JP7283397B2 - Hydrocarbon resin, hydrogenated product thereof, and hot-melt adhesive composition using these - Google Patents

Description

TECHNICAL FIELD The present invention relates to a hydrocarbon resin, a hydrogenated product thereof, and a hot-melt pressure-sensitive adhesive composition using these. The present invention relates to a hydrocarbon resin and a hydrogenated product thereof capable of providing a hot-melt pressure-sensitive adhesive composition having excellent adhesive strength and heat deterioration resistance, and a hot-melt pressure-sensitive adhesive composition using these.

Since hot-melt adhesives harden in a short time, they can be used to efficiently adhere various products. Since it is an adhesive, it is used in various fields. For example, when manufacturing paper, cardboard, and film packaging for foods, clothing, electronic devices, and cosmetics, as well as sanitary products such as disposable diapers and sanitary products, we bond the members that make up them. Hot-melt tacky adhesives are used as adhesives for bonding and as adhesives constituting the adhesive layer of adhesive tapes and labels.

Hot-melt pressure-sensitive adhesives are usually produced by blending a base polymer with a tackifying resin or the like. Various polymers are used as the base polymer for hot-melt adhesives. The agent exhibits sufficient adhesive strength even with a small amount applied, and has excellent properties such as excellent heat deterioration resistance, so it is less likely to clog nozzles for coating. ing.

For example, Patent Document 1 discloses a hot-melt pressure-sensitive adhesive composition obtained by blending an ethylene/α-olefin copolymer with a hydrogenated hydrocarbon pressure-sensitive adhesive resin having a softening point of over 120°C. there is According to the technique of Patent Document 1, although excellent heat deterioration resistance can be achieved, the viscosity of the formulation (viscosity as a hot-melt adhesive composition) is relatively high, and the ease of coating is poor. , there is a problem that the adhesive strength is not necessarily sufficient, and improvements in these have been desired.

Japanese Patent Publication No. 2007-525562

The present invention has been made in view of such circumstances, and its object is to provide a hot adhesive that has a low formulation viscosity, is excellent in ease of coating, and has excellent high-temperature adhesive performance, adhesive strength and heat deterioration resistance. An object of the present invention is to provide a hydrocarbon resin and its hydride that can give a melt pressure-sensitive adhesive composition, and a hot-melt pressure-sensitive adhesive composition using these.

The inventors of the present invention conducted studies to achieve the above object, and found that the monomer unit derived from the tetracyclododecene compound is contained in a proportion of 0.1 to 50% by weight, and the weight average molecular weight (Mw) , the Z-average molecular weight (Mz), and the ratio of the Z-average molecular weight to the weight-average molecular weight (Mz/Mw) are within a predetermined range, and the softening point is within a specific range. I found that it can be done, and came to complete the present invention.

That is, according to the present invention, a hydrocarbon resin containing a monomer unit derived from a tetracyclododecene compound in a proportion of 0.1 to 50% by weight and having a weight average molecular weight (Mw) of 500 to 4, 000, the Z-average molecular weight (Mz) is in the range of 1,000 to 10,000, and the ratio of the Z-average molecular weight to the weight-average molecular weight (Mz/Mw) is in the range of 1.0 to 4.0. C., a hydrocarbon resin having a softening point within the range of 80.degree. C. to 170.degree.

The hydrocarbon resin of the present invention contains 0.1 to 50% by weight of monomer units derived from the tetracyclododecene compound, 1 to 60% by weight of 1,3-pentadiene monomer units, and 4 to 4 carbon atoms. 1 to 30% by weight of alicyclic monoolefin monomer units of 6, 0 to 50% by weight of acyclic monoolefin monomer units having 4 to 8 carbon atoms, and 0 to 10 alicyclic diolefin monomer units It preferably contains 0 to 40% by weight of aromatic monoolefin monomer units and 0 to 50% by weight of aromatic monomer units having a structure in which two or more cyclic structures are bonded.
The hydrocarbon resin of the present invention contains tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene units are preferred.
The hydrocarbon resin of the present invention contains tetracyclo[4.4.0.1 ^2,5 . The proportion of 1 ^7,10 ]dodeca-3-ene units is preferably at least 50% by weight.

Further, according to the present invention, there is provided a hydride obtained by hydrogenating the above hydrocarbon resin of the present invention.

Furthermore, according to the present invention, there is provided a hot-melt pressure-sensitive adhesive composition containing the hydrocarbon resin of the present invention or the hydride of the present invention.
Further, according to the present invention, there is provided a hot-melt adhesive composition containing the hydrocarbon resin of the present invention or the hydrogenated product of the present invention and an ethylene/α-olefin copolymer.

According to the present invention, a hydrocarbon resin that can provide a hot-melt pressure-sensitive adhesive composition that has a low blending viscosity, is excellent in ease of coating, and has excellent high-temperature adhesive performance, adhesive strength, and heat deterioration resistance. and hydrides thereof, and hot-melt adhesive compositions using these.

The hydrocarbon resin of the present invention is a hydrocarbon resin containing 0.1 to 50% by weight of monomer units derived from a tetracyclododecene compound, and has a weight average molecular weight (Mw) of 500 to 4, 000, the Z-average molecular weight (Mz) is in the range of 1,000 to 10,000, and the ratio of the Z-average molecular weight to the weight-average molecular weight (Mz/Mw) is in the range of 1.0 to 4.0. and a softening point in the range of 80°C to 170°C.
The hydrocarbon resin of the present invention can be produced, for example, by addition polymerization of a monomer mixture containing a tetracyclododecene compound and a monomer copolymerizable therewith.

