WO2001032776A1

WO2001032776A1 - Resin for damping steel plate

Info

Publication number: WO2001032776A1
Application number: PCT/JP1999/006096
Authority: WO
Inventors: Yasuyuki Ohira; Mitsuo Hori
Original assignee: Shishiai-Kabushikigaisha
Priority date: 1999-11-01
Filing date: 1999-11-01
Publication date: 2001-05-10
Also published as: WO2001032777A1

Abstract

A resin for a damping steel plate, characterized in that the resin comprises an ester resin and, incorporated therein, an active component which increases the dipole moment of the ester resin. The damping steel plate comprising the resin is used as a structural member of a machine, a building, a vehicle and the like, or a part of the member.

Description

Itoda β 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 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 vibration damping steel sheet resin of the present invention is used in automobile oil pans, engine covers, chute portions of dash panel hoppers, stoppers of transport equipment, home electric appliances, and other vibration reducing members of metalworking machines. It can be used for the damping steel plate applied to the structural member of the above. This resin for vibration-damping steel sheets is characterized in that an ester-based resin is mixed with an active ingredient that increases the amount of dipole moment in the resin. The ester-based resin constitutes an intermediate layer of the damping steel sheet, and includes a polyether; a phthalate-based resin, a polybutylene terephthalate-based resin, a polyethylene naphthalate-based resin, a polybutylene naphthalate-based resin, and a polystyrene resin. Thermoplastic saturated polyester resins selected from 2,4-cyclohexane dimethylene terephthalate resin, polyproprolactone resin, p-hydroxybenzoic acid polyester resin, and polyarylate resin are 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, a rosin-based tackifier such as glycerol'ester or cured rosin is used for the above-mentioned ester-based resin, and a naphthene-based adhesive is used for cumarone resin. If necessary, a tackifier such as a coumarone resin-based tackifier mixed with oil or phenol resin, or a phenol-terpene-based resin tackifier such as xylene'formaldehyde resin may 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 1 and 2 is in a stable state.However, when vibration energy is transmitted to the arrangement state, the dipoles 1 2 existing inside the ester-based resin 11 1 are displaced. As shown in Fig. 2, each dipole 1 2 inside the ester-based resin 11 is placed in an unstable state, and each dipole 1 2 tries to return to a stable state as shown in Fig. 1. . At this time, energy is consumed. These ester resins It is considered that the vibration energy is absorbed through the displacement of the dipole inside 1 and the energy consumption due to the restoring action of the dipole. From the mechanism of vibration damping, as the amount of dipole moment in the ester resin 11 increases as shown in FIGS. 1 and 2, the damping of the ester resin 11 increases. It is thought that the nature will also increase. The active component is a component that dramatically increases the amount of dipole moment in the ester resin, and the active component itself has a large dipole moment amount, or the dipole of the active component itself. Although the amount of moment is small, it refers to a component that can drastically 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 resin 11 under a predetermined temperature condition and energy level can be increased by a factor of three as shown in FIG. That is to say, an increase of 0 times. 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-12-sulfenamide (DCHB SA), 2-mercaptobenzothiazole (MBT), and dibenzothiazyl sulfide (MB TS), N-cyclohexylbenzothiazyl-1-sulfenamide (CBS), N-tert-butylbenzothiazyl-2-sulfenamide (BBS), N-oxyxeti lembenzothiazilyl 2-sulfenamide (OB S ), N, N-diisopropyl benzothiazyl 2-sulfenamide (DPBS) and other benzothiazyl group-containing compounds, or one or more compounds selected from benzotriazoles having an azole group bonded to the benzene ring. A mother nucleus to which a phenyl group is bonded 2— {2'-hydroxy-1-3 '— (3, 4 ", 5", 6 "Tetrahydridophthalimide methyl 1-5 '-methylphenyl}-benzotriazole (2HPMMB), 2-{2'-hydridyloxy 5 '-methylphenyl)-benzotriazole (2HMPB), 2- {2 '—Hide mouth 3' — t—Butyl mono 5 '—Methylphenyl} — 5—Chloro benzotriazolyl (2HBMP CB), 2— {2'Hide mouth xy 3', 5 '—Di-t-butylphenyl} ― One or more compounds selected from the group consisting of compounds having a benzotriazoyl group such as benzotriazoyl (2-HDBPCB) One or more selected from compounds containing diphenyl acrylate groups such as 3,3-diphenyl acrylate, or 2-hydroxy 4-methoxybenzophenone (HMBP) , 2—Hydroxy-4-methoxybenzo One or more selected from compounds having a benzophenone group such as enone-5-sulfonic acid (HM BPS) can be mentioned. In addition to the magnitude of the dipole moment in part, consideration should also be given to applications, usage, handling, moldability, availability, temperature performance (heat and cold resistance), weather resistance, price, etc. The amount of dipole moment in the above-mentioned active ingredient is variously different depending on the type of the active ingredient, similarly to the amount of dipole moment in the ester-based resin. The temperature at which the energy is applied also changes the amount of dipole moment generated in the ester-based resin, and increases the vibration energy applied to the ester-based resin. Therefore, it is desirable to select and use the active component that gives the largest amount of dipole moment in consideration of the temperature and energy at the time of application. In determining the active ingredient to be mixed in the ester resin, the active ingredient and the S Considering the compatibility with the ter-based resin, that is, the SP value, it is good to select one having a similar value: The active ingredient has a weight ratio of 90/10 to 50 to the ester-based resin. / 50 should be blended. When the amount of the active ingredient in the ester resin is less than 90/10, the sufficient effect of dramatically increasing the amount of dipole moment in the ester resin cannot be obtained, and the weight ratio is not more than 50. If it exceeds Z50, even if the amount of the active ingredient is increased, an increase in the amount of dipole moment by the increased amount cannot be expected, and there is a risk of causing a problem that the formability is deteriorated. Because there is. 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. The ester-based resin may be filled with an inorganic filler such as calcium carbonate, talc, zeolite, silica, kaolin, alumina, titanium oxide, zinc oxide, Myriki, graphite and the like. In addition, in addition to the above 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 resin as required. -Brief description of drawings

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 shows the frequency of the samples of Examples 1-3 and Comparative Examples 1-4. Mechanical properties at each temperature under Hz E "(dyne / cm

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

DCHBSA was added to an ester resin (Byron, manufactured by Toyobo Co., Ltd.), and the weight of each of 100 / (Comparative Example), 90Z10 (Example 1), 80/20 (Example 2) and 70Z30 (Example 3). It was compounded in a ratio and formed into a sheet. With respect to each of the samples of Examples 1 to 3 and Comparative Example, the loss elastic modulus ta η δ at each temperature (_40 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 in the comparative example using only the ester resin, the loss elastic modulus tan S is about 1.7 with a peak at about 0 ° C, whereas in the example 1, the peak at tan 5 is obtained. Moves about 2 to 3 and its level is about 0 ° C to about 30. Tan S also to that the Comparative Example between C was exceeded by about 0.1 to 0 3 -. On the other hand, Examples 2 and 3 of also of the yarn (TC force al about 1 0 ^e C in temperature as but increases the loss increases modulus ta eta [delta] is about 1.7 longitudinal to about 2 or 2.4, still about 10 ^e C~ 1 5 C loss modulus in the boundary ta eta [delta] is unmeasurable -The results confirmed that the addition of D CHB S Α relatively improved the damping performance of the ester-based resin. Each sample was used to produce a damping steel sheet, and the loss coefficient was measured.The results are shown in Fig. 5. The damping steel sheet was placed between two stainless steel sheets with a thickness of 0.5 mm. Damping steel sheet formed into a 0.2 mm thick sheet The loss coefficient was measured using a dynamic viscoelasticity measurement tester (Reo Vibron DDV-25FP, manufactured by Orientec Co., Ltd.). From Fig. 5, the loss coefficient of the sample using the sample of the comparative example was in a range of about 0.1 0.14 between −20 ° C. 30 and its peak was 110 at 110. On the other hand, in the case of using the sample of Example 3, the loss coefficient was in the range of about 0.00.27 between 20 ° C and 30 ° C, and the peak was about 15 ° C. From this, it was confirmed that when the sample according to Example 3 was used, the damping performance was dramatically improved.

Claims

Speculation of Word

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 a vibration-damping steel sheet according to claim 1, wherein the weight ratio between the ester-based resin and the active ingredient is 90/10 to 50 Z50.

3. The ester resin is polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, poly 1,4-cyclohexanediene. It is a thermoplastic saturated polyester resin selected from methylene terephthalate resin, polyprolactone resin, p-hydroxybenzoic acid polyester resin, and polyarylate resin. The resin for vibration-damping steel sheets according to claim 1, wherein

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: