JPH09194637A - Vibration-damping material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vibration-damping material which exhibits an excellent vibration absorbing property over a wide temp. range by mixing polyvinyl chloride, chlorinated polyethylene, and epoxidized polyisoprene together in particular proportions. SOLUTION: A polyvinyl chloride resin (A) in an amt. of 15 to 60 pts.wt., 15 to 60 pts.wt. chlorinated polyethylene (B) having a chlorine content of 20 to 45wt.%, and 15 to 65 pts.wt. epoxidized polyisoprene (C) having a degree of epoxidation of 20 to 60mol% (the above amts. being based on 100 pts.wt. whole compsn.) are mixed together to prepare a vibration-damping material compsn. The component (A) comprises a copolymer-contg. polyvinyl chloride or chlorinated polyvinyl chloride. The component (B) is pref. one prepd. by chlorinating a polyethylene having a wt.-average mol.wt. of 50,000 to 300,000 in an aq. suspension. The component (C) is an epoxidized natural rubber or synthetic isoprene rubber. This compsn. is crosslinked by using crosslinking agents for respective components (A), (B), and (C) in combination to prepare a vibration-damping material. The compsn. has an excellent vibration absorbing property over a wide temp. range of from -20 to 100 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer material for preventing vibration and noise, and more particularly to a composition exhibiting excellent vibration absorbability in a wide temperature range and a crosslinked product thereof. The vibration-damping or vibration-damping materials are specifically vibration-damping rubber, vibration-damping steel plates, vibration-damping parts for precision measuring equipment, OA
It is used in home appliances such as equipment and speaker linings.

[0002]

2. Description of the Related Art By measuring the viscoelastic properties of a polymer material, it is possible to determine a loss coefficient Tan.delta, which is an index of damping properties. It is said that if the loss coefficient Tan δ is 0.2 or more, it has excellent vibration absorption properties. Therefore, a damping material that has a Tan δ of 0.2 or more in a wide temperature range of -20 to 100 ° C, which is the normal operating temperature condition, is required. Has been. Generally, when measuring the temperature dependence of Tan δ, which is peculiar to polyvinyl chloride (hereinafter referred to as PVC), its peak position is around 80 ° C. Therefore, when PVC is used as a vibration damping material, a PVC plasticizer etc. Attempts have been made to use PVC as a vibration absorber by shifting the temperature of the Tan δ peak position to near the operating temperature. However, this method has a drawback in that the Tan δ peak becomes sharp and the material becomes poor in vibration absorption except near the peak temperature. Chlorine content is 2
The peak temperature of Tan δ of chlorinated polyethylene (hereinafter referred to as CPE), which is 0 to 45% by weight, is around -40 to 10 ° C. It is a well-known fact that PVC and CPE are not compatibilized in a composition obtained by kneading them, and each has its own Tan δ peak, and the Tan δ value is below 0.2 in the intermediate temperature region. Also, epoxidized polyisoprene (hereinafter referred to as ENR
The epoxidation degree of 20 to 60 mol%
The peak temperature of δ is around -50 to 0 ° C. Since the composition obtained by kneading PVC and ENR or CPE and ENR is compatibilized, a sharp Tanδ peak appears in the intermediate temperature region of each unique Tanδ, and the value of Tanδ falls below 0.2 in other temperature regions. . With these two-component mixtures, it is not possible to obtain a vibration damping composition effective in a wide temperature range as intended by the present invention.

[0003]

The compositions utilizing these conventional techniques had a sharp Tan δ peak at a certain temperature. Therefore, sufficient damping performance was not obtained except near the peak temperature. The present invention provides a composition having excellent vibration absorption in a wide temperature range at -20 to 100 ° C, which is a normal use temperature condition for materials.

[0004]

[Means for Solving the Problems] Various investigations were conducted to achieve the above objects. As a result, when the total amount of the composition was 100 parts by weight, (a) polyvinyl chloride resin 15 to 60 parts by weight, (b) chlorine content A composition comprising 15 to 60 parts by weight of chlorinated polyethylene in an amount of 20 to 45% by weight and (c) 15 to 65 parts by weight of epoxidized polyisoprene having an epoxidation degree of 20 to 60% by mole is -20. It has been found that it exhibits excellent vibration absorption characteristics in a wide temperature range at -100 ° C. Further, the above composition may be crosslinked and used as a vibration damping material. Hereinafter, the configuration of the present invention will be described in detail.

The polyvinyl chloride resin used in the present invention comprises polyvinyl chloride and / or post-chlorinated polyvinyl chloride (hereinafter referred to as CPVC). Polyvinyl chloride (PVC) is produced by a conventional method such as suspension polymerization method, bulk polymerization method, fine suspension polymerization method or emulsion polymerization method of vinyl chloride or a mixture of vinyl chloride and a comonomer copolymerizable therewith. All are used. Examples of comonomers include vinyl acetates such as vinyl acetate, vinyl propionate and vinyl laurate, methacrylic acid esters such as methyl acrylate and ethyl acrylate,
Dimethyl malate, maleic acid esters such as diethyl malate, dibutyl fumarate, fumaric acid esters such as diethyl fumarate, vinyl ethers such as vinyl octyl ether, acrylonitrile, vinyl cyanide such as methacrylonitrile, ethylene, Propylene, styrene, and other α-olefins, vinylidene chloride, vinyl bromide, and other halogens other than vinyl chloride, vinylidene or vinyl halides, diacrylphthalate, ethylene glycol dimethacrylate, diallylphthalate, and other multifunctional monomers. Of course, the comonomers are not limited to those mentioned above. 30% by weight or less of comonomer in PVC constituents, preferably 2%
It is in the range of 0% by weight or less. The average degree of polymerization of PVC is not particularly limited, but is 70 in terms of processability and moldability.
It is desirable to be in the range of 0 to 8000, preferably 1000 to 5000. Also, PVC may have a gel content. The post-chlorinated polyvinyl chloride (CPVC) used in the present invention has a chlorine content of 60 to 70% by weight obtained by chlorinating a substantially vinyl chloride resin having a relatively low average degree of polymerization of 700 to 1300. Chlorinated polyvinyl chloride.

The amount of polyvinyl chloride resin used in the present invention is 10% of the total amount of polyvinyl chloride resin, CPE and ENR.
0-60 parts by weight is 15-60 parts by weight, more preferably 2
0 to 50 parts by weight. Tan less than 15 parts by weight at 50 ℃ or higher
The δ is low, and the strength of the composition is insufficient. 60
If it exceeds the amount by weight, Tan δ near room temperature becomes low and the hardness of the composition becomes too high. The chlorinated polyethylene (CPE) used in the present invention is obtained by chlorinating polyethylene powder or particles in an aqueous suspension or in an organic solvent. It is preferable to use the above. Examples of polyethylene as a raw material include ethylene homopolymers and copolymers of ethylene and α-olefins such as propylene, butene, pentene, hexene and octene. Further, copolymers of ethylene with acrylic acid, methacrylic acid and esters thereof such as ethyl acrylate and methyl methacrylate may be mentioned. The weight average molecular weight of polyethylene as a raw material is 40,000 to 700,000, preferably 50,000 to 300,000. CPE
The residual crystal amount of is 0 to 15 cal / g by the DSC method, preferably 0
~ 8 cal / g. The chlorine content of CPE used is 20
It is ~ 45%, but if it is less than 20%, Tan δ at high temperature is low.
When it exceeds 5%, the form becomes close to a single peak. Preferably the blending ratio of CPE is polyvinyl chloride resin, CPE,
And, if the total of ENR is 100 parts by weight, it is 15 to 60 parts by weight, but if it is less than 15 parts by weight, it becomes a form close to a single peak,
Further, if it exceeds 60 parts by weight, the Tan δ at 50 ° C or higher becomes low.

The ENR used in the present invention is obtained by epoxidizing a rubbery polyisoprene having a substantially cis-1,4 structure such as natural rubber and synthetic polyisoprene. The epoxidation degree of ENR is preferably 20 to 60 mol%, more preferably 25 to 55 mol%. Below 20% and above 60%, Tan δ of the composition has two peaks, a high temperature part and a low temperature part. , In the middle temperature range, Tanδ
Breaks below 0.2. Polyvinyl chloride resin, CPE, and EN
When the total amount of R is 100 parts by weight, the mixing ratio of ENR is 15 to 65.
Parts by weight are preferred. For ENR less than 15 parts by weight PVC and CPE
When the ENR exceeds 65 parts by weight, the shape becomes close to a single peak, and a temperature range in which Tan δ falls below 0.2 occurs.