The hydrocarbon resin of the present invention contains 0.1 to 50% by weight of monomer units derived from a tetracyclododecene compound, and the content is preferably 5 to 45% by weight, more It is preferably 10 to 40% by weight, more preferably 15 to 35% by weight. In the present invention, the hydrocarbon resin contains the monomer unit derived from the tetracyclododecene compound in the above content ratio, and has a weight average molecular weight (Mw), a Z average molecular weight (Mz), a weight average molecular weight The Z-average molecular weight ratio (Mz/Mw) and the softening point are within the above-described predetermined ranges, thereby blending an olefinic thermoplastic elastomer or the like to form a hot-melt adhesive composition In this case, the viscosity of the formulation is low, the easiness of coating is excellent, and the high-temperature adhesive performance, adhesive strength, and resistance to heat deterioration can be excellent.

In particular, as a result of intensive studies by the present inventors, the weight-average molecular weight (Mw ), the Z-average molecular weight (Mz), the ratio of the Z-average molecular weight to the weight-average molecular weight (Mz/Mw), and the softening point can be suitably controlled within the above ranges. It has been found that the composition can be made to have low formulation viscosity, excellent ease of coating, and excellent high-temperature adhesion performance, adhesive strength, and resistance to heat deterioration. If the content of the monomer units derived from the tetracyclododecene compound is too low, it becomes difficult to balance the low formulation viscosity with high-temperature adhesive performance, adhesive strength, and heat deterioration resistance. If the content of the monomer units derived from the compound is too high, the adhesive performance will be poor in the temperature range below room temperature.

Tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3 ^- ene structure as a basic skeleton. 1 ^7,10 ]dodeca-3-ene (tetracyclododecene), 8-methyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-ethyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-ethylidene-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-vinyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-propenyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene and the like. The tetracyclododecene compound may be used alone or in combination of two or more, but at least tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene is preferably included, and tetracyclo[4.4.0.1 ^2,5 . More preferably, the proportion of 1 ^7,10 ]dodeca-3-ene is 50% by weight or more. That is, tetracyclo[4.4.0.1 ^2,5 . More preferably, the proportion of 1 ^7,10 ]dodeca-3-ene units is at least 50% by weight.

The hydrocarbon resin of the present invention may contain monomer units derived from a tetracyclododecene compound in a proportion of 0.1 to 50% by weight, other than monomer units derived from a tetracyclododecene compound. The monomer unit of is not particularly limited, and any one can be contained, but when it is used as a hot-melt adhesive composition, the high-temperature adhesive performance, adhesive strength and heat deterioration resistance are further enhanced. From the point of view that it is possible to 0 to 50% by weight of cyclic monoolefin monomer units, 0 to 10% by weight of alicyclic diolefin monomer units, 0 to 40% by weight of aromatic monoolefin monomer units, and two or more cyclic structures It preferably contains 0 to 50% by weight of an aromatic monomer unit having a structure in which is bonded.

The content of 1,3-pentadiene (piperylene) monomer units in the hydrocarbon resin of the present invention is preferably 1 to 60% by weight, more preferably 10 to 55% by weight, still more preferably 20 to 50% by weight. %. By setting the content ratio of the 1,3-pentadiene monomer unit within the above range, the resulting hot-melt pressure-sensitive adhesive composition can be made more excellent in high-temperature adhesive performance, adhesive strength and heat deterioration resistance. can. The cis/trans isomer ratio in 1,3-pentadiene may be any ratio and is not particularly limited.

The alicyclic monoolefin having 4 to 6 carbon atoms for forming the alicyclic monoolefin monomer unit having 4 to 6 carbon atoms has one ethylenically unsaturated bond and a non-aromatic It is not particularly limited as long as it is a hydrocarbon compound having 4 to 6 carbon atoms and a ring structure, and specific examples thereof include cyclobutene, cyclopentene, cyclohexene, methylcyclobutene, and methylcyclopentene. The hydrocarbon compound having 4 to 6 carbon atoms may be used alone, or two or more may be used in combination. The proportion of cyclopentene in the alicyclic monoolefin is preferably 50% by weight or more. That is, it is preferable that the proportion of cyclopentene units in the alicyclic monoolefin monomer units having 4 to 6 carbon atoms contained in the hydrocarbon resin of the present invention is 50% by weight or more.

The content of the alicyclic monoolefin monomer unit having 4 to 6 carbon atoms in the hydrocarbon resin of the present invention is preferably 1 to 30% by weight, more preferably 5 to 30% by weight, and still more preferably 10% by weight. ~30 wt%, even more preferably 20-30 wt%. By setting the content of the alicyclic monoolefin monomer unit having 4 to 6 carbon atoms in the above range, the obtained hot melt pressure-sensitive adhesive composition has excellent high-temperature adhesive performance, adhesive strength and heat deterioration resistance. can be assumed.

The acyclic monoolefin having 4 to 8 carbon atoms for forming the acyclic monoolefin monomer unit having 4 to 8 carbon atoms has one ethylenically unsaturated bond in its molecular structure, It is not particularly limited as long as it is a chain hydrocarbon compound having 4 to 8 carbon atoms and does not have a ring structure. Specific examples thereof include 1-butene, 2-butene, isobutylene (2-methylpropene), and the like. butenes; 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene and other pentenes; 1-hexene, 2-hexene, 2- Hexenes such as methyl-1-pentene; Heptenes such as 1-heptene, 2-heptene, and 2-methyl-1-hexene; 1-octene, 2-octene, 2-methyl-1-heptene, diisobutylene (2 , 4,4-trimethylpentene-1 and 2,4,4-trimethylpentene-1); Acyclic monoolefins having 4 to 8 carbon atoms may be used alone or in combination of two or more types, but at least 2-methyl-2-butene, isobutylene and diisobutylene The total amount of 2-methyl-2-butene, isobutylene and diisobutylene in the acyclic monoolefin having 4 to 6 carbon atoms is preferably 50% by weight. It is more preferable to be above. That is, the total ratio of 2-methyl-2-butene units, isobutylene units and diisobutylene units in the acyclic monoolefin monomer units having 4 to 6 carbon atoms contained in the hydrocarbon resin of the present invention is 50. % by weight or more.

The content of the acyclic monoolefin monomer unit having 4 to 8 carbon atoms in the hydrocarbon resin of the present invention is preferably 0 to 50% by weight, more preferably 0 to 40% by weight, still more preferably 1 ~30 wt%, even more preferably 5-30 wt%. By containing the acyclic monoolefin monomer unit having 4 to 8 carbon atoms in the above ratio, the obtained hot melt pressure-sensitive adhesive composition has excellent high-temperature adhesive performance, adhesive strength and heat deterioration resistance. can be

An alicyclic diolefin for forming an alicyclic diolefin monomer unit is a hydrocarbon compound having two or more ethylenically unsaturated bonds and a non-aromatic ring structure in its molecular structure. Specific examples thereof include cyclopentadiene polymers such as cyclopentadiene and dicyclopentadiene, methylcyclopentadiene, and methylcyclopentadiene polymers. The alicyclic diolefin may be used alone or in combination of two or more, but preferably contains at least dicyclopentadiene, and dicyclopentadiene in the alicyclic diolefin More preferably, the proportion of pentadiene is 50% by weight or more. That is, it is preferable that the proportion of dicyclopentadiene units in the alicyclic diolefin monomer units contained in the hydrocarbon resin of the present invention is 50% by weight or more.

The content of the alicyclic diolefin monomer units in the hydrocarbon resin of the present invention is preferably 0 to 10% by weight, more preferably 0 to 7.5% by weight, still more preferably 0 to 5% by weight. is. By containing the alicyclic diolefin monomer unit in the above ratio, the obtained hot-melt pressure-sensitive adhesive composition can be made more excellent in high-temperature adhesive performance, adhesive strength and heat deterioration resistance. .

The aromatic monoolefin for forming the aromatic monoolefin monomer unit is a hydrocarbon compound having one ethylenically unsaturated bond in its molecular structure and an aromatic ring structure. Although not particularly limited, specific examples thereof include styrene, α-methylstyrene, vinyltoluene, and the like. The aromatic monoolefin may be used alone or in combination of two or more, but preferably contains at least styrene, and the proportion of styrene in the aromatic monoolefin is 50. % by weight or more is more preferable. That is, it is preferable that the proportion of styrene units in the aromatic monoolefin monomer units contained in the hydrocarbon resin of the present invention is 50% by weight or more.

The content of aromatic monoolefin monomer units in the hydrocarbon resin of the present invention is preferably 0 to 40% by weight, more preferably 0 to 35% by weight, still more preferably 0 to 30% by weight. By containing the aromatic monoolefin monomer unit in the above ratio, the resulting hot-melt pressure-sensitive adhesive composition can be made more excellent in high-temperature adhesive performance, adhesive strength and heat deterioration resistance.

An aromatic monomer having a structure in which two or more cyclic structures are bonded for forming an aromatic monomer unit having a structure in which two or more cyclic structures are bonded includes an aromatic ring structure, It is not particularly limited as long as it is a hydrocarbon compound having two or more ring structures. Specific examples thereof include compounds having a naphthalene skeleton such as naphthalene, compounds having a fluorene skeleton such as fluorene, and biphenyl skeletons such as biphenyl. compounds having an anthracene skeleton such as anthracene, compounds having a phenanthrene skeleton such as phenanthrene, compounds having an indene skeleton such as indene, and compounds having a benzothiophene skeleton such as benzothiophene. Only one aromatic monomer having a structure in which two or more cyclic structures are bonded may be used, or two or more thereof may be used in combination.

The content of aromatic monomer units having a structure in which two or more cyclic structures are bonded in the hydrocarbon resin of the present invention is preferably 0 to 50% by weight, more preferably 0 to 40% by weight, and still more preferably. is 0 to 30% by weight. By containing the aromatic monomer unit having a structure in which two or more cyclic structures are bonded in the above ratio, the obtained hot melt adhesive composition is improved by high temperature adhesive performance, adhesive strength and heat deterioration resistance. can be excellent.

Further, the hydrocarbon resin of the present invention may contain monomer units other than the monomer units described above. Other monomers are not particularly limited as long as they are copolymerizable with the above-described tetracyclododecene compound-containing monomers. Examples include 1,3-butadiene, 1,2 -Acyclic polyenes other than 1,3-pentadiene such as butadiene, isoprene, 1,3-hexadiene, and 1,4-pentadiene; Alicyclic monoolefins having 7 or more carbon atoms such as cycloheptene; Ethylene, propylene, nonene, etc. acyclic monoolefins other than those having 4 to 8 carbon atoms; and the like. These may be used alone, or may be used in combination of two or more. The content of other monomer units in the hydrocarbon resin of the present invention is preferably 0 to 30% by weight, more preferably 0 to 25% by weight, still more preferably 0 to 20% by weight.

The hydrocarbon resin of the present invention can be produced, for example, by addition polymerization of a monomer mixture containing a tetracyclododecene compound and each of the monomers described above. The addition polymerization method is not particularly limited, and can be selected from known addition polymerization methods for producing hydrocarbon resins. Further, after obtaining a hydrocarbon resin by addition polymerization of a monomer mixture, some or all of the unsaturated bonds remaining in the polymer molecular structure of the hydrocarbon resin are saturated by a hydrogenation reaction (hydrogenation). It may be a hydrogenated hydride.

The weight average molecular weight (Mw) of the hydrocarbon resin of the present invention is in the range of 500-4,000, preferably in the range of 750-3,500, more preferably in the range of 1,000-3,000. If the weight average molecular weight (Mw) of the hydrocarbon resin is too small, the hot-melt adhesive composition obtained by blending the hydrocarbon resin will be inferior in heat deterioration resistance, and the weight average molecular weight (Mw) If is too large, the resulting hot-melt pressure-sensitive adhesive composition will have a high formulation viscosity, resulting in poor coating easiness and poor adhesion.

