WO2001032777A1

WO2001032777A1 - Resin for high damping steel plate

Info

Publication number: WO2001032777A1
Application number: PCT/JP1999/006996
Authority: WO
Inventors: Yasuyuki Ohira; Mitsuo Hori
Original assignee: Shishiai-Kabushikigaisha
Priority date: 1999-11-01
Filing date: 1999-12-13
Publication date: 2001-05-10
Also published as: WO2001032776A1

Abstract

A resin for a high damping steel plate usable as a structural member or a part thereof of a machine, a building, a vehicle and the like, characterized in that it comprises an ester-based resin and an active component which has a function to increase the dipole moment in the resin.

Description

Itoda Resin for damping steel sheet Technical field

The present invention relates to a resin for vibration-damping steel sheets used as a structural member of a machine, a building, a vehicle, or the like, or a part thereof. Background art

A damping steel sheet is a damping material having a multilayer structure in which an intermediate layer made of a rubber material is sandwiched between metal layers. These vibration damping steel plates are used in automobile oil pans, engine covers, dash panel hopper chute, transport equipment stoppers, household appliances, and other vibration-reducing components of metalworking machinery. Has been applied to Since the damping performance of the damping steel sheet depends on the performance of the rubber material constituting the intermediate layer sandwiched between the metal layers, there was a problem that sufficient damping performance was not exhibited. SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks of the conventional damping steel sheet and to provide a higher-performance damping steel sheet. It proposes a resin. Disclosure of the invention

