JP2001072777A - Vibration-damping sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vibration-damping sheet which exhibits an excellent vibration absorption in accordance with the attempted use temperature by compounding a thermoplastic resin having chlorine groups and cyano groups as side chains and a main chain comprising C-C single bonds or double bonds with a benzothiazyl-group-containing compound. SOLUTION: A thermoplastic resin in an amount of 100 pts.wt. which has 20 wt.% or higher (based on the polymer) chlorine groups and 5-45 wt.% (based on the polymer) cyano groups as side chains, a main chain comprising C-C single bonds or double bonds, a degree of polymerization of 300-2,000, and an average mol.wt. of 40,000-400,000 is compounded with 20-200 pts.wt, benzothiazyl- group-containing compound. Since this vibration-damping sheet has a wide temperature range, wherein tan δ is 1 or higher and since the peak temperature of tan δ is adjustable to about room temperature, the sheet has a high vibration absorption capacity. The sheet can be produced by extrusion, solvent casting, bank molding or press molding.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a housing structure such as a house, an apartment, an office building, an expressway, a viaduct,
The present invention relates to a vibration damping sheet used for reducing vibration and noise generated in various structures such as railway tracks, various vehicles such as automobiles, railway vehicles, ships, and the like, home appliances, OA devices, and the like.

[0002]

2. Description of the Related Art In general, a loss tangent (tan δ) is used as an index of a vibration damping property. It is said that the larger the tan δ is, the more excellent the vibration absorbing material is. Since tan δ depends on the temperature of the atmosphere, it is necessary to increase the value of tan δ under the used atmosphere in order to maximize the damping performance of the damping sheet.

[0003] In general, polyvinyl chloride is known as a resin having a larger tan δ than other resins.
When the temperature dependence of nδ is measured, the peak position (glass transition temperature, Tg) is 80 ° C., and the peak is sharp. Therefore, at a temperature other than around 80 ° C., the vibration absorption performance is extremely reduced. That is, the operating temperature range of ordinary materials (-2
(0 to 60 ° C.), there is a disadvantage that the material is inferior in vibration absorption performance. Therefore, as a method of shifting the peak position to a lower temperature side or expanding the peak width, a method of adding a phthalic acid-based, linear dibasic acid ester-based, phosphate ester-based, trimellitic acid-based plasticizer to the resin, , A method of blending a polymer having a peak temperature of tan δ lower than that of polyvinyl chloride (see JP-A-9-316295) is generally employed.

However, when a method of blending a polyvinyl chloride resin with a plasticizer or a resin having a lower Tg than polyvinyl chloride is used, the peak position of tan δ moves to a lower temperature side,
Although the shape of the peak is broad, the peak height is reduced and the vibration absorption performance is deteriorated. In addition, in the case of adding a plasticizer, particularly when the amount of the plasticizer is large, in addition to a decrease in vibration damping performance, problems such as sticky surfaces and poor appearance due to bleeding of the plasticizer occur.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and provides a vibration damping material sheet which exhibits excellent vibration absorption according to the intended use temperature.

[0006]

According to the first aspect of the present invention,
Thermoplastic resin whose side chain is 20 wt% or more of chlorine group (for polymer), 5-45 wt% of cyano group (for polymer), and whose main chain is composed of single bond or double bond of carbon and carbon, and benzothiazyl group It is a vibration damping sheet containing a contained compound.

A second aspect of the present invention is a polymer having a benzothiazyl group containing a polymer in which a side chain of a polyvinyl chloride resin is provided with 5 to 45% by weight of a cyano group (based on a polymer) while leaving 20% by weight or more of a chlorine group (based on a polymer). It is a vibration damping sheet containing a compound.

[0008] The invention according to claim 3 is a compound comprising a benzothiazyl group and a polymer in which a side chain of a chlorinated polyolefin is provided with 5 to 25% by weight of cyano group (based on polymer) while leaving at least 20% by weight of chlorine group (based on polymer). Damping sheet consisting of

The thermoplastic resin of the present invention has a main chain mainly composed of a single bond of carbon and carbon, and in some cases a double bond, and a side chain mainly composed of hydrogen, chlorine group and cyano group. ,
There is no particular limitation as long as the chlorine group in the side chain is 20 wt% or more (based on the polymer) and the cyano group is 5 to 45 wt% (based on the polymer). Examples of the polymer include a polymer having a chlorine or cyano group added to a side chain of a polymer such as polyethylene or polypropylene, and vinyl chloride having a cyano group added to a side chain. If the amount of chlorine groups in the side chain decreases, the peak height of tan δ decreases, so that 20 w
At least t% is necessary. When the cyano group is less than 5 wt%, the temperature range where the tan δ peak height exceeds 1 becomes narrow, and when it exceeds 45 wt%, the peak height becomes low.

The average molecular weight by weight of the thermoplastic resin is not particularly limited, but is preferably from 200,000 to 400,000. If it is lower than 40,000, the mechanical properties are weak, and if it is higher than 400,000, the formability at the time of forming a sheet becomes poor.

As a thermoplastic resin containing a chlorine group and a cyano group in a side chain, for example, 20% by weight or more of chlorine group (to polymer) is left in a side chain of a polyvinyl chloride resin as described in claim 2. Thus, a polymer provided with 5 to 45% by weight (based on the polymer) of a cyano group is preferably used. The method of providing a cyano group to the side chain of the vinyl chloride resin is not particularly limited, but the polymer is dissolved in a polar aprotic solvent such as dimethylformamide or dimethylsulfoxide, and potassium cyanide is added to the solution. The method of substituting a chain with a cyano group may be advantageous in that the reaction time is short. At that time, 20 wt% or more of the chlorine group is left, and the content of the cyano group is adjusted to 5 to 5 depending on the temperature used as the vibration damping material.
It is desirable to adjust to 45 wt% (based on the polymer). Examples of the polyvinyl chloride resin used in the present invention include polyvinyl chloride, polyvinyl chloride, polyvinylidene chloride, and copolymers of polyethylene and polyvinyl chloride. Although the polymerization degree is not particularly limited, it is 300 to 2
It is desirably in the range of 000. If it is lower than 300, the mechanical properties are weak, and if it is higher than 2000, the fluidity of the resin is poor, and it is necessary to add a plasticizer or the like, and as a result, the vibration absorption performance is reduced.

As a thermoplastic resin containing a chlorine group and a cyano group in the side chain, for example, as described in claim 3, 20% by weight or more of chlorine group (to the polymer) is left in the side chain of the chlorinated polyolefin resin. And a polymer provided with 5-45 wt% of cyano group (based on the polymer). The method of providing a cyano group to the side chain of the chlorinated polyolefin is not particularly limited, but the above polymer is dissolved in a polar aprotic solvent such as dimethylformamide or dimethyl sulfoxide, and the side chain is added by adding potassium cyanide to the solution. May be replaced with a cyano group in that the reaction time is short. At this time, it is desirable to keep the chlorine group at 20 wt% or more and adjust the content of the cyano group to 5 to 45 wt% (based on the polymer) according to the temperature used as the vibration damping material. Examples of the chlorinated polyolefin of the present invention include chlorinated polyethylene and chlorinated polypropylene. For example, in the case of chlorinated polyethylene, the average weight molecular weight is not particularly limited, but is preferably 40,000 to 400,000. 4
If it is lower than 10,000, the mechanical properties are weak, and if it is higher than 400,000, the formability deteriorates.

The side chain of the thermoplastic resin contains 5 wt% or less of substituents other than hydrogen, chlorine, and cyano, such as hydroxyl, acetyl, methyl, ethyl, bromine, and fluorine. (Against the polymer). If the content exceeds 5% by weight, the vibration absorbing performance is inferior.

As the benzothiazyl group-containing compound used in the present invention, N, N-dicyclohexyl-1,
2-benzothiazolylsulfenamide, N-cyclohexyl-2-benzothiazolylsulfenamide, N-
Oxydiethylene-2-benzothiazolylsulfenamide, dibenzothiazyl disulfide and the like are selected. The blending amount of the benzothiazyl group-containing compound with respect to 100 parts by weight of the thermoplastic resin containing a chlorine group and a cyano group is from 20 to 20.
0 parts by weight is preferred. If the amount is less than 20 parts by weight, the effect of addition is not recognized, and the vibration absorption performance is poor. If the amount is more than 200 parts by weight, the polymer loses its flexibility and becomes a brittle material.

[0015] A stabilizer may be added to the vibration damping sheet in order to suppress decomposition and degradation due to dehydrochlorination reaction due to heat and light. As the stabilizer, a stabilizer generally used for polyvinyl chloride resin may be used, for example, lead white, tribasic lead sulfate, lead salts such as dibasic lead phosphite, stearic acid, Lauric acid, ricinoleic acid, etc. and lead, cadmium,
Examples thereof include metal soaps such as barium, zinc, and calcium, and organic tin compounds such as dibutyltin dilaurate, dibutyltin maleate, and dibutyltin dilaurate.

Further, a lubricant may be added to the vibration damping sheet in order to suppress the thermal decomposition of the thermoplastic resin and improve the processability. As the lubricant, a lubricant generally used for polyvinyl chloride resins may be used. For example, higher fatty acids such as stearic acid and palmitic acid and derivatives thereof (esters and ethers), waxes such as carnauba wax and candelilla wax And the like.

Examples of the method for producing the vibration damping sheet include an extrusion molding method, a solvent casting method, a bank molding method, and a press molding method. In the case of performing extrusion molding, the extruder may be a single screw extruder, but a twin screw extruder is preferable in order to improve kneading properties. At this time, as the screw form, a full flight may be used, but it is preferable to provide mixing because kneading properties are further improved. The die is preferably a T die. The take-off machine is
A narrow pressure roll such as a calender may be provided, a belt-belt molding in which narrow pressure is applied between belts, or a belt / roll take-up machine. It is desirable that the temperature be set so that the temperature is gradually lowered to Tg or lower from the upstream side.

When the solvent casting method is used, the coating machine is preferably a die coater or a comma coater in order to improve the thickness performance. The solution may be applied on an endless belt using a steel belt, or may be applied on another plastic film or sheet insoluble in the solvent used and then dried. The solvent may be any solvent that dissolves a compound containing a benzothiazyl group and a polyvinyl chloride resin to which a cyano group has been added, but in order to achieve sufficient drying, the boiling point of the polymer is not higher than the melting point or the decomposition point. And a low boiling point (66 ° C.) agent such as THF (tetrahydrofuran). After coating, the resin solution is continuously or intermittently sent to a drying furnace, and is dried and peeled off. The solvent content of the sheet at the time of peeling is desirably 3 to 20%. Since it cannot be dried from the substrate side, drying to 3% or less is time-consuming and inefficient. On the other hand, if it is 20% or more, the viscosity of the resin layer is too low to be stably peeled off, which is not preferable. After peeling, the resin layer is further dried on both sides in a drying oven to evaporate the solvent almost completely.

(Function) The vibration-damping sheet of the present invention has a side chain containing 20% by weight or more of chlorine groups (based on polymer) and 5 to 45% by weight of cyano groups.
% (Based on polymer) and a benzothiazyl group-containing compound, so that the temperature range where tan δ is 1 or more is wide and the peak temperature of tan δ can be adjusted to around room temperature, so that the vibration absorption performance is improved. A vibration-damping sheet with a high value can be obtained. Further, since it contains a benzothiazyl group-containing compound, no plasticizer is required. Therefore, the bleed-out phenomenon of the plasticizer does not occur, and the appearance is not deteriorated with time and the surface is not sticky.

[0020]

Example 1 Example 1 [Preparation of damping sheet] Polyvinyl chloride (manufactured by Sekisui Chemical Co., Ltd.)
SLP40, polymerization degree = 400) was dissolved in dimethylformamide, and sodium cyanide was added to replace 100 parts of a polymer prepared by substitution with a cyano group (chlorine group: 25% by weight, cyano group: 27% by weight vs. polymer), dibutyltin maleate: 5 parts And 2 parts of carnauba wax were kneaded with a twin screw extruder (Nippon Steel Works: TEX44) equipped with a screw of L / D = 36 equipped with a mixing part. During extrusion, N, N-dicyclohexyl-1, from a side feeder
2-Benzothiazolylsulfenamide (Ouchi Shinko Chemical Co., Ltd .; Noxeller DZ) was supplied at a weight ratio of 1: 1 to the polymer. Molding temperature is 160
° C. The discharge unit was provided with a T-die to form a sheet. In addition, confirmation of the content of the cyano group and the chlorine group was quantitatively evaluated by X-ray fluorescence.

[Evaluation of the damping sheet] (tan δ) The tan δ of the damping sheet was measured at a frequency of 1 using a viscoelasticity meter (Toyo Seiki Seisakusho, Rheograph).
It was measured at 00 Hz. The tan δ was calculated from the modulus of longitudinal elasticity (E ′, E ″). The results are shown in Table 1. (Appearance) One week after the production of the vibration damping sheet, the bleed-out (surface deposition) phenomenon of the plasticizer was determined by the following method. Was observed.

Example 2 [Preparation of vibration-damping sheet] Chlorinated polyethylene having a chlorine group of 40 wt% (Showa Denko: Eraslen 401, average weight molecular weight =
250,000) was dissolved in dimethylsulfoxide, and sodium cyanide was added to prepare a polymer (22% by weight of chlorine group, 17% by weight of cyano group vs. polymer) substituted with a cyano group. Otherwise, a vibration damping sheet was produced in the same manner as in Example 1. However, the molding temperature is 100
° C.

(Evaluation of Damping Sheet) The obtained sheet was evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 1 [Preparation of vibration-damping sheet] Dioctyl phthalate 3 was added to the polyvinyl chloride (SLP40 manufactured by Sekisui Chemical Co., Ltd.) used in Example 1.
A sheet was obtained in the same manner as in Example 1 except that 0 part was added. However, the molding temperature was 130 ° C.

[Evaluation of Damping Sheet] The obtained sheet was evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 2 [Preparation of Damping Sheet] 100 parts by weight of polyvinyl chloride (manufactured by Sekisui Chemical Co .; SLP40) used in Example 1 was chlorinated polyethylene having a chlorination degree of 40 wt% (manufactured by Showa Denko KK; Eraslen). (401, Tg ° C.) to obtain a sheet in the same manner as in Example 1 except that 100 parts by weight was added. However, the molding temperature was 160 ° C.

[Evaluation of Damping Sheet] The obtained sheet was evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 3 [Preparation of damping sheet] A sheet was obtained in the same manner as in Example 1 except that 35 parts of trioctyl phosphate was added to 100 parts by weight of the polyvinyl chloride used in Example 1. However, the molding temperature was 130 ° C.

[Evaluation of Damping Sheet] The obtained sheet was evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 4 [Preparation of vibration-damping sheet] A sheet was obtained in the same manner as in Example 1 except that chlorinated polyethylene having a chlorine content of 40 wt% (Eraslen 401 manufactured by Showa Denko KK) was used. However, the molding temperature was 140 ° C.

[Evaluation of Damping Sheet] The obtained sheet was evaluated in the same manner as in Example 1. Table 1 shows the results.

[0032]

[Table 1]

In Examples 1 and 2, the value of tan δ is high and ta
The width of the temperature region where nδ is 1 or more is as wide as 40 ° C., which indicates that the device has good vibration damping performance. In order to provide a comfortable space for vehicle occupants, a dash portion, a floor portion, and a roof portion are provided. Vibration damping material attached to a part of the vehicle such as a vehicle, noise barriers generated from vehicles such as automobiles and railways to prevent noise and vibration from propagating to the residential building, from the transportation track when passing the vehicle It can be used as a vibration damping material for preventing generated noise and vibration, and as a vibration damping material mounted on a part of a house such as a floor or a roof to cancel a child's jumping sound or rain sound.
In Comparative Examples 1 and 4, although the value of tan δ was high, tan δ
Is 1 or less, the width of the temperature region is as narrow as 10 ° C., and in Comparative Examples 2 and 3, the value of tan δ is 1 or less, and the vibration damping performance is insufficient.

[0034]

According to the first aspect of the present invention, the side chain has a chlorine group of 20% by weight or more (based on the polymer) and a cyano group of 5 to 45% by weight.
(Against polymer), where the main chain is a single bond of carbon or carbon, or
Since it contains a thermoplastic resin composed of double bonds and a benzothiazyl group-containing compound, it exhibits excellent vibration damping performance.
The invention according to claim 2 includes a benzothiazyl group-containing compound and a polymer in which 20% by weight or more of a chlorine group is left on the side chain of the polyvinyl chloride resin (based on the polymer) and 5-45% by weight of the cyano group (based on the polymer). It shows excellent vibration damping performance. The effects described in claim 1 can be more reliably achieved. The invention according to claim 3 includes a benzothiazyl group-containing compound and a polymer in which a side chain of a chlorinated polyolefin is provided with 5 to 25% by weight of cyano group (based on polymer) while leaving at least 20% by weight of chlorine group (based on polymer). Therefore, it shows excellent vibration damping performance.

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Claims (3)

[Claims] Claims 1. A thermocouple comprising a side chain having a chlorine group of 20 wt% or more (based on a polymer) and a cyano group of 5 to 45 wt% (based on a polymer) and a main chain composed of a single bond or a double bond of carbon and carbon. A vibration damping sheet comprising a plastic resin and a benzothiazyl group-containing compound. 2. A cyano group of 5 to 45 wt.% With a chlorine group remaining at least 20 wt.% (Relative to the polymer) on the side chain of the polyvinyl chloride resin.
% (Based on polymer) and a benzothiazyl group-containing compound. 3. A chlorinated polyolefin having 5 to 25 wt.
% (Based on polymer) and a benzothiazyl group-containing compound.