JP2003001762A - Laminate and gap filling method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate excellent in damping properties, steel panel reinforcing properties, vibrationproof properties, sound insulating properties and soundproof properties obtained using a resin composition containing oil extended 1,2-polybutadiene having an excellent function being the characteristic of conventional 1,2-polybutadiene and excellent in flowability and shape followability, and a gap filling method using the same. SOLUTION: The laminate is constituted by laminating the resin composition containing oil extended 1,2-polybutadiene (A), a thermoplastic polymer (B) other than the component (A) and a crosslinking agent (C) on a base layer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to novel oil extensions 1 and 2.
Using a crosslinkable resin layer containing polybutadiene,
The present invention relates to a laminated body excellent in vibration damping property, steel plate reinforcing property, sound absorbing property, sound insulating property, and sealing property, and a gap filling method.

Various techniques for laminating or filling and foaming a rubber composition in a metal base layer (between) such as a steel plate have been put into practical use. For example, JP-A-1-139534 "Rubber composition for vibration-proof / sound-proof / sound-insulating material", JP-A-62-628.
No. 82 publication, "low temperature vulcanization type high foaming sealer" and the like. However, these are only the filling of the open-cell sponge, and the dew condensation water generated in the sponge migrates into the open-cell foam structure, contacts the metal surface, and causes metal corrosion. As described above, there is a demand for a technique of filling the gap without corroding the metal and manufacturing the material in a form satisfying the material excellent in the vibration damping property, the sound absorbing property and the sealing property.

By the way, 1, which is controlled to an appropriate crystallinity,
Since 2-polybutadiene has a structure composed of a crystalline region and an amorphous portion, 2-polybutadiene has not only a function as a thermoplastic elastomer but also a carbon-carbon double bond rich in chemical reactivity in the molecule. Since it has, it also has a function as a conventional vulcanized product, a thermosetting resin having an increased crosslink density, or a rubber. Further, this 1,2-polybutadiene is applied as another resin, a thermoplastic elastomer, a modifier of a thermosetting elastomer, or a medical polymer material. The applicant of the present application makes use of such characteristics of 1,2-polybutadiene to crosslink a heat medium containing the polybutadiene, which is useful as a vibration damping material, a sound insulating material, and a restraining material. 1-297443) and a laminate containing the polybutadiene (JP-A-2-57340). However, when the 1,2-polybutadiene is used for various new uses, there is a problem that the fluidity is insufficient and the shape following property with respect to the base layer is insufficient.

[0004]

SUMMARY OF THE INVENTION The present invention is based on the conventional
The oil-extended 1,2-polybutadiene, which has the excellent functions characteristic of 2-polybutadiene and is also excellent in fluidity and shape-following property, is used for vibration damping, steel plate reinforcement, sound absorption, sound insulation,
It is an object of the present invention to provide a laminate excellent in sealing property and a gap filling method.

[0005]

SUMMARY OF THE INVENTION The present invention comprises a substrate,
(A) oil-extended 1,2-polybutadiene, (B) above (A)
The present invention relates to a laminate obtained by laminating a resin layer containing a thermoplastic polymer other than the components and (C) a crosslinking agent. Here, in the resin layer, the ratio of the components (A) to (C) is (A).
1 to 99 parts by weight of the component, 99 to 1 parts by weight of the component (B) (however, (A) + (B) = 100 parts by weight), and the total amount of 100 parts by weight of the component (C) is 0.001 to 50 parts by weight. Parts by weight are preferred. Further, the component (B) constituting the resin layer is (A)
Other than the components, at least one selected from the group consisting of thermoplastic resins, thermoplastic elastomers, natural rubber and synthetic rubber is preferable. Furthermore, the component (C) that constitutes the resin layer is
A combination of sulfur or a compound that produces sulfur by heating and a vulcanization accelerator, an organic peroxide, and a combination of an organic peroxide and a polyfunctional monomer are preferable. The resin layer further contains (D) a softening agent of 0 to 300 parts by weight, based on 100 parts by weight of the total of the components (A) and (B).
(E) 0 to 300 parts by weight of inorganic filler, (F) flame retardant, antioxidant, lubricant, colorant, foaming agent, ultraviolet absorber, antistatic agent, heat stabilizer, antiaging agent, processing aid, Light resistance (weather)
And 80% by weight of at least one other additive selected from the group of agents and antibacterial agents, and the total amount of these (D), (E) and (F) components is 1 to 60
A resin layer containing 0 parts by weight. Furthermore, in the resin layer, the total amount of the components (A) and (B) is 100
You may mix | blend 1 to 300 weight part of (G) foaming agents with respect to weight part. The laminate of the present invention may have asphalt interposed between the base layer and the resin layer. Next, the present invention relates to a gap filling method, characterized in that the resin layer containing a foaming agent is filled in gaps (pillars of automobiles, header voids) formed of a base layer, and the resin layer is crosslinked and foamed. .

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Base Layer Examples of the material of the base layer constituting the laminate of the present invention include metals such as plastic, rubber and steel, wood, paper, cloth, concrete and stone, and preferably metal. is there.
The shape of the base layer includes, for example, a face, a solid, a dot, a lattice, a line, a spiral, a sphere, a concave, a convex, and combinations or combinations thereof. Specific examples of the base layer include steel plates for automobiles. The thickness of the base layer is preferably 0.2 to 2 mm, more preferably 0.3 to 1.8 mm.

Resin layer (A) oil-extended 1,2-polybutadiene: 1,2-polybutadiene (hereinafter referred to as "(A) ') used in the component (A) of the present invention.
1,2-polybutadiene "is, for example, 1,
Any 1,2-polybutadiene may be used as long as it has a 2-bond content of 70% or more, but is preferably obtained by polymerizing butadiene in the presence of a catalyst containing a cobalt compound and aluminoxane. It is a thing.

The content of 1,2-bond in the butadiene bond unit of the (A) '1,2-polybutadiene of the present invention is 7
0% or more, preferably 80% or more, more preferably 9
It is 0% or more. When the 1,2-bond content is 70% or more, the properties of the 1,2-polybutadiene of the present invention as a good thermoplastic elastomer are exhibited.

The (A) '1,2-polybutadiene of the present invention is preferably crystalline 1,2-polybutadiene, and its melting point is preferably 50 to 130 ° C, more preferably 60 to 120 ° C. In range. When the melting point is in this range, the balance between mechanical strength such as tensile strength and tear strength and flexibility is excellent.

The (A) '1,2-polybutadiene of the present invention may be copolymerized with a small amount of a conjugated diene other than butadiene. Conjugated dienes other than butadiene include 1,3
-Pentadiene, 1,3-substituted by higher alkyl groups
Examples thereof include a butadiene derivative and 2-alkyl-substituted-1,3-butadiene. Among these, 1,3-butadiene derivatives substituted with higher alkyl groups include 1-pentyl-1,3-butadiene, 1-hexyl-1,3-butadiene, 1-heptyl-1,3-butadiene, 1 -Octyl 1,3-butadiene and the like.

Typical examples of 2-alkyl-substituted-1,3-butadiene include 2-methyl-1,3-butadiene (isoprene), 2-ethyl-1,3-butadiene and 2-propyl-. 1,3-butadiene, 2-isopropyl-1,3-butadiene, 2-butyl-1,3-butadiene, 2-isobutyl-1,3-butadiene, 2-amyl-1,3-butadiene, 2-isoamyl- 1,3-
Butadiene, 2-hexyl-1,3-butadiene, 2-
Cyclohexyl-1,3-butadiene, 2-isohexyl-1,3-butadiene, 2-heptyl-1,3-butadiene, 2-isoheptyl-1,3-butadiene, 2-
Octyl-1,3-butadiene, 2-isooctyl-
1,3-butadiene etc. are mentioned. Among these conjugated dienes, preferred conjugated dienes copolymerized with butadiene include isoprene and 1,3-pentadiene. The content of butadiene in the monomer component used for the polymerization is preferably 50 mol% or more, and particularly preferably 70 mol% or more.

As described above, the (A) '1,2-polybutadiene of the present invention is preferably obtained by polymerizing butadiene in the presence of a catalyst containing a cobalt compound and aluminoxane. As the cobalt compound, preferably, an organic acid salt of cobalt having 4 or more carbon atoms can be mentioned. Specific examples of the organic acid salt of cobalt include butyrate, hexanoate, heptylate, octylate such as 2-ethylhexylate, decanoate, and higher stearic acid, oleic acid, erucic acid and the like. Alkyl such as fatty acid salt, benzoate, tolylate, xylylate, ethylbenzoic acid, aralkyl, allyl-substituted benzoic acid salt or naphthoate, alkyl, aralkyl or allyl-substituted naphthoate can be mentioned. Of these, so-called octylates of 2-ethylhexylic acid, stearates and benzoates are preferred because of their excellent solubility in hydrocarbon solvents.

Examples of the aluminoxane include those represented by the following general formula (I) or general formula (II).

[0014]

[Chemical 1]

In the aluminoxane represented by the general formula (I) or (II), R is a hydrocarbon group such as methyl group, ethyl group, propyl group or butyl group, preferably methyl group or ethyl group. And particularly preferably a methyl group. In addition, m is an integer of 2 or more, preferably 5 or more, and more preferably 10 to 100. Specific examples of aluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, and the like,
Methylaluminoxane is particularly preferred.

It is extremely preferable that the polymerization catalyst contains a phosphine compound in addition to the above cobalt compound and aluminoxane. The phosphine compound is a component effective in activating the polymerization catalyst, controlling the vinyl bond structure and crystallinity, and preferably an organophosphorus compound represented by the following general formula (III) can be mentioned.

P (Ar) _n (R ') _3-n (III) In the general formula (III), Ar represents a group shown below.

[0018]

[Chemical 2]

(In the above groups, R ¹ , R ² and R ³ are the same or different and each preferably has a hydrogen atom and a carbon number of 1 to
6 alkyl groups, halogen atoms, preferably 1 carbon atom
~ 6 alkoxy groups or preferably 6-12 carbon atoms
Represents an aryl group. Further, in the general formula (III), R ′ represents a cycloalkyl group or an alkyl-substituted cycloalkyl group, and n is an integer of 0 to 3.

Specific examples of the phosphine compound represented by the general formula (III) include tri- (3-methylphenyl).
Phosphine, tri- (3-ethylphenyl) phosphine, tri- (3,5-dimethylphenyl) phosphine,
Tri- (3,4-dimethylphenyl) phosphine, tri- (3-isopropylphenyl) phosphine, tri-
(3-t-butylphenyl) phosphine, tri- (3,3
5-diethylphenyl) phosphine, tri- (3-methyl-5-ethylphenyl) phosphine), tri- (3-
Phenylphenyl) phosphine, tri- (3,4,5-
Trimethylphenyl) phosphine, tri- (4-methoxy-3,5-dimethylphenyl) phosphine, tri-
(4-Ethoxy-3,5-diethylphenyl) phosphine, tri- (4-butoxy-3,5-dibutylphenyl) phosphine, tri (p-methoxyphenylphosphine), tricyclohexylphosphine, dicyclohexylphenylphosphine, tribenzylphosphine. , Tri (4-methylphenylphosphine), tri (4-ethylphenylphosphine), and the like. Of these, particularly preferred are triphenylphosphine, tri- (3-methylphenyl) phosphine,
Examples thereof include tri- (4-methoxy-3,5-dimethylphenyl) phosphine.

Further, as the cobalt compound, a compound represented by the following general formula (IV) can be used.

[0022]

[Chemical 3]

The compound represented by the above general formula (IV) is a complex having as a ligand a phosphine compound in which n is 3 in the above general formula (III) with respect to cobalt chloride. When the cobalt compound is used, it may be synthesized in advance or may be used by bringing cobalt chloride and a phosphine compound into contact with each other in the polymerization system. By selecting various phosphine compounds in the complex, it is possible to control the amount of 1,2-bonds and crystallinity of the resulting 1,2-polybutadiene.

Specific examples of the cobalt compound represented by the above general formula (IV) include cobalt bis (triphenylphosphine) dichloride, cobalt bis [tris (3-methylphenylphosphine)] dichloride and cobalt bis [tris (3 -Ethylphenylphosphine)] dichloride, cobalt bis [tris (4-methylphenylphosphine)] dichloride, cobalt bis [tris (3,5-dimethylphenylphosphine)] dichloride, cobalt bis [tris (3,4-dimethylphenylphosphine) )] Dichloride, cobalt bis [tris (3-isopropylphenylphosphine)] dichloride, cobalt bis [tris (3-t-butylphenylphosphine)] dichloride, cobalt bis [tris (3,5-diethylphenyl) Sphine)] dichloride, cobalt bis [tris (3-methyl-5-ethylphenylphosphine)] dichloride, cobalt bis [tris (3-phenylphenylphosphine)] dichloride, cobalt bis [tris (3,4,5-trimethylphenyl] Phosphine)] dichloride, cobalt bis [tris (4-methoxy-3,5-dimethylphenylphosphine)] dichloride, cobalt bis [tris (4-ethoxy-3,5-diethylphenylphosphine)] dichloride, cobalt bis [tris ( 4-butoxy-3,
5-dibutylphenylphosphine)] dichloride, cobalt bis [tris (4-methoxyphenylphosphine)] dichloride, cobalt bis [tris (3-methoxyphenylphosphine)] dichloride, cobalt bis [tris (4-dodecylphenylphosphine)] dichloride , Cobalt bis [tris (4-ethylphenylphosphine)] dichloride and the like can be used.

Of these, particularly preferred are cobalt bis (triphenylphosphine) dichloride, cobalt bis [tris (3-methylphenylphosphine)] dichloride, cobalt bis [tris (3,3
5-dimethylphenylphosphine)] dichloride, cobalt bis [tris (4-methoxy-3,5-dimethylphenylphosphine)] dichloride and the like.

The amount of the catalyst used is 1 mol of butadiene in the case of homopolymerization of butadiene, and 1 mol of butadiene in the case of copolymerization.
Total amount of butadiene and conjugated dienes other than butadiene 1
The cobalt compound is 0.001 to 1 mmol, preferably 0.01 to 0.5, in terms of cobalt atom per mol.
Use about millimolar. The amount of the phosphine compound used is the ratio of phosphorus atom to cobalt atom (P / Co)
As a rule, 0.1 to 50, preferably 0.5 to 2
It is 0, more preferably 1 to 20. Further, the amount of aluminoxane used is as a ratio (Al / Co) of aluminum atoms to cobalt atoms of the cobalt compound,
Usually, it is 4 to 10 ⁷ , preferably 10 to 10 ⁶ . When the complex represented by the general formula (IV) is used, the amount of the phosphine compound used is such that the ratio of phosphorus atom to cobalt atom (P / Co) is 2, and the amount of aluminoxane used is Follow the instructions in.

Examples of the inert organic solvent used as the polymerization solvent include aromatic hydrocarbon solvents such as benzene, toluene, xylene and cumene, and aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-butane. Alicyclic hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane and mixtures thereof.

The polymerization temperature is usually from -50 to 120 ° C,
It is preferably -20 to 100 ° C. The polymerization reaction may be a batch system or a continuous system. The monomer concentration in the solvent is usually 5 to 50% by weight, preferably 10 to 35% by weight. Further, in order to produce a polymer, in order not to deactivate the catalyst of the present invention and the polymer, consideration should be given to minimizing inclusion of a compound having a deactivating action such as oxygen, water or carbon dioxide gas in the polymerization system. is necessary. When the polymerization reaction proceeds to the desired stage, the reaction mixture is added with alcohol, another polymerization terminator, an antioxidant, an antioxidant, an ultraviolet absorber, etc., and then the produced polymer is separated, washed and dried according to a usual method. Used in the present invention
Polybutadiene can be obtained.

The weight average molecular weight of the (A) '1,2-polybutadiene used in the present invention is preferably 10,000 to 50.
It is preferably 0,000, more preferably 10,000 to 1,500,000, and particularly preferably 50,000 to 1,000,000. If the weight average molecular weight is less than 10,000, the fluidity after oil extension is extremely high, making subsequent processing extremely difficult, while if it exceeds 5 million, the fluidity after oil extension is extremely low, and processing is extremely difficult. It is difficult and not preferable.

The extender oil used for preparing the (A) oil-extended 1,2-polybutadiene of the present invention by oil-extending the above-mentioned (A) '1,2-polybutadiene is based on a diene polymer. There is no particular limitation as long as it is a commonly used extender oil or softening agent, and for example, a mineral oil-based extender oil can be mentioned as a suitable example.

The mineral oil-based extender oil is preferably referred to as a viscosity specific gravity constant (or a viscosity specific gravity constant.
G. C. Abbreviated. ) 0.790 to 0.999, more preferably V. G. C. Of 0.790 to 0.949, particularly preferably V.I. G. C. Is 0.790 to 0.912. As extender oils, aromatic extender oils, naphthene extender oils, and paraffin extender oils are generally known.

Among these, as an aromatic type extender oil satisfying the viscosity specific gravity constant, Diana process oils AC-12, AC460, AH- manufactured by Idemitsu Kosan Co., Ltd.
16, AH-58, ExxonMobil (with) Mobilsol K, 22 and 130, Nikko Kyoseki Co., Ltd., Kyoseki Process X50, X100, X140, Shell Kagaku Co., Ltd. Resox No. 3, Dutrex 729UK, Koumorex 20 made by Nippon Oil Co., Ltd.
0,300,500,700, ExxonMobil (Yes)
Esso Process Oil 110 and 120 manufactured by Mitsubishi Oil Co., Ltd., Mitsubishi 34 Heavy Process Oil, Mitsubishi 44 Heavy Process Oil, Mitsubishi 38 Heavy Process Oil, and Mitsubishi 39
Examples include heavy process oils.

As the naphthenic extender oil satisfying the above viscosity specific gravity constant, Diana Process Oil NS-24, NS-100, NM-26, N manufactured by Idemitsu Kosan Co., Ltd.
M-280, NP-24, Naplex 38 made by ExxonMobil (with), Fukkor F made by Fuji Kosan Co., Ltd.
LEX # 1060N, # 1150N, # 1400N, #
2040N, # 2050N, Kyoseki Process R25, R50, R200, R1000 manufactured by Nikko Kyoseki Co., Ltd., Shelf Rex 371JY, 3 manufactured by Shell Kagaku Co., Ltd.
71N, 451, N-40, 22, 22R, 32R, 100R, 100S, 100SA, 2
20RS, 220S, 260, 320R, 68
0, Koumorex No. 2 process oil manufactured by Nippon Oil Co., Ltd., Esso Process Oil L-2 and 765 manufactured by Exxon Mobil Co., Ltd., and Mitsubishi 20 Light Process Oil manufactured by Mitsubishi Oil Co., Ltd. .

Further, as the paraffin-based extender oil satisfying the above-mentioned viscosity specific gravity constant, Diana Process Oil PW-90, PW-380, PS-3 manufactured by Idemitsu Kosan Co., Ltd.
2, PS-90, PS-430, manufactured by Fuji Kosan Co., Ltd.
Huccol process P-100, P-200, P-30
0, P400, P-500, Kyoseki Process P-200, P-300, P-500, Kyoseki E manufactured by Nikko Kyoseki Co., Ltd.
PT750, 1000, Kyoishi Process S90, Lebrex 26, 100, 46 manufactured by Shell Chemical Co., Ltd.
0, Esso process oils 815, 845, B-1 manufactured by ExxonMobil (with), Naplex 32 manufactured by ExxonMobil (with), and Mitsubishi 10 light process oil manufactured by Mitsubishi Oil Co., Ltd. .

Since the (A) '1,2-polybutadiene is oil-extended with the extending oil, the filler such as carbon black and silica can be uniformly finely dispersed in the 1,2-polybutadiene. It becomes possible and the workability and various characteristics of the molded product can be remarkably improved. Further, surprisingly, the resulting (A) oil-extended 1,2-polybutadiene and molded products have remarkably improved fluidity, particularly shape following property, and mechanical strength, particularly rigidity (vibration damping). Properties, steel plate reinforcement), and foamability (gap filling) can be significantly improved.

The amount of the extender oil used in the present invention is
The amount is 1 to 200 parts by weight, preferably 10 to 100 parts by weight, more preferably 15 to 80 parts by weight, and particularly preferably 20 to 70 parts by weight, relative to 100 parts by weight of (A) '1,2-polybutadiene. If it is less than 1 part by weight, the effect of improving the shape followability, fluidity, foamability (gap filling property) and workability of the base layer will be poor, while if it exceeds 200 parts by weight, it will be significantly softened and the workability will be poor.

The oil extending method is not particularly limited, and examples thereof include a method in which an extending oil is added to a polymerization solution of (A) '1,2-polybutadiene and mixed in a solution state. This method is preferable from the viewpoint that the step of mixing 1,2-polybutadiene and the extender oil can be omitted in operation, and the mixing uniformity of both is excellent. When the extender oil is added to the polymer solution, it is preferably after the polymerization, for example, after the addition of the terminal modifier or after the addition of the polymerization terminator. In the polymer solution containing the organic solvent, add the required amount of extending oil,
Mix well in solution (first step). Next, a crumb is obtained by a steam stripping method in which steam is blown into a polymer solution containing an extending oil, or a polymer solution containing an extending oil is directly removed by a means such as an extruder or a devolatizer. Then, the oil-extended 1,2-polybutadiene and the solvent are separated (second step). The obtained oil-extended 1,2-polybutadiene is dried by a vacuum drier, a hot air drier, a roll, or the like as needed (third step) to obtain the target (A) oil-extended 1,2-polybutadiene. It can be isolated. Further, as an oil-extending method, 1,2-polybutadiene and an extending oil may be blended in a molten state to prepare (A) oil-extended 1,2-polybutadiene. In this case, as a blending method, a single-screw extruder, a twin-screw extruder, a Banbury, a roll, a kneader, a plastomill or the like is adopted, and the melt-kneading temperature is preferably 140 to 160 ° C.

(B) Thermoplastic polymer other than the above-mentioned component (A) '; Here, the thermoplastic polymer (B) used in the present invention is a thermoplastic resin other than the component (A)' At least one selected from the group of plastic elastomer, natural rubber and synthetic rubber can be mentioned.

Of these, as the thermoplastic resin other than the above-mentioned component (A) ′, any thermoplastic resin having a plasticizing temperature of 50 to 450 ° C. can be used without particular limitation. For example, a styrene resin (for example, Polystyrene, butadiene / styrene copolymer, acrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer, etc.), ABS resin, AES resin, AAS resin, polyethylene, polypropylene, ethylene-propylene resin,
Ethylene-ethyl acrylate resin, polyvinyl chloride,
Polyvinylidene chloride, polybutene, polycarbonate,
Polyacetal, polyphenylene oxide, polymethylmethacrylate, saturated polyester resin (for example, hydroxycarboxylic acid condensate such as polylactic acid, diol and dicarboxylic acid condensate such as polybutylene succinate), polyamide resin, fluororesin, polysulfone , Polyether sulfone, polyarylate, polyether ether ketone, liquid crystal polymer, etc., or a mixture of two or more thereof. Among the thermoplastic resins, preferred are polystyrene, butadiene / styrene copolymer, acrylonitrile / styrene copolymer, ABS.
Resin, AES resin, AAS resin, polyethylene, polypropylene, polyvinyl chloride, saturated polyester resin, and polyamide resin.

Further, as the thermoplastic elastomer, for example, according to the classification according to the chemical composition of the hard segment, a styrene-based thermoplastic elastomer (abbreviated as SBC. Hereinafter, abbreviated symbols are shown in parentheses), olefin-based thermoplastic elastomer. Plastic Elastomer (TPO), Urethane Thermoplastic Elastomer (TPU), Ester Thermoplastic Elastomer (TPEE), Amide Thermoplastic Elastomer (TP
AE) and the like. In addition to these, there are vinyl chloride type thermoplastic elastomer (TPVC), ion cluster type thermoplastic elastomer (ionomer), and fluorine type thermoplastic elastomer containing a fluororesin as a constraining block. Among them, TPO by dynamic cross-linking that improves performance by kneading while kneading the rubber component that becomes the soft segment while making the rubber dispersed particle size fine is sometimes called TPV). These thermoplastic elastomers have 1
Seed or a mixture of two or more species.

The preferred SBC is styrene-
Butadiene-styrene block copolymer (SBS),
Styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene / butylene-styrene block copolymer (SEBS), functionalized SEB
S (f-SEBS), styrene-ethylene / propylene-styrene block copolymer (SEPS), random type hydrogenated styrene / butadiene polymer (H
SBR).

Preferred TPOs are PP and PE.
EP, EPDM, EBM, EB to polyolefin such as
Simple blend type T, which is made by mixing elastomers such as DM and compounding with a mixer such as Banbury or Plastomill.
PO (s-TPO), an implantable TPO, in which the hard segment olefin monomer is polymerized and then the soft segment olefin monomer is polymerized in the same plant or in the same reactor (the order may be reversed). i-TPO), a dynamic vulcanization type TPO (TPV) made by vulcanizing rubber simultaneously with mixing with a mixer such as Banbury or Plastomill. Furthermore, as TPV, PP-EPDM in which PP is combined with a hard segment and EPDM is combined with a soft segment (hereinafter, the left side is a hard segment, the right side is a soft segment), PP-nitrile rubber (NBR), PP-acrylic rubber ( ACM), PP-natural rubber (NR), PP-butyl rubber (IIR), PE-EPDM, PE-NR, nylon-NBR, nylon-ACM, polyester-chloroprene (CR), PVC-NBR.

Preferred TPUs are those in which the diisocyanate used in the hard segment is toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6 hexamethylene diisocyanate, 2,2,4 (2 , 4, 4)-
Trimethylhexamethylene diisocyanate, p-phenylene diisocyanate, 4,
4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-disisocyanate, 1,5 'naphthalene diisocyanate, trans-1,4-cyclohexyl diisocyanate , Lysine diisocyanate, and mixtures of two or more thereof.

The preferred TPEE is a polyester / polyether type TPEE in which the hard segment is an aromatic crystalline polyester and a polyether is used as the soft segment, and the hard segment is an aromatic crystalline polyester and an aliphatic is used as the soft segment. Polyester / polyester type TPEE using a system polyester, liquid crystal TPEE in which a hard segment is a liquid crystal molecule and a soft segment is an aliphatic polyester
Is. More preferably, as the polyester / polyether type TPEE, the hard segment is a polycondensate of butanediol and dimethyl terephthalate, a polycondensate of ethylene glycol and dimethyl terephthalate, and a polycondensate of butanediol and 2,6-naphthalenedicarboxylic acid. Body, a polycondensation product of ethylene glycol and 2,6 naphthalenedicarboxylic acid, or a mixture thereof, wherein the soft segment is polytetramethylene ether glycol, poly (1,
2-propylene oxide) glycol, poly (ethylene oxide) glycol, or a mixture. The polyester / polyester type TPEE is more preferably the same as the polyester / polyether type TPEE, but the soft segment is a polylactone type aliphatic polyester.
Further, as the liquid crystalline TPEE, more preferably, the hard segment is a thermotropic liquid crystal polymer, and in particular, a low molecular weight liquid crystal compound such as dihydroxy-paraquaterphenyl is used, and an aliphatic polyester is used as the soft segment in a multi-block copolymer. Is.

As TPAE, the hard segment is preferably a polyamide, the soft segment is a multiblock copolymer using a polyether or polyester having a low Tg, and more preferably the hard segment is nylon-6, nylon-6,6, Nylon-6,1
0, nylon-11, nylon-12, the soft segment is a polyether diol or a polyester diol, and particularly preferably, the soft segment is a diol poly (oxytetramethylene) glycol, poly (oxypropylene) glycol, poly (ethylene adipate). ) Glycol and poly (butylene-1,4-adipate) glycol.

As the TPVC, it is preferable to use high-molecular-weight polyvinyl chloride (hereinafter abbreviated as PVC) in the hard segment, which has a function of a cross-linking point in the microcrystalline portion, and which is plasticized in the soft segment with a plasticizer. Used, PVC using partially crosslinked or branched structure introduced into the hard segment, PVC using plasticizer in the soft segment, rubber having a PVC in the hard segment and partially crosslinked in the soft segment, such as NBR And / or one using TPE such as TPU or TPEE, or a mixture of two or more kinds.

The natural rubber can be used without particular limitation, and examples thereof include one or a mixture of two or more of gum arabic and gum india. The synthetic rubber may be used without particular limitation, and examples thereof include polybutadiene rubber, polyisoprene rubber, isobutylene / isoprene rubber, ethylene-α-olefin- (diene) copolymer (for example, EPM, EBM, EOM, EP.
DM, EBDM, etc.), aromatic vinyl compound-conjugated diene compound- (α-olefin) copolymer (for example, SB
R, SBS, SEBS, etc.), acrylonitrile-butadiene rubber, fluororubber, silicone rubber, halogenated butyl rubber (eg, chlorinated butyl rubber, brominated butyl rubber, etc.), liquid butadiene rubber, liquid acrylonitrile-butadiene rubber, etc. or 2 Mixtures of more than one species are mentioned. The above-mentioned thermoplastic resin, thermoplastic elastomer, natural rubber, synthetic rubber and the like can be used alone or as a mixture of two or more kinds.

In the resin layer of the present invention, (A) oil extension 1,
The blending ratio of 2-polybutadiene and (B) other thermoplastic polymer is such that the component (A) is 1 to 99 parts by weight, preferably 10 parts by weight.
To 90 parts by weight, the component (B) is 99 to 1 parts by weight, preferably 90 to 10 parts by weight (where (A) + (B) = 100).
Parts by weight]. By using such a (B) thermoplastic polymer in the above range, the vibration damping property suitable for the present invention,
It is possible to obtain a resin layer for a laminate and a gap-filling resin layer which are excellent in steel plate reinforcing property, sound absorbing property, sound insulating property, and sealing property.

(C) Crosslinking agent: Examples of the (C) crosslinking agent of the present invention include, for example, a combination of sulfur or a compound capable of generating sulfur by heating and a vulcanization accelerator, an organic peroxide, and an organic peroxide and a mixture thereof. At least one selected from the group of combinations of functional monomers can be mentioned.

As sulfur, powdered sulfur, precipitable sulfur, colloidal sulfur, surface-treated sulfur and the like can be used, and as a compound which produces sulfur by heating, tetramethylthiuram disulfide, tetraethylthiuram disulfide and the like can be used. Examples of the vulcanization accelerator used in combination with sulfur or a compound that produces sulfur by heating include tetramethylthiuram disulfide (TMTD) N-oxydiethylene-2-benzothiazolyl sulfenamide (O
BS), N-cyclohexyl-2-benzothiazylsulfenamide (CBS), dibenzothiazyl disulfide (MBTS), 2-mercaptobenzothiazole (M
BT), zinc di-n-butyl dithiocarbite (Zn
BDC), zinc dimethyldithiocarbide (ZnMD
C) etc. Here, the amount of the vulcanization accelerator used is usually 0.1 to 300 parts by weight, and preferably 0.1 to 300 parts by weight with respect to 100 parts by weight of sulfur or a compound which produces sulfur by heating.
5 to 200 parts by weight.

In the case of blending with organic peroxide, dicumyl peroxide, di-t-butylperoxy-3,3,5
-Trimethylcyclohexane, α, α'-di-t-butylperoxy-di-p-diisopropylbenzene, n-
Butyl-4,4-bis-t-butylperoxyvalerate, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane Etc. can be used. In the case of organic peroxide crosslinking, various polyfunctional monomers may be added at the same time. Specific examples of the polyfunctional monomer include trimethylolpropane trimeacrylate, ethylene glycol dimethacrylate, triallyl isocyanate and diallyl phthalate. In this case, the amount of the polyfunctional monomer used is
Usually, the molar ratio of the organic peroxide is 1/1 to 50/1,
Preferably 2/1 to 40/1 molar ratio (polyfunctional monomer /
Organic peroxide).

The amount of the (C) crosslinking agent used is from (A) to (B).
Generally, 0.001 to 100 parts by weight of the total amount of the components
It is 50 parts by weight, preferably 0.01 to 50 parts by weight.
If it is less than 0.001 part by weight, the crosslinking is insufficient and the rigidity (vibration damping property, steel plate reinforcing property) is impaired, and the desired resin layer cannot be obtained. On the other hand, when it exceeds 50 parts by weight, the storage stability is impaired and the laminate becomes brittle at the same time, and the object of the present invention cannot be achieved. The resin layer used in the present invention has the above (A) to
Although the component (C) is contained as an essential component, the following components (D) to (G) may be further added, if necessary.

(D) Softener: The (D) softener is an extender oil other than that used in (A) oil-extended 1,2-polybutadiene, and can be separately blended in the resin layer of the present invention. . Examples of the extending oil include the same types as the extending oil used in the component (A). In this case, the blending amount of the extender oil is 1 (A) to (B)
0 to 300 parts by weight, preferably 1 to 100 parts by weight
It is about 100 parts by weight.

(E) Inorganic filler: Examples of the (E) inorganic filler to be blended in the resin layer of the present invention include glass fiber, glass beads, potassium titanate, talc, mica, barium sulfate, carbon black, Examples thereof include silica, carbon-silica dual phase filler, clay, calcium carbonate, magnesium carbonate and the like. The compounding amount of the inorganic filler (E) is usually 0 to 300 parts by weight, preferably 1 to 200 parts by weight, based on 100 parts by weight of the total amount of the components (A) to (B). As the inorganic filler (E), it is preferable to use carbon black and silica in combination, use carbon-silica dual phase filler, or use carbon-silica dual phase filler in combination with carbon black and / or silica. .

The carbon black is manufactured by the furnace method and has a nitrogen adsorption specific surface area of 5
0~200m ² / g, DBP oil absorption amount 80~200ml
/ 100 g of carbon black is preferred, for example F
Examples include EF, HAF, ISAF, SAF classes. Among them, the high aggregation type is preferable.

The amount of carbon black blended is from (A) to
The total amount of the component (B) is 100 parts by weight, preferably 2 to 100 parts by weight, more preferably 5 to 95 parts by weight.

As the silica, for example, wet process silica,
Examples thereof include dry process silica and synthetic silicate silica. Silica having a small particle size has a high reinforcing effect, and those having a small particle size and a high aggregation type (high surface area, high oil absorption) have good dispersibility in the polymer and are preferable from the viewpoint of physical properties and processability. The average particle diameter of silica is a primary particle diameter, preferably 5 to 60 μm, more preferably 10 to 3
It is 5 μm. The specific surface area (BET method) is preferably 45 to 280 m ² / g.

The amount of silica blended is preferably 30 to 100 parts by weight of the total amount of components (A) to (B).
100 parts by weight, more preferably 30 to 95 parts by weight.

It is also possible to combine carbon black and silica in combination, and the mixing amount at that time is (A) to (total) as the total amount of carbon black and silica.
With respect to 100 parts by weight of the total amount of the component (B), preferably,
The amount is 30 to 100 parts by weight, more preferably 30 to 95 parts by weight.

By blending the above-mentioned carbon black and silica in the above-mentioned range in the resin layer of the present invention, these fillers having a reinforcing effect are finely dispersed uniformly in the polymer, and roll processability, extrudability, etc. It is possible to improve the mechanical strength of the molded product and further to provide excellent wear resistance.

In the resin layer, carbon-
Silica Dual Phase Filler (Dual Ph
Ase Fi11er: carbon-silica dual phase filler) may be blended alone or in combination with carbon black and / or silica. By blending the carbon-silica dual phase filler, even when used alone, the same excellent advantages as when carbon black and silica are used in combination can be obtained. Carbon-Silica Dual Phase
The filler is so-called silica-coated carbon black in which silica is chemically bonded to the surface of carbon black, and the product name is CRX200 from Cabot Corporation.
0, CRX2002, CRX2006. The blending amount of the carbon-silica dual phase filler is preferably 30 to 100 parts by weight, more preferably 30 to 95 parts by weight, based on 100 parts by weight of the total amount of the components (A) to (B). .

In the resin layer, carbon-silica dual phase filler can be used in combination with other fillers. The filler that can be used in combination is not particularly limited, and examples thereof include the above-mentioned carbon black and / or silica, clay, calcium carbonate, magnesium carbonate and the like. Of these, carbon black and / or silica are preferable. These fillers that can be used in combination include the carbon-silica dual phase filler and the total amount of the components (A) to (B) is 1
With respect to 00 parts by weight, preferably 3 to 100 parts by weight,
More preferably, it is 5 to 95 parts by weight.

When silica is blended as the above-mentioned filler, and when a carbon-silica dual phase filler is blended, it is preferable to blend a silane coupling agent, and the blending amount thereof is silica and / or carbon. -Silica Dual Phase Filler-100
The amount is preferably 1 to 20 parts by weight, more preferably 5 to 15 parts by weight, based on parts by weight.

As the silane coupling agent, a functional group capable of reacting with a silica surface such as an alkoxysilyl group in a molecule and a carbon-carbon double bond of a polymer such as a polysulfide, a mercapto group and an epoxy group can be reacted. Those having a functional group are also preferable. For example, bis- (3-triethoxysilylpropyl) tetrasulfide, bis-
(2-triethoxysilylethyl) tetrasulfide,
Examples thereof include 3-mercaptopropyltrimethoxysilane, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, and 3-triethoxysilylpropylbenzothiazoletetrasulfide. By using such a silane coupling agent, when carbon black and silica are used together as a filler, or when carbon-silica dual phase filler is used as a filler, its reinforcing effect is enhanced. Can be increased.

(F) Other additives: In the resin layer of the present invention,
Bituminous materials, flame retardants, antioxidants, lubricants, colorants, UV absorbers, antistatic agents, heat stabilizers, antioxidants, processing aids, light resistance (weathering), if necessary, within the range that does not impair the purpose.
Agents, antibacterial agents, etc. can be added.

Examples of the bituminous material that can be used in the present invention include straight asphalt, blown asphalt, which are often used in automobile damping materials, and compounds of these with inorganic substances. Examples of the flame retardant include a halogen-based flame retardant, a phosphorus-based flame retardant, and an inorganic-based flame retardant. However, considering a dioxin problem, a halogen-free phosphorus-based flame retardant or an inorganic flame-retardant is preferable. As the phosphorus-based flame retardant, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, resorcinol-bis- (diphenyl phosphate), 2-ethylhexyl diphenyl phosphate, dimethyl methyl phosphate, Examples thereof include triallyl phosphate and the like, and condensation products thereof, ammonium phosphate and condensation products thereof, and diethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate. Examples of the inorganic flame retardant include magnesium hydroxide, aluminum hydroxide, zinc borate, barium borate, kaolin clay, calcium carbonate, albite, basic magnesium carbonate, calcium hydroxide and the like. The above-mentioned flame retardants include so-called flame retardant assistants, which have a low flame retardancy-developing effect by themselves, but exhibit synergistically superior effects when used in combination with other flame retardants.

The resin layer of the present invention can have a long product life by using an antioxidant. Examples of the antioxidant used in this case include phenol-based antioxidants, sulfur-based antioxidants, amine-based antioxidants, and the like, and phenol-based antioxidants are particularly preferable. Specific examples of the above-mentioned phenolic antioxidant include styrenated phenol, 2,6-di-t-butyl-4-methylphenol, and 2,6-di-t-butyl-p.
-Ethylphenol, 2,4,6-tri-t-butylphenol, butylhydroxyanisole, 1-hydroxy-3-methyl-4-isopropylbenzene, mono-t
-Butyl-p-cresol, mono-t-butyl-m-cresol, 2,4-dimethyl-6-t-butylphenol, butylated bisphenol A, 2,2'-methylene-
Bis- (4-methyl-6-t-butylphenol),
2,2'methylene-bis- (4-ethyl-6-t-butylphenol), 2,2'-methylene-bis (4-methyl-6-t-nonylphenol), 2,2'-isobutylidene-bis- ( 4,6-dimethylphenol), 4,
4'-butylidene-bis- (3-methyl-6-t-butylphenol), 4,4'-methylene-bis- (2,6
-Di-t-butylphenol), 2,2-thio-bis-
(4-methyl-6-t-butylphenol), 4,4 '
-Thio-bis- (3-methyl-6-t-butylphenol), 4,4'-thio-bis- (2-methyl-6-butylphenol), 4,4'-thio-bis- (6-t- Butyl-3-methylphenol), bis (3-methyl-4)
-Hydroxy-5-t-butylbenzene) sulfide,
2,2-thio [diethyl-bis-3- (3,5-di-t
-Butyl-4-hydroxyphenol) propionate], bis [3,3-bis (4'-hydroxy-3'-
t-Butylphenol) butyric acid] glycol ester, bis [2- (2-hydroxy-5-methyl-3-t-butylbenzene) -4-methyl-6-t-butylphenyl] terephthalate, 1,3,5 -Tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) isocyanurate, N, N'-hexamethylene-
Bis (3,5-di-t-butyl-4-hydroxy-hydroxyamide), N-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenol) propionate, tetrakis [methylene-] (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,1'-bis (4-hydroxyphenyl) cyclohexane, mono (α-methylbenzene) phenol, di (α-methyl) Benzyl) phenol, tri (α-methylbenzyl) phenol, bis (2′-hydroxy-3′-t-butyl-5′-methylbenzyl) 4
-Methyl-phenol, 2,5-di-t-amylhydroquinone, 2,6-di-butyl-α-dimethylamino-
Examples thereof include p-cresol, 2,5-di-t-butylhydroquinone, and diethyl ester of 3,5-di-t-butyl-4-hydroxybenzylphosphoric acid. These antioxidants can be used alone or in combination of two or more kinds. The content of the antioxidant is 0.1 to 100 parts by weight of the total of the components (A) and (B).
It is preferably 10 parts by weight, particularly preferably 0.2 to 5 parts by weight.

Lubricants usable in the present invention include paraffinic and hydrocarbon resins generally used for imparting extrusion stability, metal soaps, fatty acids, fatty acid amides, fatty acid esters, and aliphatic metal salts. Is mentioned. As the colorant, an inorganic pigment or an organic pigment is appropriately selected and used. The blending ratio of the above-mentioned (F) other additives is not particularly limited, but with respect to the total amount of the above-mentioned components (A) to (B) of 100 parts by weight, respectively,
It is 0 to 80 parts by weight, preferably 1 to 70 parts by weight. The total amount of the components (D), (E) and (F) above is (A)
To 1 to 600 parts by weight, preferably 3 to 500 parts by weight, based on 100 parts by weight of the total of the component (B).

(G) Foaming agent: The foaming agent varies depending on the composition of the resin composition of the present invention. For example, as the foaming agent, an inorganic foaming agent or an organic foaming agent known per se can be used. Specific examples of the foaming agent include sodium bicarbonate, ammonium bicarbonate, sodium carbonate, ammonium carbonate, azodicarbonamide, dinitrosopentamethylenetetramine, dinitrosoterephthalamide,
Examples thereof include azobisisobutyronitrile, barium azodicarboxylic acid, and sulfonylhydrazides such as toluenesulfonylhydrazide. Among them, azodicarbonamide, dinitrosopentamethylenetetramine, and sulfonylhydrazides are more preferable. These foaming agents may be used in combination with known foaming aids such as urea and urea derivatives. The blending amount of the foaming agent depends on the type of polymer of the molding material and the use of the molded product,
1 to 100 parts by weight of the total amount of the components (A) to (B)
˜300 parts by weight, preferably 2 to 300 parts by weight.
When the amount of the foaming agent used is small, only a foam having a low expansion ratio can be obtained. On the other hand, when the amount of the foaming agent is more than 300 parts by weight, the amount of gas generated by the decomposition of the foaming agent increases and the gas pressure becomes abnormally high. The resulting foam may crack.
Further, as a method of foaming the composition, there is a method of containing a predetermined amount of carbon dioxide gas, water and the like and obtaining a foamed molded article by various molding methods. For example, in the case of injection molding, carbon dioxide gas is added to 100 parts by weight of the total amount of components (A) to (B).
The composition containing about 0.5 parts by weight does not foam due to high temperature and high pressure when it is in the measuring part in a plasticized and melted state, but when it is filled in the mold by injection molding, the pressure drops. The contained carbon dioxide gas is vaporized, and a molded product in which the inside of the molded product is foamed can be obtained.

The crosslinked product of the resin layer used in the laminate of the present invention has a hardness of preferably from 50 to 98, more preferably from 60 to 96, as measured by JIS K 6301 (C type).
Is. If it is less than 50, the vibration damping property and the steel plate reinforcing property do not satisfy the contents of this patent, while if it exceeds 98,
It is fragile and causes problems such as damage during actual use, which is not preferable. The hardness of the crosslinked product can be easily adjusted by the component (C). Further, the resin layer used in the present invention is excellent in shape following property with respect to the base layer. This shape-following property is measured by the method shown in the example, but is preferably 30 degrees to 1
Fits a given jig with a 20 degree vertex angle,
More preferably, it fits to a predetermined jig having an apex angle of less than 30 degrees to 120 degrees. When it exceeds 120 degrees, the shape following property is poor. This shape following property can be easily adjusted by the components (A) to (D) of this patent.

When preparing the resin composition of the present invention, a conventionally known kneader, extruder, vulcanizer or the like can be used. That is, the mixing method and mixing order of (C) a crosslinking agent, a filler, a softening agent, a foaming agent, etc., which are mixed with (A) oil-extended 1,2-polybutadiene and (B) another thermoplastic polymer are: For example, the components (A) to (B) are usually mixed in advance with an extruder or a Banbury mixer in an amount of 50 to 50.
A melt-blended product at 120 ° C., preferably 60 to 100 ° C., using a Banbury mixer or the like, a filler,
A method of adding (C) a crosslinking agent, (G) a foaming agent, etc. using a roll or the like after blending with a softening agent and the like can be mentioned.
It is not limited to this. The uncrosslinked compound thus obtained is molded into, for example, a sheet using a calender roll, an extruder or the like.

Laminate The laminate of the present invention has a non-crosslinked sheet obtained as described above attached to one or both sides of a base layer such as an automobile steel plate, and crosslinked (and foamed) in a heat medium. It is obtained by doing. As the heat medium, hot air, hot gas such as hot nitrogen, hot fluid such as hot liquid paraffin, and hot fine particles such as fine glass beads can be used. Among these, hot gas, particularly hot air is preferable. . Alternatively, heating by microwave may be used. The heating temperature is usually 120 to 25
0 ° C., preferably 140 to 180 ° C., heating time is 15
~ 120 minutes, preferably 20-90 minutes. On this occasion,
The thickness of the crosslinked (foamed) product is a dry film thickness and is usually 0.1 to 10.
It is about 20 mm, preferably about 0.2 to 15 mm. Since the laminate of the present invention contains the above-mentioned (A) oil-extended 1,2-polybutadiene, it has excellent fluidity and shape-following property, and has vibration damping property, sound absorbing property, sound insulating property, sealing property, and steel. It has the effect of metal reinforcement.

In the laminated body of the present invention, an asphalt layer may be interposed between the base layer and the resin layer. Examples of the asphalt include straight asphalt and asphalt for damping material to which blown asphalt is applied. By interposing the asphalt layer, it is possible to obtain the effects of vibration damping performance assistance and cost reduction.
The thickness of the asphalt layer is usually 0.1 to 20 mm, preferably 0.2 to 15 mm.

Gap Filling Method The gap filling method of the present invention includes, for example, one or both surfaces of a base layer such as a metal having one surface or an opposing surface.
Affixing the resin layer sheet containing the foaming agent of the present invention,
After that, the sheet surfaces are pasted together. Then
Under the same heating conditions as described above, crosslinking and foaming are performed to fill a predetermined gap. As the gap filling method of the present invention, in addition to this, a resin layer is filled in a gap such as a recess formed by the base layer by a means such as pasting or leaving, and the filled resin is heated under the same heating conditions as above. A method of cross-linking / foaming the layer, a method of compressing an existing open-cell sponge inside the resin layer to assist foaming, and in the case of vertical surface foaming, a base layer is applied to the bottom of the resin layer so that the resin layer can efficiently foam. Examples include methods to prevent dripping. According to the gap filling method of the present invention, the resin layer of the present invention fills the gap, and can exhibit sound insulation, sound absorption, sound insulation, and heat insulation effects. The expansion ratio of the foam is 1.5 to 30 times,
It is preferably 2 to 25 times.

The crosslinked or crosslinkable foamable laminate of the present invention is suitable as a sound insulating material, a sound insulating material, a vibration damping material, a steel plate reinforcing material, a gap filling material, a vibration damping material, a sealing material, and the like, and other uses. For example, it can be widely used for various linings, industrial products, automobile interior materials, road materials, building materials, daily necessities, exercise products, toys, and the like. Further, according to the gap filling method of the present invention, it is possible to easily fill the gap between the base layers by using the resin composition of the present invention having excellent fluidity and shape-following property.

[0076]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The various measurements in the examples are based on the following methods.

(1) 1,2-Vinyl bond content Determined by infrared absorption spectrum method (Morero method). (2) Weight average molecular weight gel permeation chromatography (GPC)
(Manufactured by Waters Co., 244 type) was used to determine the weight average molecular weight (Mw) in terms of polystyrene. (3) Melt flow index (MI) in accordance with ASTM DI238 (conditions: 150 ° C, 2
1.2N)

(4) Kneading workability The roll winding property was evaluated. Roll used: Lab 10 inch test roll machine Surface temperature = 90 ± 5 ° C Roll interval = 2.0mm Rubber width = 250mm Rotational speed Front roll: Back roll = 224: 20r
The pm evaluation standard was evaluated by the time until 1 kg of the compound cooled to room temperature was tightly wound around the roll. A: Wraps within 5 minutes. ◯: Wraps within more than 5 minutes and within 7 minutes. B: Wrapped within more than 7 minutes and within 10 minutes. X: It takes more than 10 minutes.

(5) Crosslinking hardness JIS K 6301 Spring hardness test (C type)
Compliant with. ◎: 70 or more ○: 60 to 69 Δ: 50 to 59 ×: less than 50 (6) Shape followability (index of fluidity of material) A steel plate having a length of 150 mm, a width of 100 mm, and a thickness of 1 mm,
What was processed into a chevron shape having apex angles of 30 °, 45 °, 60 °, 90 ° and 120 ° was used, and the sample was placed on this apex angle, and the state in which the sample fits the apex angle was determined. ⊚: Fits at an angle of 30 ° to less than 120 °, and there is no abnormality in the external shape of the sample. ◯: Fits at an angle of 45 ° to less than 120 °, and there is no abnormality in the external shape of the sample. Δ: Fits at an angle of 90 ° to less than 120 °, and there is no abnormality in the external shape of the sample. X: Does not fit at an angle of 120 ° or more.

(7) Foaming ratio (gap filling property: viscosity at the time of foaming is a major factor → fluidity has a large causal relationship) A value obtained by dividing the thickness of the sample after foaming by the thickness of the sample before foaming was used as a judgment index. ◎: 10 times or more ○: 5 times or more and less than 10 times △: 2 times or more and less than 5 times ×: Less than 2 times

Foaming appearance Foaming ratio Evaluation of the surface appearance of the sample ⊚: There is almost no trace of foaming gas escape, and a round chevron shape is taken. ◯: A bubble gas escape is noticeable, but a round chevron shape is taken. Δ: Blowing out of foaming gas is noticeable, and foaming form is also bad. X: Many gas escapes and almost no foaming.

(8) Adhesion of steel plate (oil surface) After applying rust preventive oil on a steel plate having a smooth surface (applied three times with gauze impregnated with oil so that the rust preventive oil does not drip), Place a sample 4 cm square and 2 mm thick, and in an atmosphere at 150 ° C. for 30 min. Perform processing (crosslinking foaming). Then, the adhesion of the steel plate of the sample left at room temperature for 2 hours was measured with a force of 3 kg / cm and 50 mm / min. It peeled off at the speed of and evaluated. ◎: Cohesive failure without interfacial peeling ○: Partial interfacial peeling and most cohesive failure △: Half interfacial peeling ×: All interfacial peeling

(9) Damping property SPC steel plate / foamed asphalt / resin layer = 0.8 mm thickness / 3 mm
Using the impedance method (JAS
Method) was used to determine the loss coefficient. A: 0.4 or more O: 0.3 to 0.39 B: 0.2 to 0.29 X: less than 0.2

(10) Heat sinkability (evaluation of cross-linking fluidity) A 100 mm square × 2 mm thick sample was placed on a 1 mm steel plate (with a support) in which 60 mmΦ was hollowed, and 150 ° C. × 30 m
in. The cross-linking fluidity is evaluated under the conditions of. Judgment was made based on the distance between the surface of the steel sheet adhered sample and the depressed apex. A: Exceeds 15 mm O: 10 to 15 mm B: 5 to 10 mm X: less than 5 mm

(11) Preparation of Samples Samples used in Examples and Comparative Examples are as follows. (1) Oil-extended RBA 1,2-vinyl bond content = 90%, weight average molecular weight 2
Extension oil = 30% by weight, extension oil = Fuji Kosan Fuccol Flex # 2050PN, MI = 11 (2) Oil-extended RB B 1,2-vinyl bond content = 90%, weight average molecular weight 1
50,000, extending oil amount = 30% by weight, extending oil = Fuji Kosan Fuccole Flex # 2050PN, MI = 15 (3) Oil extended RB C 1,2-vinyl bond content = 90%, weight average molecular weight 3
Extension oil = 30% by weight, extension oil = Fuji Kosan Fuccol Flex # 2050PN, MI = 5 (4) RB810 JSR Corporation, 1,2-polybutadiene (1,2-vinyl bond content = 90%, weight average molecular weight = 180,000, M
I = 2.9) (5) TR2000 JSR Co., Ltd. sales, styrene-butadiene block polymer (bonded styrene = 40%, multiblock type) (6) Liquid polybutadiene Idemitsu Petrochemical Co., Ltd. R-45M number average molecular weight 3,00
0-4,000 (7) SBR1507 JSR Corporation styrene-butadiene rubber (bound styrene = 23.5%, Mooney viscosity ML _{1 + 4} (100 ° C) (8) Zinc Hua Sakai Chemical Industry Co., Ltd. Zinc oxide 1 No. (9) Stearate Asahi Denka Co., Ltd. Melting point 71-72 ° C. White powder (10) Calcium carbonate Maruo Calcium Co., Ltd. Super S Oil absorption 23 cc
/ 100g (11) Talc Nippon Talc Co., Ltd. Hydrous magnesium silicate Talc
SW (12) FEF carbon black Asahi Carbon Co., Ltd. Asahi # 60 (13) Straight asphalt Showa Shell Co., Ltd. Penetration 60-80 (14) Diethylene glycol Nippon Shokubai Co., Ltd SG = 1.18 (15) Sulfur Made by Tsurumi Chemical Industry Co., Ltd. Kinka Inui Fine Sulfur (16) Vulcanization accelerator TMTD: Ouchi Shinko Co., Ltd. Knockseller TT MBT: Same as above Knockseller M MBTS: Same as above Knockseller DM (17) Peroxide Park Mill D : Nippon Oil & Fats Co., Ltd. Half-life 117 ° C Perhexa 3M: Same as above Half-life 90-95 ° C (18) High Cross M Seiko Chemical Co., Ltd., trimethylolpropane trimethacrylate (polyfunctional monomer)

Examples 1 to 6 and Comparative Examples 1 to 6 Examples 1 and 2 and Comparative Examples 1 and 2 shown in Table 1 relate to a laminate in which a resin restraining material (resin layer) is laminated on a base layer. 3 to 4 and Comparative Examples 3 to 4 shown in Table 3 relate to a laminated body in which a steel plate reinforcing material (resin layer) is laminated on a base layer, and Examples 5 to 6 and Comparative Examples 5 to 6 shown in Table 3 are gaps. The present invention relates to a laminated body formed by laminating a filler (resin layer) on a base layer. According to the compounding recipes shown in Tables 1 to 3, the compounding agents excluding the crosslinking agent, the crosslinking accelerator, and the (foaming agent) were kneaded at a temperature of 90 to 130 ° C for 5 minutes with a Banbury mixer, and then 70 to 90 ° C Temperature condition 1
An uncrosslinked resin layer was prepared by adding a predetermined amount with a 0 inch roll machine. The produced uncrosslinked resin layer was molded into a predetermined shape, placed on the base layer, and heat-treated in a heat circulation oven at 150 ° C. for 30 minutes to crosslink (foam) to obtain a laminate. The results are shown in Table 1.
~ 3.

Table 1 is an example of the composition of the resin restraining material resin layer. Examples 1 and 2 which are resin layers of the present invention are examples using the oil-extended RB-A of the present invention, and compared with the conventional RB810, kneading processability, heat dropability as an index of fluidity, It is preferable because of its excellent shape following property. The cross-linking hardness and vibration-damping property improved by cross-linking are good in Examples 1 and 2 and Comparative Examples 1 and 2, and there is no difference. Table 2 is an example of the compound of the steel plate reinforcing material resin layer. Examples 3 to 4, which are resin layers of the present invention, are examples using the oil-extended RB-B of the present invention, and are excellent in shape followability, which is an index of fluidity, as compared with the conventional RB810, and are preferable. Further, this example is superior to the comparative example in terms of the adhesiveness to the steel plate (oil surface) which is improved by crosslinking, which is preferable. The kneading processability and the cross-linking hardness are good in Examples 3 to 4 and Comparative Examples 3 to 4, and there is no difference. Table 3 is an example of compounding the resin layer for the gap filling sponge. Examples 5 to 6, which are the resin layers of the present invention, are examples using the oil-extended RB-C of the present invention. In the kneading processability as compared with the conventional RB810, the compound cooled to room temperature is tightly placed on a roll machine. The time required for wrapping around was more favorable. Examples 5 to 6 are excellent in cross-linking expansion ratio (the higher the fluidity, the more excellent the foamability), which is an index of fluidity, and are preferable, as compared with the corresponding Comparative Examples 5 to 6. The foaming appearance was good in both Examples and Comparative Examples, but Example 5 was particularly preferable. The steel plate adhesion that is improved by cross-linking is
Examples 5-6 were superior to Comparative Examples 5-6 and were preferable.

[0088]

[Table 1]

[0089]

[Table 2]

[0090]

[Table 3]

[0091]

The laminate of the present invention contains oil-extended 1,2-polybutadiene which has the excellent function characteristic of the conventional 1,2-polybutadiene and further has excellent fluidity and shape-following property. Since the resin composition is used, even a base layer having a complicated shape can be uniformly laminated, and has excellent vibration damping property, vibration damping property, sound insulating property, sound insulating property, sound insulating material, sound insulating material,
Suitable as damping material, steel plate reinforcing material, gap filling material, vibration damping material, sealing material, etc. Other applications include various linings, industrial products, automobile interior materials, road materials, building materials, daily necessities, exercise products. It can also be widely used for toys, toys, etc. Further, according to the gap filling method of the present invention, it is possible to easily fill the gap between the base layers by using the resin composition of the present invention having excellent fluidity and shape-following property.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Katsuaki Morino             2-11-24 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. (72) Inventor Jinji Junji             2-11-24 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. F-term (reference) 4F100 AB00C AK01B AK29B AL05B                       AL09B AM00B AN01B AN02B                       AT00A BA03 BA07 BA10A                       BA10B CA01B CA02B CA04B                       CA05B CA06B CA07B CA08B                       CA12B CA13B CA19B CA22B                       CA23B JB16B JH01 JH02                       JK11                 4J002 AC013 AC033 AC041 AC063                       AC073 AC083 AC123 AE052                       BB033 BB073 BB123 BB153                       BB173 BC033 BC043 BC053                       BC063 BD043 BD103 BD153                       BG063 BN073 BN153 BP013                       BP023 CB003 CF033 CF163                       CF193 CG013 CH073 CH093                       CK023 CL003 CN033 CP033                       DA046 EK036 EK046 EK056                       EK086 EV027 EV047 EV166                       EV167 EV277 EV327 FD010                       FD020 FD070 FD090 FD130                       FD146 FD157 FD170 FD320

Claims (8)

[Claims] 1. A resin layer containing (A) an oil-extended 1,2-polybutadiene, (B) a thermoplastic polymer other than the component (A), and (C) a cross-linking agent, which is laminated on the base layer. Laminate. 2. In the resin layer, the ratio of the components (A) to (C) is from 1 to 99 parts by weight of the component (A) and from 99 to the component (B).
1 part by weight (however, (A) + (B) = 100 parts by weight) is added in an amount of 0.001-
The laminate according to claim 1, which is 50 parts by weight. 3. The component (B) constituting the resin layer is (A)
The laminate according to claim 1 or 2, which is at least one selected from the group consisting of a thermoplastic resin, a thermoplastic elastomer, a natural rubber and a synthetic rubber other than the components. 4. The component (C) constituting the resin layer comprises sulfur or a combination of a compound capable of generating sulfur by heating and a vulcanization accelerator, an organic peroxide, and a combination of an organic peroxide and a polyfunctional monomer. The laminated body according to any one of claims 1 to 3, which is at least one selected from the group of. 5. The resin layer further comprises 100 parts by weight of the total amount of the components (A) and (B),
(D) 0 to 300 parts by weight of softening agent, (E) 0 to inorganic filler
300 parts by weight, (F) bituminous material, flame retardant, antioxidant, lubricant, colorant, foaming agent, ultraviolet absorber, antistatic agent, heat stabilizer, antiaging agent, processing aid, light resistance (weathering agent) And at least one other additive selected from the group of antibacterial agents 0-8
The laminate according to any one of claims 1 to 4, wherein 0 part by weight is blended, and the total amount of the components (D), (E) and (F) is blended in the range of 1 to 600 parts by weight. . 6. The resin layer further comprises 100 parts by weight of the total amount of the components (A) and (B),
(G) 1 to 300 parts by weight of a foaming agent is blended.
[5] The laminated body according to any one of [5] to [5]. 7. The laminate according to claim 1, wherein an asphalt layer is interposed between the base layer and the resin layer. 8. A gap filling method, characterized in that the gap formed from the base layer is filled with the resin layer according to claim 6, and is crosslinked and foamed.