JP4460426B2 - Resin composition, resin sheet and laminated material - Google Patents

Description

  The present invention relates to a resin composition, a resin sheet, and a laminated material, and is used as various structural members such as general machines, building structures, vehicles, home appliances, OA equipment, and containers.

  In recent years, noise and vibration generated from transportation and factories have become obvious as social problems with the development of transportation and the approach of housing to the factory area. There is a tendency to regulate noise and vibration as the purpose. In addition, at home, in order to reduce the noise of reading and writing even in home appliances that have reduced noise and vibration, as well as precision electronic parts such as personal computers, in order to pursue comfort, resonance due to electromagnetic noise and vibration is prevented. A member that can be used is widely demanded.

  In order to respond to such social needs, it is required to impart vibration damping performance to a member that includes a noise source and a vibration source and to further improve its function. Here, the damping performance is a function that absorbs the vibration energy of the member that generates noise and vibration and converts it into thermal energy, attenuates the vibration speed or vibration amplitude, and reduces acoustic radiation and vibration. It is. As one of the vibration damping materials exhibiting such performance, a composite vibration damping material having a multilayer structure in which a viscoelastic intermediate layer is sandwiched between metal materials has been proposed. This composite damping material is considered as a vibration reducing member for automobile oil pans, engine covers, home appliances and other metal processing equipment, and as a structural member for precision equipment such as OA equipment for which vibration prevention is desired. Has been adopted.

  In general, the vibration damping performance of such a vibration damping material depends on the performance of the viscoelastic intermediate layer constituting the intermediate layer. This damping performance can be evaluated by a loss factor (tan δ (δ is the loss angle), a measure for converting external vibration energy into heat energy by internal friction), where tan δ is a certain temperature (specifically, glass Peak characteristics are shown at the transition temperature (Tg). That is, it is known that it is most effective to use near this peak characteristic temperature.

  Conventionally, as a viscoelastic intermediate layer of such a vibration damping material, a polyester resin alone (Patent Document 1), or a material added with a plasticizer (Patent Document 2), an organic peroxide is blended with polyester. There are known techniques for using a crosslinked material (Patent Documents 3 and 4), a polyurethane foam resin (Patent Document 5), and a polyamide resin alone (Patent Document 6). However, since both of these use a single resin, the temperature range for exhibiting vibration damping properties is limited.

  Damping materials are often required to exhibit damping properties in a wide temperature range without depending on the use environment temperature. For example, when used as a vehicle component such as an automobile, the assumed operating temperature range is -50 to 180 ° C., and it is difficult to stably maintain the vibration damping performance with a single resin. As a method of expanding the effective temperature range of vibration damping properties, technologies for combining resins with different Tg are being studied. Specifically, 1) a method of blending multiple resins, 2) multiple resins A method of copolymerization and 3) a method of laminating a plurality of resin films or sheets are known. Among these, the blending method 1) is the most preferable method from the viewpoints of economy and moldability.

  Patent Documents 7 and 8 disclose a method of blending two types of polyesters having different glass transition temperatures as methods for expanding the vibration damping temperature range by the blending method. However, since these are two-component systems and exhibit damping properties only in the temperature range near each Tg of the constituent resins, the use temperature range could not be sufficiently widened. As a method for solving this drawback, Patent Document 9 discloses a thermoplastic polyester elastomer, a resin composition obtained by blending rubber and polyamide or polybutylene terephthalate, and Patent Document 10 discloses a polyester resin and an addition polymerization block. A polyester resin composition in which a copolymer, a polyester block copolymer, a polypropylene resin, and a tackifying resin are blended is disclosed. Any of these compositions is a resin composition composed of three or more resins having different Tg and can exhibit vibration damping ability in a wide temperature range. However, in the resin composition, compatibility with each resin is poor, and the other two components adhere and coalesce in the main component, so that a very large domain may be formed and dispersed. As a result, in the resin composition, the mechanical strength as a vibration damping material may be reduced, or it may be difficult to make the resin thin or thin.

  In addition, since all of the above disclosed technologies express the vibration damping property using the viscoelastic effect, if the resin is made rigid, the storage elastic modulus increases and the vibration damping property is sacrificed. If the loss elastic modulus is increased with emphasis on, the resin becomes liquid and the rigidity decreases. That is, a technique that combines vibration damping and rigidity has not been disclosed in these documents. As a result, in fields where storage in a limited space is required, such as precision electronic components such as personal computers, designs and component sizes are often limited. Furthermore, there are cases where parts that are required to be downsized cannot be used because even if the vibration damping property can be exhibited, bending occurs and the dimensional system is sacrificed.

  Further, Patent Document 11 discloses a resin composition excellent in impact resistance and adhesion to a metal, but the resin composition sometimes has low rigidity and barrier properties.

Japanese Patent Laid-Open No. 50-143880 JP 51-93770 JP 51-41080 JP-A-51-83640 JP 51-91981 JP 56-159160 JP-A-62-295949 Japanese Unexamined Patent Publication No. 63-202446 JP-A-8-176352 JP-A-9-227766 International Patent Publication No. WO99 / 27026

  The present invention solves the problems of the above conventional resin composition, exhibits vibration damping performance in a wide temperature range, and has moldability that can be easily made thin and thin, and further provides vibration damping and rigidity. The object is to provide a resin composition having excellent adhesion and adhesion to metal and a resin composition having both impact resistance, rigidity and barrier properties. Furthermore, it aims also at providing the resin sheet containing the said resin composition, the laminated material using this resin composition, etc.

The present invention has been found as a result of intensive studies on a resin composition that can exhibit a certain damping performance in a temperature range of -50 to 180 ° C. and a resin composition that has both impact resistance, rigidity, and barrier properties. The following contents are summarized.
(1) terpolymer of α-olefin, α, β-unsaturated carboxylic acid ester and glycidyl ester of α, β-unsaturated carboxylic acid, glycidyl ester of α-olefin and α, β-unsaturated carboxylic acid Or at least four components of a vinyl polymer, a polyester resin, a rubber-like elastic resin and an inorganic layered compound selected from an ionomer resin , the vinyl polymer, The mass% of the polyester resin and the rubber-like elastic body are equal to each other, or the mass% of the vinyl polymer, the polyester resin, and the rubber-like elastic body is vinyl polymer: polyester resin: rubber-like elastic body = 34 to Resin group in which 80:10 to 33:10 to 33, the addition amount of the inorganic layered compound is 0.1 to 60% by mass of the total resin mass, and the inorganic layered compound is an organically modified inorganic layered compound Thing.
(2) The resin composition according to (1), wherein the vinyl polymer is a matrix, and the polyester resin and the rubber-like elastic body are independently dispersed therein.
(3) The resin composition according to (1), wherein the rubber-like elastic body is a matrix, and polyester encapsulated with the vinyl polymer is dispersed in the matrix.
(4) before SL rubbery elastomer resin is one or both of the polyolefin-based elastomer, or a polystyrene-based elastomer (1) resin composition according to any one of - (3).
(5) vinyl-polymer, according to the resin composition 100 parts by weight of polyester resin and the rubbery elastomer resin, either the tackifier contains 0.1 to 60 parts by weight (1) to (3) Resin composition.
( 6 ) The resin composition according to (1), wherein the inorganic layered compound has a particle size of 1 μm or less and is dispersed in the matrix resin.
( 7 ) The resin composition according to (1) or ( 6 ), wherein the inorganic layered compound is one or more selected from organically modified mica group minerals, smectite minerals, or vermiculite.
( 8 ) A vibration damping material obtained by molding the resin composition according to any one of (1) to ( 7 ) by any one of injection molding, extrusion molding, and blow molding.
( 9 ) A sealing material obtained by molding the resin composition according to any one of (1) to ( 7 ) by any one of injection molding, extrusion molding, and blow molding.
(1 0 ) The resin composition according to any one of (1) to ( 7 ) is molded alone, or laminated in combination with one or both of the other resin composition or adhesive. Resin sheet.
(1 1 ) A laminated material obtained by laminating members on at least one side of the resin sheet according to (1 0 ).
(1 2 ) The laminated material according to (1 1 ), wherein the member is a metal material.

The resin composition of the present invention is a resin composition containing at least four components of a vinyl polymer containing a unit having a polar group of 1% by mass or more, a polyester resin, a rubbery elastic resin, and an organically modified inorganic layered compound. is there. By containing the above three resin components, it has excellent chemical resistance and can exhibit vibration damping properties and adhesive properties over a wide temperature range. Furthermore, rigidity, mechanical strength, and storage elastic modulus can be increased by containing an inorganic layered compound. At the same time, the dispersed inorganic layered compound rubs against the external vibration and dissipates energy, so the loss elastic modulus can be increased, and the increase in storage elastic modulus is complemented by the increase in loss elastic modulus, thereby improving the vibration damping property. Can hold. Furthermore, it contains a polyester resin which is a rubber component and a plastic component, and is excellent in compatibility between the rubber-like elastic body and the polyester resin by the vinyl polymer, and can exhibit excellent impact resistance. In addition, since it contains an organically modified inorganic layered compound, it is excellent in rigidity and barrier properties. As a result, it can also be used as a plastic material having impact resistance, rigidity and barrier properties.

  Since the vibration damping material of the present invention is formed by molding the resin composition of the present invention, vibration damping, chemical resistance, adhesiveness, rigidity, mechanical strength, thin film workability, adhesion to metal in a wide temperature range Can combine sex. As a result, it can be effectively used as a noise / vibration suppression material for vehicles, buildings, general machines and the like. Moreover, the sealing material of this invention can be used conveniently for various packing materials using favorable chemical resistance and adhesiveness.

  Furthermore, the resin sheet of the present invention has the above-mentioned characteristics because it is composed of a single layer or a laminate of the resin composition of the present invention.・ Can also be used as a damping laminate sheet.

  In addition, since the laminated material of the present invention has at least one layer of the resin sheet of the present invention laminated, it can be widely used as a vibration damping member or a seal member, such as an automobile roof, body, bumper, bonnet, door panel, floor panel, Wheel covers, oil pans, instrument panels, air spoilers, automobile parts such as various motors, copiers and printers, toys, containers, home appliances / computers, washing machines, refrigerators, CD / MD / LD / DVD players It can be used for OA / AV equipment parts such as VTRs, speakers, mobile phones, etc., electrical parts such as housings, architectural relations such as hinged doors and vibration-isolating rubber, and parts such as ships and railway vehicles.

  Furthermore, since the laminated material is formed by laminating the resin composition layer of the present invention, it is possible to achieve both vibration damping properties and rigidity that were difficult in the prior art. As a result, even if it is processed into a fine part, it is possible to prevent bending due to rigidity, maintain a dimensional system, and develop vibration damping properties. Therefore, it can be suitably used for a hard disk cover, particularly a miniaturized hard disk cover. Further, since the laminated material itself has a vibration damping ability, the vibration damping ability can be expressed without separately attaching a vibration damping seal. As a result, when this laminated material is used in a suspension of a hard disk drive, the vibration-proofing sticker attached to the outside can be omitted and the weight can be reduced, and at the same time, the size can be reduced with good dimensional accuracy. Therefore, the present laminated material can be particularly suitably used for a suspension of a hard disk drive.

  Hereinafter, the resin composition, the resin sheet, and the vibration damping material of the present invention will be described in detail.

The resin composition for a vibration damping material of the present invention contains at least four components of a vinyl polymer containing 1% by mass or more of a unit having a polar group, a polyester resin, a rubbery elastic resin, and an organically modified inorganic layered compound. It is a resin composition. By containing the above three resin components, it has excellent chemical resistance and can exhibit vibration damping properties and adhesive properties over a wide temperature range. That is, rubber-like elastic resin is mainly used in the low temperature range (-50 ° C to room temperature), vinyl polymer is mainly used in the medium temperature region (room temperature to 60 ° C), and polyester resin is mainly used in the high temperature region (60 to 180 ° C). Therefore, even if the resin composition is single, stable vibration damping performance can be maintained over a wide temperature range. Furthermore, rigidity, mechanical strength, and storage elastic modulus can be increased by containing an inorganic layered compound. At the same time, the dispersed inorganic layered compound rubs against the external vibration and dissipates energy, so the loss elastic modulus can be increased, and the increase in storage elastic modulus is complemented by the increase in loss elastic modulus, thereby improving the vibration damping property. Can hold. Furthermore, since the polyester resin which is a rubber component and a plastic component is contained, and the compatibility between the rubber-like elastic body and the polyester resin is excellent due to the vinyl polymer, excellent impact resistance can be expressed. In addition, since it contains an organically modified inorganic layered compound, it is excellent in rigidity and barrier properties.

The resin composition of the present invention only needs to contain at least four components of a vinyl polymer containing a unit having a polar group of 1% by mass or more, a polyester resin, a rubbery elastic resin, and an organically modified inorganic layered compound. The resin dispersion structure and the resin dispersed phase particle size are not particularly specified, but the preferred resin dispersion structure when used as a vibration damping material or a sealing material is the following two structures (a) and (b) . When the resin composition of the present invention is used as a plastic material having impact resistance, rigidity, and barrier properties, the resin structure (c) is preferable.

  (a) A structure in which a polyester resin phase and a rubber-like elastic phase are dispersed independently in a vinyl polymer matrix containing 1% by mass or more of units having a polar group.

  (b) A structure in which a polyester resin phase encapsulated with a vinyl polymer containing 1% by mass or more of a unit having a polar group is dispersed in a rubber-like elastic resin matrix.

  (c) A structure in which a rubber-like elastic resin phase encapsulated with a vinyl polymer containing 1% by mass or more of a unit having a polar group in a polyester resin matrix is dispersed.

  By making the matrix a vinyl copolymer or rubber-like elastic body, it is easy to develop vibration damping characteristics and adhesive characteristics. On the other hand, the rigidity can be further improved by using a polyester resin as a matrix. And, by forming the structure of (a) to (c), it is thermodynamically stable, the dispersed phase can be controlled uniformly and finely, and can be easily processed into a thin film molded body like a film It becomes. Furthermore, in order to ensure the mechanical strength of a molded body or sheet obtained from this resin composition, the dispersed phase diameter is preferably 4 μm or less. From the viewpoint of enabling thin film forming on the order of several μm, it is desirable that the dispersion diameter is 2 μm or less, more preferably 1 μm or less. Furthermore, the dispersion diameter is preferably 5 nm or more. If it is less than 5 nm, the dispersed phase cannot sufficiently dissipate vibration energy in the vicinity of the Tg of the dispersed phase, and may exhibit vibration damping performance only near the Tg of the matrix, or the shock absorption capacity may be insufficient. . In order to sufficiently secure the vibration damping performance and impact resistance of the dispersed phase, 10 nm or more, more preferably 50 nm or more is desirable.

  The structure of the above (a) of the present invention is a structure in which a polyester resin phase and a rubber-like elastic body phase are dispersed without contacting in a vinyl polymer matrix containing 1% by mass or more of units having a polar group. It is. Specifically, the structure is schematically shown in FIG. A method for confirming such a dispersion structure is not particularly limited as long as it is a method that can identify each resin phase and its morphology, and the following method is simple and preferable as a specific method. After the resin composition is cut under liquid nitrogen, or a microtome is cut to produce an ultrathin slice, contrast between the resins can be created by using characteristic differences such as dyeability and etching properties. Examples include a method of observing with an electron microscope after chemical treatment, a method of observing the smooth surface of the resin composition with a scanning probe microscope, and identifying each phase using frictional force and chemical bonding force. It is done. Here, the state where there is no contact is recognized as being dispersed independently when the polyester resin phase and the rubber-like elastic body phase are not in contact at all clearly from the image identifying each phase. it can. Further, even if a part of the recognized polyester dispersed phase is in contact with the rubber-like elastic body, if the proportion of the number of dispersed phases in contact is 20% or less of the total number of polyester phases, the polyester dispersed phase is substantially independently dispersed. Can be judged. The same applies to the rubbery elastic resin phase.

The structure of (b) of the present invention is a structure in which a polyester resin phase whose surface is covered with a vinyl polymer phase containing 1% by mass or more of polar group-containing units is dispersed in a rubber-like elastic resin matrix. It is. Specifically, the structure is shown schematically in FIG. Specific examples of the identification method include the methods exemplified above. From the image in which each phase is identified, the phase that is clearly in contact with the surface of the polyester resin phase is 1% by mass or more of the polar group-containing unit. In the case of the vinyl polymer phase to be recognized, it can be recognized as the structure (b). Further, when the identified image is subjected to two-dimensional image processing, the total interface length between the polyester resin / vinyl polymer is L ₁ , and the total interface length of the polyester resin / rubber-like elastic body is L ₂ , L ₁ / (L ₁ + When L ₂ ) is 0.8 or more, it can be recognized that the vinyl polymer phase substantially covers the polyester resin phase.

  Further, the structure (c) is a structure in which a rubber-like elastic resin phase whose surface is covered with a vinyl polymer phase containing 1% by mass or more of polar group-containing units is dispersed in a polyester resin matrix. Specifically, it is the structure schematically shown in FIG. 3, and can be identified by the same method as the structure of (b) above. Similarly, when 80% or more of the total interface length of the rubber-like elastic body is the interface with the vinyl polymer, it is recognized that the vinyl polymer phase substantially covers the rubber-like elastic body phase. Can do.

  The dispersion diameter and dispersion state of the layered inorganic compound contained in the resin composition of the present invention are not particularly specified. However, the inorganic layered compound is preferably dispersed in the resin with a particle size of 1 μm or less. If the particle size of the inorganic layered compound is more than 1 μm, the interface strength with the resin is insufficient and brittle fracture may occur. More preferably, the dispersion diameter of the inorganic layered compound is 200 nm or less, more preferably 100 nm or less, more preferably 50 nm or less, and most preferably, resin molecules intercalate between the layers of the layered inorganic compound, and the inorganic layered compound is a unit. It is preferable that the particle diameter is equal to the layer thickness and is dispersed in the resin phase. The smaller the particle size of the dispersed inorganic layered compound, the greater the interface area with the resin phase and the aspect ratio. Therefore, even when a small amount of the inorganic layered compound is added, the effect of improving the rigidity and mechanical strength is increased. At the same time, the contact opportunities between the dispersed inorganic layered compounds also increase, and when vibration is applied from the outside, the amount of energy dissipation due to friction between the inorganic layered compound layers is increased, and the vibration damping property can be improved. Furthermore, since the substance from the outside must enter the resin layer more detoured, the barrier property can be improved.

  The dispersion state of the inorganic layered compound is not particularly defined, and may be dispersed in the entire resin, or may be dispersed in any part of the matrix phase or the dispersed phase, and the dispersion is unevenly distributed. Also good. Most preferred is a structure in which the inorganic layered compound is uniformly dispersed in the matrix resin. In many cases, the continuous phase dominates the bulk mechanical properties, and by uniformly dispersing the layered inorganic compound in the matrix phase, the effect of improving rigidity and mechanical strength is easily exhibited.

  Examples of the method for confirming the dispersion diameter and dispersion state of the inorganic layered compound include a method of directly observing with an electron microscope, a method of calculating a distance between planes from a peak of a specific crystal plane by wide-angle X-ray diffraction, and the like. In wide-angle X-ray diffraction, if the resin molecules intercalate between the layers of the layered inorganic compound, the crystal plane peak shifts to the low angle side or becomes broad, so the degree of intercalation by the resin molecules can be determined and dispersed. The state can be predicted. In particular, when the crystal peak disappears, it means that the intercalation of the inorganic layered compound between the resin molecules has progressed and the layer has peeled off, and the inorganic layered compound is dispersed in the resin at the unit layer thickness. Corresponds to the structure.

The composition ratio of the resin composition for damping material of the present invention is such that the mass percentages of the vinyl polymer, the polyester resin, and the rubber-like elastic body are the same, or the vinyl polymer, the polyester resin, and the rubber. The mass% of the elastic material is vinyl polymer: polyester resin: rubbery elastic material = 34-80: 10-33: 10-33, and the composition ratio of each resin component is controllability to a desired resin structure It is determined by the balance between (viscosity and composition balance) and performance. In particular, the resin that is to be the matrix component must be the resin component with the highest content, and is preferably at least 34% by mass of the total resin composition. In order to prevent flow at a high temperature, the polyester resin is desirably contained in an amount of 10% by mass or more, preferably 20% by mass or more based on the total resin composition.

In particular, when used as a vibration damping material, the vinyl polymer is further contained in an amount of 10% by mass or more, preferably 20% by mass or more of the total resin composition in order to sufficiently exhibit the damping performance at a medium temperature. It is desirable. Therefore, as a vibration damping material, the composition ratio of the resin composition of the present invention is mass% and is rubbery elastic resin: vinyl polymer: polyester resin = 34-80: 10-33: 10-33. It is preferable when used. Similarly, when used as a sealing material, the composition is preferably used in order to exhibit adhesiveness.

Furthermore, the addition amount of the inorganic layered compound, Ru 0.1 to 60% by mass of the total resin weight. If it is less than 0.1% by mass, a sufficient improvement effect of mechanical strength and rigidity is hardly exhibited. On the other hand, if it exceeds 60% by mass, it may become brittle.

The rubber-like elastic resin used in the present invention is a resin that exhibits the properties of a rubber elastic body at room temperature, and is a resin having a tensile elastic modulus at room temperature of 49 kN / cm ² or less. As long as the tensile elastic modulus is a resin in the region, the glass transition temperature (Tg, sample amount of about 10 mg, temperature increase rate 10 ° C / min differential thermal analyzer (DSC) is not particularly limited. A rubber-like elastic resin having a measurement) of −50 ° C. or more and 50 ° C. or less, a Young's modulus at room temperature of 1000 MPa or less, and a breaking elongation of 50% or more is preferable. If the Tg of the rubber-elastic part is more than 50 ° C., the Young's modulus at room temperature is more than 1000 MPa, and the elongation at break is less than 50%, sufficient vibration damping performance and mechanical strength cannot be expressed. In order to ensure vibration damping performance and mechanical strength in a low temperature range, Tg is preferably 10 ° C. or lower, more preferably 0 ° C. or lower. In order to ensure more reliable vibration damping performance and mechanical strength, the Young's modulus at room temperature should be 100 MPa or less, more preferably 10 MPa or less, and the elongation at break should be 100% or more, more preferably 300% or more. Preferably there is.

  Specific examples of rubber-like elastic resins include the elastomers described in Shinzo Yamashita / Mitsuei Komatsu, Rubber and Elastomer Research Group “Rubber and Elastomer Utilization Notes” (Industry Research Committee, Inc., published in 1985), etc. Is applicable. More specifically, there can be mentioned a non-polar elastomer consisting mostly of C—C, C═C and C—H bonds, and a polar elastomer containing oxygen, nitrogen and the like in the constituent units.

  Specific examples of nonpolar elastomers include styrene elastomers and olefin elastomers. More specifically, a styrene elastomer is exemplified by a resin in which the hard segment is polystyrene and the soft segment is a nonpolar rubber-like elastic body, or a resin in which a nonpolar rubber-like elastic body phase is dispersed in a styrene matrix. Styrene copolymer (SBS), its hydrogenated styrene-ethylene / butylene-styrene copolymer (SEBS), styrene-isoprene-styrene copolymer (SIS), butadiene-styrene copolymer (SBR), Examples thereof include styrene-ethylene / propylene copolymer (SEP), rubber-modified styrene (HIPS), and the like.

Examples of the olefin elastomer include polyolefin resin, polyisoprene (IPR), polybutadiene (BR), hydrogenated polybutadiene, and the like. Illustrative of olefin resin, the following general formula (i)
-R ¹ CH-CR ² R ^3- … (i)
(In the formula, R ¹ and R ³ each independently represents an alkyl group having 1 to 12 carbon atoms or hydrogen, and R ² represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, or hydrogen.)
It is resin which has a repeating unit represented by these. Examples of the repeating unit include a monomer unit exemplified by the formula (ii) described later, which is one kind of monomer unit or two or more kinds of copolymers.

  Examples of the polyolefin resin include polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyoctenylene and the like which are homopolymers of α-olefin. Examples of the polyolefin resin include polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyoctenylene and the like which are homopolymers of α-olefin. Further, the copolymer of the above unit includes ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-propylene-1,4-hexadiene copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer. Examples thereof include aliphatic polyolefins such as coalescence, aromatic polyolefins such as styrene-based polymers, and the like, but are not limited thereto, as long as the above repeating units are satisfied. These resins may be used alone or in combination of two or more.

  Moreover, the polyolefin resin should just have said olefin unit as a main component, and the vinyl monomer, polar vinyl monomer, and diene monomer which are the substituted bodies of said unit may be copolymerized by the monomer unit or the resin unit. The copolymer composition is 50 mol% or less, preferably 30 mol% or less with respect to the unit. If it exceeds 50 mol%, the properties as a polyolefin resin such as dimensional stability will deteriorate, and it will be difficult to control to a desired structure. Examples of polar vinyl monomers include the unsaturated polar monomers listed above. Examples of the diene monomer include butadiene, isoprene, 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, cyclopentadiene, 1,4-hexadiene, and the like.

  In the case of a nonpolar elastomer, it is desirable that a polar group described later is introduced at 15% by mass or less in order to ensure adhesion with a metal. As the polar group, an acid anhydride group or an epoxy group is most desirable from the viewpoint of improving adhesion.

  More specifically, polar elastomers are exemplified by polyester elastomer (polyester for hard segment, polyester or polyether for soft segment), polyamide elastomer (polyamide for hard segment, polyester or polyether for soft segment), acrylic elastomer (core: butadiene) Alternatively, siloxane, shell: polymethyl methacrylate, methyl methacrylate-styrene copolymer), acrylonitrile-containing elastomer (styrene-acrylonitrile-butadiene copolymer, acrylonitrile-butadiene rubber) and the like can be mentioned.

A vinyl polymer containing 1% by mass or more of a unit having a polar group used in the present invention is 1% by mass of a unit having a group to which an element having a Pauling electronegativity difference of 0.39 (eV) ^0.5 or more is bonded. The vinyl polymer contained above. If the unit having a polar group is less than 1% by mass, vibration damping may be deteriorated.

Specific examples of groups in which Pauling's electronegativity difference is 0.39 (eV) ^0.5 or more are combined are: -CO-, -C = O, -COO-, epoxy group, C ₂ O ₃ , C ₂ O ₂ N—, —CN, —NH ₂ , —NH—, —X (X; F, Cl, Br), —SO ₃ — and the like can be mentioned. Moreover, you may have the acid radical ion neutralized with the metal ion as a polar group. In this case, examples of metal ions include Na ⁺ , K ⁺ , Li ⁺ , Zn ²⁺ , Mg ²⁺ , Ca ²⁺ , Co ²⁺ , Ni ²⁺ , Pb ²⁺ , Cu ²⁺ , Mn ^{2+ Monovalent} , divalent or trivalent metal cations such as Ti ³⁺ , Zr ³⁺ and Sc ³⁺ .

Specific examples of units having a polar group include vinyl alcohol as an example having a -CO- group, vinyl chloromethyl ketone as an example having a -C = O group, acrylic acid and methacrylic acid as examples having a -COO- group. , Vinyl acetate such as vinyl acetate and vinyl propionate and its metal salts or ester derivatives, examples having an epoxy group include α, β-unsaturated acids such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaconate Glycidyl ester, maleic anhydride as an example having a C ₂ O ₃ group, maleic anhydride imide derivative as an example having a C ₂ O ₂ N- group, acrylonitrile as an example having a —CN group, and an —NH ₂ group acrylic amines examples include vinyl chloride examples with acrylamide, a -X group as an example having a -NH- group, -SO ₃ - example having the group Styrene sulfonic acid, and the like, and compounds in which all or part of these acidic functional groups are neutralized with the above metal ions are included, and these are contained alone or in plural in the vinyl polymer. May be. The unit having a polar group contained in the vinyl polymer may be a unit having a group to which an element having a Pauling electronegativity difference of 0.39 (eV) ^0.5 or more is bonded, and is limited to the above specific examples. It is not a thing.

  The vinyl polymer used in the present invention is a vinyl polymer containing 1% by mass or more of units having a polar group, and examples of such vinyl polymers include the above-mentioned polar group-containing vinyl unit alone or 2 Examples thereof include polymers of more than one type, and copolymers of the above polar group-containing vinyl units and nonpolar vinyl monomers represented by the following general formula (ii).

CHR ¹ = CR ² R ³ … (ii)
(In the formula, R ¹ and R ³ each independently represent an alkyl group having 1 to 12 carbon atoms or hydrogen, and R ² represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, or hydrogen.)
Specific examples of the nonpolar vinyl monomer represented by the general formula (ii) include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1 -Α-olefins such as dodecene, aliphatic vinyl monomers such as isobutene and isobutylene, styrene monomers, o-, m-, p-methylstyrene, o-, m-, p-ethylstyrene, t-butylstyrene, etc. And aromatic vinyl monomers such as addition polymer units of styrene monomers such as alkylated styrene and α-methylstyrene.

  Examples of the homopolymer of the polar group-containing unit include polyvinyl alcohol, polymethyl methacrylate, polyvinyl acetate and the like. Examples of copolymers of polar group-containing units and nonpolar vinyl monomers include ethylene-methacrylic acid copolymers, ethylene-acrylic acid copolymers, ethylene-vinyl acetate copolymers, and copolymers thereof. Ionomer resin, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-methacrylic acid obtained by neutralizing some or all of the acidic functional groups with metal ions Ethyl copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-maleic anhydride copolymer, butene-ethylene-glycidyl methacrylate copolymer, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene- Maleic anhydride copolymers, etc., and all or part of their acidic functional groups are gold Ionomer resins neutralized with ions.

  As ionomer resins, known ionomer resins can be widely used. Specifically, a copolymer of a vinyl monomer and an α, β-unsaturated carboxylic acid is obtained by neutralizing a part or all of the carboxylic acid in the copolymer with a metal cation. Examples of vinyl monomers include the above α-olefins and styrene-based monomers, and examples of α, β-unsaturated carboxylic acids include α, β-unsaturated carboxylic acids having 3 to 8 carbon atoms. Acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic acid monomethyl ester, maleic anhydride, maleic acid monoethyl ester and the like.

Examples of neutralizing metal cations are Na ⁺ , K ⁺ , Li ⁺ , Zn ²⁺ , Mg ²⁺ , Ca ²⁺ , Co ²⁺ , Ni ²⁺ , Pb ²⁺ , Cu ²⁺ , Mn ^{2+. Monovalent} , divalent or trivalent metal cations such as Ti ³⁺ , Zr ³⁺ and Sc ³⁺ . Further, a part of the remaining acidic functional group that is not neutralized with the metal cation may be esterified with a lower alcohol.

  Specific examples of the ionomer resin include a copolymer of ethylene and an unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid, or a copolymer of ethylene and an unsaturated dicarboxylic acid such as maleic acid or itaconic acid. Examples thereof include a resin in which a part or all of the carboxyl groups in the copolymer are neutralized with a metal ion such as sodium, potassium, lithium, zinc, magnesium, calcium.

  Among them, a copolymer of ethylene and acrylic acid or methacrylic acid is most preferable for the purpose of improving the compatibility between the polyester resin and the rubber-like elastic resin body because it has a high ability to improve vibration damping and mechanical strength. This is a resin in which 30 to 70% of the carboxyl groups in the polymer are neutralized with a metal cation such as Na, Zn, Mg or Li. In particular, among metal cations, Na and Zn are most preferable from the viewpoint of compatibility.

  Glass transition temperature (Tg, sample amount about 10mg, differential heating type 10 ° C / min differential thermal type with high performance to improve vibration damping and impact resistance in the middle temperature range from room temperature to around 60 ° C A vinyl polymer having a measuring device (measured by DSC) of 20 ° C. or higher and 60 ° C. or lower, a Young's modulus at room temperature of 1000 MPa or lower, and a breaking elongation of 50% or higher is preferable.

  The vinyl polymer may be a vinyl polymer containing 1% by mass or more of units having a polar group, and is not limited to the above specific examples. The molecular weight of the vinyl polymer is not particularly limited, but is preferably 2000 or more and 500000 or less in terms of number average molecular weight. If it is less than 2000 or more than 500000, vibration damping and workability may be deteriorated.

  The polyester resin used in the present invention is a thermoplastic polyester, polycarbonate, or polyester carbonate having a hydroxycarboxylic acid compound residue, a dicarboxylic acid residue and a diol compound residue, or a dihydroxy compound residue as a constituent unit. Furthermore, a mixture thereof may be used.

