JP3298122B2 - Polyvinyl chloride resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used in various fields of transportation equipment, precision electronic equipment, audio equipment and the like for controlling vibrations to improve an operation response speed, a measurement accuracy, and a sound quality. The present invention relates to a polyvinyl chloride resin composition having excellent vibration energy-absorbing performance.

[0002]

2. Description of the Related Art Conventionally, butyl rubber is most often used as a vibration energy absorbing material. Also, recently, polynorbornene and special urethane-based elastomers have been found to have higher performance and have attracted attention.

[0003] The primary evaluation of these vibration energy-absorbing materials is based on storage elastic modulus (E ') and loss coefficient (tan δ = loss elastic modulus (E ") / obtained by measuring the viscoelasticity of the material.
(Storage modulus (E ')).

[0004] In order to design as a vibration energy absorbing material, there is an optimum value as the loss coefficient increases and the storage elastic modulus depends on the form used.

[0005] These two factors are usually highly temperature dependent. That is, the storage elastic modulus gradually decreases as the temperature increases, and sharply decreases from a temperature range usually exceeding the glass transition point. Further, the loss coefficient shows the highest value in a temperature range exceeding the glass transition point, but generally tends to decrease in a temperature range around the glass transition point.

Therefore, as a standard conventionally required for such a vibration energy absorbing material, first, it has to have a high loss coefficient in a temperature range where the material is used.

On the other hand, the storage elastic modulus can be adjusted to an optimum value by adding an inorganic or metal filler, a softening agent, rubber, or the like, so that the value can be adjusted within a considerable range. . Therefore, butyl rubber, polynorbornene, special urethane-based elastomer and the like have a maximum loss coefficient value of tan δ = 1.4, 2..
It shows an excellent value of 8,1.3. However, these materials have difficulties in workability and formability, and their use range is limited.

[0008] Further, polyvinyl chloride resin has a long history as one of the five major general-purpose resins, and most molding methods have been established in addition to economic efficiency. In addition, it is advantageous in that it is an amorphous resin, and that it can be easily compounded with an inorganic / metal filler or a softener. The loss factor of polyvinyl chloride alone has a peak value of about 1.1 at around 90 ° C.
However, a typical plasticizer such as di-2-ethylhexyl phthalate (hereinafter abbreviated as DOP) is a resin 100
If 100 parts by weight is added to the parts by weight, the peak temperature of the loss coefficient becomes about 5 ° C., and the peak value is reduced to about 0.7. This phenomenon was naturally understood when it is considered that heterogeneous molecules are mixed in a single molecular chain of polyvinyl chloride, and as a result, the distribution of relaxation time is widened. However, as a result of our recent studies, it was found that the addition of a very limited number of plasticizers or oligomers to polyvinyl chloride lowers the peak temperature of the loss factor but increases the peak value to about 2.0. Was issued. However, if the peak temperature of the loss coefficient of the composition obtained here is compounded around room temperature, which is a general use temperature range, the surface of the obtained composition becomes sticky. Therefore, there have been problems such as migration of a plasticizer due to contact with another base material and trouble in adhesion to another base material.

[0009]

SUMMARY OF THE INVENTION The present invention provides a polyvinyl chloride resin composition having excellent vibration energy-absorbing performance with reduced surface stickiness while utilizing the characteristics of the polyvinyl chloride resin. The purpose is to:

[0010]

Means for Solving the Problems In view of the above situation, the present inventors have conducted intensive studies and as a result have completed the present invention.

That is, in the present invention, 5-200 parts by weight of a phthalic acid ester represented by the following general formula (1) is added to 100 parts by weight of a polyvinyl chloride resin, and a phosphoric acid ester represented by the following general formula (2) A polyvinyl chloride resin composition comprising 5 to 200 parts by weight, and 5 to 100 parts by weight of at least one resin selected from the following groups (a) to (c): The present invention relates to a polyvinyl chloride resin composition comprising 3 to 200 parts by weight of at least one resin selected from the following groups (d) to (k) based on 100 parts by weight of the polyvinyl chloride resin.

