JP2008208213A - Hydrogenated copolymer for vibration-damping material, and asphalt vibration-damping material composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogenated copolymer for vibration-damping material, excellent in mold-processability, enabling further light weight, and also excellent in vibration-damping and sound insulation performance, and an asphalt vibration-damping material composition. <P>SOLUTION: This hydrogenated copolymer for the vibration damping material (A) obtained by hydrogenating a non-hydrogenated random copolymer containing a conjugated diene monomer unit and a vinyl aromatic monomer unit is provided by having the following characteristics (1) to (4); (1) the peak molecular weight measured by GPC is 40,000 to 400,000 based on a standard polystyrene, (2) the content of the vinyl aromatic monomer unit contained in the (A) is in 20 to 80 wt.% range, (3) the vinyl-bonded amount of the non-hydrogenated polymer consisting of the conjugated diene monomer unit in the (A) is <40%, and (4) in the dynamic viscoelastic spectrum obtained in association with the (A), at least one peak of loss tangent coefficient (tanδ) presents in ≥-40 and <70°C range. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a hydrogenated copolymer for damping material and an asphalt damping material composition.

  2. Description of the Related Art In recent years, vibration control sheets and sound insulation sheets that prevent vibration and noise generated from a power unit are mounted on industrial equipment having a power unit. For example, in the case of an automobile, the vibration-damping sheet or the like on the boundary between the engine room and the automobile room is not used to prevent the engine sound or vibration generated from the bottom of the vehicle body or the engine room from being transmitted to the car room in order to prevent vibration during driving. A sound insulation sheet is attached. Similarly, home appliances having a drive unit are equipped with a vibration damping sheet and a sound insulation sheet for preventing vibration and noise generated from the power unit. Furthermore, floor impact sound transmitted from the floor to the lower floor is a problem in the floors of buildings, condominiums, and ordinary houses made of reinforced concrete or wooden structures.

  In order not to transmit these impact sounds to the downstairs, measures are taken by laying various floor structures or combinations of various floor components and sound insulation sheets. Various rubbery polymers such as SBS, SIS, SEBS, SEPS and other thermoplastic elastomers such as SBS, SIS, SEBS, SEPS, natural rubber, IR, SBR, butyl rubber, chloroprene rubber, acrylic rubber, etc. Base resin compositions and asphalt compositions are used.

For example, JP-A No. 2002-284830 (Patent Document 1) discloses a block copolymer comprising a polymer block comprising an aromatic vinyl monomer and a polymer block comprising a mixture of isoprene and styrene. JP-A-8-128128 discloses a composition comprising petroleum asphalt, thermoplastic elastomer, mineral particles, iron powder and a surfactant.
JP 2002-284830 A JP-A-8-128128

  However, although conventional vibration damping materials and sound insulation materials have excellent performance at a specific temperature, they do not necessarily have satisfactory performance at other temperatures. For this reason, the current situation is to cope with the combination of structures and constituent materials. Therefore, development of simpler and thinner sheet-shaped vibration damping materials and sound insulation materials is expected without combining complicated structures and components.

  In view of such market demands, the present invention is superior in molding processability and weight reduction, which is not found in conventional vibration damping materials and sound insulation materials, and is excellent in vibration damping and sound insulation performance excellent in each temperature. It aims at providing a damping material and an asphalt damping material composition.

As a result of intensive studies to solve the above problems, the present inventors have obtained a non-hydrogenated random copolymer containing a specific conjugated diene monomer unit and a vinyl aromatic monomer unit. The inventors have found that the above object can be achieved by the hydrogenated copolymer obtained by addition and the asphalt vibration damping composition containing the hydrogenated copolymer, and have completed the present invention.
That is, the present invention
[1] A hydrogenated copolymer for damping material (A) obtained by hydrogenating a non-hydrogenated random copolymer containing a conjugated diene monomer unit and a vinyl aromatic monomer unit, The hydrogenated copolymer for damping material (A) has the following characteristics (1) to (4):
(1) The peak molecular weight by GPC of the hydrogenated copolymer (A) is 40,000 to 400,000 in terms of standard polystyrene,
(2) The content of the vinyl aromatic monomer unit contained in the hydrogenated copolymer (A) is in the range of 20 to 80% by weight,
(3) The vinyl bond amount of the non-hydrogenated polymer containing the conjugated diene monomer unit in the hydrogenated copolymer (A) is less than 40%,
(4) In the dynamic viscoelastic spectrum obtained for the hydrogenated copolymer (A), at least one peak of loss factor (tan δ) exists in the range of −40 ° C. or more and less than 70 ° C.
[2] A hydrogenated block copolymer for damping material, comprising at least one hydrogenated copolymer for damping material (A) according to [1] above as a block,
[3] The hydrogenated block copolymer for a vibration damping material according to the above item [2], further comprising at least one polymer block (B) mainly composed of a vinyl aromatic monomer unit,
[4] The hydrogenated block copolymer for a damping material according to [3], wherein the content of all vinyl aromatic monomer units in the block copolymer is 40 to 80% by weight,
[5] The hydrogenation for damping material according to the above [3] or [4], wherein the ratio of the polymer block (B) containing vinyl aromatic monomer units in the block copolymer is less than 40% by weight Block copolymer,
[6] A vibration damping material obtained by crosslinking the hydrogenated block copolymer according to any one of [2] to [5],
[7] A vibration-damping material comprising the hydrogenated block copolymer according to any one of [2] to [5] above and another rubbery polymer,
[8] The vibration damping material according to [7], obtained by crosslinking,
[9] An asphalt vibration damping composition comprising the hydrogenated block copolymer according to any one of [2] to [5] above and asphalt,
[10] The hydrogenated block copolymer for a vibration damping material according to any one of the above items [2] to [5], or the hydrogenated block copolymer and another rubbery polymer as the component (a) An asphalt vibration-damping material composition comprising, as a component, and asphalt as a component (d),
[11] The asphalt damping material composition according to [10], further including a tackifier resin as a component (b),
[12] The asphalt vibration damping composition according to the above item [10] or [11], further comprising a softener as the component (c),
I will provide a.

  ADVANTAGE OF THE INVENTION According to this invention, the damping material and asphalt damping material composition which are excellent in molding processability, enable weight reduction, and are excellent also in the damping and sound-insulating performance excellent in each temperature can be provided.

  The following embodiment is an example for explaining the present invention, and is not intended to limit the present invention only to this embodiment. The present invention can be implemented in various forms without departing from the gist thereof.

The present invention is described in detail below.
The hydrogenated copolymer for damping material of the present invention is a hydrogenated copolymer obtained by hydrogenating a non-hydrogenated random copolymer containing a conjugated diene monomer unit and a vinyl aromatic monomer unit ( A). A hydrogenated block copolymer for a damping material containing at least one hydrogenated copolymer for damping material (A) as a block may be used.

  The conjugated diene monomer unit means a structural unit of a polymer resulting from polymerization of a conjugated diene monomer, and its structure is composed of two olefins derived from the conjugated diene monomer. It is the molecular structure that is the binding site. Examples of the conjugated diene include monomers such as 1,3-butadiene, isoprene, 2,3-dimethyl-butadiene, 3-butyl-1,3-octadiene, phenyl 1,3-butadiene, and the like. 3-butadiene and isoprene are preferred, and 1,3-butadiene is more preferred. These monomers may be used alone or in combination of two or more.

  Further, the vinyl aromatic monomer unit means a structural unit of a polymer resulting from polymerization of a vinyl aromatic compound as a monomer, and the structure thereof is a substituted ethylene group derived from a substituted vinyl group. This is a molecular structure in which the two carbons are binding sites. Examples of the vinyl aromatic include monomers such as styrene, P-methylstyrene, tertiary butylstyrene, α-methylstyrene, 1,1-diphenylethylene, and among them, styrene is preferable. These monomers may be used alone or in combination of two or more.

  Furthermore, the content of the vinyl aromatic monomer unit contained in the hydrogenated copolymer (A) is 20 to 80% by weight from the viewpoint of vibration damping performance of the resulting hydrogenated copolymer (A). The range is preferably 25 to 75% by weight, more preferably 30 to 70% by weight, and still more preferably 35 to 50% by weight.

  Furthermore, the microstructure (the ratio of cis, trans, vinyl) of the conjugated diene monomer unit in the pre-hydrogenation polymer of the hydrogenated copolymer (A) can be arbitrarily changed by using a polar compound described later. it can. In the present invention, the vinyl bond amount of the conjugated diene monomer unit in the non- (pre-hydrogenation) hydrogenated random copolymer block containing the conjugated diene monomer unit and the vinyl aromatic monomer unit is obtained water. From the viewpoint of vibration damping performance of the additive copolymer, it is less than 40%, preferably less than 30%, and more preferably less than 20%. The vinyl bond amount can be measured by using NMR even after hydrogenation.

  The peak molecular weight of the hydrogenated copolymer (A) of the present invention is 40,000 to 400,000. The hydrogenated copolymer (A) of the present invention has an excellent balance between mechanical strength and molding processability when the peak molecular weight is in the above range. From the viewpoint of the balance between mechanical strength, impact absorbability and moldability, the peak molecular weight of the hydrogenated copolymer (A) of the present invention is preferably 60,000 to 350,000, more preferably 80,000 to 30. Ten thousand.

  The hydrogenated copolymer (A) of the present invention has a loss tangent (tan δ) peak of −40 ° C. or higher and lower than 70 ° C. in the dynamic viscoelastic spectrum obtained for the hydrogenated copolymer (A). Preferably at least one exists in the range of -30 degreeC-60 degreeC, More preferably, -20-50 degreeC, More preferably, it is 0-50 degreeC. The presence of at least one loss tangent peak in the range of -40 ° C. or higher and lower than 70 ° C. is necessary in terms of the balance between the low temperature characteristics, impact absorption and flexibility of the hydrogenated copolymer (A). It is. Note that the peak of loss tangent (tan δ) in the dynamic viscoelastic spectrum is measured using a viscoelasticity measuring and analyzing apparatus with a frequency of 10 Hz.

  The tan δ value of the hydrogenated copolymer (A) of the present invention is preferably 1.0 or more, more preferably 1.1 or more, and further preferably 1.2 or more. The greater the value of tan δ is 1.0 and the greater the value, the better the damping performance.

  The hydrogenated block copolymer of the present invention comprises a block comprising the above-mentioned hydrogenated copolymer (A) and at least one polymer block (B) mainly composed of vinyl aromatic monomer units. It is a hydrogenated block copolymer.

  Here, the polymer block mainly composed of a vinyl aromatic monomer unit is a vinyl aromatic monomer homopolymer block or a substantially vinyl aromatic monomer containing 50% by weight or more of a vinyl aromatic monomer. The copolymer block which has a monomer as a main component is shown. The content of the polymer block (B) in the hydrogenated block copolymer is preferably 40 to 80% by weight from the viewpoint of the balance between the mechanical strength and the impact absorbability of the resulting hydrogenated copolymer. Preferably it is 50 to 70% by weight.

  The proportion of the polymer block (B) composed of vinyl aromatic monomer units in the hydrogenated block copolymer is preferably less than 40% by weight from the viewpoint of the balance between mechanical strength and impact absorption.

In the present invention, the specific structure of the hydrogenated copolymer containing the hydrogenated copolymer (A) and the polymer block (B) composed of vinyl aromatic monomer units is as follows:
(AB) n, A- (BA) n, B- (AB) n
[(B−A) n] m + 1−X, [(A−B) n] m + 1−X
[(B−A) n−B] m + 1−X, [(A−B) n−A] m + 1−X
(In the above formula, A is a hydrogenated copolymer block, B is a polymer block containing vinyl aromatic monomer units. The boundary between the A block and the B block is not necessarily clearly distinguished. N is a positive number of 1 or more, generally an integer of 1 to 5. m is a positive number of 1 or more, generally an integer of 1 to 10. X is a polyvalent halogen such as silicon tetrachloride, for example. Organosilicon compounds, polyvalent halogenated organotin compounds such as tin tetrachloride, epoxidized soybean oil, 2-6 functional epoxy group-containing compounds, polyhalogenated hydrocarbons, carboxylic acid esters, polyvinyl compounds such as divinylbenzene, (Represents a residue of a coupling agent such as dialkyl carbonates such as dimethyl carbonate or an initiator such as a polyfunctional organolithium compound.)

  The pre-hydrogenation copolymer block of the hydrogenated copolymer (A) constituting the present invention, for example, in an inert hydrocarbon solvent, simultaneously charged a predetermined ratio of styrene and butadiene using an organolithium compound as a polymerization initiator, It is obtained by polymerizing. At that time, the molecular weight is adjusted by controlling the amount of the organolithium compound.

  Examples of the inert hydrocarbon solvent used in the present invention include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane and isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane and the like. Hydrocarbon solvents such as alicyclic hydrocarbons, aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene can be used. These may be used alone or in combination of two or more.

  Examples of the organic lithium compound used in the present invention include known compounds such as ethyl lithium, propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, phenyl lithium, propenyl lithium, hexyl lithium and the like. can give. Of these, n-butyllithium and sec-butyllithium are preferable. The organolithium compound is used not only as one type but also as a mixture of two or more types. The amount used is selected within a range that provides a desired peak molecular weight.

  In order to adjust the vinyl bond amount of the conjugated diene compound in the hydrogenated copolymer (A), for example, ethers and tertiary amines, such as ethylene glycol dimethyl ether, tetrahydrofuran, α-methoxytetrahydrofuran. , N, N, N ′, N′-tetramethylethylenediamine or the like, or a mixture of two or more thereof is used.

It is obtained by hydrogenating an unsaturated double bond derived from a conjugated diene of a non-hydrogenated polymer polymerized by the above method. It does not specifically limit to a hydrogenation catalyst, A well-known hydrogenation catalyst technique can be used. Examples of hydrogenation catalysts include the following:
(1) A supported heterogeneous hydrogenation catalyst in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like;
(2) a so-called Ziegler type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt together with a reducing agent such as organoaluminum; and (3) Ti, Ru, Rh, Homogeneous hydrogenation catalysts such as so-called organometallic complexes such as organometallic compounds such as Zr.

  Specific hydrogenation catalysts include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841 (corresponding to US Pat. No. 4,501,857), Japanese Patent Publication No. Hydrogenation catalysts described in Japanese Patent No. 37970 (corresponding to US Pat. No. 4,673,714), Japanese Patent Publication No. 1-53851 and Japanese Patent Publication No. 2-9041 can be used. Examples of preferred hydrogenation catalysts include titanocene compounds and mixtures of titanocene compounds and reducing organometallic compounds.

  As the titanocene compound, compounds described in JP-A-8-109219 can be used. Specifically, it has at least one ligand having a (substituted) cyclopentadienyl skeleton, indenyl skeleton or fluorenyl skeleton such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Compounds. Examples of the reducing organometallic compound include organoalkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

  A hydrogenated copolymer solution is obtained by the above hydrogenation reaction. The catalyst residue is removed from the hydrogenated copolymer (A) solution as necessary, and the hydrogenated copolymer (A) is separated from the solution. As an example of a method for separating the solvent, a method of adding a polar solvent which is a poor solvent for the hydrogenated copolymer (A) such as acetone or alcohol to the reaction solution after hydrogenation to precipitate and recover the polymer; Examples thereof include a method in which the reaction solution is poured into hot water with stirring and the solvent is removed by steam stripping; and a method in which the solvent is distilled off by directly heating the polymer solution.

  Although the hydrogenation rate of the hydrogenated copolymer (A) of this invention is not specifically limited, It is 10% or more, Preferably it is 20% or more, More preferably, it is 30% or more. Particularly in applications where thermal stability is required, it is at least 80% or more, preferably 90% or more, more preferably 95% or more. In applications where processability is required, the hydrogenation rate is 10 to 90%, preferably 20 to 80%, more preferably 30 to 70%.

  A hydrogenated block copolymer containing a block comprising a hydrogenated copolymer (A) and a vinyl aromatic monomer polymer block (B) is prepared by, for example, polymerizing an organolithium compound in an inert hydrocarbon solvent. Styrene is polymerized, and then a predetermined ratio of styrene and butadiene are simultaneously charged, polymerized, and optionally, these operations are repeated.

  When the hydrogenated block copolymer of the present invention is obtained by a coupling method, examples of the coupling agent include bifunctional epoxy compounds, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethoxymethylsilane, triethoxysilane, Tetramethoxysilane, alkoxysilicon compounds such as tetraethoxysilane, methyl benzoate, ester compounds such as ethyl benzoate, vinyl allenes such as divinylbenzene, halogens such as dichlorodimethylsilane and phenylmethyldichlorosilane Silicon compound, dichlorodimethyltin, tin compound such as tetrachlorotin, silicon compound such as tetrachlorosilane, and the like. The coupling agent compound may be used alone or in a mixture of two or more.

  In the present invention, the hydrogenated block copolymer obtained by crosslinking exhibits heat resistance, bending resistance and oil resistance in the state of a crosslinked product. The kind of the crosslinking agent is not particularly limited and may be generally used. Specific examples of cross-linking agents include powdered sulfur, precipitated sulfur, colloidal sulfur, colloidal sulfur, surface-treated sulfur, inert sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol, disulfide, and many polymers. Sulfur compounds such as sulfides, inorganic vulcanizing agents such as selenium, terium, magnesium oxide, risurge, zinc white, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, tetrachloro-p-benzoquinone, poly Oximes such as p-dinitrosobenzene, nitroso compounds, hexamethylene diamine, triethylene tetramine, tetraethylene pentamine, hexamethylene diamine carbamate, N, N′-dicinnamylidene-1,6-hexanediamine, 4 , 4'-Methylenebis (cyclohexylamine) Carbamate, polyamines such as 4,4'-methylenebis- (2-chloroaniline), tert-butyl hydroperoxide, 1,1,3,3, tetramethylbutyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, diisopropyl Benzene hydroperoxide, 2,5-dimethylhexane 2,5-dihydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, 1,1-bis (tertiary butyl peroxy) cyclododecane, etc. Organic peroxides, alkylphenol-formaldehyde resins, melamine-formaldehyde condensates and triazine-formaldehyde condensates, octylphenol-formaldehyde resins, alkylphenol-sulfide resins, hexa Resin vulcanizing agents such as Tokishimechiru melamine resins. The amount of the crosslinking agent is 0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the hydrogenated block copolymer. . When the amount is less than 0.1 part by weight, there is no effect of adding a crosslinking agent, and even when the amount exceeds 5 parts by weight, an effect exceeding the effect intended by the present invention is not exhibited. The method of crosslinking the hydrogenated block copolymer with a crosslinking agent can be carried out by a commonly practiced method. For example, crosslinking is performed at a temperature of 120 to 200 ° C, preferably 140 to 180 ° C.

  The vibration damping material containing the hydrogenated block copolymer of the present invention and another rubber polymer is rich in flexibility and excellent in impact resistance. The rubbery polymer is not particularly limited, but specific examples include natural rubber, synthetic rubber (SBR, IR, NBR, EPDM, etc.), thermoplastic elastomer (styrene-based, olefin-based, ester-based). , Vinyl chloride, etc.). The compounding amount of the rubber polymer is less than 200 parts by weight, preferably less than 100 parts by weight with respect to 100 parts by weight of the hydrogenated copolymer. When the amount is 200 parts by weight or more, the effect exceeding the intended effect of the present invention is not exhibited. Thus, what mixed the rubbery polymer with the hydrogenated copolymer can also be used as a crosslinked body using the above-mentioned crosslinking agent.

  The asphalt damping material composition of the present invention comprises the hydrogenated block copolymer of the present invention and asphalt as essential components, has low melt viscosity, processability, vibration damping in a wide temperature range, adhesion to a substrate It refers to a composition exhibiting properties that are particularly excellent in low-temperature adhesive strength. Specifically, in the dynamic viscoelastic spectrum, in the range of 0 ° C. or higher and 70 ° C. or lower, the asphalt damping material having a dynamic elastic modulus (G ′) of 10,000 Pa or more and a loss coefficient (tan δ) of 0.2 or more. Refers to the composition.

  In the asphalt vibration damping composition of the present invention, as the component (a), the hydrogenated block copolymer, or a composition of the hydrogenated block copolymer and another rubber polymer is used, Examples of other rubbery polymers include natural rubber, synthetic rubber (SBR, IR, NBR, EPDM, etc.), thermoplastic elastomer (styrene, olefin, ester, vinyl chloride, etc.). The compounding quantity of a component (I) is 3-40 weight part, Preferably it is 5-30 weight part.

  In the asphalt vibration damping composition of the present invention, a wide variety of tackifier resins are selected as the component (b) depending on the use and required performance of the obtained asphalt vibration damping material. For example, coumarone resin, aromatic hydrocarbon resin, rosin resin, terpene resin, petroleum resin, phenol resin, terpene-phenol resin, alicyclic hydrocarbon resin, hydrogenated alicyclic hydrocarbon Known tackifier resins such as resins, hydrogenated terpene resins, and hydrogenated rosin resins can be used, and these tackifier resins can be used in combination of two or more. When using a component (b), 0-60 weight part and 1-50 weight part are preferable.