The Z-average molecular weight (Mz) of the hydrocarbon resin of the present invention is in the range of 1,000 to 10,000, preferably in the range of 1,500 to 8,500, more preferably in the range of 2,000 to 7,000. Range. If the Z-average molecular weight (Mz) of the hydrocarbon resin is too small, the hot-melt adhesive composition obtained by blending the hydrocarbon resin will be inferior in heat deterioration resistance, and the Z-average molecular weight (Mz) If is too large, the resulting hot-melt pressure-sensitive adhesive composition will have a high formulation viscosity, resulting in poor coating easiness and poor adhesion.

Further, the hydrocarbon resin of the present invention has a ratio of Z-average molecular weight to weight-average molecular weight (Mz/Mw) in the range of 1.0 to 4.0, preferably in the range of 1.2 to 3.5. More preferably, it is in the range of 1.4 to 3.0. If this ratio is too small, the resulting hot-melt pressure-sensitive adhesive composition obtained by blending the hydrocarbon resin will be inferior in heat deterioration resistance. is inferior in adhesive strength.

Further, the hydrocarbon resin of the present invention may have a weight-average molecular weight (Mw) and a Z-average molecular weight (Mz) within the above ranges, and the number-average molecular weight (Mn) is not particularly limited, but is preferably 300 to 2, 000.

In the present invention, the weight-average molecular weight (Mw), Z-average molecular weight (Mz), and number-average molecular weight (Mn) of the hydrocarbon resin are determined as polystyrene-equivalent values measured by high-performance liquid chromatography. In addition, the weight average molecular weight (Mw), Z average molecular weight (Mz), and number average molecular weight (Mn) of the hydrocarbon resin are 0.1 to 50% by weight of monomer units derived from the tetracyclododecene compound. After that, it can be controlled by adjusting the composition of each monomer or by adjusting the production conditions in the production method of the hydrocarbon resin to be described later.

The softening point of the hydrocarbon resin of the present invention is in the range of 80°C to 170°C, preferably 85°C to 160°C, more preferably 90°C to 150°C. If the softening point of the hydrocarbon resin is too low, the hot-melt pressure-sensitive adhesive composition obtained by blending the hydrocarbon resin will be inferior in high-temperature adhesion performance and heat deterioration resistance. The resulting hot-melt pressure-sensitive adhesive composition is inferior in adhesive strength. In addition, the softening point of the hydrocarbon resin is obtained by adjusting the composition of each monomer after setting the proportion of the monomer unit derived from the tetracyclododecene compound to 0.1 to 50% by weight, or by adjusting the carbonization described later. In the method for producing hydrogen resin, it can be controlled by adjusting the production conditions.

As a method for producing the hydrocarbon resin of the present invention, a monomer mixture containing a tetracyclododecene compound and each of the above monomers is subjected to addition polymerization to obtain a weight average molecular weight (Mw), a Z average molecular weight ( Mz), the ratio of the Z-average molecular weight to the weight-average molecular weight (Mz/Mw), and the softening point are not particularly limited as long as it is possible to obtain a hydrocarbon resin having the above range, but for example, free It can be produced by addition polymerization using a Dell-Crafts-type cationic polymerization catalyst, and a method by addition polymerization using a Lewis acid catalyst (A) is particularly preferred.

The Lewis acid catalyst (A) is not limited, but is preferably composed of a metal halide, and from the viewpoint of having good reaction activity, it is preferably a halide of an element belonging to Group III of the periodic table or a complex thereof. preferable. Specific examples of such Lewis acid catalysts include aluminum trichloride (AlCl ₃ ), aluminum tribromide (AlBr ₃ ), gallium trichloride (GaCl ₃ ), boron trifluoride diethyl ether complex (BF ₃ Et ₂ O) and the like. Among them, AlCl ₃ or BF ₃ ·Et ₂ O is preferably used from the viewpoint of versatility. The Lewis acid catalyst (A) may be used alone or in combination of two or more.

The amount of the Lewis acid catalyst (A) used is not particularly limited, but is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the monomer mixture used for polymerization. is.

In addition, since the Lewis acid catalyst (A) can further increase its polymerization activity, the halogenated hydrocarbon (B1) having a halogen atom bonded to a tertiary carbon atom and the carbon-carbon unsaturated bond are adjacent to It may be used in combination with at least one halogenated hydrocarbon (B) selected from halogenated hydrocarbons (B2) having a halogen atom bonded to the carbon atom.

Specific examples of the halogenated hydrocarbon (B1) having a halogen atom bonded to the tertiary carbon atom include t-butyl chloride, t-butyl bromide, 2-chloro-2-methylbutane and triphenylmethyl chloride. Among these, t-butyl chloride is particularly preferably used because of its excellent balance between activity and ease of handling. Specific examples of the halogenated hydrocarbon (B2) in which a halogen atom is bonded to the carbon atom adjacent to the carbon-carbon unsaturated bond include benzyl chloride, benzyl bromide, (1-chloroethyl)benzene, allyl chloride, 3-chloro- 1-propyne, 3-chloro-1-butene, 3-chloro-1-butyne, cinnamon chloride. Among these, benzyl chloride is preferably used because of its excellent balance between activity and ease of handling. The halogenated hydrocarbon (B) may be used alone or in combination of two or more.

The amount of the halogenated hydrocarbon (B) used is not particularly limited, but is preferably in the range of 0.05 to 50, more preferably in the range of 0.1 to 10, in terms of molar ratio to the Lewis acid catalyst (A). .

In carrying out the polymerization reaction, the order of adding the respective components of the monomer mixture and the polymerization catalyst to the polymerization reactor is not particularly limited, and may be added in any order, from the viewpoint of good control of the polymerization reaction. Then, a part of the monomer components constituting the monomer mixture and the Lewis acid catalyst (A) are added in advance to the polymerization reactor, and a part of the monomer components constituting the monomer mixture, It is preferable to start the polymerization reaction by adding the remainder of the monomer components constituting the monomer mixture to the polymerization reactor after contacting the Lewis acid catalyst (A) in advance. In this case, at least an alicyclic monoolefin having 4 to 6 carbon atoms is used as a part of the monomer components constituting the monomer mixture, and the Lewis acid catalyst (A) is added in advance to the polymerization reactor. Then, after contacting an alicyclic monoolefin having 4 to 6 carbon atoms with the Lewis acid catalyst (A) in advance, the remainder of the monomer components constituting the monomer mixture is added to the polymerization reactor. , to initiate the polymerization reaction.

When the halogenated hydrocarbon (B) is used in addition to the Lewis acid catalyst (A), the monomer mixture and the Lewis acid catalyst (A) are added to the polymerization reactor to initiate the polymerization reaction. It is preferred to add the halogenated hydrocarbon (B) to the polymerization reactor after initiation. Alternatively, the monomer mixture, the Lewis acid catalyst (A), and a portion of the halogenated hydrocarbon (B) are added to the polymerization reactor to initiate the polymerization reaction, and then the remainder of the halogenated hydrocarbon (B) is also preferably added to the polymerization reactor.

From the viewpoint of better control of the polymerization reaction, it is preferable to add a solvent to the polymerization reaction system and carry out the polymerization reaction. The type of solvent is not particularly limited as long as it does not inhibit the polymerization reaction, but saturated aliphatic hydrocarbons or aromatic hydrocarbons are suitable. Examples of saturated aliphatic hydrocarbons used as solvents include n-pentane, n-hexane, 2-methylpentane, 3-methylpentane, n-heptane, 2-methylhexane, 3-methylhexane, and 3-ethylpentane. , 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 2,2,3-trimethylbutane, 2,2,4-trimethylpentane, etc. chain saturated aliphatic hydrocarbons of 5 to 10; and cyclic saturated aliphatic hydrocarbons of 5 to 10 carbon atoms such as cyclopentane, cyclohexane, cycloheptane and cyclooctane. Examples of aromatic hydrocarbons used as solvents include aromatic hydrocarbons having 6 to 10 carbon atoms such as benzene, toluene and xylene. One solvent may be used alone, or two or more solvents may be used as a mixed solvent. The amount of the solvent used is not particularly limited, but it is preferably 10 to 1000 parts by weight, more preferably 50 to 500 parts by weight, based on 100 parts by weight of the monomer mixture used in the polymerization reaction. In addition, for example, a mixture of an addition polymerizable component and a non-addition polymerizable component, such as a mixture of cyclopentane and cyclopentene derived from a C5 fraction, is added to the polymerization reaction system, and the addition polymerizable component is a monomer. It can also be used as a component of the solid mixture, and the non-addition polymerizable component can be used as a solvent.

The polymerization temperature for the polymerization reaction is not particularly limited, but is preferably 85°C or less, more preferably -20 to 85°C, and still more preferably 0 to 65°C. If the polymerization temperature is too low, the polymerization activity may decrease, resulting in poor productivity. If the polymerization temperature is too high, the hue of the resulting hydrocarbon resin may be poor. The pressure during the polymerization reaction may be atmospheric pressure or increased pressure. The polymerization reaction time can be selected as appropriate, and is usually selected within the range of 10 minutes to 12 hours, preferably 30 minutes to 6 hours.

The polymerization reaction can be terminated by adding a polymerization terminator such as methanol, an aqueous sodium hydroxide solution, an aqueous ammonia solution, or the like to the polymerization reaction system when a desired polymerization conversion rate is obtained. The solvent-insoluble catalyst residue that is generated when the polymerization catalyst is deactivated by adding a polymerization terminator may be removed by filtration or the like. After termination of the polymerization reaction, unreacted monomers and solvent are removed, and low-molecular-weight oligomer components are removed by steam distillation or the like, followed by cooling to obtain a solid hydrocarbon resin.

Further, with regard to the hydrocarbon resin of the present invention thus obtained, if necessary, some or all of the unsaturated bonds remaining in the polymer molecular structure of the hydrocarbon resin are removed by a hydrogenation reaction (hydrogenation). It may be saturated to form a hydride.

The hydrogenation reaction method for the hydrogenation reaction of the hydrocarbon resin is not particularly limited, but known methods can be used without limitation, such as a method of contacting with hydrogen in the presence of a nickel catalyst. is mentioned. The nickel catalyst is not particularly limited, but from the viewpoint of high reactivity, a catalyst containing, as a main component, a compound formed by supporting nickel as a metal on an inorganic compound supported as a carrier is preferable. Specific examples of supported inorganic compounds as carriers include silica, alumina, boria, silica-alumina, diatomaceous earth, clay, clay, magnesia, magnesia-silica (silica-magnesium oxide), titania, and zirconia.

The hydrocarbon resin and hydride of the present invention obtained as described above are suitably used as a tackifying resin for pressure-sensitive adhesives, and particularly suitably used as a tackifying resin for hot-melt pressure-sensitive adhesives.

In the case of obtaining a hot-melt adhesive by using the hydrocarbon resin and hydride of the present invention as a tackifying resin, the thermoplastic elastomer as the base polymer of the hot-melt adhesive is not particularly limited. Plastic elastomers, styrene-based thermoplastic elastomers such as styrene/conjugated diene block copolymers, ethylene/vinyl acetate copolymers, and the like can be used. is preferably an olefinic thermoplastic elastomer, and particularly preferably an ethylene/α-olefin copolymer. That is, the hot-melt pressure-sensitive adhesive composition of the present invention preferably contains the hydrocarbon resin and/or hydride of the present invention and an ethylene/α-olefin copolymer.

The α-olefin to be copolymerized with ethylene to obtain the ethylene/α-olefin copolymer used in the present invention is not particularly limited, but examples include propylene, isobutylene, 1-butene, 1-pentene, 1-hexene , 4-methyl-1-pentene, 1-octene, etc. are preferred, α-olefins having 6 to 8 carbon atoms are more preferred, and 1-octene is even more preferred. The α-olefins may be used singly or in combination of two or more.

The content ratio of the α-olefin units in the ethylene/α-olefin copolymer is not particularly limited, but the ratio of the α-olefin units to the total monomer units is preferably 20 to 40 mol%. .

The polymerization method for obtaining the ethylene/α-olefin copolymer is not particularly limited, but from the viewpoint of obtaining a hot-melt pressure sensitive adhesive having particularly excellent adhesive strength and heat deterioration resistance, a method using a metallocene polymerization catalyst is preferred. is preferred.

Although the density of the ethylene/α-olefin copolymer used as the thermoplastic elastomer is not particularly limited, it is preferably 0.86 to 0.90 g/cm ³ . By using an ethylene/α-olefin copolymer having a density within this range, the resulting hot-melt pressure-sensitive adhesive composition can be made particularly excellent in adhesive strength.

In addition, the melt index of the ethylene/α-olefin copolymer used as a thermoplastic elastomer (value (g/10 minutes) measured according to ASTM D-1084 (E condition, 190°C, 2.16 kg)) is preferably 100 or more, more preferably 200 to 1,500. By using an ethylene/α-olefin copolymer having a melt index within this range, the obtained hot-melt pressure-sensitive adhesive composition can be particularly excellent in ease of coating.

The thermoplastic elastomer, which is an ethylene/α-olefin copolymer as described above, is available as a commercial product. be able to.

The blending ratio of the thermoplastic elastomer and the hydrocarbon resin and/or hydride of the present invention in the hot-melt adhesive composition of the present invention is not particularly limited, but the hydrocarbon resin per 100 parts by weight of the thermoplastic elastomer And/or the amount of the hydride is preferably 50 to 500 parts by weight, more preferably 80 to 300 parts by weight. By setting the blending ratio of the hydrocarbon resin and/or the hydride within this range, the adhesive strength of the hot-melt pressure-sensitive adhesive composition of the present invention can be made particularly good.

The hot-melt pressure-sensitive adhesive composition of the present invention may consist solely of hydrocarbon resins and/or hydrides and thermoplastic elastomers, and may further contain other components. good. Other components that can be contained in the hot-melt pressure-sensitive adhesive composition of the present invention include waxes, antioxidants, tackifying resins other than the hydrocarbon resins and hydrides of the present invention, and polymers other than the above-described polymers. , heat stabilizers, UV absorbers, fillers, etc., can be added. The hot-melt pressure-sensitive adhesive composition of the present invention is preferably a solventless composition containing no solvent.

Waxes that can be blended in the hot-melt adhesive composition of the present invention are not particularly limited, and examples include polyethylene wax, ethylene-vinyl acetate copolymer wax, polyethylene oxide wax, paraffin wax, microcrystalline wax, Fischer-Tropsh. Waxes, oxidized Fischer-Tropsh wax, hydrogenated castor oil wax, polypropylene wax, by-product polyethylene wax, hydroxylated stearamide wax, and the like can be used. One type of wax may be used alone, or two or more types may be used in combination. The content of the wax in the hot-melt adhesive composition is not particularly limited, but is preferably 10 to 200 parts by weight, more preferably 20 to 150 parts by weight, relative to 100 parts by weight of the thermoplastic elastomer. When the wax content is within this range, the resulting hot-melt pressure-sensitive adhesive composition is particularly excellent in ease of coating.

Antioxidants that can be blended in the hot-melt adhesive composition of the present invention are not particularly limited, and examples include pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate ], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-p-cresol, di-t-butyl-4-methylphenol, etc. thiodicarboxylate esters such as dilaurylthiopropionate; phosphites such as tris(nonylphenyl)phosphite; and the like. The amount of the antioxidant used is not particularly limited, but it is usually 10 parts by weight or less, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the thermoplastic elastomer. In addition, antioxidant may be used individually by 1 type, and may be used in combination of 2 or more type.

The softening agent that can be blended in the hot-melt pressure-sensitive adhesive composition of the present invention is not particularly limited, and examples include aromatic, paraffinic or naphthenic process oils; liquid polymers such as polybutene and polyisobutylene. can be used. A softening agent may be used individually by 1 type, and may be used in combination of 2 or more type.

Conventionally known tackifying resins can be used as the tackifying resin other than the hydrocarbon resin of the present invention that can be blended in the hot-melt pressure-sensitive adhesive composition of the present invention. Specifically, rosin; modified rosins such as disproportionated rosin and dimerized rosin; esters of polyhydric alcohols such as glycol, glycerin and pentaerythritol with rosin or modified rosins; terpene resins; , aromatic, alicyclic or aliphatic-aromatic copolymer hydrocarbon resins or hydrides thereof; phenolic resins; coumarone-indene resins; These tackifying resins may be used singly or in combination of two or more.

Other polymers that can be blended in the hot-melt adhesive composition of the present invention include conjugated diene homopolymers such as polybutadiene and polyisoprene, (styrene-butadiene) random copolymers, and (styrene-isoprene). Aromatic vinyl-conjugated diene random copolymers such as random copolymers, (styrene-butadiene) block copolymers, aromatic vinyl-conjugated diene block copolymers such as (styrene-isoprene) block copolymers, polystyrene Aromatic vinyl homopolymers such as isobutylene polymers, acrylic polymers, ester polymers, ether polymers, urethane polymers, and polymers having elasticity at room temperature (23°C) such as polyvinyl chloride. and the like, but are not limited to these. The content of these polymers in the hot-melt pressure-sensitive adhesive composition of the present invention is preferably 20% by weight or less, and 10% by weight or less, relative to the total amount of the hot-melt pressure-sensitive adhesive composition. is more preferable.

In preparing the hot-melt pressure-sensitive adhesive composition of the present invention, the method of mixing the hydrocarbon resin and/or hydride, thermoplastic elastomer, and other optional components is not particularly limited. Alternatively, for example, a method of dissolving each component in a solvent and uniformly mixing them, followed by removing the solvent by heating or the like, or a method of melting and mixing each component with a kneader or the like can be used. Among these methods, melt mixing is preferable from the viewpoint of more efficient mixing. The temperature for melt-mixing is not particularly limited, but is usually in the range of 100 to 200°C.

Since the hot-melt pressure-sensitive adhesive composition of the present invention contains the hydrocarbon resin and/or hydride of the present invention as a tackifying resin, the formulation viscosity (as a hot-melt pressure-sensitive adhesive composition Viscosity) is low, it is excellent in ease of coating, and is excellent in high-temperature adhesive performance, adhesive strength, and heat deterioration resistance. Therefore, the hot-melt pressure-sensitive adhesive composition of the present invention can be applied to the adhesion of various members, and can achieve energy-saving, highly productive adhesion with high holding power. The hot-melt pressure-sensitive adhesive composition of the present invention can be applied to various uses by taking advantage of such properties, and the use is not limited, but the application amount is small. It also exhibits sufficient adhesive strength, and has the property of being excellent in heat deterioration resistance, and is difficult to deteriorate in sealing machines, etc., so it is especially useful for sealing industrial transportation packaging materials It can be suitably used as an adhesive for

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited only to these Examples. "Parts" and "%" are by weight unless otherwise specified.
Various measurements were performed according to the following methods.

[Weight average molecular weight, Z average molecular weight and molecular weight distribution]
The hydrocarbon resin used as a sample is subjected to gel permeation chromatography analysis to obtain the weight average molecular weight (Mw) and Z average molecular weight (Mz) in terms of standard polystyrene, and the molecular weight distribution is indicated by the ratio of Mz/Mw. rice field. In addition, the gel permeation chromatography analysis uses "HLC-8320GPC" manufactured by Tosoh Corporation as a measuring device, and the column is made by connecting three "TSKgel SuperMultiporeHZ" manufactured by Tosoh Corporation, and tetrahydrofuran is used as a solvent. , 40° C. and a flow rate of 1.0 ml/min.

[Softening point (°C)]
The hydrocarbon resin used as a sample was measured according to JIS K 6863.

[Composition viscosity]
A sample hot-melt pressure-sensitive adhesive composition was heated and melted, and the melt viscosity (mPa·s) at 177°C was measured using a rotor No. No. 27 was used and measured with a thermosel Brookfield viscometer, which was taken as the formulation viscosity. The smaller the value, the better the ease of coating.

[Cloud point]
A sample hot-melt pressure-sensitive adhesive composition was placed in a test tube, a thermometer was inserted to the bottom, and then heated to 180° C. to melt. Then, it was allowed to cool, and the temperature at which the bottom of the test tube became cloudy was recorded as the cloud point. The lower the value, the better the compatibility between the components constituting the hot-melt pressure-sensitive adhesive composition, and as a result, the hot-melt pressure-sensitive adhesive composition has a long open time and high adhesive strength. Become.

[Shear failure temperature (SAFT)]
A sample hot-melt pressure-sensitive adhesive composition was melt-coated on a 25 μm PET film so as to have a thickness of 20 μm. Using this coating sheet, stainless steel was used as an adherend, brought into contact with the adherend so that the adhesion portion was 10×25 mm, and heat-pressed at 140° C. for 2 seconds. A load was applied to the test piece obtained in this way using stainless steel as an adherend with an adhesive portion of 10 × 25 mm and a weight of 500 g. SAFT) was measured. The higher the value, the better the high-temperature adhesion performance.

[Skinning test]
A sample hot-melt pressure-sensitive adhesive composition was placed in a stainless steel beaker, and the ratio of skinning on the upper surface of the beaker was measured after a storage test at 180° C. for 72 hours. 0% indicates no skinning and 100% indicates that the entire surface layer is skinned. The lower the value, the better the heat deterioration resistance.

[Example 1]
A polymerization reactor was charged with 42.7 parts of cyclopentane, 14.8 parts of cyclopentene and 0.5 parts of toluene, and after heating to 55° C., 1.2 parts of aluminum chloride was added. Subsequently, tetracyclododecene (tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene) 24.6 parts, 1,3-pentadiene 41.1 parts, cyclopentene 15.2 2.2 parts isobutylene, 1.2 parts diisobutylene, 0.4 parts dicyclopentadiene, 0.5 parts C4-C6 unsaturated hydrocarbons, and 10.3 parts C4-C6 saturated hydrocarbons was continuously added to the polymerization reactor while the temperature was maintained at 75° C. for 60 minutes. After that, an aqueous sodium hydroxide solution was added to the polymerization reactor to stop the polymerization reaction. The polymerization conversion rate at this time was 85%, and the composition of the obtained polymer was substantially the same as the ratio of components constituting the monomer mixture. The types and amounts of the components in the polymerization reactor during the polymerization reaction depend on the components constituting the monomer mixture (addition-polymerizable components), the components corresponding to the solvent (non-addition-polymerizable components), and the polymerization catalyst. They are classified and shown in Table 1. After removing the precipitate formed by the termination of the polymerization by filtration, the obtained polymer solution was put into a still and heated under a nitrogen atmosphere to remove the polymerization solvent and unreacted monomers. Then, while blowing saturated steam at 240° C. or higher, low-molecular-weight oligomer components were distilled off. Pentaerythritol tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate] ("Irganox 1010" manufactured by BASF) as an anti-aging agent for 100 parts of molten resin1. After adding 25 parts and mixing, the molten resin was taken out from the still and allowed to cool to room temperature to obtain the hydrocarbon resin of Example 1. The weight-average molecular weight (Mw), Z-average molecular weight (Mz), molecular weight distribution (Mz/Mw), and softening point of the obtained hydrocarbon resin of Example 1 were measured. These measurement results are summarized in Table 1.

[Examples 2 to 5, Comparative Examples 1 to 3]
Carbonization of Examples 2 to 5 and Comparative Examples 1 to 3 was carried out in the same manner as in Example 1, except that the types and amounts of the components added to the polymerization reactor and the polymerization temperature were changed as shown in Table 1. A hydrogen resin was obtained respectively. The same measurements as in Example 1 were performed on the obtained hydrocarbon resins of Examples 2 to 5 and Comparative Examples 1 to 3. These measurement results are summarized in Table 1. Also in Examples 2 to 5 and Comparative Examples 1 to 3, the compositions of the obtained polymers were almost the same as the proportions of components constituting the monomer mixture.

[Example 6]
100 parts of the hydrocarbon resin obtained in Example 1, ethylene/octene copolymer thermoplastic elastomer (melt index: 500 g/10 min, density: 0.874 g/cm ³ , "Affinity GA1950" manufactured by Dow Chemical Company) 100 and 50 parts of paraffin wax (melting point: 63° C.) were kneaded at 180° C. for 1 hour to obtain a hot-melt adhesive composition of Example 6. The obtained hot-melt pressure-sensitive adhesive composition of Example 6 was measured for formulation viscosity, cloud point, and shear breaking temperature, and subjected to a skinning test. These measurement results and test results are summarized in Table 2.

[Examples 7 to 10, Comparative Examples 4 to 6]
The type of hydrocarbon resin used was changed from the hydrocarbon resin obtained in Example 1 to the hydrocarbon resins of Examples 2 to 5 and Comparative Examples 1 to 3, respectively, as shown in Table 2. Hot-melt adhesive compositions of Examples 7-10 and Comparative Examples 4-6 were obtained in the same manner as in Example 6. Then, the hot-melt adhesive compositions of Examples 7-10 and Comparative Examples 4-6 were subjected to the same measurements and tests as in Example 6. These measurement results and test results are summarized in Table 2.

From Tables 1 and 2, the following points can be confirmed.
That is, the hot-melt adhesive compositions (Examples 6 to 10) obtained using the hydrocarbon resins of the present invention (Examples 1 to 5) have low formulation viscosities, making them easy to apply. In addition, the low cloud point means a long open time, high adhesive strength, and a high shear breaking temperature, so it has excellent high-temperature adhesion performance. It can be said that it is excellent.
On the other hand, when the monomer unit derived from the tetracyclododecene compound is not contained, when the softening point is adjusted to the range specified by the present invention, the obtained hydrocarbon resin has a weight average molecular weight (Mw) and Z The average molecular weight (Mz) becomes too high (Comparative Examples 1 and 2), and the hot-melt pressure-sensitive adhesive composition obtained using this (Comparative Examples 4 and 5) has a high blending viscosity and is difficult to apply. It was inferior in ease of use, had a high cloud point, a short open time, and inferior adhesive strength.
Further, in the case of not containing a monomer unit derived from a tetracyclododecene compound, when the weight average molecular weight (Mw) and the Z average molecular weight (Mz) are adjusted to the predetermined ranges of the present invention, the obtained hydrocarbon resin has a softening point that is too low (Comparative Example 3), and the hot-melt pressure-sensitive adhesive composition (Comparative Example 6) obtained using this has a low shear fracture temperature, poor high-temperature adhesive performance, and , the value in the skinning test was high, and the heat deterioration resistance was poor.

Claims (7)

A hydrocarbon resin containing 24.6 to 50% by weight of monomer units derived from a tetracyclododecene compound,
The weight average molecular weight (Mw) is in the range of 500 to 4,000, the Z average molecular weight (Mz) is in the range of 1,000 to 10,000, and the ratio of the Z average molecular weight to the weight average molecular weight (Mz/Mw) is 1 .0 to 4.0 and a hydrocarbon resin having a softening point in the range of 80°C to 170°C. In addition to 0.1 to 50% by weight of monomer units derived from the tetracyclododecene compound,
1 to 60% by weight of 1,3-pentadiene monomer unit, 1 to 30% by weight of alicyclic monoolefin monomer unit having 4 to 6 carbon atoms, and an acyclic monoolefin monomer having 4 to 8 carbon atoms 0 to 50% by weight of units, 0 to 10% by weight of alicyclic diolefin monomer units, 0 to 40% by weight of aromatic monoolefin monomer units, and an aromatic having a structure in which two or more cyclic structures are bonded 2. The hydrocarbon resin of claim 1 containing 0 to 50% by weight of group monomer units. Tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene units. Tetracyclo[4.4.0.1 ^2,5 . 4. The hydrocarbon resin according to claim 3, wherein the proportion of 1 ^7,10 ]dodeca-3-ene units is 50% by weight or more. A hydride obtained by hydrogenating the hydrocarbon resin according to any one of claims 1 to 4. A hot-melt adhesive composition containing the hydrocarbon resin according to any one of claims 1 to 4 and/or the hydride according to claim 5. A hot-melt adhesive composition comprising the hydrocarbon resin according to any one of claims 1 to 4 and/or the hydrogenated product according to claim 5, and an ethylene/α-olefin copolymer.