  Examples of hydroxycarboxylic acid compounds that are raw materials for hydroxycarboxylic acid compound residues include p-hydroxybenzoic acid, p-hydroxyethylbenzoic acid, 2- (4-hydroxyphenyl) -2- (4′-carboxyphenyl) propane Etc.

  Examples of dicarboxylic acid compounds that form dicarboxylic acid residues include terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2 , 7-Naphthalenedicarboxylic acid, diphenic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid and other aromatic dicarboxylic acids and adipic acid, pimelic acid, sebacic acid, azelaic acid, decanedicarboxylic acid, malonic acid, succinic acid, malic acid And aliphatic dicarboxylic acids such as citric acid and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.

  In order to improve the vibration damping performance, it is preferable that the obtained polyester is amorphous, within a range that does not cause a decrease in the degree of polymerization of the aromatic ring and the alkyl chain constituting the hydroxycarboxylic acid compound and dicarboxylic acid compound exemplified above, It is preferable to use a compound having a side chain such as a methyl group. These may be used alone or in combination of two or more.

  Next, diol compounds that form diol residues are exemplified by 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “bisphenol A”), bis (4-hydroxyphenyl) methane, bis ( 2-hydroxyphenyl) methane, o-hydroxyphenyl-p-hydroxyphenylmethane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy Phenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) -p-diisopropylbenzene, bis (3,5-dimethyl-4-hydroxyphenyl) methane, Bis (3-methyl-4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5-dimethyl-4-hydroxy) Cyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) ethane 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenyl Ethane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis ( 3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2 , 2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 1,1,1,3,3,3-he Safluoro-2,2-bis (4-hydroxyphenyl) propane, 4,4'-biphenol, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, 4,4'-dihydroxybenzophenone Aromatic diols such as ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, 1,4-butanediol, pentamethylene glycol, neopentyl glycol, hexamethylene glycol, dodecamethylene glycol, diethylene glycol, triethylene glycol, tetra Examples thereof include aliphatic diols such as ethylene glycol, polyethylene glycol and hydrogenated bisphenol A, and alicyclic diols such as cyclohexanedimethanol. In order to improve the vibration damping performance, it is preferable that the obtained polyester is amorphous, and a compound having a side chain is used as long as the aromatic ring and the alkyl chain constituting the exemplified diol compound do not cause a decrease in the degree of polymerization. It is preferable to use it. These can be used alone or in combination of two or more.

  Moreover, the polyester resin obtained from these may be used independently or may be used in mixture of 2 or more types. The polyester resin used for this invention should just be comprised by these compounds or those combinations.

  The polyester resin used in the present invention is a small amount of structural units derived from a polyfunctional compound such as trimesic acid, pyromellitic acid, trimethylolethane, trimethylolpropane, trimethylolmethane, pentaerythritol, for example, 2 mol%. The following amounts may be included.

  Among them, preferred polyester resins include polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, and thermoplastic polyester resins such as polyethylene-2,6-naphthalate and polybutylene-2,6-naphthalate, Polycarbonates having a bisphenol A residue as the main skeleton can be mentioned. Among them, considering amorphous and metal adhesion, modified polyethylene terephthalate, modified polybutylene terephthalate, polycyclohexylene dimethylene containing isophthalic acid as a dicarboxylic acid component. Most preferred are terephthalate, polyethylene-2,6-naphthalate, polybutylene-2,6-naphthalate and mixtures of two or more thereof.

  In addition, the polyester resin contained in the resin composition of the present invention contains a metal compound such as germanium, antimony, and titanium, which is a residue of a polyester production catalyst. A polyester resin containing such a metal compound may cause degradation of the vinyl polymer under normal kneading and molding process conditions, more specifically, at a temperature higher than the decomposition temperature of the vinyl polymer. The content of the metal compound in the polyester resin used in the resin composition of the present invention is not particularly limited, but generally, the metal compound as a residue of the polymerization catalyst remains in the range of about 1 to 500 ppm, more preferably about 1000 ppm. However, it is preferably 200 ppm or less in order to prevent the vinyl polymer from being decomposed.

  When the polycarbonate resin which can be used as a polyester resin is illustrated, in addition to the above-mentioned dihydroxy compound, the polycarbonate resin which consists of the residue of the following aromatic polyhydroxy compounds can be mentioned. For example, a polyhydroxy compound represented by 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -2-heptene, 1,1,1-tri (4-hydroxyphenyl) ethane, or 3 , 3-bis (4-hydroxyaryl) oxindole and the like. However, it is not limited to these polycarbonates, and any polymer having a main chain bonded by a carbonate bond may be used. Furthermore, when a preferable polycarbonate resin is exemplified, a polycarbonate composed of a bisphenol A residue is preferable from the viewpoint of thermal stability and vibration damping properties.

  Moreover, if the polyester carbonate resin which can be used as a polyester resin is illustrated, the copolymer of said polycarbonate unit and a polyester unit etc. will be mentioned. However, it is not limited to these polyester carbonates, and any polymer in which the main chain is bonded by an ester bond and a carbonate bond may be used.

  The polyester resin used in the present invention preferably has an intrinsic viscosity of usually 0.3 to 2.0 dl / g, more preferably 0.40 to 1.7 dl / g, and still more preferably 0.50 to 1.5 dl / g. When the intrinsic viscosity is less than 0.3 dl / g, it does not mix uniformly with the polar monomer-containing vinyl polymer, so the mechanical strength and impact resistance are low, while when the intrinsic viscosity exceeds 2.0 dl / g, the sheet The molding processability such as is poor, and both are not preferable.

The intrinsic viscosity is measured at a concentration of 0.5% in o-chlorophenol at 25 ° C., and is obtained by the following formula (iii). In the formula, C represents the concentration expressed in grams of resin per 100 ml of solution, t ₀ represents the solvent flow time, and t represents the solution flow time.

Intrinsic viscosity = {ln (t / t ₀ )} / C (iii)
The polyester resin used in the present invention has a glass transition temperature (Tg, sample amount of about 10 mg, measured with a differential thermal analyzer (DSC) at a heating rate of 10 ° C./min), usually −20 to 200 ° C., more preferably Is preferably 0 to 150 ° C. When two or more types are used in combination, the Tg of each polyester resin is preferably different by 20 ° C. or more.

  This polyester resin is preferably amorphous from the viewpoint of sufficiently exhibiting vibration damping performance. In the case of crystallinity, the crystallization rate is preferably 10% or less, and a plurality of the diols or dicarboxylic acids listed above are copolymerized to reduce crystallinity. It is desirable to suppress. Further, when it is crystalline, the crystal melting temperature (Tm) is usually 210 to 265 ° C., preferably 210 to 245 ° C., and the low temperature crystallization temperature (Tc) is usually 110 to 220 ° C., preferably It is desirable that it is 120-215 degreeC. If it exceeds 265 ° C, a high temperature is required during kneading or molding, and if Tm is less than 210 ° C or Tc is less than 110 ° C, the heat resistance may be insufficient and the sheet shape may not be maintained during processing.

  By the way, in order to form the above-described resin structure (a), (b) or (c), the interfacial tension balance between these three component resins is appropriately controlled, and vinyl polymer resin or rubber-like elasticity is used. This can be achieved by controlling the composition and melt viscosity so that the body resin becomes a matrix. Specifically, the interfacial tension between the vinyl polymer / polyester and the vinyl polymer / rubber-like elastic body may be controlled to be lower than the interfacial tension between the polyester resin / rubber-like elastic body resin. In this case, in the resin composition, the contact of the polyester resin / rubber-like elastic resin becomes the most unstable, and the resin composition is self-organized so as to avoid the contact with the polyester resin / rubber-like elastic resin. Therefore, when the vinyl polymer is a matrix, the polyester resin and the rubber-like elastic resin are dispersed independently to avoid contact with the polyester resin / rubber-like elastic resin, and the rubber-like elastic resin When controlled to be a matrix, the vinyl polymer phase encapsulates the polyester resin phase to avoid contact of the polyester resin / rubbery elastic resin phase. When the polyester resin is controlled to be a matrix, the vinyl polymer phase encapsulates the rubber-like elastic resin phase to avoid contact between the polyester resin / rubber-like elastic resin phase.

Specifically, the chemical structure of the vinyl polymer may be designed according to the following policy in accordance with the chemical structure of the polyester resin or rubber-like elastic resin. The balance of interfacial tension can be evaluated by Spread Parameter (λ _{(Resin C) / (Resin B)} ) as SY Hobbs showed in Polym., Vol. 29, p1598 (1989), and λ _{(Resin C) / When (Resin B)} becomes positive, the contact between the polyester resin / rubber-like elastic resin becomes the most unstable.

λ _{(Resin C) / (Resin B)} = Υ _{(Resin A) / (Resin C)} -Υ _{(Resin B) / (Resin C)} -Υ _{(Resin B) / (Resin A)} … (I)
(In the formula, Resin A is a polyester resin, Resin B is a vinyl polymer, Resin C is a rubber-like elastic body, and _{i / j} is an interfacial tension between resin i and resin j.)
Furthermore, it is known that Υ _{i / j} is approximately proportional to the 0.5th power of the parameter Χ _{i / j} indicating the compatibility between resin i and resin _j [showing a smaller value as the compatibility is better]. ing. Therefore, equation (I) is approximated by equation (II).

λ _{(Resin C) / (Resin B)} = Χ _{(Resin C) / (Resin A)} -Χ _{(Resin C) / (Resin B)} -Χ _{(Resin B) / (Resin A)} … (II)
On the other hand, when the vinyl polymer is a random copolymer of monomers (Monomer V) and (Monomer U), the interaction parameter ビ ニ ル_{A / B} between the vinyl polymer and the polyester resin and the vinyl polymer and the rubber-like elastic body The interaction parameter Χ _{B / C} between them is expressed by equations (III) and (IV), respectively.

Χ _{A / B} = φΧ _{(Resin A) / (Monomer V)} + (1-φ) Χ _{(Resin A) / (Monomer U)} -φ (1-φ) Χ _{(Monomer V) / (Monomer U)}
… (III)
Χ _{B / C} = φΧ _{(Resin C) / (Monomer V)} + (1-φ) Χ _{(Resin C) / (Monomer U)} -φ (1-φ) Χ _{(Monomers V) / (Monomer U)}
… (IV)
Therefore, by selecting a monomer having a high affinity for the polyester resin and the rubbery elastic body for each of the monomers V and U, the second term of the formula (III) and the first term of the formula (IV) are reduced, respectively. _{A / B} and Χ _{B / c} can be reduced. As a result, the second and third terms of the formula (II) are reduced, and λ _{(Resin C) / (Resin B)} can be positively controlled.