The resin for vibration-damping steel sheets of the present invention can be used as an oil pan for automobiles, an engine cover, a chute for a dash panel hopper, a stopper for transport equipment, home electric appliances, and other vibration reducing members for metalworking machinery. It can be used for damping steel sheets applied to structural members of machines. The resin for vibration damping steel sheets is characterized in that an ester-based resin is mixed with an active component that increases the amount of dipole moment in the resin. The ester resin constitutes an intermediate layer of the damping steel sheet, and is made of polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, or polybutylene naphthalate resin. Thermoplastic saturated polyester resin selected from 1,4-cyclohexane dimethylene terephthalate resin, polyproprolactone resin, p-hydroxybenzoic acid polyester resin, and polyarylate resin is preferred. Can be used. Further, when the ester resin itself has adhesiveness, it is not necessary to bond the ester resin between the metal layers by interposing an adhesive between the ester resin and the metal layer. The above-mentioned ester resin itself has some adhesiveness, but in order to secure stronger adhesiveness, epoxy resin or other epoxy-based tackifier, glycerol ester or cured rosin, etc. Rosin-based tackifier, bear-mouth resin-based tackifier obtained by mixing naphthenic oil or phenolic resin with bear-mouth resin, xylene (formaldehyde resin, etc.) A tackifier such as an agent can be added as needed. The present inventors have elucidated a new mechanism of absorption and attenuation of vibration energy. The mechanism is as follows. That is, FIG. 1 shows an arrangement state of the dipoles 12 in the ester resin 11 before the vibration energy is transmitted. It can be said that the arrangement state of the dipoles 12 is in a stable state. However, when vibration energy is transmitted to this, displacement occurs in the dipoles 12 existing inside the ester-based resin 11, and as shown in FIG. 2, each dipole 1 inside the ester-based resin 11 is displaced. 2 will be placed in an unstable state, and each dipole 1 2 will try to return to a stable state as shown in Figure 1. At this time, energy is consumed. It is considered that the vibration energy is absorbed through the displacement of the dipole inside the ester resin 11 and the energy consumption due to the restoring action of the dipole. From the vibration damping mechanism, the larger the amount of dipole moment in the ester resin 11 as shown in FIGS. 1 and 2, the higher the damping property of the ester resin 11 It is considered to be. The active component is a component that dramatically increases the amount of dipole moment in the ester resin. The active component itself has a large dipole moment, or the active component itself has a dipole moment. Although it is small, it means a component that can dramatically increase the amount of dipole moment in the ester resin by blending the active component. For example, the amount of dipole moment generated in the ester-based resin 11 under the given temperature conditions and energy level can be increased by 3 times or 10 times as shown in Fig. 3 by adding an active ingredient to the ester resin. In other words, the amount of power increases. Along with this, the energy consumption due to the restoring action of the dipole when energy is transmitted will also increase dramatically, and it is thought that the vibration suppression performance far exceeds the prediction. Examples of active ingredients that induce such effects include N, N-dicyclohexylbenzothiazyl-2-sulfenamide (DCHB SA), 2-mercaptobenzothiazolyl (MBT), and dibenzothiazyl sulfide (MBT). MBTS), N-cyclohexyl benzothiazyl di-2-sulfenamide (CB S), N-tert—Ptinolebenzothiazinole-1 2-snolefenamide (BB S), N-oxyzetj Lenbenzothiaziru 2-sulfenamide (OB S), N, N-diisopropyl benzothiazyl-2-sulfenamide (DPBS) and other benzothiazyl group-containing compounds containing one or more benzotriazoles with an azole group bonded to the benzene ring With the mother nucleus Phenyl group-bonded 2— {2 'one-side oxy-one 3'-(3 ", A", 5 ", 6" tetrahydrophtalidamidemethyl) -5'-methylphenyl} -benzotriazole (2HPMMB), 2-{2 '—Hydrox xy-5' —methylphenyl} —Benzotriazole (2HMPB), 2- {2 '—Hydrox xy-1 3' — t—Butyl-5 '—Methylphenyl} — 5—Black mouth benzotriazole (2HBMP CB), 2— {2 ′ —Hide mouth xyl 3 ′, 5 ′ di-t-t-butylphenyl} 1—5—Black mouth benzotriazole (2 HDBPCB ) Or a compound containing a diphenyl acrylate group such as ethyl 2-cyano 1,3,3-diphenyl acrylate One or two or more selected from the group consisting of two hydroxy-2-4-methoxybenzenes One or more compounds selected from compounds having a benzophenone group, such as zophenone (HMBP) and 2-hydroxy-14-methoxybenzophenone-15-sulfonic acid (HMBPS) be able to. In addition, when selecting the ester-based resin, in addition to the magnitude of the dipole moment inside the molecule, the purpose, use form, handleability, moldability, availability, temperature performance (heat resistance and cold resistance) ), Weather resistance, price, etc. should be considered. Incidentally, the amount of dipole moment in the above-mentioned active ingredient varies depending on the kind of the active ingredient, similarly to the amount of dipole moment in the ester-based resin. Even when the same active component is used, the amount of dipole moment generated in the ester resin changes depending on the temperature when vibration energy is applied. Also, the amount of dipole moment changes depending on the magnitude of vibration energy applied to the ester resin. For this reason, it is desirable to select and use the active ingredient that gives the largest amount of dipole moment in consideration of the temperature and energy at the time of application. In deciding the active ingredient to be mixed in the ester resin, it is good to select the one having a similar value in consideration of the compatibility between the active ingredient and the ester resin, that is, the SP value. This active ingredient is preferably blended in such a manner that the weight ratio with the above-mentioned ester-based resin becomes 907 10 to 50 50. If the ester-based resin Z active component is less than 90/10, the effect of dramatically increasing the amount of dipole moment in the ester resin cannot be obtained, and the weight ratio is 50 Z. If it exceeds 50, even if the amount of the active ingredient is increased, an increase in the amount of the dipole moment cannot be expected by the increased amount, and there is a risk of causing a problem that the formability is deteriorated. Because. When two or more active ingredients are mixed, at least two or more active ingredients having different glass transition points can be added to the ester resin to extend the temperature range in which vibration absorption performance is exhibited. It is. The ester resin may be filled with an inorganic filler such as calcium carbonate, talc, zeolite, silica, kaolin, alumina, titanium oxide, zinc white, myriki, and graphite. In addition, in addition to the above-mentioned components, an antioxidant, a reinforcing agent, a reinforcing agent, an antistatic agent, a flame retardant, a lubricant, a foaming agent, a coloring agent, and the like can be added to the ester-based resin as necessary. . BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a schematic diagram showing dipoles in an ester-based resin.

FIG. 2 is a schematic diagram showing a state of a dipole in an ester resin when vibration energy is applied.

FIG. 3 is a schematic diagram showing a state of a dipole in an ester resin when an active ingredient is blended. FIG. 4 is a graph showing mechanical properties E ″ (dyne / cm ² ) at each temperature under a frequency of 110 Hz for the samples of Examples 1 to 3 and Comparative Examples 1 to 4.

FIG. 5 is a graph showing the loss coefficient at each temperature of a damping steel sheet obtained by using the samples of Example 2 and Comparative Example and sandwiching them between two stainless steel sheets. Example

DCHB SA was added to an ester-based resin (Byron, manufactured by Toyobo Co., Ltd.) for 100/0 (Comparative Example), 90/10 (Example 1), 80Z20 (Example 2) and 70Z30 (Example 3). Each weight ratio was blended and formed into a sheet. With respect to each of the samples of Examples 1 to 3 and Comparative Example, the loss elastic modulus tan 6 at each temperature (at 140 ° C. to 40 ° C.) under a frequency of 110 Hz was measured, and is shown in FIG. The measurement of the loss elastic modulus tan S was performed using a dynamic viscoelasticity measurement test device (Rheovaiblon DDV-25FP, manufactured by Orientec Co., Ltd.). From Fig. 4, it can be seen that the comparative example using the ester resin alone has a loss elastic modulus tan S of about 1.7 with a peak at about 0 ° C, whereas the example 1 has a peak tan S Moved about 2-3 ° C, and the level was between about 0 ° C and about 30 ° C, and tan S was about 0.1-0.3 higher than that of the comparative example. On the other hand, in Examples 2 and 3, as the temperature increases from about 0 ° C to about 10 ° C, the loss elastic modulus taηδ increases from about 1.7 to about 2 or 2.4, Furthermore, the loss elastic modulus ta η δ rose sharply to an unmeasurable level at about 10 ° C to 15 ° C. From the above results, it was confirmed that the compounding of D CHB S 比較的 relatively improved the vibration damping performance of the ester resin. Next, damping steel sheets were manufactured using the samples of Example 3 and Comparative Example, respectively, and the results of measuring their loss coefficients are shown in FIG. The damping steel sheet has a thickness of 0.5 The resin for vibration damping steel sheets formed into a sheet with a thickness of 2 mm is sandwiched between two stainless steel plates of 2 mm in thickness, and the loss coefficient is measured by a dynamic viscoelasticity measurement test. The measurement was performed using a device (Leo Vibron DDV-25FP, manufactured by Orientec Co., Ltd.). According to Fig. 5, the loss coefficient of the sample using the comparative example was in the range of about 0.1 to 0.14 between 20 ° C and 30 ° C, and the peak was at 110 ° C. In contrast, the sample using the sample of Example 3 had a loss coefficient in the range of about 0.08 to 0.27 between 20 ° C and 30 ° C, and its peak was about 15 ° C. Met. From this, it was confirmed that when the sample according to Example 3 was used, the damping performance was dramatically improved.

Claims

Scope of word blue

1. A resin for vibration-damping steel sheets, wherein an active ingredient that increases the amount of dipole moment in the resin is mixed with the ester resin.

2. The resin for damping copper plate according to claim 1, wherein the weight ratio between the ester resin and the active ingredient is 90 / lO to 50Z50.

3. The ester resin is polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, poly-1,4-cyclohexanedimethylene terephthalate resin, poly 2. The vibration-damping steel sheet according to claim 1, wherein the resin is a thermoplastic saturated polyester resin selected from the group consisting of a power prolactone resin, a ρ-hydroxybenzoic acid polyester resin, and a polyarylate resin. resin.

4. The active ingredient is one or more compounds selected from a compound containing a benzothiazyl group, a compound containing a benzotriazole group, a compound containing a diphenylacrylate group, and a compound containing a benzophenone group. The resin for vibration-damping steel sheet according to claim 1, which is characterized in that: