JPH061890A - Damping resin composition - Google Patents

Abstract

(57) [Summary] [Purpose] To provide a resin composition having excellent vibration damping performance and impact resistance. [Structure] (A) A conjugated diene polymer comprising 0 to 50% by weight of an aromatic vinyl compound and 100 to 50% by weight of a conjugated diene and / or 5 to 75% by weight of a hydrogenated product thereof and (B) an olefin resin 95. ~ 25% by weight (however,
(A) + (B) = 100% by weight] partially crosslinked product 5-5
0 to 50 parts by weight, and (C) 95 to 50 parts by weight of a thermoplastic resin other than the component (B) [where (A) + (B) +
(C) = 100 parts by weight] as a main component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vibration damping resin composition having excellent vibration damping properties.

[0002]

2. Description of the Related Art In recent years, noise and vibration caused by transportation means such as automobiles have become a big social problem, and low vibration and low noise are required inside the automobile. In addition, reduction of noise and vibration generated from office equipment such as copiers and printers has become an important issue. Further, due to changes in household machinery, household electric appliances are also becoming larger, and there is a demand for low vibration and low noise in refrigerators, washing machines, and vacuum cleaners. Conventionally, ABS resin and polyamide resin, which is a general-purpose engineering plastic, have been widely adopted as automobile parts, electric / electronic parts, and OA equipment parts, but these requirements of low vibration and low noise cannot be satisfied. .

[0003]

The present invention has been made in view of the above-mentioned problems of the prior art, and not only has physical properties equivalent to those of conventional ABS resins and polyamide resins, but also has excellent damping performance. The purpose is to provide a vibrating resin.

[0004]

According to the present invention, (A) an aromatic vinyl compound (0 to 50% by weight) and a conjugated diene (100 to 50) are used.
5 to 75% by weight of a conjugated diene polymer and / or hydrogenated product thereof and 95 to 25% by weight of a (B) polyolefin resin (where (A) + (B) = 100).
% By weight], and 5 to 50 parts by weight of a partially crosslinked product, and (C) 95 to 50 parts by weight of a thermoplastic resin other than the component (B) [where (A) + (B) + (C) = 100 parts by weight]. Part] as a main component.

The component (A) used in the resin composition of the present invention is a conjugated diene polymer and / or its hydrogenated product. Here, examples of the aromatic vinyl compound constituting the conjugated diene polymer include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, distyrene. Bromstyrene, fluorostyrene, pt-butylstyrene, ethylstyrene, vinylnaphthalene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, N, N-diethyl-p-amino. Examples thereof include ethyl styrene, vinyl pyridine and vinyl naphthalene, and styrene is particularly preferable.

The conjugated diene constituting the diene polymer is 1,3-butadiene, isoprene, 2,3
-Dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene,
Examples thereof include 3-butyl-1,3-octadiene and chloroprene, but 1,3-butadiene and isoprene are preferable, and 1,3-butadiene is more preferable because they can be industrially used and have excellent physical properties. is there. (A)
The diene polymer constituting the component may be a polymer of a conjugated diene alone, a block copolymer or a random copolymer of an aromatic vinyl compound and a conjugated diene, or a mixture thereof, and further hydrogenated After that, a mixture may be used.

As the diene polymer, specifically, at least one of the following block A or the following block C,
At least one of the following block B or block A / B
And a diene polymer based on block B or A / B. The specific constitution thereof is: A: vinyl aromatic compound polymer block, B: conjugated diene polymer block, A / B: vinyl aromatic compound / conjugated diene random copolymer block, C: conjugated diene and vinyl aromatic When defined as a taper block composed of a compound copolymer and gradually increasing the vinyl aromatic compound, those having the following structures are mentioned.

(1) A-B (2) A-B-A (3) A-B-C (4) A-B ₁ -B ₂ (wherein the vinyl bond content of B ₁ is preferably 20% As described above, the vinyl bond content of B ₂ is 20
% Less) (5) B (6) A / B (7) A-A / B (8) A-A / B-C (9) A-A / B-A (10) B 2 -B 1 - B ₂ (Here, B ₁ and B ₂ are the same as above) (11) C-B (12) C-B-C (13) C-A / B-C (14) C-A-B

Further, there may be mentioned a copolymer having these basic skeletons repeatedly, and a diene polymer obtained by coupling these may be used. The use of the above-mentioned diene polymers (4) to (8) makes it possible to obtain the composition of the present invention which is more excellent. In particular, the diene-based polymers (6) to (8) are preferable because they are excellent in low temperature characteristics and fatigue characteristics. The structure of (4) A-B ₁ -B ₂ is described in JP-A-2-133406, and the structures of (5) B and (6) A / B are described in JP-A-63-63406.
-127400 publication. The structures (7) A-A / B and (8) A-A / B-C are disclosed in JP-A-2-305814.

The vinyl aromatic compound / conjugated diene ratio of these block copolymers or random copolymers is 0 to 50/100 to 50 by weight, preferably 5 to 50.
45 / 95-45, and when the vinyl aromatic compound is essential, it is preferably 10-50 / 90-50.
Here, when the content of the vinyl aromatic compound exceeds 50% by weight, the vinyl aromatic compound becomes a resin and the flexibility of the obtained composition decreases. The vinyl bond content of the conjugated diene moiety in the block copolymer or random copolymer is preferably 10% by weight or more, more preferably 20 to 80% by weight,
Particularly preferably, it is 30 to 60% by weight, and when it is less than 10% by weight, the structure after hydrogenation becomes close to that of polyethylene, and the flexibility is lowered when it is made into a composition. After addition, the rubber-like property is lost, so that the flexibility is also deteriorated, which is not preferable. The number average molecular weight of the diene polymer is preferably 5,000 to 1,000.
30,000, more preferably 30,000 to 300,
It is 000, and when it is less than 5,000, the diene polymer or hydrogenated product becomes liquid rather than rubber-like, while when it exceeds 1,000,000, workability tends to be deteriorated, which is not preferable.

The hydrogenated product of the diene polymer constituting the component (A) has a double bond in the conjugated diene portion of the diene polymer of preferably 70% or more, more preferably 90%.
As described above, particularly preferably 95% or more hydrogenated. The method for hydrogenating the diene polymer is described in detail in, for example, Japanese Patent Application Laid-Open No. 2-133406.

Next, the (B) polyolefin resin is a resin obtained by polymerizing one or more monoolefins by either a high pressure method or a low pressure method. Here, as the mono-olefin, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4
-Methyl-1-pentene, 2-methyl-1-propene,
Examples thereof include 3-methyl-1-pentene, 5-methyl-1-hexene, and a mixture thereof, preferably ethylene, propylene, 4-methyl-1-pentene, and more preferably propylene. Preferred polyolefin resins are polyethylene, polypropylene and poly-4-methyl-1-pentene, and as the copolymer type component (B), ethylene, 1-butene, 1-pentene, 1
-Hexene, 4-methyl-1-pentene, 2-methyl-
1-propene, 3-methyl-1-pentene, and 5-
Examples thereof include polypropylene in which at least one selected from the group of methyl-1-hexene is copolymerized. The polyolefin resin is more preferably polypropylene, isotactic polypropylene, or the above-mentioned copolymer type polypropylene.

The partially crosslinked product used in the present invention is obtained by adding a crosslinking agent to the above components (A) to (B) and reacting it at a constant temperature while applying shear deformation using a kneader to give a rubber. A part is partially crosslinked. As the kneading machine, rolls, Banbury mixers, kneaders, single-screw or twin-screw extruders, etc. are used.

The cross-linking agent used here is one that is commonly used for cross-linking rubbers, such as those described in "Handbook of Cross-linking Agents" (written by Shinzo Yamashita, Tosuke Kaneko, Taiseisha). Can be used. As this preferable crosslinking agent,
Sulfur, sulfur compounds, p-benzoquinone dioxime,
p, p'-dibenzoylquinone dioxime, 4,4'-
Resin crosslinking agents such as dithio-bis-dimorpholine, poly-p-dinitrosobenzene, tetrachlorobenzoquinone, alkylphenol-formaldehyde resin, brominated alkylphenol-formaldehyde resin, ammonium benzoate, bismaleimide compound, diepoxy compound, dicarboxylic acid compound, diol Compounds, diamine compounds, amino resins, organic metal salts, metal alkoxides,
Examples thereof include organic metal compounds and organic peroxides.

These cross-linking agents can be used alone or as a mixture. Further, depending on the type of the cross-linking agent, the cross-linking may proceed more efficiently by using it in combination with other compounds. Especially when sulfur or a sulfur compound is used as a crosslinking agent,
It is desirable to use together a vulcanization accelerator, a vulcanization acceleration aid, and an activator that accelerate the sulfur crosslinking reaction, and the appropriate combination and the amount to be used can be determined, for example, by utilizing the above-mentioned documents. Moreover, when using an organic peroxide as a crosslinking agent, the method of using a crosslinking auxiliary together is preferable.

As the crosslinking aid, sulfur, sulfur compounds such as dipentamethylene thiuram pentasulfide, mercaptobenzothiazole, oxime nitroso compounds, ethylene glycol dimethacrylate, aryl methacrylate, triaryl cyanurate, diaryl phthalate, polyethylene glycol diethylene Monomers such as methacrylate, divinyl adipate, maleic anhydride, bismaleimide compound, trimethylolpropane trimethacrylate, divinylbenzene, liquid polybutadiene, liquid styrene-butadiene copolymer, poly 1,2
-Polymers such as butadiene.

It is desirable to determine the appropriate selection of the crosslinking system and the amount to be used with reference to the above-mentioned documents and the like. Usually, 0.1 to 8 parts by weight of a crosslinking agent, 0.1 to 10 parts by weight of a vulcanization accelerator, and 0.5 to 10 parts by weight of a vulcanization accelerator aid with respect to 100 parts by weight of components (A) to (B). Parts, 0.5 to 10 parts by weight of the activator, and 0.1 to 20 parts by weight of the cross-linking aid. In the present invention, the term "partially crosslinked" means a state in which the rubber component in the composition is crosslinked while maintaining a state in which injection molding is possible.

The kneading temperature is 120 to 300.
C., preferably 150 to 250.degree. C., and the kneading time is arbitrary, but is usually about 15 seconds to 30 minutes. The degree of crosslinking depends on the amount of the crosslinking agent, the amount of the crosslinking aid, the kneading temperature, the kneading time, etc. Therefore, it is necessary to find the optimum conditions for each combination. As the degree of crosslinking, it is preferable to use the cyclohexane insoluble content represented by the following formula as a measure of the degree of crosslinking. Insoluble matter (% by weight) = [(Wex-Wpp-Wadd) /
Wrb] × 100 [wherein, Wex is the amount of the polymer [(A) to (B) component] after extraction with cyclohexane, Wpp is the amount of the component (B), Wpp]
add is the cyclohexane insoluble content in the additives other than the components (A) to (B), and Wrb is the amount of the component (A). ] In addition,
The extraction is carried out in cyclohexane at 60 ° C. for 4 hours.

The cyclohexane insoluble content of the partially crosslinked product used in the present invention is preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 85-100.
%, And if less than 70% by weight, the impact resistance of the resulting composition is lowered. The weight ratio of component (A) / component (B) in the partially crosslinked product is 5 to 75/95 to 25% by weight, preferably 10 to 70/90 to 30% by weight.
When the component (A) is less than 5% by weight, the impact resistance of the composition is low, while when it exceeds 75% by weight, the vibration damping property is deteriorated.

Next, as the thermoplastic resin (C) other than the polyolefin resin (B), the glass transition point is 25.
It is a thermoplastic polymer having a temperature of ℃ or more, and includes an amorphous polymer, a crystalline polymer, a liquid crystal polymer and the like. Specifically, styrene resin, acrylic resin, polyphenylene ether resin, polyarylene sulfide resin, PEE
Examples thereof include K resin, polycarbonate resin, polyester resin, polyamide resin, polyether sulfone resin, polysulfone resin, polyimide resin, and polybutylene resin. Of these, styrene resins, polyamide resins, polycarbonate resins and polyester resins are preferable.

Examples of the styrene resin include polystyrene, polychlorostyrene, poly α-methylstyrene,
Styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, styrene-maleic anhydride copolymer, styrene-α-methylstyrene copolymer, styrene-α-methylstyrene-methyl methacrylate copolymer, styrene Examples thereof include -α-methylstyrene-acrylonitrile-methyl methacrylate copolymer and the like, and aromatic vinyl compound-vinyl cyanide compound copolymer such as styrene-acrylonitrile copolymer is particularly preferable.

As the polyamide resin, H ₂ N-
(CH _{2) x} -NH ₂ (wherein, x is 3-12 integer) linear diamine represented by, HOOC- (CH _{2) y} -C
Those produced by condensation with a linear dicarboxylic acid represented by OOH (wherein y is an integer of 2 to 12) or those produced by ring-opening polymerization of lactam can be used. Preferred examples of these polyamide resins include nylon 6,66, nylon 6,10, nylon 6,12, nylon 4,6, nylon 3,4, nylon 6,9, nylon 6, nylon 12, nylon 11,
Examples include nylon 4 and the like. Also, nylon 6/6,
10, nylon 6 / 6,12, nylon 6 / 4,6, nylon 6/12, nylon 6 / 6,6, nylon 6 /
6,6 / 6,10, nylon 6 / 4,6 / 6,6, nylon 6 / 6,6 / 6,12, nylon 6 / 4,6 / 1
Examples thereof include copolymer polyamides such as 0 and nylon 6/4, 6/12. Furthermore, nylon 6/6,
T (T is a terephthalic acid component), a semi-aromatic polyamide resin obtained from an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid and metaxylylenediamine or an aliphatic diamine, metaxylylenediamine and the above linear dicarboxylic acid The polyamide, polyester amide, polyether amide, polyester ether amide and the like obtained by the above can be mentioned.

Further, as the polycarbonate resin,
An aromatic polycarbonate resin, an aliphatic polycarbonate resin, an aliphatic-aromatic polycarbonate resin, etc. can be mentioned. In general, heavy polymers obtained by polymerizing bisphenols such as 2,2-bis (4-oxyphenyl) alkane-based, bis (4-oxyphenyl) ether-based, bis (4-oxyphenyl) sulfone sulfide or sulfoxide-based. It is a polymer or a copolymer, and is a polymer using bisphenols optionally substituted with halogen. For the type and manufacturing method of polycarbonate resin, issue by Nikkan Kogyo Shimbun (Showa 44)
See “Polycarbonate resin” published on September 30, 2014.

Further, as the polyester resin, polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PB)
T), polypentamethylene terephthalate, polyhexamethylene terephthalate, and other polyester resins obtained from aromatic dicarboxylic acids and dihydric alcohols, and aromatic polyester resins obtained from aromatic dicarboxylic acids and aromatic diphenols. A so-called polyarylate resin can be mentioned. Specific examples of the polyarylate resin include a polyester resin and a copolyester resin containing bisphenol A and terephthalic acid or isophthalic acid. Of these,
Particularly preferred are PET and PBT.

The thermoplastic resin (C) is particularly preferably a polyamide and / or an aromatic vinyl compound-vinyl cyanide compound copolymer. When these thermoplastic resins are used, a composition having excellent compatibility with the partially crosslinked product and excellent vibration damping and impact resistance can be obtained.

Further, the partially crosslinked product comprising the components (A) to (B) and (C) in the vibration-damping resin composition of the present invention.
The ratio of the thermoplastic resin is 5 to 50/95 to 50 parts by weight,
It is preferably 10 to 45/90 to 55 parts by weight. When the amount of the partially cross-linked product is less than 5 parts by weight, the impact resistance is low, while 50
If it exceeds the weight part, the rigidity becomes low and it is not a resin.

In the vibration-damping resin composition of the present invention, when the partially crosslinked product and the thermoplastic resin (C) are heated and mixed, acrylic acid, methacrylic acid, maleic acid, or the like is added to these compounding systems. Carboxyl group-containing unsaturated compounds, maleic anhydride, acid anhydride group-containing unsaturated compounds such as itaconic anhydride, oxazoline group-containing unsaturated compounds such as vinyl oxazoline, glycidyl methacrylate, epoxy group-containing unsaturated compounds such as allyl glycidyl ether Etc. may be added. By adding these unsaturated compounds, it is possible to further improve various properties of the obtained vibration-damping resin composition.

The vibration-damping resin composition of the present invention also contains a filler (reinforcing agent) used for other general resins and rubbers.
Can be blended. As the filler, carbon black, calcium carbonate, titanium oxide, barium sulfate, potassium titanate, iron oxide, clay, talc, silica, mica, alumina, glass fibers, carbon fibers, metal fibers, glass beads, glass flakes, Examples thereof include inorganic fillers such as wollastonite, process oils, bituminous substances such as asphalt, antioxidants and tackifiers.

The vibration-damping resin composition of the present invention comprises the partially crosslinked product, the (C) thermoplastic resin, and various additives used as necessary, for example, a single-screw extruder, a twin-screw extruder, It is produced by heating and mixing using a rubber mill, a Brabender mixer, a Banbury mixer, a pressure kneader, a mixing roll and the like. The composition obtained is molded by a roll, an extruder or an injection molding machine and used as a damping material. Incidentally, in producing the resin composition of the present invention,
The partially crosslinked product and the thermoplastic resin (C) may be mixed, and this may be directly injection-molded. Further, by using an extruder having a large L / D (L = screw length, D = diameter),
The component (B) may be mixed and passed through an extruder, and the thermoplastic resin (C) may be charged and kneaded in the middle of the extruder to be kneaded.

[0030]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the above unless the gist of the present invention is exceeded.
The present invention is not limited to the following examples. In the examples, parts and% are based on weight unless otherwise specified.
In addition, in the examples, various physical properties were evaluated by the following methods. The loss factor was measured by the resonance method using a test piece having a thickness of 2 mm. Impact resistance: Measured according to ASTM D256. The unit is kg
cm / cm. Flexural modulus was measured according to ASTM D790 (1/2 ″ × 3/2 ″ × 5 ″), in kg / cm ² .

Reference Example Each component used in Examples and Comparative Examples is as follows. (A) Component (A-1-1) Using a pressure resistant reaction vessel substituted with dry nitrogen gas, n-butyllithium was used as a polymerization catalyst with cyclohexane as a solvent, and TMEDA was used as a vinylating agent. Add in sequence and polymerize, AB
-A type block copolymer was obtained. The number average molecular weight of this block copolymer was 150,000, the number average molecular weight of the polystyrene block was 11,000, the number average molecular weight of the polyisoprene block was 128,000, and the vinyl bond content was 76%. (A-2-1) Using (A-1-1) above in cyclohexane with Pd-C as a hydrogenation catalyst, hydrogen pressure of 20 kg / cm.
^The hydrogenation reaction was carried out at ² . The hydrogenation rate was 75%. (A-2-2) A block copolymer composed of ABC, wherein block A is a polystyrene block, B is a styrene-butadiene random copolymer block, and C is a styrene-butadiene copolymer block in which styrene is gradually increased. The styrene content of the entire block copolymer is 15%, the bound styrene content of the block A is 5%, the butadiene bond content of the block B is 80%, the number average molecular weight of the entire block copolymer is 160,000, and water. With an additive rate of 98%.

Component (B) Polypropylene [J5910B manufactured by Tosoh Corporation] (C) Component (C-1); Nylon 6 (Capron 6, manufactured by JSR Allied) (C-2); AS resin [acrylonitrile-styrene Copolymer (acrylonitrile content = 23.5%, weight average molecular weight = 105,000)] Preparation of partially crosslinked product The compounded formulation shown in Table 1 was partially crosslinked at 220 ° C. using an extruder (40 mmφ). Was produced.

[0033]

[Table 1]

Examples 1 to 8 and Comparative Examples 1 to 5 The formulations shown in Tables 2 and 3 were used in an extruder to produce 25
Pellets were formed at 0 ° C., and the pellets were injection-molded by an injection molding machine to prepare test pieces and evaluated for physical properties. The results are shown in Tables 2-3. As is clear from Table 2,
Examples 1 to 8 are resin compositions of the present invention, and are excellent in mechanical strength such as vibration damping property, impact resistance, and bending elastic modulus. On the other hand, as is clear from Table 3, Comparative Example 1
Is an example outside the scope of the present invention in which the component (A) is not used,
Vibration control and impact resistance are poor. Comparative Example 2 and Comparative Example 4 are examples in which the component (C) exceeds the range of the present invention, and the vibration damping property and impact resistance are poor. Comparative Example 3 is an example in which the component (C) is below the range of the present invention, and the flexural modulus is poor. Comparative Example 5
Is an example outside the scope of the present invention in which the component (B) is not used,
Inferior in vibration damping, impact resistance and flexural modulus.

[0035]

[Table 2]

[0036]

[Table 3]

Comparative Example 6 14 parts of the same (A) component as in the above (A-1-1), 6 parts of polypropylene (the same as the above), 80 parts of nylon 6 (the same as the above), 1 part of maleic anhydride and dichroic acid. When 0.2 part of mill peroxide was mixed and pelletized using an extruder, injection molding was performed using this pellet with an injection molding machine, a test piece was prepared, and physical properties were evaluated in the same manner as in Example 1. , Loss factor 0.07, Izod impact strength 2
5 and the flexural modulus was 2.3 × 10 ⁻⁴ , and the vibration damping property was poor.

[0038]

The vibration-damping resin composition of the present invention is a material that reduces the generation of vibration and noise without losing the moldability of the resin body, and is used for automobile parts, electric / electronic parts, and OA equipment parts. Useful for.

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Claims (1)

[Claims] 1. A conjugated diene polymer comprising (A) 0 to 50% by weight of an aromatic vinyl compound and 100 to 50% by weight of a conjugated diene and / or a hydrogenated product thereof in an amount of 5 to 75% by weight.
And (B) a polyolefin resin 95 to 25% by weight (however, (A) + (B) = 100% by weight) 5
To 50 parts by weight, and (C) 95 to 50 parts by weight of a thermoplastic resin other than the component (B) (however, (A) + (B)
+ (C) = 100 parts by weight] as a main component.