  In the asphalt vibration damping composition of the present invention, a softener can be used as the component (c). The kind of the softening agent is not limited, and known paraffinic, naphthenic, and aromatic process oils and mixed oils thereof can be used. When using a component (ha), 0-50 weight part and 1-40 weight part are preferable.

  In the asphalt damping material composition of the present invention, as the component (d), asphalt is obtained as a by-product (petroleum asphalt), a natural product (natural asphalt) during petroleum refining, or these and petroleum The main component is what is called bitumen. Specifically, straight asphalt, semi-blown asphalt, blown asphalt, tar, pitch, cutback asphalt added with oil, asphalt emulsion and the like can be used. These may be used as a mixture. In the present invention, straight asphalt having a penetration of 30 to 300 is preferable. The compounding amount of component (d) is preferably 5 to 97 parts by weight and 10 to 80 parts by weight.

  A predetermined amount of an antioxidant is added to the hydrogenated block copolymer and the asphalt vibration damping composition of the present invention, if necessary. In order to further improve the thermal stability of the vibration damping composition of the present invention, it is possible to add an antioxidant when blending the vibration damping composition. Antioxidants include, for example, 2,4-bis (n-octylthiomethyl) -O-cresol, 2,4-bis (n-dodecylthiomethyl) -O-cresol as block copolymer antioxidants. 2,4-bis (phenylthiomethyl) -3-methyl-6-tert-butylphenol, n-octadecyl-3- (3 ′, 5′di-tert-butyl-4′-hydroxyphenyl) propionate, 2, 2′-methylenebis (4-ethyl-6-tert-butylphenol), tetrakis- [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] -methane, 1,3 , 5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,6-di-tert-butyl 4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methyl Phenyl acrylate, 2,4-di-tert-amyl-6- [1- (3,5-di-tert-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate, 2- [1- (2-hydroxy-3) , 5-Di-tert-pentylphenyl) -ethyl] -4,6-di-tert-pentylphenyl acrylate, 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5- Hindered fe such as methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane Compound, pentaerythritol-tetrakis- (β-lauryl-thio-propionate), dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3, Sulfur compounds such as 3′-thiodipropionate, tris (nonylphenyl) phosphite, cyclic neopentanetetraylbis (octadecyl phosphite), tris (2,4-di-tert-butylphenyl) phosphite, etc. And the like. These can be used alone or in admixture of two or more. These addition amounts are arbitrary depending on the use, but are preferably 5 parts by weight or less with respect to 100 parts by weight of the asphalt vibration damping composition.

  In addition to the above-mentioned antioxidants and light stabilizers, the composition for vibration damping materials of the present invention includes various additives such as silica, talc, calcium carbonate, mineral powder, glass fiber and other fillers and reinforcements as necessary. Agents, mineral aggregates, pigments such as bengara and titanium dioxide, waxes such as paraffin wax, microcrystalline wax, low molecular weight polyethylene wax, or foaming agents such as azodicarbonamide, polyethylene, polypropylene, general-purpose polystyrene, Synthetic resins such as impact polystyrene, polyphenylene ether, acrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer, polyvinyl chloride, polymethyl methacrylate, polyamide, polycarbonate, polyacetal, polyethylene terephthalate, epoxy resin, etc. It may be pressurized.

  The method of mixing the hydrogenated block copolymer of the present invention with a crosslinking agent, rubbery polymer, asphalt, etc. is not particularly limited, and if desired, the various additives can be mixed with known mixers, hot melt kettles. , Roll, kneader, Banbury mixer, extruder, and the like, and are prepared by a method of heating, melt-kneading and uniformly mixing. In the case of forming into a sheet, it can be molded by heating and melting with a calendar roll, an extruder, a press or the like.

  In order to describe the present invention in more detail, examples and comparative examples will be shown below. These examples specifically illustrate the description of the present invention and the effects obtained thereby. It is not intended to limit the scope of the invention. Various measurements were performed according to the following methods.

The characteristics and physical properties of the polymer were measured by the following method.
I. Various hydrogenated copolymers I-1) Styrene content The content of styrene monomer units with respect to the hydrogenated copolymer block was measured with an ultraviolet spectrophotometer (UV-2450) using the base non-hydrogenated copolymer as a specimen. : Manufactured by Shimadzu Corporation). The content of the styrene monomer unit with respect to the hydrogenated copolymer block was determined as the content of the styrene monomer unit with respect to the base non-hydrogenated copolymer.
In addition, when using a hydrogenated copolymer as a test substance, it measured using the nuclear magnetic resonance apparatus (Germany BRUKER company make, DPX-400).

I-2) Styrene polymer block content The styrene polymer block content of the non-hydrogenated copolymer is M.M. Kolthoff, et. Polym. Sci. 1, 429 (1946). For the decomposition of the non-hydrogenated copolymer, a 0.1 g / 125 ml tertiary butanol solution of osmic acid was used. The styrene polymer block content obtained here was defined as the Os value.
In the case of measuring the styrene polymer block content of the hydrogenated copolymer, a nuclear magnetic resonance apparatus (JMN-270WB; manufactured by JEOL Ltd.) was used. Measurement was performed according to the method described in Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981). Specifically, ¹ H-NMR was measured using a sample obtained by dissolving 30 mg of a hydrogenated copolymer in 1 g of deuterated chloroform. The styrene polymer block content (Ns value) of the hydrogenated copolymer obtained by NMR measurement is the total integrated value, the integrated value of chemical shift 6.9 to 6.3 ppm, and the chemical shift 7.5 to 6.9 ppm. The Ns value was converted into an Os value. The calculation method is shown below.

Block styrene (St) strength = (6.9 to 6.3 ppm) integrated value / 2
Random styrene (St) strength = (7.5-6.9 ppm) integrated value-3 (block St strength)
Ethylene / Butylene (EB) Strength = Total Integrated Value-3 {(Block St Strength) + (Random St Strength)} / 8
Styrene polymer block content obtained by NMR measurement (Ns value)
= 104 (Block St intensity) / [104 {(Block St intensity) + (Random St intensity)} + 56 (EB intensity)]
Os value = −0.012 (Ns value) ² +1.8 (Ns value) −13.0

I-3) Vinyl bond amount The vinyl bond amount of the conjugated diene monomer portion in the copolymer block before hydrogenation was measured using an infrared spectrophotometer (FT / IR-230; manufactured by JASCO Corporation) before hydrogenation. Measured. The vinyl bond amount of the conjugated diene / styrene random copolymer block as the copolymer block was calculated by the Hampton method.

I-4) Peak molecular weight The peak molecular weight of the hydrogenated copolymer was measured by GPC (using an apparatus manufactured by Waters, USA). Tetrahydrofuran was used as a solvent, and the temperature was measured at 35 ° C. The peak molecular weight was determined from the GPC chromatogram using a calibration curve prepared using a commercially available standard monodisperse polystyrene gel having a known molecular weight.

I-5) Hydrogenation rate of double bond of conjugated diene monomer unit The hydrogenation rate was measured using a nuclear magnetic resonance apparatus (DPX-400: manufactured by BRUKER, Germany).

I-6) Loss tangent (tan δ), peak temperature of loss factor, and dynamic modulus of elasticity (G ′)
Using a viscoelasticity measuring / analyzing apparatus (model DVE-V4; manufactured by Rheology Co., Ltd.), the viscoelasticity spectrum was measured. The measurement frequency was 10 Hz.

  In the examples and comparative examples, the hydrogenation catalyst used for the hydrogenation reaction of the copolymer was produced as follows.

Reference Example 1 Preparation of Hydrogenation Catalyst 2 liters of dried and purified cyclohexane was charged into a nitrogen-substituted reaction vessel, and 40 mmol of bis (η ⁵ -cyclopentadienyl) titanium di- (p-tolyl) and a molecular weight of about 1 , 1,000 1,2-polybutadiene (1,2-vinyl bond content: about 85%) 150 g, dissolved in cyclohexane solution containing 60 mmol of n-butyllithium, reacted at room temperature for 5 minutes, Immediately after adding 40 mmol of n-butanol and stirring, a hydrogenation catalyst was obtained.

[Example 1]
Using a stirrer having an internal volume of 10 liters and a tank reactor with a jacket, the non-hydrogenated copolymer was continuously polymerized by the following method.
N-Butyllithium with respect to a cyclohexane solution having a butadiene concentration of 24% by weight of 3.48 liters / hr, a cyclohexane solution having a styrene concentration of 24% by weight of 6.43 liters / hr, and 100 parts by weight of monomers (total of butadiene and styrene). The n-butyllithium cyclohexane adjusted to a concentration of 0.091 parts by weight was supplied to the bottom of the reactor at 2.0 liter / hr of cyclohexane, and continuous polymerization was performed at 90 ° C. The reaction temperature was adjusted by the jacket temperature, the temperature near the bottom of the reactor was about 88 ° C., and the temperature near the top of the reactor was about 90 ° C. The average residence time in the polymerization reactor was about 45 minutes, the conversion of butadiene was almost 100%, and the conversion of styrene was 99%.
When the non-hydrogenated copolymer obtained by continuous polymerization was analyzed, the styrene content was 67% by weight, the polystyrene block content was 2% by weight, and the vinyl bond content of the butadiene portion was 15% by weight.
Next, to the non-hydrogenated copolymer obtained by continuous polymerization, the above-mentioned non-hydrogenated catalyst was added at 100 ppm as titanium per 100 parts by weight of the non-hydrogenated copolymer, and water was added at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. Addition reaction was performed. After completion of the reaction, methanol was added and 0.3 part by weight of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by weight of the polymer. A coalescence (polymer 1) was obtained.
Polymer 1 had a hydrogenation rate of 98% and a peak molecular weight of 170,000. The properties of polymer 1 are shown in Table 1.

[Example 2]
Two reactors identical to those in Example 1 were used, and continuous polymerization of the non-hydrogenated copolymer was carried out by the following method. The supply amount of the butadiene solution supplied to the first group is 4.51 liter / hr, the supply amount of the styrene solution is 5.97 liter / hr, and the supply amount of n-butyllithium is 0.1 part by weight with respect to 100 parts by weight of the monomer. The concentration was changed to 082 parts by weight, N, N, N ′, N′-tetramethylethylenediamine (hereinafter referred to as TMEDA) was added as a polar compound, and continuous polymerization was performed in the same manner as in Example 1. .
The polymer solution from the first unit is supplied to the bottom of the second unit, and at the same time, the supply amount of the styrene solution is set to 2.38 liters / hr, and continuous polymerization is performed to produce a copolymer (non-hydrogenated copolymer). ) The addition rate of styrene at the second outlet was 98%. Next, a hydrogenation reaction was performed in the same manner as in Example 1 to obtain a hydrogenated copolymer (Polymer 2). The properties of polymer 2 are shown in Table 1.

[Example 3]
The supply amount of butadiene solution to be supplied is 4.25 liter / hr, the supply amount of styrene solution is 4.98 liter / hr, and the supply amount of n-butyllithium is 0.044 parts by weight with respect to 100 parts by weight of monomer. A non-hydrogenated copolymer was obtained by continuously operating in the same manner as in Example 1 except that TMEDA was added and the concentration was changed. Next, a hydrogenation reaction was performed in the same manner as in Example 1 to obtain a hydrogenated copolymer (Polymer 3). The properties of Polymer 3 are shown in Table 1.

[Example 4]
Except for changing the supply amount of n-butyllithium to 0.167 parts by weight with respect to 100 parts by weight of the monomer, the same procedure as in Example 2 was used, and two reactors were used for continuous operation. A non-hydrogenated copolymer was obtained. Next, a hydrogenation reaction was performed in the same manner as in Example 1 to obtain a hydrogenated copolymer (Polymer 4). The properties of polymer 4 are shown in Table 1.

[Example 5]
Three reactors identical to those in Example 1 were used, and continuous polymerization of the non-hydrogenated copolymer was carried out by the following method.
Styrene was supplied in the same manner as in Example 1 except that the amount of styrene supplied to the first unit was changed to 0.77 liter / hr, the amount of n-butyllithium supplied was changed to 0.097 parts by weight, TMEDA was added. Only was continuously polymerized.
The polymer solution from the first unit is supplied to the bottom of the second unit, and at the same time, the supply amount of the butadiene solution is 3.18 liter / hr and the supply amount of the styrene solution is 5.59 liter / hr to continuously polymerize. did.
Further, the polymer solution discharged from the second group is supplied to the bottom of the third group, and at the same time, the supply amount of the styrene solution is set to 0.77 liter / hr, and continuous polymerization is performed to produce a copolymer (non-hydrogenated copolymer). Polymer). The addition rate of styrene at the third outlet was 99%. Next, a hydrogenation reaction was performed in the same manner as in Example 1 to obtain a hydrogenated copolymer (Polymer 5). The properties of polymer 5 are shown in Table 1.

[Example 6]
The supply amount of the butadiene solution to be supplied is 6.24 liter / hr, the supply amount of the styrene solution is 2.16 liter / hr, and the supply amount of n-butyllithium is 0.052 parts by weight with respect to 100 parts by weight of the monomer. A non-hydrogenated copolymer was obtained by continuously operating in the same manner as in Example 1 except that TMEDA was added and the concentration was changed. Next, in the same manner as in Example 2, a supply amount of the second styrene solution was supplied at 2.06 liter / hr, and continuous polymerization was performed to obtain a non-hydrogenated copolymer. Next, a hydrogenation reaction was performed in the same manner as in Example 1 to obtain a hydrogenated copolymer (Polymer 6). The properties of polymer 6 are shown in Table 1.

[Example 7]
Except for changing the supply amount of n-butyllithium to a concentration of 0.113 parts by weight with respect to 100 parts by weight of the monomer, two reactors are used in the same manner as in Example 2 and continuous operation is performed. The obtained non-hydrogenated copolymer was coupled with ethyl benzoate so that the coupling rate was 50% to obtain a coupling type non-hydrogenated copolymer. Next, a hydrogenation reaction was performed in the same manner as in Example 1 to obtain a hydrogenated copolymer (Polymer 7). The properties of polymer 7 are shown in Table 1.

[Example 8]
Except for changing the supply amount of n-butyllithium to a concentration of 0.121 parts by weight with respect to 100 parts by weight of the monomer, two reactors are used in the same manner as in Example 2 and continuous operation is performed. The obtained non-hydrogenated copolymer was coupled with ethyl benzoate so that the coupling rate was 70% to obtain a coupling type non-hydrogenated copolymer. Next, the hydrogenation reaction was carried out in the same manner as in Example 1 except that the amount of titanium added was 30 ppm and hydrogen was supplied so that the hydrogenation rate was 30% to obtain a hydrogenated copolymer (polymer 7). It was. The properties of polymer 7 are shown in Table 1.

[Comparative Example 1]
The supply amount of butadiene solution to be supplied is 5.82 liter / hr, the supply amount of styrene solution is 1.12 liter / hr, and the supply amount of n-butyllithium is 0.047 parts by weight with respect to 100 parts by weight of monomer. A non-hydrogenated copolymer was obtained by continuously operating in the same manner as in Example 1 except that TMEDA was added and the concentration was changed. Next, in the same manner as in Example 2, the supply amount of the second styrene solution was changed to 1.73 liters / hr, and continuous polymerization was performed to obtain a non-hydrogenated copolymer. Next, a hydrogenation reaction was performed in the same manner as in Example 1 to obtain a hydrogenated copolymer (Polymer 9). The properties of polymer 9 are shown in Table 1.

[Comparative Example 2]
In the same manner as in Example 5, three reactors were used, the supply amount of styrene supplied to the first unit was changed to 0.97 liter / hr, and the supply amount of n-butyllithium was changed to 0.065 parts by weight. And styrene was continuously polymerized in the same manner as in Example 1.
The polymer solution from the first unit is supplied to the bottom of the second unit, and at the same time, the supply amount of the butadiene solution is changed to 4.32 liter / hr, and the supply amount of the styrene solution is changed to 3.33 liter / hr, Continuous polymerization.
Further, the polymer solution from the second group is supplied to the bottom of the third group, and at the same time, the supply amount of the styrene solution is set to 0.97 liter / hr, and continuous polymerization is carried out to produce a copolymer (non-hydrogenated copolymer). Polymer). The addition rate of styrene at the third outlet was 99%. Next, a hydrogenation reaction was performed in the same manner as in Example 1 to obtain a hydrogenated copolymer (Polymer 10). The properties of polymer 10 are shown in Table 1.

[Comparative Example 3]
As in Example 5, three reactors were used, the supply amount of styrene supplied to the first unit was changed to 0.83 liter / hr, and the supply amount of n-butyllithium was changed to 0.225 parts by weight. Only styrene was continuously polymerized in the same manner as in Example 1 except that was added.
The polymer solution from the first unit was supplied to the bottom of the second unit, and at the same time, the supply amount of the butadiene solution was changed to 4.38 liter / hr, and only butadiene was continuously polymerized.
Further, the polymer solution from the second unit is supplied to the bottom of the third unit, and at the same time, the supply amount of the styrene solution is set to 0.83 liter / hr, and continuous polymerization is performed to produce a copolymer (non-hydrogenated copolymer). Polymer). The addition rate of styrene at the third outlet was 99%. Next, a hydrogenation reaction was performed in the same manner as in Example 1 to obtain a hydrogenated copolymer (Polymer 11). The properties of polymer 11 are shown in Table 1.
The amount of TMEDA added to the polymers 2 to 11 was adjusted so that the vinyl content in the total butadiene of the block copolymer before hydrogenation obtained would be the value shown in Table 1.

[Examples 9 to 12]
Asphalt compositions having the compositions shown in Table 2 were produced. Specifically, 400 g of asphalt was put into a 750 ml metal can, and the metal can was sufficiently immersed in an oil bath at 180 ° C. Next, the asphalt was completely melted, and a predetermined amount of a hydrogenated copolymer (polymer 2), a rubbery polymer, a tackifier resin, and a softener were charged in small amounts into the stirred asphalt. After all the predetermined additives were added, the mixture was stirred for 90 minutes at a rotational speed of 6000 rpm to obtain a composition.
The properties of the obtained asphalt composition are shown in Table 2. The asphalt composition of the present invention exhibits a high tan δ value particularly in the range of 0 ° C to 70 ° C.

  The hydrogenated copolymer and the asphalt damping material composition of the present invention can be suitably used in the fields of automobiles, building damping materials, sound insulation materials and the like.

Claims (12)

A hydrogenated copolymer for damping material (A) obtained by hydrogenating a non-hydrogenated random copolymer containing a conjugated diene monomer unit and a vinyl aromatic monomer unit, the damping material The hydrogenated copolymer for vibration damping material (A) has the following characteristics (1) to (4):
(1) The peak molecular weight by GPC of the hydrogenated copolymer (A) is 40,000 to 400,000 in terms of standard polystyrene,
(2) The content of the vinyl aromatic monomer unit contained in the hydrogenated copolymer (A) is in the range of 20 to 80% by weight,
(3) The vinyl bond amount of the non-hydrogenated polymer containing the conjugated diene monomer unit in the hydrogenated copolymer (A) is less than 40%,
(4) In the dynamic viscoelastic spectrum obtained for the hydrogenated copolymer (A), at least one peak of loss factor (tan δ) exists in the range of −40 ° C. or higher and lower than 70 ° C.   A hydrogenated block copolymer for damping material, comprising at least one hydrogenated copolymer for damping material (A) according to claim 1 as a block.   The hydrogenated block copolymer for a vibration damping material according to claim 2, further comprising at least one polymer block (B) mainly composed of vinyl aromatic monomer units.   The hydrogenated block copolymer for a damping material according to claim 3, wherein the content of all vinyl aromatic monomer units in the block copolymer is 40 to 80% by weight.   The hydrogenated block copolymer for a vibration damping material according to claim 3 or 4, wherein the proportion of the polymer block (B) containing a vinyl aromatic monomer unit in the block copolymer is less than 40% by weight.   A vibration damping material obtained by crosslinking the hydrogenated block copolymer according to any one of claims 2 to 5.   A vibration damping material comprising the hydrogenated block copolymer according to any one of claims 2 to 5 and another rubbery polymer.   The vibration damping material according to claim 7 obtained by crosslinking. Hydrogenated block copolymer according to any one of claims 2 to 5,
With asphalt,
Asphalt damping material composition containing. As component (a), a hydrogenated block copolymer for a damping material according to any one of claims 2 to 5, or a composition of the hydrogenated block copolymer and another rubbery polymer,
Asphalt as ingredient (d),
Asphalt damping material composition containing.   The asphalt vibration damping composition according to claim 10, further comprising a tackifier resin as a component (b).   The asphalt damping material composition according to claim 10 or 11, further comprising a softening agent as component (c).