JP5221487B2 - Damping resin composition - Google Patents

Description

  The present invention relates to an attenuating resin composition that exhibits the performance of attenuating energy such as vibration energy and impact energy.

  Conventionally, for example, a vibration-damping paint of Patent Document 1 is known as a damping resin composition containing mica. The aspect ratio of mica contained in this vibration damping paint is in the range of 20-60. Moreover, the mica contained in the vibration-damping coating material of Patent Document 2 has a particle size distribution in the range of 1 to 100 μm and an average particle size of 20 μm.

International Publication No. 99/06491 Pamphlet JP 2004-18670 A

  By the way, a new technique for improving the performance of the damping resin composition is desired. The present invention has been made by finding a damping resin composition capable of enhancing damping performance. An object of the present invention is to provide an attenuating resin composition that can easily exhibit excellent attenuation performance.

  In order to achieve the above object, the invention described in claim 1 is an attenuating resin composition obtained by blending mica into a resin material, wherein the mica has an aspect ratio in the range of 60 to 110. The gist is that the average particle size is in the range of 23 to 55 μm, and the particle size distribution indicated by the frequency in the particle size range of X μm ± 10 μm is 15% or more when the average particle size is X μm.

  The gist of the invention described in claim 2 is that, in the attenuating resin composition according to claim 1, the resin material is contained as an aqueous resin dispersion in which resin particles are dispersed in an aqueous dispersion medium.

  According to a third aspect of the present invention, there is provided the damping resin composition according to the first or second aspect, wherein the benzothiazyl compound, the benzotriazole compound, the diphenyl acrylate compound, the orthophosphate compound, the aromatic compound The gist is to contain at least one compound selected from secondary amine compounds and halogenated ester compounds.

  Invention of Claim 4 is the damping resin composition as described in any one of Claims 1-3. WHEREIN: The said mica is 1-300 mass parts with respect to 100 mass parts of said resin materials. The gist is to be blended in a range.

  The invention according to claim 5 is the damping resin composition according to any one of claims 1 to 4, wherein the resin material is at least one selected from an acrylic resin and an acrylic / styrene resin. The main point is that it is made of a polymer material.

  ADVANTAGE OF THE INVENTION According to this invention, the damping resin composition which is easy to exhibit the outstanding damping performance is provided.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments embodying the present invention will be described in detail.
The attenuating resin composition in the present embodiment is configured by mixing mica with a resin material. The aspect ratio of mica is in the range of 60-110. The average particle size of mica is in the range of 23-55 μm. The particle size distribution of mica is in the range of 15% or more. This particle size distribution is indicated by the frequency in a particle size range of X μm ± 10 μm, where the average particle size of mica is X μm.

  As the resin material, well-known general-purpose plastics and engineering plastics can be used. General-purpose plastics include polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyvinyl acetate, polymethyl methacrylate, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, ethylene / Methacrylic acid copolymer, ethylene / methacrylic acid ester copolymer, acrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene resin copolymer, and the like. Examples of the ethylene / acrylic acid ester copolymer include an ethylene / methyl acrylate copolymer and an ethylene / ethyl acrylate copolymer. Examples of the ethylene / methacrylic acid ester copolymer include an ethylene / methyl methacrylate copolymer and an ethylene / ethyl methacrylate copolymer. Examples of the engineering plastic include polyamide, polyester, polyacetal, polyester elastomer, and various liquid crystal polymers. A single kind of resin material may be used, or a plurality of kinds may be blended.

When the damping resin composition is configured as an aqueous damping resin coating, the resin material contained in the damping resin composition is contained as an aqueous resin dispersion in which resin particles are dispersed in an aqueous dispersion medium.
Examples of the material constituting the resin particles contained in the aqueous resin dispersion include acrylic resins, acrylic / styrene resins, urethane resins, phenol resins, vinyl chloride resins, vinyl acetate resins, vinyl acetate / acrylics. Resin, ethylene / vinyl acetate resin, epoxy resin, polyester resin, alkyd resin, acrylonitrile / butadiene copolymer rubber, styrene / butadiene copolymer rubber, butadiene rubber, and isoprene rubber. . These polymer materials may be modified.