The cross-linking agent used in the present invention may be any cross-linking agent capable of cross-linking the constituent components of the present invention, and the cross-linking agent of each component may be mixed and used. For example, polyvinyl chloride resin, which is a chlorine polymer, CPE
Examples of the cross-linking agent include organic peroxides, thiol-based cross-linking agents, amine-based cross-linking agents and the like, and a cross-linking aid is optionally used in combination. Examples of the organic peroxide include dicumylperoxide, di-t-butylperoxide, t-butylcumylperoxide, 1,3-bis-t- (butylperoxypropyl) benzene, and 1,1-bis (t-butylperoxide). -Oxy) -3,3,5 trimethylcyclohexane,
Examples include n-butyl-4,4bis (t-butylperoxy) valerate. Further, as a crosslinking aid, ethylene glycol dimethacrylate, trimethylpropane trimethacrylate, polyfunctional methacrylate monomer,
Polyvalent alcohol methacrylate and acrylate, N, N '
-m-Phenylene dimaleimide, triallyl isocyanurate, diallyl phthalate and the like can be mentioned. As a thiol-based cross-linking agent, 2,4,6-trimercaptotriazine, 2-anilino 4,6-dimercaptotriazine, 2-dibutyl 4,6-dimercaptotriazine, s, s (6-methylquinoxaline-2, 3
Dill) dithiopermeate, dimercaptothiadiazo
And 2-mercaptoimidazoline and dialkylthiourea. Examples of the amine-based cross-linking agent include aliphatic diamines such as hexamethylene diamine and aromatic polyfunctional amines such as P-phenylenediamine. Further, as the ENR crosslinking agent, the above-mentioned organic peroxide,
Examples thereof include sulfur-based cross-linking agents used for ordinary diene-based rubbers, cross-linking agents based on amines utilizing epoxy groups in ENR, and cross-linking agents such as polyvalent phenols.

It is preferable to use a plasticizer in the composition of the present invention, and the kind thereof is not particularly limited.
The amount of the plasticizer used varies depending on the type of polyvinyl chloride resin, CPE, ENR, the amount added and the presence or absence of a filler, etc., but is 0 to 300 parts by weight, preferably 10 to 2 parts by weight per 100 parts by weight of the resin component.
The time is selected from the range of 00 parts by weight. For example, di-2-
Phthalate ester plasticizers such as ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, dibutyl phthalate, dihexyl phthalate, dihexyl phthalate, linear dibasic ester plasticizers such as dioctyl adipate and dioctyl sebacate,
Trimellitic acid ester plasticizer, polyester polymer plasticizer, epoxidized soybean oil, epoxidized linseed oil, liquid epoxy plasticizer, triphenyl phosphate, trixylyl phosphate, tricresyl phosphate, and other phosphate ester plasticizers An agent is mentioned, and these 1 type (s) or 2 or more types are mixed and used. It is preferable to use a filler in the composition of the present invention, and the type thereof is not particularly limited, and examples thereof include carbon black, calcium carbonate, titanium oxide, talc, aluminum hydroxide, hydrotalcite, clay, silica, Examples include graphite and mica. The amount of filler added is 10
It is 600 parts by weight or less, preferably 10 to 550 parts by weight, relative to 0 parts by weight. If the amount of filler added is small, kneading,
The effect of improving the moldability is small, and when the amount is 600 parts by weight or more, the kneading and moldability tend to be deteriorated, so it is desirable to add it within a range that does not impair the moldability.

Further, if necessary, the composition of the present invention contains a stabilizer, a lubricant, a processing aid, an antioxidant, an ultraviolet absorber, a foaming agent, a flame retardant, a pigment, an impact modifier, and a heat other than the above. You may mix | blend various additives, such as a plastic resin. The composition of the present invention comprises (a) a polyvinyl chloride resin of 15 to 60 parts by weight, (b) a chlorine content of 20 to 45% by weight of CPE of 15 to 60 parts by weight, and (c) an epoxidation degree of 20 to 60% by mole. It is desirable to add 15 to 65 parts by weight of ENR to a mixer, add various compounding agents as necessary, and mix and knead to produce a composition which is operationally and uniform in composition. That is, first, a vinyl chloride resin and a plasticizer are dry blended in advance, and then the CPE, ENR and, if necessary, a crosslinking agent, a stabilizer, a processing aid and other additives are mixed and kneaded. The kneading temperature is selected within the range of room temperature to 230 ° C. according to the compounding ingredients. The device used for mixing the above-mentioned blending components may be any device as long as it can be mixed substantially uniformly, for example, Henschel mixer, ribbon blender, planetary mixer, and the like,
To knead the mixture, for example, an extruder, roll, Banbury mixer, kneader, or other device capable of kneading under heating while being heated is used. It is also possible to allow the composition of the present invention to have a gel component during kneading, in which case a closed type kneader such as a Banbury mixer, an intensive mixer, a pressure kneader or a twin-screw extruder in the same direction is used. It is desirable because it has a great effect.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific embodiments for carrying out the present invention will be described below with reference to examples.

[0012]

【Example】

The composition of the present invention will be described in detail with reference to Examples.
The present invention is not limited to the following embodiments without departing from the gist thereof. A. CPE production method 1 3 liters of carbon tetrachloride and 300 g of powdered polyethylene were placed in a 5 liter separable flask, and while stirring,
It was chlorinated to a predetermined chlorine content at 60 ° C., washed with water, precipitated with methanol, added with 10 g of calcium stearate and dried under reduced pressure at 60 ° C., and then subjected to the tests of Example 10 and Comparative Example 9. B. CPE manufacturing method 2 70 liters of water in a 100 liter autoclave, 4000 g
100g of powdered polyethylene, surfactant and humectant are added, chlorinated with stirring at 80 ° C and 125 ° C to a specified chlorine content, and after washing with water, 10 parts of calcium stearate is added.
0 g was added and dried in an oven at 50 ° C., and subjected to the test of Comparative Example 8. Commercially available CPE was used in other examples and comparative examples.

C. Method for producing ENR 300 g of polyisoprene (manufactured by Japan Synthetic Rubber) was masticated with a 6-inch roll at room temperature for 10 minutes, cut, put in a 5 liter separable flask, and toluene 3 Added liters. Polyisoprene is dissolved with stirring at room temperature, formic acid is added, 30% hydrogen peroxide solution is added dropwise at 25 ° C. for 30 minutes, and the reaction is further continued, followed by precipitation with 2-propanol, and a phenolic stabilizer after washing. Epoxidation degree of 16 and 6
4 mol% ENR was prepared and used for Comparative Examples 10 and 11.
Commercial ENRs were used in the other examples and comparative examples.
The ENRs used in Examples 1 to 16 and Comparative Examples 1 to 11 are made from natural rubber. A viscoelasticity spectrometer was used as a dynamic viscoelasticity measuring device for measuring the loss coefficient Tan δ. While increasing the temperature of the sample from -50 ℃ to 150 ℃ 10
Viscoelastic measurements were made at Hz. However, for those creeped up to 150 ° C, the measurement was stopped at that temperature.

[Examples 1 to 4, Comparative Examples 1 to 7] Used
All ENRs used were those that had been previously masticated with a roll at room temperature for 8 minutes. PVC, CPE, stabilizer and lubricant were blended in the composition shown in Table 1 and kneaded for 2 minutes with an 8-inch roll adjusted to 170 ° C., a predetermined amount of ENR was added, and further kneaded for 8 minutes to obtain a mixture. This was hot pressed at 170 ° C. for 5 minutes and cooled by a cold press to obtain a sheet having a thickness of 2 mm. The sample size for measuring viscoelastic properties is 4 mm × 55 mm × 2 mm. The results of viscoelasticity measurement are shown in FIGS. 1 and 2 as an example. -20 ~ 100
In the temperature range of ℃
T was used as an index of vibration absorption in the following examples and comparative examples.

Table 1. Relationship between composition (parts by weight) of PVC, CPE and ENR and ΔT (° C) Example (1 to 4) Comparative example (1 to 7) 1 2 3 4 1 2 3 4 5 6 7 PVC * 1 40 20 55 20 50 50 44.5 65 20 15 CPE * 2 40 20 20 55 50 50 44.5 15 65 15 ENR * 3 20 60 25 25 50 50 11 20 15 70 (part by weight) ΔT (℃) 104 113 106 116 31 51 42 59 31 69 62 Other compounding agents: polyethylene external lubricant 1 part by weight tin stabilizer 1 part by weight * 1 Polymerization degree: 1050 (Nippon Zeon, 103EP) * 2 Molecular weight: 200,000, chlorine content: 35 Weight%, crystallinity: about 0 cal / g * 3 Epoxidation degree: 50 mol% (Kumpulan Guthrie BHD)

The compositions obtained in Examples 1 to 4 have a large temperature range ΔT (° C) of 0.2 or more in succession of Tan δ in the temperature range of -20 to 100 ° C which is usually used. The composition in which PVC and CPE are kneaded expresses their respective Tan δ, and the value of Tan δ is less than 0.2 in the intermediate temperature region. The compositions of Comparative Examples 2 and 3 in which PVC and ENR and CPE and ENR were kneaded express the Tan δ peak position in the intermediate temperature region of their respective Tan δ, but the value of Tan δ is less than 0.2 outside the temperature region. . As a result, in Comparative Examples 1 to 3, the value of ΔT becomes small. Also in Comparative Examples 4 to 7, the value of ΔT is small outside the composition range of the present invention.

[Examples 5 to 11 and Comparative Examples 8 to 11] Samples were obtained in the same manner as in Example 1 with the formulations shown in Tables 2, 3 and 4. In Examples 5 to 11, the value of ΔT is large. On the other hand, in Comparative Examples 8, 10 and 11, the value of Tan δ falls below 0.2 in the intermediate temperature range, and in Comparative Example 9, almost a single peak occurs and the value of ΔT is small. [Example 12] As shown in Table 3, PVC, CPE, dioctyl phthalate, polyethylene external lubricant, tin stabilizer, carbon black (FEF carbon), and a predetermined amount of masticated ENR were measured in the same manner as in Example 1. A 1.7 liter Banbury mixer adjusted to 150 ° C was charged with 1000 g of a polymer amount, kneaded at 60 rpm for 3 minutes, discharged, and then at room temperature.
It was cooled with an inch roll and rolled to obtain a sheet having a thickness of over 2 mm. This was hot pressed at 70 ° C. for 5 minutes and cooled by a cold press to obtain a sheet having a thickness of 2 mm. Similarly, in the composition in which carbon black (FEF carbon) is added as a reinforcing agent and dioctyl phthalate is added as a plasticizer, the peak position shifts to the low temperature side, and the value of Tan δ exceeds 0.2, so ΔT
Is 120 ° C.

[Examples 13 and 14] 100 set at 170 ° C
A cc plastomill was charged with 70 g of the polymer in the composition shown in Table 3, polyethylene-based external lubricant and tin-based stabilizer and kneaded for 3 minutes. Then, a cross-linking agent below the underlined part was added and kneaded for 3 minutes and discharged. Roll with a 6 inch roll set to 100 ° C. 2
A sheet with a thickness of a little over mm was obtained. This at 180 ℃ for 10 minutes,
After hot pressing and cooling with a cold press, a sheet having a thickness of 2 mm was obtained. Example 1 in which the crosslinking agent component of ENR was added to Example 8.
3. The value of ΔT was large in Example 14 in which the cross-linking agent components of PVC and CPE were added, indicating that these compositions are effective damping materials in a wide temperature range.

[Examples 15 and 16] Compositions shown in Table 5 containing post-chlorinated polyvinyl chloride (Kanebuchi Chemical Industry Co., Ltd., heat-resistant Kanebeer, H-827) having a chlorine content of 63 wt% were prepared. Using, kneading and pressing temperature is 180 ℃ instead of 170 ℃
A sample was obtained in the same manner as in Example 1 except that It was shown that CPVC can also be used for damping material.

[0021] Other compounding agents: polyethylene external lubricant 1 part by weight tin stabilizer 1 part by weight * 4 Polymerization degree: 2000 (Shin-Etsu Chemical Co., Ltd., TK2000E) * 5 Polymerization degree: 1300, gel content 22% (Shin-Etsu Chemical) Industry Co., Ltd.
(Made by GK1300S)

Table 3. Relationship between chlorine content of CPE, epoxidation degree of ENR, and additive and ΔT (° C) Example (7 to 14) 7 8 9 10 11 11 12 13 14 PVC * 1 33.3 33.3 33.3 33.3 33.3 33.3 33.3 33.3 CPE * 2 33.3 33.3 CPE * 6 33.3 CPE * 7 33.3 33.3 33.3 CPE * 8 33.3 CPE * 9 33.3 ENR * 3 33.3 33.3 33.3 33.3 33.3 33.3 33.3 ENR * 10 33.3 FEF Carbon 20 Dioctyl phthalate 33.3 Calcium carbonate 3 Paraphenylenediamine 5 Bisphenol A 10 M-181 * 11 2 OF-100 * 12 1 Magnesium oxide 5 (part by weight) ΔT (℃) 105 111 100 104 120 120 101 110 Other compounding agents: polyethylene external lubricant 1 part by weight Tin stabilizer 1 part by weight * 6 Molecular weight: 150,000 Chlorine content: 22% by weight Crystallinity: 7cal / g * 7 Molecular weight: 100,000 Chlorine content: 35% by weight Crystallinity: 5cal / g * 8 Molecular weight: 100,000 chlorine Content: 45% by weight Crystallinity: 0cal / g * 9 Molecular weight: 100,000 Chlorine content: 45% by weight Crystallinity: 0cal / g * 10 Epoxy Degree 25 mol% (manufactured by Kumpulan Guthrie BHD) * 11 vulcanizer, die Sonnet M-181 (Daiso Co., Ltd.) * 12 vulcanizing die SONET OF-100 (manufactured by Daiso)

[0023] Other compounding agents: Polyethylene external lubricant 1 part by weight Tin stabilizer 1 part by weight * 13 Molecular weight: 150,000 Chlorine content: 17% by weight Crystallinity: 8cal / g * 14 Molecular weight: 100,000 Chlorine content: 48% by weight Crystal Degree: 0 cal / g * 15 Epoxidation degree: 16 mol% * 16 Epoxidation degree: 64 mol%

[0024]

[0025]

As described above, the composition comprising polyvinyl chloride resin, chlorinated polyethylene and epoxidized polyisoprene has a large loss coefficient in a wide temperature range.
It exhibits Tan δ and has excellent properties as a vibration damping material.

[0026]

[Brief description of the drawings]

FIG. 1 Loss factor Ta of the compositions shown in Examples 1-4
It is a figure which shows the temperature dependence of n (delta).

FIG. 2 is a loss coefficient Ta of the compositions shown in Comparative Examples 1 to 4.
It is a figure which shows the temperature dependence of n (delta).

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 27/06 LEQ C08L 27/06 LEQ LES LES

Claims (5)

[Claims] 1. When the total amount of the composition is 100 parts by weight, (a)
Polyvinyl chloride resin 15-60 parts by weight, (b) chlorine content 20
15 to 60 parts by weight of chlorinated polyethylene of 45% by weight to (c) epoxidized polyisoprene 15 having an epoxidation degree of 20 to 60 mol% 15
A composition for vibration damping material, characterized in that the composition is blended in an amount of up to 65 parts by weight. 2. A polyvinyl chloride resin in an amount of 20 to 50 parts by weight,
The composition for vibration damping material according to claim 1, further comprising epoxidized polyisoprene having an epoxidation degree of 25 to 55 mol%. 3. The composition for damping material according to claim 1, wherein the polyvinyl chloride resin is polyvinyl chloride and / or post-chlorinated polyvinyl chloride having a chlorine content of 60 to 70% by weight. 4. The composition for vibration damping material according to claim 1, wherein the epoxidized polyisoprene is epoxidized natural rubber. 5. A vibration damping material obtained by crosslinking the composition according to any one of claims 1 to 4.