reprecipitation, washing, and drying under the same conditions as in Production Example 10 except that hydrogen gas, which is a chain transfer agent, was not used. , NB content: 14 mol%) 109 g was obtained.

Production Example 13 (Production of olefin resin (BP4))
The amount of toluene solution of dimethylanilinium tetrakis (pentafluorophenyl) borate (Borate) at a concentration of 5 mM was changed to 0.40 mL (2 μmol), and bis (cyclopentadienyl) zirconium dichloride (Cp _{2) at a concentration of 5 mM was used as the main catalyst.} Toluene solution of ZrCl ₂ ) at a concentration of 5 mM dimethylsilylene- (tetramethylcyclopentadienyl _{) (t-butylamide) titanium dichloride (Me 2} Si (Me ₄ Cp) (t-BuN) Tycol ₂ ) toluene solution 0. After changing to 20 mL (1 μmol) and introducing ethylene gas, the olefin was subjected to polymerization reaction, reprecipitation, washing, and drying under the same conditions as in Production Example 10 except that the internal temperature was 80 ° C. 111 g of the system resin (BP4) (Mw: 84,000, NB content: 18 mol%) was obtained.

Production Example 14 (Production of olefin resin (BP5))
Polymerization reaction, reprecipitation, washing, and drying were carried out under the same conditions as in Production Example 13 except that the amount of toluene was changed to 305 mL and the amount of norbornene (NB) in a toluene solution was changed to 95 mL (0.80 mol). By doing so, 30 g of an olefin resin (BP5) (Mw: 28,000, NB content: 21 mol%) was obtained.

Production Example 15 (Production of olefin resin (BP6))
Olefin resin (BP6) (Mw: 45,000, NB content: 24 mol) was subjected to polymerization reaction, reprecipitation, washing, and drying under the same conditions as in Production Example 13 except that the solvent was changed to cyclohexane. %) 50 g was obtained.

Production Example 16 (Production of olefin resin (BP7))
In a stainless steel 1L autoclave, under a nitrogen atmosphere, at room temperature, 296 mL of toluene as a solvent and 104 mL (0.85 mol) of a toluene solution of norbornene (NB) having a concentration of 80% by weight as a monomer (first-class reagent, alumina-treated). In addition, while stirring at 100 rpm, 1.0 mL of a heptane solution of triisobutylaluminum (TIBA) having a concentration of 2 M as a scavenger and a toluene solution of dimethylanilinium tetrakis (pentafluorophenyl) borate (Borate) having a concentration of 20 mM as a co-catalyst 1. Toluene solution 2 of 5 mL (30 μmol), 10 mM dimethylsilylene- (tetramethylcyclopentadienyl _{) (t-butylamide) titanium dichloride (Me 2} Si (Me ₄ Cp) (t-BuN) Tycol _{2) as the main catalyst} After adding 0.0 mL (20 μmol) and increasing the stirring rate to 400 rpm, hydrogen gas as a chain transfer agent was introduced at a pressure of 0.05 MPa.
Subsequently, while introducing propylene gas as the second monomer, the internal temperature was raised to 80 ° C. and the total pressure was raised to 0.70 MPa to polymerize for 1 hour, and then the unreacted propylene gas and hydrogen gas were depressurized. After removal, a small amount of ethanol was added to terminate the 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 with ethanol several times, and then vacuum dried at 190 ° C. for 6 hours. Obtained 73 g of an olefin resin (BP7) (Mw: 43,000, NB content: 18 mol%).

Production Example 17 (Production of olefin resin (BP8))
The amount of toluene was changed to 272 mL, the amount of the toluene solution of norbornene (NB) was changed to 128 mL (1.05 mol), hydrogen gas as a chain transfer agent was introduced at a pressure of 0.10 MPa, and ethylene gas was introduced. The olefin resin (BP8) (Mw: 25,000,) was subjected to the polymerization reaction, reprecipitation, washing, and drying under the same conditions as in Production Example 16 except that the total pressure was 0.80 MPa. NB content: 27 mol%) 53 g was obtained.

Production Example 18 (Production of olefin resin (BP9))
The olefin resin (BP9) (Mw:) was subjected to a polymerization reaction, reprecipitation, washing, and drying under the same conditions as in Production Example 17 except that hydrogen gas, which is a chain transfer agent, was introduced at a pressure of 0.05 MPa. 4,000,000, NB content: 27 mol%) 66 g was obtained.

Production Example 19 (Production of olefin resin (BP10))
Production Example 16 except that the amount of toluene was changed to 242 mL, the amount of norbornene (NB) in a toluene solution was changed to 158 mL (1.30 mol), and hydrogen gas, which is a chain transfer agent, was introduced at a pressure of 0.10 MPa. By carrying out the polymerization reaction under the same conditions as above, 27 g of an olefin resin (BP10) (Mw: 22,000, NB content: 32 mol%) was obtained.

Production Example 20 (Production of Olefin Resin (BP13))
In the <polymerization reaction step>, the amount of heptane was 347 mL, dicyclopentadiene (DCPD) heptane solution (primary reagent, alumina-treated) 50 mL (0.36 mol), boronate heptane solution 3.0 mL (60 μmol), 2.0 mL (40 μmol) of Cp ₂ ZrCl ₂ heptane solution, ethylene was used as the second monomer, the pressure of hydrogen gas was 0.05 MPa, the total pressure was 0.80 MPa, and in the <hydrogenation reaction step>, 150 ° C. The polymerization reaction, reprecipitation, washing, and drying were carried out under the same conditions as in Production Example 5, except that the hydrogenation reaction was carried out for 3 hours, and a part of the polymerization yield of 137 g was hydrogenated and stripped to form an olefin. 137 g of a resin (BP13) (Mw: 64,000, DCPD content: 6 mol%) was obtained.

Production Example 21 (Production of olefin resin (BP14))
The polymerization reaction was carried out under the same conditions as in Production Example 20 except that the amount of heptane was 188 mL, the amount of the heptane solution of DCPD was 200 mL (1.42 mol), and the pressure of hydrogen gas was 0.30 MPa. 158 g of a resin (BP14) (Mw: 29000, DCPD content: 22 mol%) was obtained.

Production Example 22 (Production of olefin resin (BP15))
By carrying out the polymerization reaction under the same conditions as in Production Example 21 except that the pressure of hydrogen gas was set to 0.05 MPa, 72 g of an olefin resin (BP15) (Mw: 48,000, DCPD content: 23 mol%) was obtained. Obtained.

Production Example 23 (Production of olefin resin (BP16))
188 mL of toluene as a solvent, 200 mL (1.42 mol) of a toluene solution of dicyclopentadiene (DCPD) (primary reagent, treated with alumina), 3.0 mL (60 μmol) of a toluene solution of Borate, and dimethylsilylene- (tetra) as the main catalyst. Except for 2.0 mL (40 μmol) of a toluene solution of methylcyclopentadiene (t-butylamide) titanium dichloride (Me ₂ Si (Me ₄ Cp) (t-BuN) Tycol _{2) and propylene as the second monomer.} By carrying out the polymerization reaction under the same conditions as in Production Example 20, 35 g of an olefin resin (BP16) (Mw: 24,000, DCPD content: 36 mol%) was obtained.

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

Other resin raw materials (olefin elastomer (BP12))
Low melting point polypropylene (PP) (manufactured by Idemitsu Kosan Co., Ltd., trade name: L-MODU S400), which is an olefin-based elastomer, was designated as BP12 and used for evaluation as a base polymer.

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

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

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

As clearly shown in Tables 7 to 10, it can be seen that the olefin-based resin of the present disclosure has good adhesiveness even when used as a base polymer.

Claims

An olefin-based resin containing a structural unit derived from an alicyclic olefin (A) and satisfying the following (a) and (b).
(A) Aromatic part is 1% or less (b) Linearity is 70% or more
The olefin-based resin according to claim 1, wherein the alicyclic olefin (A) is one or more selected from dicyclopentadiene, cyclopentene, cyclohexene, norbornene and derivatives thereof.
The olefin-based resin according to claim 1 or 2, further comprising a structural unit derived from α-olefin (B).
The olefin-based resin according to claim 3, wherein the α-olefin (B) has 2 to 10 carbon atoms.
The olefin-based resin according to claim 3 or 4, wherein the α-olefin (B) is one or more selected from a linear α-olefin and a branched α-olefin.
Claims 3-5, wherein the α-olefin (B) is one or more selected from ethylene, propylene, butene, 3-methyl-1-butene, 4-methyl-1-pentene and 2-ethyl-1-hexene. The olefin-based resin according to any one of the above.
The olefin resin according to any one of claims 1 to 6, wherein the volatile component contained in the olefin resin is 10 ppm or less.
The olefin-based resin according to any one of claims 1 to 7, which has a molecular weight distribution (Mw / Mn) of 2.5 or more.
The olefin-based resin according to any one of claims 1 to 8, which has a molecular weight distribution (Mz / Mw) of more than 2.5.
The olefin-based resin according to any one of claims 1 to 9, wherein the weight average molecular weight is 5,000 to 200,000.
The invention according to any one of claims 3 to 10, wherein the molar ratio [(A) / (B)] of the alicyclic olefin (A) to the α-olefin (B) is 40/60 to 100/0. Olefin resin.
The invention according to any one of claims 3 to 10, wherein the molar ratio [(A) / (B)] of the alicyclic olefin (A) to the α-olefin (B) is 1/99 to 40/60. Olefin resin.
A hot melt adhesive containing the olefin resin according to any one of claims 1 to 12.
The hot melt adhesive according to claim 13, further comprising a base polymer.
The hot melt adhesive according to claim 14, wherein the difference between the Hansen solubility parameter of the base polymer and the Hansen solubility parameter of the olefin resin is 5 or less.
The hot melt adhesive according to any one of claims 13 to 15, further comprising a tackifier resin.
A method for producing an olefin resin, which comprises 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.
The method for producing an olefin resin according to claim 17, further comprising a step of hydrogenating at 100 to 300 ° C. in the presence of a catalyst.
The method for producing an olefin resin according to claim 17 or 18, wherein the stripping step uses an inert gas as a medium and the stripping treatment is performed at 150 to 300 ° C. for 0.5 to 5 hours.
Any of claims 17 to 19, which polymerizes in the presence of two or more metallocene catalysts 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. The method for producing an olefin resin according to one.