  The resin particles may be formed of a single type of polymer material or may be formed of a plurality of types of polymer material. Furthermore, the aqueous resin dispersion may contain resin particles composed of these polymer materials alone, or may contain a plurality of types of resin particles.

  Examples of the aqueous dispersion medium in which the resin particles are dispersed include water and a mixed liquid of water and alcohol. Examples of the alcohol include methanol and ethanol. The aqueous resin dispersion can be obtained according to a known method such as emulsion polymerization in which a monomer and a polymerization initiator are dropped into an aqueous solution containing an emulsifier.

  Among these resin materials, at least one selected from acrylic resins and acrylic / styrene resins is preferable from the viewpoint that excellent damping performance is easily exhibited. Examples of the acrylic resin include a homopolymer having acrylic acid, acrylic ester, methacrylic acid and methacrylic ester as monomers, a mixture of these homopolymers, and a copolymer obtained by polymerizing these monomers. Can be mentioned. Examples of acrylic acid esters and methacrylic acid esters include methyl esters, ethyl esters, propyl esters, 2-ethylhexyl esters, ethoxyethyl esters, and the like. Examples of the acrylic / styrene resin include a copolymer of a monomer that forms the acrylic resin and a styrene monomer.

  Mica gives the resin material the ability to attenuate energy such as vibration energy and impact energy. Examples of mica include non-swellable mica and swellable mica. The aspect ratio of mica is in the range of 60 to 110, preferably in the range of 70 to 105. When the aspect ratio of mica is less than 60, it is difficult to exhibit excellent damping performance. On the other hand, even when the aspect ratio of mica exceeds 110, it is difficult to exhibit excellent attenuation performance. The aspect ratio indicates the long diameter / thickness of mica, and the aspect ratio of the present specification indicates that the mica is selected by randomly selecting 50 mica in the observation with a scanning electron microscope. Obtained by calculating the average of the measured values.

  The average particle diameter of mica is in the range of 23 to 55 μm, preferably in the range of 25 to 53 μm. When the average particle diameter of mica is less than 23 μm, it is difficult to exhibit excellent damping performance. On the other hand, even when the average particle diameter of mica exceeds 55 μm, it is difficult to exhibit excellent damping performance. The average particle diameter in this specification means an average particle diameter measured by a laser diffraction method.

  In addition to the above aspect ratio and average particle size, the particle size distribution indicated by the frequency in the particle size range of X μm ± 10 μm when the average particle size is X μm is extremely important for improving the damping performance of the damping resin composition. is there. The particle size distribution is in the range of 15% or more, preferably in the range of 17% or more. When the particle size distribution of mica is less than 15%, it is difficult to exhibit excellent damping performance. The upper limit of the particle size distribution of mica is not particularly limited from the viewpoint of enhancing attenuation, but is preferably in the range of 55% or less from the viewpoint of easy preparation of mica.

  The aspect ratio, average particle diameter, and particle size distribution of mica are adjusted to the above ranges by adjusting mica pulverization conditions, sieving conditions, and the like. The mica may be natural mica or synthetic mica. The mica may be a swellable mica that has been subjected to a treatment for enhancing the swellability.

  In the damping resin composition, the amount of mica is preferably 1 to 300 parts by mass, more preferably 5 to 270 parts by mass, and still more preferably 10 to 250 parts by mass with respect to 100 parts by mass of the resin material. When the blending amount of mica is less than 1 part by mass with respect to 100 parts by mass of the resin material, it may be difficult to exhibit excellent damping performance. On the other hand, when the compounding amount of mica exceeds 300 parts by mass with respect to 100 parts by mass of the resin material, the moldability of the attenuating resin composition cannot be sufficiently obtained due to excessive increase in the viscosity of the attenuating resin composition There is a fear. In addition, when comprised as a water-based attenuating resin coating, the amount of mica is preferably less than 200 parts by mass, more preferably less than 150 parts by mass with respect to 100 parts by mass of the resin particles. In the case of constituting as a water-based damping resin coating, if the amount of mica exceeds 200 parts by mass with respect to 100 parts by mass of the resin particles, there is a possibility that sufficient applicability as an attenuating resin coating may not be obtained. There is.

  The attenuating resin composition includes a benzothiazyl compound, a benzotriazole compound, a diphenyl acrylate compound, a normal phosphate ester compound, an aromatic secondary amine compound, and a halogen-containing ester compound as an attenuation imparting component. It is preferable to contain at least one compound selected from Attenuating component increases the amount of dipole moment in the coating to efficiently convert energy (excluding light energy and electrical energy) such as vibration energy, impact energy, and sound energy into thermal energy. Convert.

  Examples of the benzothiazyl compound include N, N-dicyclohexylbenzothiazyl-2-sulfenamide (DCHBSA), 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), N-cyclohexylbenzothiazyl-2- Sulfenamide (CBS), Nt-butylbenzothiazyl-2-sulfenamide (BBS), N-oxydiethylenebenzothiazyl-2-sulfenamide (OBS), and N, N-diisopropylbenzothia There may be mentioned at least one selected from dil-2-sulfenamide (DPBS).

  The benzotriazole-based compound is a compound in which a benzotriazole having an azole group bonded to a benzene ring is used as a mother nucleus and a phenyl group is bonded thereto, and 2- [2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole (2HPMMB), 2- (2′-hydroxy-5′-methylphenyl) benzotriazole (2HMPB), 2- (2 '-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole (2HBMPCB), 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) -5 -Chlorobenzotriazole (2HDBPCB) and 2- (2'-hydroxy-5'-t-octylphenyl) benzoto It includes at least one selected from azoles (2HOPB).

  Examples of the diphenyl acrylate compound include at least one selected from ethyl-2-cyano-3,3-diphenyl acrylate (ECDPA) and octyl-2-cyano-3,3-diphenyl acrylate (OCDPA).

  Examples of orthophosphate compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, tris (butoxyethyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl Examples thereof include at least one selected from phosphate and 2-ethylhexyl diphenyl phosphate.

  Examples of the aromatic secondary amine compound include p- (p-toluenesulfonylamide) diphenylamine, N, N′-di-2-naphthyl-p-phenylenediamine, N, N′-diphenyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, N-phenyl-1-naphthylamine, alkylated diphenylamine, octylated diphenylamine And at least one selected from 4,4′-bis (α, α-dimethylbenzyl) diphenylamine.

  Examples of the halogen-containing ester-based compound include at least one selected from tris (2-chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, and tris (tribromoneopentyl) phosphate.

  The content of the attenuating component is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less with respect to the total amount of the resin material and the attenuating component. When the content of the damping property-imparting component exceeds 20% by mass, the improvement rate of the damping performance tends to decrease, which may be uneconomical. The content of the attenuating component is preferably 1% by mass or more, and most preferably 1 to 5% by mass with respect to the total amount of the resin material and the attenuating component. If the content of the damping component is less than 1% by mass, it may be difficult to impart excellent damping properties.

  The damping resin composition includes other components such as a filler, gelling agent, foaming agent, foaming aid, dispersant, viscosity modifier, thickener, flow improver, curing agent, antifoaming agent, A film aid, an anti-settling agent, a wetting agent and the like can be blended as necessary. Examples of the filler include talc, clay, barium sulfate, magnesium carbonate, silica, diatomaceous earth, zeolite, ferrite, and carbon. Gelling agents are classified into organic gelling agents and inorganic gelling agents. Examples of organic gelling agents include starch and starch derivatives. Examples of inorganic gelling agents include ammonium nitrate, calcium nitrate, potassium carbonate, and chloride. Examples include potassium, calcium chloride, and ammonium chloride.

  The attenuating resin composition can be prepared by mixing the resin material and the mica described above by a known mixing means such as a stirrer. The damping performance of such a damping resin composition, that is, the damping performance of a molded article obtained from the same composition is indicated by a loss elastic modulus or a loss coefficient. That is, it is shown that the higher the loss elastic modulus or loss coefficient of the molded body, the higher the damping property of the molded body. The loss elastic modulus of the molded body can be measured by a known dynamic viscoelasticity measuring apparatus. The loss factor of the molded body can be measured by a known central excitation method loss factor measuring device.

  The damping resin composition can be used as a damping resin composition that attenuates vibration energy, a shock absorbing resin composition that attenuates impact energy, and the like. Examples of the application field of the attenuating resin composition include automobiles, building materials, home appliances, industrial machines, sports equipment, and medical equipment.

  As a molding method for molding the damping resin composition, a known resin molding method such as an injection molding method or an extrusion molding method can be used. When using the damping resin composition as a paint, it is possible to use paint means such as air spray guns, airless spray guns, brush paints, etc., in addition to the method of discharging paint from slits and applying it to the application site. It is.

  The molded body obtained from the damping resin composition contains mica. For this reason, when energy such as vibration energy, impact energy, and sound energy (excluding light energy and electrical energy) is transmitted to the molded product, such energy is generated by the interaction between the molecular chains of the resin material and mica. Is converted to thermal energy, the above-mentioned mica having the aspect ratio, average particle diameter, and particle size distribution is presumed to increase the interaction with the molecular chains of the resin material. Thereby, it becomes easy to exhibit excellent damping performance.

The effects exhibited by this embodiment will be described below.
(1) The aspect ratio of mica blended in the damping resin composition is in the range of 60 to 110, and the average particle size is in the range of 23 to 55 μm. Further, the particle size distribution of mica is in the range of 15% or more in the particle size distribution indicated by the frequency in the particle size range of X μm ± 10 μm when the average particle size is X μm. For this reason, it is easy to exhibit excellent damping performance.

  (2) When configured as an attenuating resin composition containing a resin material as an aqueous resin dispersion in which resin particles are dispersed in an aqueous dispersion medium, the resin particles can be used as an aqueous attenuating resin coating. Therefore, it is easy to exhibit excellent damping performance in consideration of the influence on the environment.

(3) It is preferable that the damping resin composition further contains the above-described damping component. In this case, it becomes easier to exhibit excellent damping performance.
(4) It is preferable that mica is mix | blended with the attenuating resin composition in 1-300 mass parts with respect to 100 mass parts of resin materials. In this case, it is easy to exhibit excellent damping performance and formability is easily maintained.

  (5) The resin material is preferably composed of at least one polymer material selected from acrylic resins and acrylic / styrene resins. In this case, it becomes easy to exhibit the attenuation performance in a temperature range of 10 ° C. to 50 ° C., for example.

Next, the embodiment will be described more specifically with reference to examples and comparative examples.
(Examples 1-11, Comparative Examples 1-13)
A damping resin composition was prepared by mixing 50 parts by mass of mica shown in Table 1 and 50 parts by mass of acrylic resin. Mixing of the mica and the acrylic resin was performed by melt-kneading the resin material using a mixing roll machine (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) at a heating temperature of 230 ° C. for 5 minutes. For the mica of each example, a scanning electron microscope S-2400 (manufactured by Hitachi) is used for measuring the aspect ratio, and Microtrac (trade name) particle size distribution measurement is used for measuring the average particle size and particle size distribution. It measured using apparatus MT3000 (made by Nikkiso).

<Measurement of dynamic viscoelasticity>
A sheet material having a thickness of 1 mm was obtained by molding the damping resin composition obtained in each example into a sheet. Each sheet material was cut into a size of 35 mm × 3 mm to obtain a test piece for dynamic viscoelasticity measurement. Using a dynamic viscoelasticity measuring device (RSA-II: manufactured by Rheometric Co., Ltd.), the loss elastic modulus E ″ was measured while the test pieces were continuously heated while being vibrated. The frequency was 10 Hz, the measurement temperature range was −40 ° C. to + 90 ° C., and the rate of temperature increase was 5 ° C./min. The peak value of the loss elastic modulus E ″ is also shown in Table 1 for each example.

表１に示されるように、各実施例では、アスペクト比、平均粒径及び粒度分布のいずれも前記範囲内である。各比較例では、アスペクト比、平均粒径又は粒度分布が前記範囲外であるものについて、表１に（※）で示している。表１の結果から明らかなように、実施例における損失弾性率Ｅ″のピーク値は、各比較例における損失弾性率Ｅ″のピーク値よりも高い値を示している。このように各実施例では、優れた減衰性能を発揮させることができる。

As shown in Table 1, in each example, all of the aspect ratio, the average particle diameter, and the particle size distribution are within the above ranges. In each comparative example, those having an aspect ratio, average particle size, or particle size distribution outside the above range are indicated by (*) in Table 1. As is clear from the results in Table 1, the peak value of the loss modulus E ″ in the examples is higher than the peak value of the loss modulus E ″ in each comparative example. Thus, in each Example, the outstanding attenuation | damping performance can be exhibited.

(Example 12 and Comparative Example 14)
In Example 12 and Comparative Example 14, a damping resin coating containing an aqueous resin dispersion was prepared. As shown in Table 2, in the damping resin coating, about 200 parts by mass of mica is blended with 100 parts by mass of the acrylic resin contained in the aqueous resin dispersion. Further, N-cyclohexylbenzothiazyl-2-sulfenamide (CBS) is added as an attenuation imparting component so as to be about 3.2 mass% with respect to the total amount of the acrylic resin and the attenuation imparting component. doing. In addition, in the attenuating resin coating material of each example, additives such as calcium carbonate and a thickener are blended so as to have the same mass ratio with respect to the acrylic resin.

<Measurement of loss factor>
After applying the damping resin paint of Example 12 and Comparative Example 14 to a steel plate (thickness 0.8 mm), a coating film was formed by heating and drying at 140 ° C. for 43 minutes, and these coating films were used as test pieces. did. In addition, the coating amount was adjusted so that the thickness of the coating film with respect to a steel plate might become the same. About the test piece of each example, using a central excitation method loss factor measuring device (CF5200 type, manufactured by Ono Sokki Co., Ltd.), the loss factor at 20 ° C., 40 ° C. and 60 ° C., and the peak value of the loss factor It was measured. Table 2 also shows the loss factor at each temperature, and the peak value and peak temperature of the loss factor.

表２に示されるように、実施例１２では、アスペクト比、平均粒径及び粒度分布のいずれも前記範囲内である。比較例１４では、アスペクト比、平均粒径及び粒度分布が、前記範囲外である。表２の結果から明らかなように、実施例１２における損失係数のピーク値は、比較例１４における損失係数のピーク値よりも高い値を示している。このように実施例１２では、優れた減衰性能を発揮させることができる。

As shown in Table 2, in Example 12, all of the aspect ratio, the average particle size, and the particle size distribution are within the above ranges. In Comparative Example 14, the aspect ratio, average particle size, and particle size distribution are outside the above ranges. As is clear from the results in Table 2, the peak value of the loss factor in Example 12 is higher than the peak value of the loss factor in Comparative Example 14. Thus, in Example 12, excellent attenuation performance can be exhibited.

Claims (5)

A damping resin composition comprising mica mixed with a resin material,
The mica has an aspect ratio in the range of 60 to 110 and an average particle size in the range of 23 to 55 μm. When the average particle size is X μm, the particle size distribution indicated by the frequency in the particle size range of X μm ± 10 μm is A damping resin composition characterized by being in a range of 15% or more. The damping resin composition according to claim 1, wherein the resin material is contained as an aqueous resin dispersion in which resin particles are dispersed in an aqueous dispersion medium. It contains at least one compound selected from benzothiazyl compounds, benzotriazole compounds, diphenyl acrylate compounds, orthophosphate compounds, aromatic secondary amine compounds, and halogenated ester compounds. The damping resin composition according to claim 1 or 2. The said mica is mix | blended in 1-300 mass parts with respect to 100 mass parts of said resin materials, The attenuating resin composition as described in any one of Claims 1-3 characterized by the above-mentioned. The damping resin according to any one of claims 1 to 4, wherein the resin material is composed of at least one polymer material selected from an acrylic resin and an acrylic / styrene resin. Composition.