JP2005271304A - Method for manufacturing attenuation molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing an attenuation molding which can easily improve attenuation performance. <P>SOLUTION: The method includes a raw material preparation process, a heating process, and a cooling process. In the raw material preparation process, an active component for increasing the amount of the dipole moment of a matrix material is added to the matrix material to prepare a raw material composition. In the heating process, the raw material composition is heated to the melting point of the active component or above to melt the active component. In the cooling process, the melted active component is solidified by cooling the raw material composition after the completion of the heating process. The cooling speed for ten seconds after the start of cooling in the cooling process is at least 13°C/s. In the heating process, the raw material composition is preferably pressurized. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for manufacturing a damping molded article having damping performance for damping energy such as vibration energy and impact energy. More specifically, the present invention relates to a method for manufacturing an attenuation molded product applied to automobiles, interior materials, building materials, home appliances, and the like, for example, as vibration damping molded products and shock absorbing molded products.

2. Description of the Related Art Conventionally, as this type of damping molded product, a material in which an active ingredient that increases the amount of dipole moment is blended with a base material is known (see Patent Document 1). In this damping molded product, the loss tangent (tan δ) value of the damping molded product is improved by blending the active ingredient. In this type of damping molded product, it is known that damping performance such as vibration energy absorption performance and impact energy absorption performance increases as the loss tangent value increases.
Japanese Patent No. 3318593

  In recent years, in applications (home appliances, automobiles, etc.) to which a damping molded product is applied, it is desired to reduce the weight of the damping molded product in order to reduce the weight. For this reason, there is a demand for an attenuation molded product that exhibits higher attenuation performance.

  The present invention has been made paying attention to such problems existing in the prior art. An object of the present invention is to provide a method for manufacturing an attenuation molded article that can easily improve the attenuation performance.

  In order to achieve the above object, a method for producing a damping molded product according to claim 1 is characterized in that a raw material composition is blended with an active ingredient that increases the amount of dipole moment of the base material. A raw material preparation step to be prepared, a heating step for melting the active ingredient by heating the raw material composition to a temperature equal to or higher than the melting point of the active ingredient, and a melting by cooling the raw material composition after the heating step is completed. A cooling step of solidifying the active ingredient in a state, and the gist is that the cooling rate for 10 seconds from the start of cooling in the cooling step is 13 ° C./second or more.

According to a second aspect of the present invention, there is provided a method for producing an attenuation molded article according to the first aspect, wherein the heating step is performed in a state where the raw material composition is pressurized.
In the method for producing an attenuation molded article according to claim 3, in the invention according to claim 1 or 2, the active ingredient is a compound having a benzothiazyl group, a compound having a benzotriazole group, and a diphenylacrylate group. The gist of the invention is that it is at least one selected from compounds having

  According to a fourth aspect of the present invention, there is provided the method for producing an attenuation molded article according to any one of the first to third aspects, wherein an organic solvent in which the base material is dissolved is further added in the raw material preparation step. The gist is to prepare the raw material composition by blending, and to perform the heating step and the cooling step after the forming step of forming the raw material composition by the solvent casting method is completed.

  According to the method for manufacturing an attenuation molded product of the present invention, the attenuation performance can be easily improved.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments embodying the present invention will be described in detail.
The manufacturing method of the attenuation molding in this embodiment is provided with the raw material preparation process, the heating process, and the cooling process.

In the raw material preparation step, an active ingredient that increases the amount of dipole moment of the base material is blended with the base material to prepare a raw material composition.
Examples of the base material include synthetic resins, thermoplastic elastomers, and rubbers. Synthetic resins include halogenated polyolefins and other synthetic resins. Examples of the halogenated polyolefin include polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, and polyvinylidene fluoride. Other synthetic resins include polyethylene, polypropylene, polyurethane, ethylene / vinyl acetate copolymer, polymethyl methacrylate, polyisoprene, polystyrene, styrene / butadiene / acrylonitrile copolymer, styrene / acrylonitrile copolymer, and the like. . Examples of the thermoplastic elastomer include polyolefin elastomers, polyurethane elastomers, polyvinyl chloride elastomers, chlorinated polyethylene elastomers, and the like. Examples of rubbers include acrylonitrile / butadiene copolymer rubber (NBR), styrene / butadiene copolymer rubber (SBR), butadiene rubber (BR), natural rubber (NR), and isoprene rubber (IR).

  These base materials may be blended singly or in combination of two or more. Among these base materials, a halogenated polyolefin is preferable, and polyvinyl chloride is more preferable because it has an excellent effect of improving the damping performance.

  The active ingredient is formulated to increase the amount of dipole moment of the matrix, and the active ingredient molecules are present as dipoles in the matrix. Here, when vibration energy, impact energy, or the like propagates from the outside to the damping molded product to be manufactured, the dipole rotates or its phase shifts, causing displacement of the dipole. Since the dipole in which the displacement has occurred becomes an unstable state, it tries to return to the original stable state. Since the energy consumption such as vibration energy and impact energy is generated by the restoring action of the dipole, the damping performance of the damping molded product is exhibited.

  Examples of the active component include a compound having a benzothiazyl group, a compound having a benzotriazole group, a compound having a diphenyl acrylate group, and a compound having a benzophenone group. Examples of the compound having a benzothiazyl group include N, N-dicyclohexylbenzothiazyl-2-sulfenamide (DCHBSA), 2-mercaptobenzothiazole (MBT), dibenzothiazyl sulfide (MBTS), N-cyclohexylbenzothiazyl- 2-sulfenamide (CBS), Nt-butylbenzothiazyl-2-sulfenamide (BBS), N-oxydiethylenebenzothiazyl-2-sulfenamide (OBS), N, N-diisopropylbenzo And thiazyl-2-sulfenamide (DPBS).

  The compound having a benzotriazole group 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 (2HPMM), 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), 2- (2'-hydroxy-5'-t-octylphenyl) ben Triazole (2HOPB), and the like.

  Examples of the compound having a diphenyl acrylate group include ethyl-2-cyano-3,3-diphenyl acrylate (ECDPA), octyl-2-cyano-3,3-diphenyl acrylate (OCDPA), and the like. Examples of the compound having a benzophenone group include 2-hydroxy-4-methoxybenzophenone (HMBP) and 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (HMBPS).

  Among these active ingredients, since it is excellent in the action of increasing the amount of dipole moment in the base material, it is preferably at least one selected from a compound having a benzothiazyl group, a compound having a benzotriazole group, and a compound having a diphenyl acrylate group More preferred is a compound having a benzothiazyl group, and further preferred is DCHBSA.

  The amount of the active ingredient is preferably 5 to 100 parts by weight, more preferably 10 to 90 parts by weight, and still more preferably 20 to 80 parts by weight with respect to 100 parts by weight of the base material. If the blending amount is less than 5 parts by weight, it may be difficult to exhibit sufficient damping performance. On the other hand, when it exceeds 100 parts by weight, the moldability of the attenuation molded product may be deteriorated.

  In the raw material composition, as other components, a filler, a flame retardant, a corrosion inhibitor, a colorant, an antioxidant, an antistatic agent, a stabilizer, a wetting agent and the like can be appropriately blended as necessary. Fillers include carbonates, hydroxides, oxides, silicates and silicic acids, synthetic silicic acids, fibrous fillers, balun fillers, organic fillers, recycled rubber, rubber powder, ebonite powder, petroleum System softener, sub (factis), mica and the like. Precipitated calcium carbonate, heavy calcium carbonate, magnesium carbonate, etc. as carbonates, aluminum hydroxide, magnesium hydroxide, etc. as hydroxides, zinc oxide, magnesium oxide, etc. as oxides, silicic acid as silicates Synthetic silicates such as hydrous calcium silicate (talc), hydrous aluminum silicate, hydrous silicic acid, anhydrous silicic acid, etc. As fibrous filler, asbestos, mineral fiber, zonotlite , Potassium titanate, elastadite, etc., balun fillers such as glass balun, fly ash balun, etc., organic fillers include high styrene resin, coumarone indene resin, phenol formaldehyde resin, modified melamine resin, petroleum resin, lignin, etc. It is done.

For mixing each component in the raw material preparation step, a known mixer such as a dissolver, a Banbury mixer, a planetary mixer, a Glen mill, a kneader or the like can be used.
The obtained raw material composition is heated in the heating step, so that the active ingredient in the raw material composition is melted. The heating temperature in a heating process is more than melting | fusing point of the active ingredient to mix | blend. The heating temperature is preferably such that the compatibility between the base material and the active ingredient is improved, and excellent damping performance can be exhibited. Therefore, the glass transition point of the base material is preferably + 50 ° C. or more, more preferably the glass transition of the base material. It is a point +70 degreeC or more. On the other hand, since the upper limit of the heating temperature can maintain the stability of the base material, the glass transition point of the base material is preferably + 120 ° C. or less, more preferably the glass transition point + 110 ° C. or less, more preferably the glass transition point +100. It is below ℃. In this heating step, a hot plate, a dryer, an electric furnace, a thermostatic bath, or the like can be used.

  The heating step is preferably performed in a state where the raw material composition is pressurized because the raw material composition can be efficiently heated and the raw material composition can be simultaneously molded. The pressure in pressurizing the raw material composition is preferably 490 kPa or more. When this pressure is less than 490 kPa, it may be difficult to mold the raw material composition. On the other hand, the upper limit of the pressure is not particularly limited, but is preferably 20000 kPa or less in consideration of productivity. For pressurization in the heating step, a heat press machine, a heatable nip roll, or the like can be used.

  The active ingredient in the raw material composition is solidified by cooling the raw material composition after the heating process in the cooling process. In the cooling step, the cooling rate for 10 seconds from the start of cooling is 13 ° C./second or more. The upper limit of the cooling rate for 10 seconds from the start of cooling is preferably 20 ° C./second or less, more preferably 18 ° C./second or less, and further preferably 16 ° C./second or less, in consideration of ease of production. A constant temperature bath, a freezer, etc. can be used for this cooling process.

  The cooling step is preferably performed in a state where the raw material composition is pressurized because the raw material composition can be efficiently cooled and the shape of the obtained attenuation molded product can be formed into a predetermined shape. . The pressure in pressurizing the raw material composition is preferably 490 kPa or more. When this pressure is less than 490 kPa, the cooling efficiency may not be sufficiently improved. On the other hand, the upper limit of the pressure is not particularly limited, but is preferably 20000 kPa or less in consideration of productivity. For pressurization in the cooling step, a cooling press, a nip roll that can be cooled, or the like can be used.

  This damping molded product is applied to, for example, automobiles, interior materials, building materials, home appliances, and the like as vibration damping molded products that absorb vibration energy, and can be applied to vibration-suppressed locations such as motors. When this damping molded product is used as a vibration damping molded product, it can be used as an unconstrained vibration damping sheet by molding the raw material composition into a sheet. The unconstrained vibration damping sheet is used in a state where one side surface of the vibration damping sheet is not restrained by being bonded to an application location.

  Further, when this damping molded product is used as a damping molded product, the damping sheet obtained by molding the raw material composition into a sheet is used as a damping layer, and the damping layer is constrained on the surface of the damping layer. A constraining vibration damping sheet can be obtained by bonding a constraining layer for the purpose. Examples of the constraining layer include metal foils such as aluminum and lead, films formed from synthetic resins such as polyethylene and polyester, and nonwoven fabrics. This constrained vibration damping sheet is used in a state where both surfaces of the vibration damping layer are constrained by bonding the vibration damping layer side to an application location.

  This damping molded product is an impact absorbing molded product that absorbs impact energy, for example, sports equipment such as shoes, gloves, various armor, grips, headgear, medical equipment such as casts, mats, supporters, wall materials, floor materials, fences, etc. It can be applied to building materials such as, various cushioning materials, various interior materials and the like. When this damping molded product is used as a shock absorbing molded product, it can be made into a shock absorbing sheet by making it into a sheet shape. This shock absorbing sheet can be used by being bonded to an application location.