In particular, when the rubber-like elastic body is nonpolar, λ _{(Resin C) / (Resin B)} can be easily controlled positively for the following reason. Since the polyester resin is a polar resin, the first term _{(Resin A) / (Resin C)} itself of the formula (I) is large. Furthermore, since the monomers U and V having high affinity with the polyester resin and the rubber-like elastic body are polar and nonpolar monomers, respectively, the third term itself of the formulas (III) and (IV) is large, and _{A / B} Χ Easy to reduce _{B / C.} Therefore, among the rubber-like elastic bodies mentioned above, the nonpolar rubber-like elastic body is preferable from the viewpoint that the interfacial tension can be easily controlled appropriately. Furthermore, among the nonpolar elastomers, polyolefin elastomers and styrene elastomers are particularly preferred because of their high barrier properties against metal corrosion-causing substances and high vibration damping performance.

Furthermore, when the rubber-like elastic body is made of a polyolefin-based elastomer and a styrene-based elastomer, the above-mentioned ionomer or a copolymer of an α-olefin and a glycidyl ester of an α, β-unsaturated carboxylic acid is used as a vinyl polymer. One or two or more resins selected from any one of terpolymers, terpolymers of α-olefin, α, β-unsaturated carboxylic acid ester, and glycidyl ester of α, β-unsaturated carboxylic acid preferable. Χ _{B / C} is small for various polyolefin elastomers and styrene elastomers, and Χ _{A / B} is small for various polyester resins. Can be formed. Furthermore, these resins are excellent in barrier properties and adhesion to metals.

  Next, the inorganic layered compound used in the present invention will be described.

The inorganic layered compound used in the present invention is an inorganic compound formed by laminating a planar crystal layer. Specific examples include layered silicate compounds such as natural or synthetic layered clay compounds. More specifically, various mica group minerals, smectite group minerals, kaolin minerals such as kaolinite, dickite, naclite or hyrosite, and others, chrysotite, pyrophyllite, talc, vermiculite, hydrotalcite, clintonite, etc. Can be mentioned. Further, these inorganic layered compounds are modified with an organic group . In addition, examples of the inorganic layered compound include compounds in which some atoms and atomic groups are substituted with other inorganic atoms and atomic groups. Only one of these may be used, or two or more may be used in combination.

  The major axis of these compounds is not particularly defined, but the major axis average particle diameter in the aggregated state is preferably 100 nm to 500 μm. If it exceeds 500 μm, kneading and molding may be difficult, or may be broken by multiple kneading during recycling. If it is less than 100 nm, the aspect ratio is small, and even when finely dispersed to a single layer thickness, mechanical strength and rigidity may not be sufficiently improved.

The inorganic layered compound organically modified can be used in the following viewpoint RaYoshimi suitable. When the organic modification is performed, the hydrophilic layered inorganic compound can be made oleophilic to increase the compatibility with the resin. Further, the interlayer distance can be increased to facilitate the intercalation of the resin molecules. Organic modification methods include replacing all or part of metal ions disposed between layers with organic onium ions, reacting surface hydroxyl groups of layered compound particles with organic compounds, or a combination of both. Etc.

  The former organic onium ions include ammonium ions, imidazolium ions, pyridinium ions, phosphonium ions, sulphonium ions, etc. modified with C2-C30 alkyl chains. Good. From the viewpoint of compatibility with the resin and expansion of the layer interval by organic formation, organic onium ions having a long chain or a plurality of organic chains that can be introduced are preferable. Specifically, ammonium ions such as dimethyl distearyl ammonium, distearyl ammonium, octadecyl ammonium, hexyl ammonium, octyl ammonium, 2-hexyl ammonium, dodecyl ammonium, trioctyl ammonium, methyl stearyl imidazolium, distearyl imidazolium, methyl Hexilimidazolium, dihexylimidazolium, methyloctylimidazolium, dioctylimidazolium, methyldodecylimidazolium, imidazolium ions such as didodecylimidazolium, pyridinium ions such as stearylpyridinium, hexylpyridinium, octylpyridinium, dodecylpyridinium, dimethyl Stearyl phosphonium, distearyl phosphonium Phosphonium ions such as octadecylphosphonium, hexylphosphonium, octylphosphonium, 2-hexylphosphonium, dodecylphosphonium, trioctylphosphonium, dimethyldistearylsulfonium, distearylsulfonium And sulfonium ions such as octadecylsulfonium.

  Examples of the organic compound to be reacted with the latter surface hydroxyl group include silane coupling agents such as vinyltrialkylsilane, epoxy group-containing compounds (butyl glycidyl ether, neopentyl diglycidyl ether, epoxidized vegetable oil or propylene oxide), isocyanate Group-containing compound (hexyl isocyanate, dodecyl isocyanate), isothiocyanate-containing compound, acid anhydride group-containing compound (maleic anhydride-modified polyolefin, styrene resin or oligomer thereof), carboxyl group-containing compound (terminal carboxylic acid polyolefin, styrene type) Resin, acrylic acid or methacrylic acid modified polyolefin, styrene resin or oligomer thereof, or partially ionized resin or oligomer thereof). Or more can be used.

  Further, a known radical inhibitor may be added to the organically modified inorganic layered compound for the purpose of increasing the heat stability after modification. The specific addition amount is preferably 0.001 to 7 parts by mass of a radical inhibitor with respect to 100 parts by mass of the modified organic substance. Addition of 0.001 part by mass or less is not preferable because a remarkable effect cannot be obtained. On the other hand, even if a radical inhibitor exceeding 7 parts by mass is added, it becomes substantially excessive and uneconomical. In order to achieve a higher effect, it is preferable to add 0.005 to 1 part by mass of a radical inhibitor to 100 parts by mass of the resin composition. Radical inhibitors include phenolic radical inhibitors and nitrogen radical inhibitors that have the effect of stopping radical reactions by scavenging radicals, and inhibiting radical reaction initiation and deactivating reaction intermediates. A phosphorus-based or sulfide-based radical inhibitor containing

  For the organic modification reaction, known ion exchange methods and organic modification methods can be widely used. Usually, an excess amount of organic onium ions or an organic compound and an inorganic layered compound are stirred in one or both of water and an organic solvent. Mixed. At this time, it is desirable that the inorganic layered compound swells by intercalating water or an organic solvent. For this purpose, the layer charge is desirably 0.2 to 1.0, more preferably 0.6 to 1.0. Here, the layer charge is the magnitude of the negative charge per unit composition formula, and is expressed as an absolute value. Furthermore, it is preferable that it has an ion exchange capacity of 50 to 200 meq / 100 g for ease of modification. As the inorganic layered compound having such characteristics, mica group minerals, smectite minerals, vermiculite and the like are preferable.

  Examples of mica group minerals are muscovite, biotite, phlogopite, margarite or deniolite, lithium-type 4 silicon mica, sodium-type 4 silicon mica, and organically modified compounds thereof. Examples of the smectite compound include montmorillonite, beidellite, saponite, iron saponite, nontronite, hectorite, soconite, stevensite, bentonite, and organically modified compounds thereof. Examples of vermiculite include natural vermiculite and various organic modified products thereof.

The resin composition of the present invention is a resin composition containing at least four components of a vinyl polymer containing a unit having a polar group of 1% by mass or more, a polyester resin, a rubbery elastic resin, and an organically modified inorganic layered compound. The manufacturing method is not particularly specified, but specifically, the following manufacturing method can be suitably applied. Vinyl polymer, a rubber-like elastic body, in a common solvent for dissolving the three components of the polyester resin, three components of the resin and the inorganic layered compound organically modified, as well as compatibilizer between the resin and the organic modified inorganic layered compound as necessary the after stirring mixture was dissolved, the mixed solution was added to a large excess of 3 components common poor solvent, a method for recovering the resin composition, further, the inorganic layered compound with a resin and an organic modified ternary, and, A method of melt-kneading the above-described compatibilizing agent with a melt extruder as necessary may be mentioned. The melt kneading method is most preferable from the viewpoint of economy and convenience of work.

  As the compatibilizing agent for the resin and the organically modified inorganic layered compound, an organic compound having reactivity and affinity with the surface of the layered inorganic compound described above and having good compatibility with the resin can be used. Specifically, as a compatibilizing agent for rubbery elastic bodies / layered inorganic compounds, rubbery elastic bodies modified with acid anhydride groups or carboxyl groups and oligomers thereof, specifically, polyethylene grafted with maleic anhydride , Modified polyolefin elastomers such as polypropylene, maleic anhydride grafted styrene-butadiene-styrene copolymer (SBS), hydrogenated styrene-ethylene / butylene-styrene copolymer (SEBS), styrene- Examples include modified styrene elastomers such as isoprene-styrene copolymer (SIS), and copolymers of polyolefin and acrylic acid or methacrylic acid. Examples of the compatibilizer between the polyester resin and the organically modified inorganic layered compound include organic compounds capable of reacting with the surface hydroxyl groups of the inorganic layered compounds listed above, silane coupling agents, epoxy group-containing compounds, isocyanate group-containing compounds. Etc. Of these, compounds containing an epoxy group and a polar organic chain are preferred. Since the affinity between the vinyl polymer and the organically modified inorganic layered compound is superior to the other two components because it has a polar unit, a compatibilizer is often not required. However, if necessary, an organic compound containing an acid anhydride or epoxy group having good reactivity with the hydroxyl group of the inorganic layered compound and having good compatibility with the vinyl polymer is suitable as a compatibilizing agent. Can be used.

  A more detailed example of the melt-kneading method is a method of mixing by dry blending using a tumbler blender, Henschel mixer, V-type blender, etc., and then melt-kneading using a single or twin screw extruder, kneader, Banbury mixer, or the like. A particularly preferable manufacturing apparatus from the viewpoint of economy and dispersion controllability is a coaxially rotating twin-screw kneader. By making it rotate coaxially, a shearing force is secured and the inorganic layered compound is easily dispersed efficiently. In addition, for the purpose of quantitatively adding the inorganic layered compound, a kneader composed of a main feeder and a side feeder is used, and the pellet-shaped resin component is sent out from the main feeder and melted, and the molten resin is used using the side feeder. It is preferable to add and knead the inorganic layered compound. When a powdery inorganic compound and a pellet-shaped resin are added together from the main feeder, they cannot be added quantitatively in many cases. Furthermore, since the powder adheres only to the unmelted resin pellets electrostatically, the amount of addition tends to vary.

  The magnitude of the shearing force applied during kneading is the driving force that releases the aggregation of the inorganic layered compound and efficiently intercalates the resin molecules between the layers, and the driving force that prevents organic detachment of the organicated inorganic layered compound. Determined by balance. Strong shearing is preferable from the former viewpoint, and weak shearing is preferable from the latter viewpoint, and it is desirable to determine an optimal screw arrangement based on a balance between these. Specifically, it is desirable to set the kneader part installed from the side feeder to the strand nozzle at a volume ratio of 15% to 95%, more preferably 30% to 90%, more preferably 50%. It is preferable to set it to 80% or less. Furthermore, it is preferable from the viewpoint of preventing heat generation that these kneader parts are not arranged continuously but are divided into several parts. In addition, it is desirable to appropriately arrange a backflow kneader or a kneader having a neutral flow in a part of the kneader portion to ensure a residence time. The appropriate residence time is determined according to the apparatus, but usually 2 minutes or more, more preferably 6 minutes or more can be ensured in order to uniformly and finely disperse the inorganic layered compound.

  Moreover, after manufacturing the masterbatch which disperse | distributed the inorganic stratiform compound in a part of constituent resin first by the said method, you may mix another resin component with the said masterbatch. This method is particularly effective when it is desired to disperse the inorganic layered compound only in the matrix resin. Specifically, only the matrix resin and the inorganic stratiform compound are kneaded by the above method to prepare a master batch, and then the dispersion resin and the master batch are mixed, whereby the inorganic stratiform compound is dispersed only in the matrix resin. In many cases, a resin composition can be obtained.

  Furthermore, a radical inhibitor may be added to the resin composition of the present invention for the purpose of preventing resin degradation due to heat, oxygen, hydrolysis, etc. during kneading and molding. The addition amount is preferably 0.001 to 7 parts by mass of a radical inhibitor with respect to 100 parts by mass of the resin composition. Addition of 0.001 part by mass or less is not preferable because a remarkable effect cannot be obtained. On the other hand, addition of a radical inhibitor exceeding 7 parts by mass is not preferable because it is substantially excessive and uneconomical, and further, the resin properties such as the elastic modulus and adhesiveness of the resin are lowered. In order to achieve a higher effect, it is preferable to add 0.005 to 1 part by mass of a radical inhibitor to 100 parts by mass of the resin composition.

  As the radical inhibitor, it reacts with phenolic radical inhibitors and nitrogen radical inhibitors, and peroxides, which have the effect of stopping radical reactions by scavenging radicals, thereby suppressing the initiation and reaction of radical reactions. A phosphorus-based or sulfide-based radical inhibitor having a function of inactivating the intermediate is preferable.

  Furthermore, a known plasticizer or pressure-sensitive adhesive can be added to the resin composition for the purpose of improving the vibration damping performance by activating the intermolecular entanglement. Examples of specific plasticizers and adhesives include mineral oil-based rubber softeners such as process oils, known tackifiers, and the like. Among them, tackifiers have a large effect of activating entanglement between molecules. Most preferred. Specific examples of tackifiers include natural resin-based tackifiers composed of rosin and terpene resin derivatives, petroleum-based resins composed of C5-based, C9-based resins and hydrogenated resins, phenolic resins, xylene resins, and the like. A synthetic resin tackifier may be mentioned. More specifically, rosin, hydrogenated rosin, heterogeneous rosin, polymerized rosin, rosin derivatives such as rosin esters, terpene resins, terpene derivatives such as aromatic terpene resins, petroleum hydrocarbon resins, coumarone resins, alkylphenol resins, One type or a mixture of two or more types such as xylene resin may be used. Among these, rosin derivatives, terpene derivatives, petroleum resins, and alkylphenol resins are preferable for the purpose of improving vibration damping performance. The amount of these plasticizers to be added is not particularly specified. Desirably, 60 parts by mass or less is preferable with respect to 100 parts by mass of the resin composition of the vinyl polymer, the polyester resin, and the rubber-like elastic resin, and a more preferable addition amount is 40 parts by mass or less, and more preferably 20 parts by mass. It is below mass parts. If it exceeds 60 parts by mass, the resin composition becomes too sticky and the rigidity is lost. On the other hand, the lower limit of the addition amount is preferably 0.1 parts by mass or more. If it is less than 0.1 part by mass, a sufficient plasticizing effect cannot be exhibited. More preferably, it is 1 part by mass or more.

  In addition, the resin composition of the present invention may contain a pigment and a colorant. For example, alumina, titanium dioxide, calcium carbonate, barium sulfate, carbon black, ultramarine, petal, bitumen, azo pigment, nitrone pigment, and the like can be mentioned. The average particle diameter of the pigment is preferably 2.5 μm or less. The addition amount of the pigment is an amount necessary for achieving the coloring function, and is used within a range of about 3 to 50% by mass. The addition method of a pigment can be based on a well-known method.

  In addition to the radical inhibitor, plasticizer, filler, etc., the resin composition includes a light stabilizer, an ultraviolet absorber, an anti-aging agent, a release agent, a lubricant, a flame retardant, a charging agent, depending on the purpose. It is also possible to add an appropriate amount of an inhibitor, an antibacterial and antifungal agent.

  The vibration damping material and sealing material of the present invention can be obtained by widely applying known injection molding, blow molding, and extrusion molding of the resin composition of the present invention to a desired shape. In these moldings, it is possible to use a resin composition that has been previously kneaded and pelletized with the above-mentioned extruder, or it is possible to simultaneously perform kneading and molding by connecting a mold to the extruder. It is. The molding conditions are not particularly specified, but in the case of injection molding or extrusion molding, the mold temperature is preferably set to 10 to 60 ° C. If it exceeds 60 ° C, the releasability from the mold may deteriorate due to the adhesive properties. On the other hand, when the temperature is lower than 10 ° C., the flow in the mold deteriorates, and it may not be possible to process the desired shape.

  In the case of blow molding, it is desirable to select a composition having an inorganic layered compound content of 0.5% by mass or more, more preferably 1% by mass, and more preferably 2% by mass or more. More preferably, the content is not less than the amount and the dispersion diameter is not more than 1 μm. By containing 0.5 mass% or more, the extensional viscosity can be increased and molding defects such as drawdown can be prevented. The extensional viscosity can be increased as the inorganic layered compound content is increased or the dispersion diameter is decreased, and it becomes easier to prevent molding defects.

  Next, the resin sheet of the present invention will be described.

  The resin sheet of the present invention may be a sheet of the resin composition alone or a resin sheet containing the resin composition of the present invention. The processing method to a sheet | seat is not specifically limited, Said shaping | molding method can be used widely. Specific examples of extrusion molding methods are: 1) a method of continuously molding kneaded pellets with an extruder with a T-die, 2) a method of sandwiching between heating rolls and heating rolls and continuous molding while reducing, 3) press machine 4) Molding into batch type under pressure under heating, and 4) Mixing the raw material of the resin composition by dry blending, then directly feeding it into the hopper of a single or twin screw extruder with a T die and melting A method of forming with a T-die while kneading (direct film forming method) can be mentioned. Among them, the preferred method is the direct film forming method 4) because the kneading step can be omitted. Examples of the injection molding method include a method in which a flat plate mold having a predetermined thickness is prepared and heated to a temperature equal to or higher than the melting point, and a method of forming a film by an inflation method as blow molding.

The sheet thickness is determined in consideration of necessary vibration damping performance, workability, etc., and is not particularly limited. Therefore, it may be a film. The sheet layer thickness of the resin composition of the present invention is preferably 10 μm to 5 mm. If it is less than 10 μm, the vibration damping performance and impact resistance of the sheet may not be sufficient, and if it exceeds 5 mm, the economy is poor. Further, the surface roughness of the sheet is preferably 500 nm or less in terms of R _max as a result of measuring the sheet surface roughness arbitrarily by 1 mm length. If it exceeds 500 nm, bubbles may be entrained when it is laminated on other materials by thermocompression bonding. Note that the sheet surface may be subjected to corona treatment or plasma treatment for the purpose of improving adhesion to other materials and printability.

  The sheet of the present invention is basically a sheet obtained by molding the above resin composition, but other resin sheets and films can be laminated on the upper layer or the lower layer. Specifically, an adhesive layer can be laminated, or a hard coat layer, an antistatic layer, a fender layer, a lubricating layer, or the like can be laminated. Furthermore, it is possible to laminate a resin layer having a Tg different from that of the resin composition of the present invention and further expand the vibration suppression temperature region. Specific examples of the multilayering method include a method of laminating at the time of molding using a multilayer die, a method of laminating using a thermocompression bonding or an adhesive after sheet forming. Furthermore, when other resin sheets are laminated on the top and bottom of the sheet of the present invention, the total thickness after lamination is preferably 11 μm to 5 mm. Since the preferred thickness of the sheet of the present invention is 10 μm or more, if the total thickness is less than 11 μm, the sheets to be laminated are less than 1 μm, and the functions of the laminated sheets are hardly exhibited. On the other hand, if it exceeds 5 mm, the economic effect is hardly exhibited.

  The laminated material of the present invention is obtained by laminating a member on at least one side of the resin sheet. The material of the laminated member is not particularly limited, and specific examples include a metal member, a concrete member, a glass member, a ceramic member, wood, a plastic member, and the like. In particular, metal members that are often used as various structural members are preferable because the vibration damping performance is greatly improved by lamination with the resin composition of the present invention. Although the material is not specifically limited as a metal member, Various metals or alloys, such as iron, aluminum, and titanium, are mentioned. The shape of the resin composition is not particularly limited as long as the resin composition can be laminated, and can be applied to members of various shapes including a plate material, a strip material, a foil material, a bar material, a shape material, a wire material, and a pipe material. From the standpoint of ease of lamination, etc., it is preferable to have a shape having a flat surface such as a plate, strip, foil, etc., specifically, tinplate, thin tin-plated steel sheet, electrolytic chromate-treated steel sheet (tin-free steel), Steel plates for container materials such as nickel-plated steel plates, hot-dip galvanized steel plates, hot-dip zinc-iron alloy-plated steel plates, hot-dip zinc-aluminum-magnesium alloy-plated steel plates, hot-dip aluminum-silicon alloy-plated steel plates, hot-dip lead-tin alloy-plated steel plates Surface-treated steel sheets such as hot dip galvanized steel sheets, electrogalvanized steel sheets, electrogalvanized-nickel plated steel sheets, electrogalvanized-iron alloy plated steel sheets, electrogalvanized-chromium alloy plated steel sheets, cold rolled steel sheets and stainless steel, Examples of the metal plate include aluminum, copper, nickel, zinc, and magnesium. The thickness of the metal plate is not particularly limited, but from 1 μm thick foil to about 100 mm thick plate can be suitably used.

  The shape of the laminated material of the present invention is not particularly limited as described above, but a member in which the sheet of the present invention is laminated on one side, a member laminated on both sides, a member having a sandwich structure with a sheet sandwiched between the members, and a plurality of these members There are stacked shapes. Furthermore, you may laminate | stack the sheet | seat of this resin composition on a member through another material. Specifically, it can be laminated via an adhesive layer or via another functional layer. Moreover, it is also possible to laminate | stack functional layers, such as a resin film and a sheet | seat, on the sheet | seat of a resin composition. Specifically, it is possible to laminate a hard coat layer, an antistatic layer, a fender layer, a lubricating layer, and the like. Moreover, you may coat | cover and laminate | stack directly on a member, without making this resin composition into a sheet | seat.

  The thickness of the resin sheet of the present invention laminated on the laminated material is appropriately determined in consideration of the thickness of the member and the necessary vibration damping performance, workability, and in some cases, sealing characteristics, and is not particularly limited. . As the layer thickness of the resin composition of the present invention, the desired thickness of the resin sheet is 1/100 to 100 times, more preferably 1/10 to 10 times the average thickness of the member. If it is less than 1/100 times, the resin composition may not exhibit vibration damping properties and seal characteristics. If it exceeds 100 times, the rigidity as a member may not be maintained.

  For lamination to the member, known methods such as film pressure bonding (indirect / direct) and direct lamination can be used. Specifically, (1) A method in which the present resin composition prepared by melting and kneading a raw material resin in advance with a kneader is formed into a sheet with an extruder with a T die, and this is thermocompression bonded to a member, (2) And a method of directly thermocompression bonding the sheet from the T-die. Further, as another method of directly thermocompression bonding the sheet, (3) instead of the resin composition, the resin as the raw material of the resin composition is put into the hopper of the extruder with a T die, The method of kneading | mixing to this resin composition and carrying out the thermocompression-bonding directly is mentioned. Furthermore, (4) a method in which the resin composition is melted and coated with a bar coater or a roll, (5) a method in which a member is immersed in the molten resin composition, (6) a resin composition is dissolved in a solvent and spin-coated. It is also possible to laminate on a member by a method or the like, and the lamination method is not particularly limited.

The method (1), (2) and (3) are the most preferable from the viewpoint of work efficiency as a method of laminating the members. When using the method (2), the sheet thickness is preferably 10 μm to 5 mm from the viewpoint of vibration damping performance and work efficiency. Further, the surface roughness of the sheet is preferably 500 nm or less in terms of R _max as a result of arbitrarily measuring 1 mm length. If it exceeds 500 nm, bubbles may be entrained when closely contacting by thermocompression bonding.

  As described above, the resin composition of the present invention contains at least four components of a vinyl polymer, a polyester resin, a rubbery elastic resin, and an inorganic layered compound containing 1% by mass or more of units having a polar group. It is a resin composition. By containing the above three resin components, it has excellent chemical resistance and can exhibit vibration damping properties and adhesive properties over a wide temperature range. Furthermore, rigidity, mechanical strength, and storage elastic modulus can be increased by containing an inorganic layered compound. At the same time, the dispersed inorganic layered compound rubs against the external vibration and dissipates energy, so the loss elastic modulus can be increased, and the increase in storage elastic modulus is complemented by the increase in loss elastic modulus, thereby improving the vibration damping property. Can hold. Furthermore, it contains a polyester resin which is a rubber component and a plastic component, and is excellent in compatibility between the rubber-like elastic body and the polyester resin by the vinyl polymer, and can exhibit excellent impact resistance. In addition, since it contains an inorganic layered compound, it is excellent in rigidity and barrier properties. As a result, it can also be used as a plastic material having impact resistance, rigidity and barrier properties.

  Since the vibration damping material of the present invention is formed by molding the resin composition of the present invention, vibration damping, chemical resistance, adhesiveness, rigidity, mechanical strength, thin film workability, adhesion to metal in a wide temperature range Can be combined. As a result, it can be effectively used as a noise / vibration suppression material for vehicles, buildings, general machines and the like. Moreover, the sealing material of this invention can be used conveniently for various packing materials using favorable chemical resistance and adhesiveness.

  Furthermore, the resin sheet of the invention is provided with the above-mentioned characteristics because the layer made of the resin composition of the present invention is alone or laminated, and is provided with the above-mentioned characteristics. It can also be used as a damping laminate sheet.

  In addition, since the laminated material of the present invention has at least one layer of the resin sheet of the present invention laminated, it can be widely used as a vibration damping member or a seal member, such as an automobile roof, body, bumper, bonnet, door panel, floor panel, Wheel covers, oil pans, instrument panels, air spoilers, automobile parts such as various motors, copiers and printers, toys, containers, home appliances / computers, washing machines, refrigerators, CD / MD / LD / DVD players It can be used for OA / AV equipment parts such as VTRs, speakers, mobile phones, etc., electrical parts such as housings, architectural relations such as hinged doors and vibration-isolating rubber, and parts such as ships and railway vehicles.

  Furthermore, since the laminated material is formed by laminating the resin composition layer of the present invention, it is possible to achieve both vibration damping properties and rigidity that were difficult in the prior art. As a result, even if it is processed into a fine part, it is possible to prevent bending due to rigidity, maintain a dimensional system, and develop vibration damping properties. Therefore, it can be suitably used for a hard disk cover, particularly a miniaturized hard disk cover. In addition, since the laminated material itself has a damping capability, the damping capability can be expressed without attaching a damping seal separately. As a result, when this laminated material is used in a suspension of a hard disk drive, the vibration-proofing sticker attached to the outside can be omitted and the weight can be reduced, and at the same time, the size can be reduced with good dimensional accuracy. Therefore, the present laminated material can be particularly suitably used for a suspension of a hard disk drive.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

  As rubber-like elastic resin, acid-modified styrene-olefin copolymer (SEBS) [Asahi Kasei Kogyo Co., Ltd., Tuftec M1913] (Tg = about -40 ℃ and about 105 ℃), acid-modified polyethylene (PEMAH) [Mitsui LB548] (Tg = −10 ° C.) manufactured by Chemical Co., Ltd. was used.

  As a vinyl polymer having 1% by mass or more of a unit having a polar group, an ethylene ionomer [manufactured by Mitsui DuPont, Himiran 1706] (Tg = 40 to 50 ° C.), ethylene-vinyl acetate-glycyl methacrylate ternary A copolymer (Sumitomo Chemical Co., Ltd .: Bondfast 7L) was used.

  As a polyester resin, modified polyethylene terephthalate (PET-G) containing cyclohexanedimethanol as a diol residue [Eastman Chemical Co., Easter 6673] (Tg = about 80 ° C.), polyarylate (PAr) [Unitika Ltd. U-100] (Tg = 200 ° C.) was used.

  As the layered inorganic compound, montmorillonite (MMT) modified with dimethyl-disteayl ammonium (Esven NX: manufactured by Hojun Co.) was used.

  As the tackifier, hydrogenated petroleum resin (Arakawa Chemical Co., Ltd .: Alcon P-90) was used.

  All the raw materials other than the above MMT were in the form of pellets, and only MMT was powder.

(Examples 1-7, Comparative Examples 1-3)
Each resin was dry blended in pellets using a V-type blender at each composition ratio shown in Table 1. This mixture is fed from the main feeder and MMT from the side feeder, and is quantitatively fed so as to have a predetermined resin amount to MMT ratio. The condition is that the barrel temperature is 150 ° C. and the screw rotation speed is 150 rpm with a coaxial rotary twin screw extruder. To obtain a shearing force and forcibly cooled to a resin temperature of 250 ° C., and then melt-kneaded (Laboplast Mill (manufactured by Toyo Seiki Co., Ltd.)). As comparative examples, a polyester resin alone, a binary resin composition of polyester and vinyl polymer, and a ternary resin composition to which no MMT was added were used.

  From this resin composition, an ultrathin section was cut out with a microtome and then stained with ruthenic acid, and the dispersion state of the obtained resin composition was analyzed with a transmission electron microscope. As a result, the resin compositions of Examples 1, 2, 3 and 7 have a structure in which the rubber-like elastic phase and the polyester resin phase are independently dispersed in the vinyl polymer matrix, and Examples 4, 5, 6 and 8 are A structure in which a polyester resin phase encapsulated with a vinyl polymer phase was dispersed in a rubber-like elastic matrix was formed, and the resin dispersed phase diameter was 1 μm or less. Further, MMT was uniformly dispersed in any resin phase, and the particle size of the MMT dispersed phase having a dispersion number distribution of 90% or more was 100 nm or less. Further, the resin composition of Comparative Example 3 was almost the same as Example 1 except that MMT was not dispersed in the resin.

(Examples 9 to 10)
High Milan 1706 and MMT are supplied from the main feeder from the side feeder, and quantitatively supplied so that the mass ratio of 1706: MMT is 31: 7, with a coaxial rotary twin screw extruder, barrel temperature 150 ° C, screw rotation speed Set the condition at 150 rpm to gain shearing force, forcibly cool the resin temperature to 250 ° C, melt knead (Laboplast Mill (Toyo Seiki Co., Ltd.)), master batch resin pellets Manufactured. A predetermined amount of the master batch pellets, vinyl polymer, and polyester resin are mixed in a V-shaped mixer, and then kneaded from the main feeder of the coaxial twin-screw kneader at a barrel temperature of 250 ° C. and a rotation speed of 75 rpm. A product was obtained (Example 9). Similarly, a master batch composed of M1913 and MMT was produced, and then the composition of Example 10 was obtained. As a result of analyzing the higher order structures of the resin compositions of Examples 9 and 10 in the same manner as in Examples 1 to 7, both were almost the same as Examples 1 and 4 except that MMT was dispersed only in the matrix resin. It was the same.

  The sheet moldability of these resin compositions was evaluated according to the following evaluation criteria by molding a sheet having a width of 300 mm and a thickness of 1 mm using a twin screw extruder with a T die. The evaluation criteria were as follows: a sheet can be stably formed with a thickness accuracy within a range of ± 5%: ◯, variation in width and thickness is large and sheet forming is difficult: Δ, sheet cannot be formed: x. The evaluation results are shown in Table 3.

  Further, the vibration damping performance was evaluated under the following conditions, using a test piece as a strip of 10 mm width and 30 mm length cut from each obtained sheet. The evaluation method was to use a dynamic viscoelasticity measuring device (Seiko Instruments Co., Ltd., DMS-6100) under conditions of chuck distance: 10 mm, heating rate: 2 ° C / min, 10 Hz. The loss angle of dynamic viscoelasticity (tan δ: the greater the greater, the greater the damping performance, 0.05 or more is a measure of the function manifestation as a damping material) The evaluation results are shown in Table 3.

  Further, in order to compare the rigidity of the resin compositions of Examples 1 to 10 and Comparative Example 3, the strip samples were subjected to a tensile test at a tensile speed of 20 mm / min. The samples of Examples 1-8 were all 500-600 MPa. Furthermore, in the samples of Examples 9 and 10, since MMT was dispersed in the matrix resin, it was 700 MPa. On the other hand, the sample of Comparative Example 3 was 95 MPa.

  As shown in the test results of Table 3, the resin compositions (Examples 1 to 10) of the present invention have a good dispersion state of the polyester resin and rubber-like elastic resin in the vinyl polymer, and sheet moldability. In addition, there was no problem, and high damping performance was expressed in a wide temperature range of −40 to 100 ° C. In particular, in Examples 7 and 8, since 30% by mass of tackifier was added to the total amount of the resin, compared with Examples 1 and 4, good vibration damping properties were expressed in a wide temperature range. Furthermore, in Examples 5 and 6, since a mixture of polyarylate and PET-G was used for polyester, good vibration damping performance could be secured from -40 to 180 ° C.

  On the other hand, since Comparative Example 1 is composed of one component, it was able to exhibit damping properties only near 80 ° C. Furthermore, since Comparative Example 2 is composed of only two components, it hardly exhibits damping properties at 80 ° C. or higher. Further, in Comparative Example 3, since it is composed of three components and has the same high-order structure as Example 1, good vibration damping properties similar to those of Example 1 are achieved in a wide temperature range of −50 to 100 ° C. Although it is expressed but does not contain an inorganic layered compound, the rigidity is low compared to the samples of Examples 1 to 10, and vibration damping and rigidity cannot be combined.

(Examples 11 to 18)
Both sides of the sheets of Examples 1 to 10 were sandwiched with a SUS foil having a length of 100 mm, a width of 100 mm, and a thickness of 100 μm, and heated press (temperature: 250 ° C., pressure: 1 to ² kg / cm ² , pressure bonding time: 10 minutes) )did. After pressing, it was cooled and the peel strength of the sheet and SUS foil was measured. All of the resin sheets exhibited a peel strength of 9.8 N / cm or more and had good adhesion. Cut out a 30mm x 300mm specimen from the manufactured sandwich SUS foil, apply the force by the mechanical impedance method (vibrator connected to the impedance head, read the vibration acceleration of the sample with the vibration analyzer, and measure the frequency response function The damping factor (characteristic equivalent to the above-mentioned loss factor) was measured at 500 Hz with various temperatures by the half-width method (-3 dB) from the resonance peak. Table 4 shows the evaluation results. In all the examples, good damping performance was expressed in a wide temperature range of -50 to 120 ° C. In particular, in Examples 15 and 16, since the resin composition sheet of Examples 5 and 6 that expresses vibration damping properties in the temperature range of -40 to 180 ° C is used, even sandwich SUS foils are good in the temperature range. It was possible to express a good vibration control.

(Comparative Example 4)
In accordance with Example 1 disclosed in JP-A-63-202446, Toyobo Co., Ltd. linear saturated polyester (Byron 103M (Tg = 47 ° C.)) toluene / methyl ethyl ketone (4: 1) A 20% by mass solution obtained by dissolving in a mixed solvent and a 20% by mass solution obtained by dissolving a linear saturated polyester (byron RV550 (Tg = -15 ° C.)) manufactured by the same in a toluene / methyl ethyl ketone (4: 1) mixed solvent The same amount of the coating solution (A solution) was prepared, and the melamine resin (Sumimar 40S) manufactured by Sumitomo Chemical Co., Ltd. as a crosslinking agent was added to the A solution, totaling 100 parts by mass of linear saturated polyester in the A solution. A coating solution (solution B) was prepared by mixing the mixture so as to be 24 parts by mass. The liquid B was applied to the same SUS foil as used in Examples 11 to 20 by a bar coater so as to have a thickness of 15 μm after drying. The two obtained SUS foils were overlapped so that the coated surfaces were in contact with each other, and baked in an oven at 110 ° C. for 10 minutes to evaporate the solvent and baked and crosslinked the resin. Then, it took out from oven and cooled to room temperature. The vibration damping properties of the present SUS foil were measured in the same manner as in Examples 10-20. Table 5 shows the results. In this system, sufficient damping performance could be exhibited only in the vicinity of -20 to 60 ° C.

(Comparative Example 5)
In accordance with Example 3 described in JP-A-8-176352, as a thermoplastic polyester elastomer, Toray DuPont Hytrel (softening point 110 ° C.), as a rubber, Japan Synthetic Rubber Acrylonitrile Butadiene Rubber (NBR) As the polybutylene terephthalate (PBT), using Toray PBT resin, each resin was compounded at a composition ratio of 50:30:20, and the conditions shown in the publication, that is, with a twin screw extruder It was melt-kneaded under the conditions of a temperature of 230 ° C. and a screw rotation speed of 50 rpm, and a 30 μm-thick sheet was formed in the same manner as in Examples 1 to 10. However, defects were generated everywhere, and a healthy sheet could not be obtained.

(Comparative Example 6)
In accordance with Example 6 described in JP-A-9-227766, a polyester-based resin, an addition-polymerized block copolymer, a polyester-based block copolymer, a polypropylene-based resin, and a polyester-based resin blended with a tackifier resin, respectively. Resin composition A resin composition was prepared and melt-kneaded under the conditions of a screw rotation speed of 50 rpm in the same manner as in Comparative Example 5 to form a 30 μm-thick sheet in the same manner as in Examples 1 to 10, but there were defects everywhere. It was not possible to make a healthy sheet.

  From Examples 10 to 20, the resin composition of the present invention can be processed to be thin and has excellent adhesion to a metal plate. And even if it laminates | stacks on a metal plate, it turns out that it has sufficient damping property. Further, from the comparison with Comparative Example 4, the vibration damping material of the present invention has vibration damping properties over a wider temperature range than the prior art, and from the comparison with Comparative Examples 5 and 6, the resin composition of the present invention is It can be seen that, while exhibiting vibration damping properties, it is superior in workability than the prior art and can be easily processed into a thin wall.

(Examples 21 to 28) Application as a sealing material The films of Examples 1, 9, and 10 were each two steel plates (plate thickness: 0.32 mm, basis weight: Ni plating; 100 mg / m ² , Zn plating; 45 g / m ² , Electrolytic chromate; 50 mg / m ² , Chromate treatment (Cr amount conversion): 50 mg / m ² ), and thermocompression bonded at 240 ° C. By immersing the sandwich steel plate in an acidic aqueous solution at 80 ° C., pH = 2-4, distilled water at pH = 7, strong alkaline aqueous solution at pH = 14, and comparing the peel strength before immersion and after 500 hours of continuous immersion Sealability was evaluated.

  The sheet comprising the resin composition of the present invention has good initial adhesion to any steel sheet, and can maintain good adhesion equivalent to initial adhesion even after being immersed in acid, distilled water, or strong alkali. It was.

(Comparative Examples 7 to 10)
A 30 μm-thick sheet of nylon 6, nylon 12, and acid anhydride-modified PP (Mitsubishi Chemical: AP-P501) was used and sandwiched between two steel plates, and thermocompression bonded at 200 to 250 ° C. The sandwich steel plate was immersed in an acid, a strong alkaline aqueous solution and distilled water in the same manner as in Examples 17 to 24, and the sealing property was evaluated by peel strength.

  Although the nylon 6 and nylon 12 sheets exhibited good initial adhesion, they were easily peeled off when immersed in acid and strong alkali, and sufficient sealability could not be exhibited. Furthermore, when the acid anhydride-modified PP sheet was immersed in a strong alkaline aqueous solution, it was easily peeled off, and sufficient sealability could not be exhibited.

Examples 29 and 30 Application as high-strength / impact-resistant plastic material The compositions shown in Table 8 were kneaded under the same conditions as in Examples 1 to 8 to obtain resin compositions. As in Examples 1-8, the dispersion state of the resin composition was analyzed with a transmission electron microscope, and a structure in which a rubber-like elastic body encapsulated with a vinyl polymer phase was dispersed in a polyester resin matrix was formed. All the resin dispersed phase diameters were 1 μm or less. Further, MMT was uniformly dispersed in any resin phase, and the particle size of the MMT dispersed phase having a dispersion number distribution of 90% or more was 100 nm or less.

  A 25 μm thick film was obtained in the same manner as in Examples 1-8. The rigidity of this film was evaluated by the tensile modulus. Furthermore, after laminating this film on the electrolytic chromated steel plate of Example 24 under the same conditions, a DuPont impact test (dropping an iron ball (r = 8 mm) from a height of 30 cm) was conducted. Was used as a cathode, and the transmission current under a voltage of + 6V in 1.0% saline was measured (the lower the better the impact resistance), and the impact resistance of this film was evaluated. Moreover, the barrier property of this film was evaluated by the water vapor transmission rate measured according to JIS Z-0208 (cup method).

(Comparative Examples 11 and 12)
Except not containing MMT, a resin composition was obtained in the same manner as in Examples 29 and 30, and the higher order structure was analyzed. It was the same as Examples 29 and 30 except that MMT was not dispersed, and it was confirmed that the resin composition was disclosed in Patent Document 11. In the same manner as in Examples 29 and 30, a 25 μm-thick film was obtained and evaluated for rigidity, impact resistance, and barrier properties.

  By comparing Examples 29 and 30 with Comparative Examples 11 and 12, the resin of the present invention retains the same level of impact resistance as the conventional resin composition, and is superior in rigidity and barrier properties than the conventional resin composition. I was able to confirm.

The schematic diagram which shows the structure of the resin composition of this invention (an inorganic layered compound is not shown). The schematic diagram which shows another structure of the resin composition of this invention (an inorganic layered compound is not shown). The schematic diagram which shows the other structure of the resin composition of this invention (an inorganic layered compound is not shown in figure).

Claims (12)

A terpolymer of α-olefin, α, β-unsaturated carboxylic acid ester and glycidyl ester of α, β-unsaturated carboxylic acid, copolymer of α-olefin and glycidyl ester of α, β-unsaturated carboxylic acid A polymer, or at least four components of a vinyl polymer, a polyester resin, a rubber-like elastic resin and an inorganic layered compound selected from one or more resins selected from ionomer resins , the vinyl polymer, the polyester resin, And the mass percentages of the rubber-like elastic bodies are equal to each other, or the mass percentages of the vinyl polymer, the polyester resin, and the rubber-like elastic bodies are vinyl polymer: polyester resin: rubber-like elastic body = 34 to 80:10. ~ 33: 10 to 33, the addition amount of the inorganic layered compound is 0.1 to 60% by mass of the total resin mass, and the inorganic layered compound is an organically modified inorganic layered compound .   The resin composition according to claim 1, wherein the vinyl polymer is a matrix, and the polyester resin and the rubber-like elastic body are independently dispersed therein.   The resin composition according to claim 1, wherein the rubber-like elastic body is a matrix, and the polyester resin encapsulated with the vinyl polymer is dispersed in the matrix.   The resin composition according to any one of claims 1 to 3, wherein the rubber-like elastic resin is one or both of a polyolefin-based elastomer and a polystyrene-based elastomer. Vinyl-polymer, the resin composition 100 parts by weight of polyester resin and the rubbery elastomer resin, any one of claims 1 to 3, characterized in that it contains 0.1 to 60 parts by weight of the tackifier The resin composition described in 1.   The resin composition according to claim 1, wherein the inorganic layered compound has a particle size of 1 µm or less and is dispersed in the matrix resin. The resin composition according to claim 1 or 6 , wherein the inorganic layered compound is one or more selected from organically modified mica group minerals, smectite minerals, or vermiculite. A vibration damping material obtained by molding the resin composition according to any one of claims 1 to 7 by any one of injection molding, extrusion molding, and blow molding. Sealing material a resin composition according to any one of claims 1-7, formed by molding in any molding method of injection molding, extrusion molding or blow molding. The resin composition according to any of claims 1 to 7, obtained by molding alone or a resin sheet formed by laminating in combination with one or both of the other resin composition or adhesive. Laminated material formed by laminating at least one side member of the resin sheet according to claim 1 0, wherein. Laminate material of claim 1 1 wherein the member is a metallic material.

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