  The attenuation molded product is manufactured by sequentially performing a raw material preparation step, a heating step, and a cooling step. The active component is melted in the heating step, and the active component in the molten state is cooled in the cooling step. At this time, the cooling rate for 10 seconds from the start of cooling in the cooling step is 13 ° C./second or more. Thus, it is presumed that by rapidly cooling the molten active ingredient, the crystal growth of the active ingredient is suppressed and the compatibility between the molecular chain of the base material and the active ingredient is improved. As a result, it is considered that the energy conversion performance by friction between the base material and the molecular chain of the active ingredient is improved.

The effects exhibited by this embodiment will be described below.
-In the manufacturing method of the attenuation molding of this embodiment, it has a raw material preparation process, a heating process, and a cooling process, and the cooling rate for 10 seconds from the start of cooling in the cooling process is 13 ° C / second or more. In the case of this production method, it is presumed that the compatibility between the base material and the active ingredient is improved, and the active ingredient can be allowed to act efficiently, and the damping performance can be easily improved. In addition, since high damping performance is exhibited, for example, when the damping molded product is formed in a sheet shape, the thickness can be reduced, and the weight of the applied product can be reduced.

  -In the manufacturing method of the attenuation | damping molded product of this embodiment, it is preferable to perform a heating process in the state which pressurized the raw material composition. In the case of this manufacturing method, the raw material composition can be formed in the heating step, and the manufacturing step can be simplified.

  -In the manufacturing method of the attenuation molding of this embodiment, it is preferable that an active ingredient is at least 1 type chosen from the compound which has a benzothiazyl group, the compound which has a benzotriazole group, and the compound which has a diphenyl acrylate group. Since these components are excellent in the action of increasing the amount of dipole moment, the damping performance can be further improved.

In addition, the said embodiment can also be changed and comprised as follows.
-In the raw material preparation step, an organic solvent for dissolving the base material is blended, and a raw material composition in which the base material is dissolved in the organic solvent is formed, and the raw material composition is molded by a solvent casting method. Good. The attenuation molded product is obtained by subjecting the attenuation molded product precursor that has undergone the molding process to a heating process and a cooling process. The organic solvent to be blended is not particularly limited as long as the base material dissolves, and examples thereof include tetrahydrofuran, toluene, acetate ester, and ketone. When using polyvinyl chloride as a base material, it is preferable to use tetrahydrofuran because of excellent solubility. In the case of this manufacturing method, a sheet-like attenuation molded product can be easily manufactured.

  -After forming the raw material composition obtained by the raw material preparation step into various shapes such as a sheet shape, a pellet shape, a bead shape, and a block shape by a molding machine such as an extruder, a T-die, an injection molding machine, The heating step and the cooling step may be performed. Moreover, an attenuation molded product precursor may be manufactured by molding the raw material composition in the heating step, and then the cooling step may be performed. According to this manufacturing method, the manufacturing process of the attenuation molded product can be simplified, and the production efficiency can be improved.

Next, the technical idea that can be grasped from the above embodiment will be described below.
(1) The manufacturing method of the attenuation | damping molded product as described in any one of Claims 1-4 which heats a raw material composition to the glass transition point +50 degreeC or more of a base material in the said heating process. According to this manufacturing method, the damping performance can be improved more easily.

  (2) The method for producing an attenuation molded article according to any one of claims 1 to 4 and (1), wherein the cooling step is performed in a state where the raw material composition is pressurized. According to this manufacturing method, the cooling efficiency can be improved, and the production efficiency can be improved.

Next, the embodiment will be described more specifically with reference to examples and comparative examples.
(Examples 1-3)
As a base material, 7 parts by weight of polyvinyl chloride (manufactured by Taiyo PVC Co., Ltd., TH-1000, glass transition point 82 ° C), 3 parts by weight of DCHBSA (Sunceller DZ, manufactured by Sanshin Chemical Industry Co., Ltd., melting point 90 ° C), And 90 weight part of tetrahydrofuran was mixed with the stirrer, and the raw material composition was prepared. This raw material composition was molded into a sheet by a solvent casting method to obtain an attenuation molded product precursor. In this solvent casting method, after casting the raw material composition, the organic solvent was volatilized under a reduced pressure of about 25 ° C. The obtained damping molded product precursor was set in a heating press machine, and a heating process was performed in which heating was performed for 5 minutes under conditions of a pressure of 7845 kPa and a temperature of 170 ° C. Then, the cooling process was performed by making the temperature of the metal mold | die of a press machine into the temperature shown in Table 1, and the sheet-like attenuation molding (thickness 1mm) was manufactured. Table 1 shows the cooling rate for 10 seconds from the start of cooling in the cooling step. The damping molded product of each example was cut to a size of 35 mm × 5 mm to obtain a test piece for dynamic viscoelasticity measurement.

(Comparative Examples 1 and 2)
A damping molded product precursor was obtained using the same raw material composition as in Examples 1 to 3. This damping molded product precursor is set in a heating press machine and heated for 5 minutes under conditions of pressure 7845 kPa and temperature 170 ° C., and then normal cooling is performed by setting the mold of the press machine to the temperature shown in Table 1. It was. Table 1 shows the cooling rate for 10 seconds from the start of cooling. In the same manner as in Examples 1 to 3, the attenuation molded product of each comparative example was cut to obtain a test piece for dynamic viscoelasticity measurement.

(Measurement of dynamic viscoelasticity)
Loss tangent (tan δ) was measured when the temperature of the test piece of each example was continuously raised using a dynamic viscoelasticity measuring device (RSA-II: manufactured by Rheometric Co., Ltd.) while vibrating. The measurement conditions were an excitation frequency of 10 Hz, a measurement temperature range of −60 ° C. to + 60 ° C., and a temperature increase rate of 5 ° C./min. Table 1 shows the peak value of loss tangent in each example.

表１の結果から明らかなように、各実施例の冷却工程における冷却開始から１０秒間の冷却速度は１３℃／秒以上であり、ｔａｎδのピーク値は２．４７以上である。一方、各比較例における冷却開始から１０秒間の冷却速度は、１２℃／秒以下であるため、ｔａｎδのピーク値は２．４３以下となっている。このように各実施例におけるｔａｎδのピーク値は、各比較例におけるｔａｎδのピーク値よりも高いことがわかる。よって、各実施例の冷却工程を行うことにより、ｔａｎδのピーク値が容易に向上され、得られる減衰成形物の減衰性能を容易に向上することができることがわかる。

As is clear from the results in Table 1, the cooling rate for 10 seconds from the start of cooling in the cooling step of each example is 13 ° C./second or more, and the peak value of tan δ is 2.47 or more. On the other hand, since the cooling rate for 10 seconds from the start of cooling in each comparative example is 12 ° C./second or less, the peak value of tan δ is 2.43 or less. Thus, it can be seen that the peak value of tan δ in each example is higher than the peak value of tan δ in each comparative example. Therefore, it can be understood that the peak value of tan δ can be easily improved by performing the cooling step of each example, and the attenuation performance of the obtained attenuation molded product can be easily improved.

Claims (4)

A raw material preparation step of preparing a raw material composition by blending the base material with an active ingredient that increases the amount of dipole moment of the base material, and heating the raw material composition to a temperature equal to or higher than the melting point of the active ingredient A heating step for melting the active ingredient, and a cooling step for solidifying the molten active ingredient by cooling the raw material composition after the heating step, and a cooling rate of 10 seconds from the start of cooling in the cooling step Is a method for producing an attenuation-molded product, characterized by being 13 ° C./second or more. The manufacturing method of the attenuation | damping molded product of Claim 1 which performs the said heating process in the state which pressurized the said raw material composition. The method for producing an attenuation molded article according to claim 1 or 2, wherein the active ingredient is at least one selected from a compound having a benzothiazyl group, a compound having a benzotriazole group, and a compound having a diphenyl acrylate group. In the raw material preparation step, a raw material composition is prepared by further blending an organic solvent in which the base material is dissolved, and after the forming step of forming the raw material composition by a solvent casting method is completed, the heating step and The manufacturing method of the attenuation | damping molded product as described in any one of Claims 1-3 which performs a cooling process.