[0012]

Embedded image

[0013]

Embedded image (A) a chlorosulfonated polyethylene having a chlorine content of 25 to 45% by weight; (b) 15 to 50% by weight of acrylonitrile;
Mooney viscosity (ML _{1 + 4} (100 ℃)) is 20 ~ 90
Certain nitrile rubber (c) Ethylene-vinyl acetate copolymer having a vinyl acetate unit content of 20% by weight or more (d) Coumarone resin (e) Ketone resin (f) Low molecular weight polystyrene (g) Maleic Acid resin (h) rosin-based resin (i) terpene-based resin (j) xylene resin (k) petroleum resin Furthermore, the present invention relates to a vibration energy absorbing material comprising these compositions. Hereinafter, the details will be described.

The polyvinyl chloride resin used in the present invention is a random copolymer of at least one of vinyl chloride homopolymer resin, chlorinated vinyl chloride resin, and all monomers copolymerizable with vinyl chloride monomer. A vinyl chloride copolymer resin (for example, vinyl acetate-vinyl chloride copolymer, ethylene-vinyl chloride copolymer, etc.) obtained by polymerization or block copolymerization, such as a single product of these resins or a mixture of two or more thereof.

[0015] The phthalic acid ester having the structural formula (1) is _a compound R 1, _{R 2} consists of monocyclic hydrocarbon of _C 3 -C _6, R 1, _{R 2} are different and the same And the hydrogen on the ring may be substituted with another substituent. Specifically, dicyclohexyl phthalate (DC
HP), dimethylcyclohexyl phthalate, diphenyl phthalate and the like, and preferably dicyclohexyl phthalate is used. As the amount of addition,
From the viewpoint of economy, the amount is preferably 5 to 200 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin.

The phosphate having the structure of the general formula (2) is a compound in which R ₃ is a C _{6 to} C ₉ aromatic monocyclic hydrocarbon. R _{3 to} R ₅ may be the same or different, and hydrogen on the ring may be substituted with another substituent. Specifically, tricresyl phosphate (TCP),
Trixylenyl phosphate (TXP) and the like are preferably used, and trixylenyl phosphate is preferably used. From the viewpoint of processability and economy, the amount of addition is 5 parts by weight or more to 100 parts by weight of the polyvinyl chloride resin.
It is preferably not more than 10 parts by weight, more preferably not less than 10 parts by weight and not more than 100 parts by weight.

In such a composition, by adjusting the blending amount of phthalic acid ester and phosphoric acid ester, tan
The temperature at which δ has the maximum value can be set in a wide range from room temperature to about 80 ° C., and the value can be kept at 1.2 or more. Therefore, it can be said that it is extremely useful as a vibration energy absorbing material. However, when the temperature at which tan δ is maximum is set to around room temperature, the composition surface causes stickiness on the composition surface. Therefore, the resins (a) to (c) are used together for the purpose of reducing stickiness without lowering the loss coefficient.

The chlorosulfonated polyethylene (a) used in the present invention is a vulcanizable elastic material produced by chemically reacting chlorine and sulfurous acid gas with polyethylene having a molecular weight of about 20,000 to chlorinate and chlorosulfonate. And is generally called CSM. The presence or absence of chain branching in the polyethylene used in this reaction does not pose any particular problem. However, the absence thereof increases the crystallinity of the polyethylene, causes stiffness in the resulting elastic body, and makes processing of unvulcanized rubber difficult. Chlorination also has the effect of eliminating the crystallinity of polyethylene, but if the amount is too large, the properties of the rubber will be affected. So the chlorine content is 25-45% by weight
A resilient member, more preferably 25 to 35 wt%. Further, chlorosulfonation is for the purpose of introducing a vulcanization point, and this amount greatly affects various properties of the vulcanized product. However, in the present invention, there is no particular problem because it is used without being vulcanized. However, considering the workability, an elastic body having a sulfur content of about 1.0% by weight is preferable.

The nitrile rubber (b) used in the present invention
The term “butadiene-acrylonitrile copolymer” refers to what is generally called NBR. However, when the amount of bound acrylonitrile is 60% by weight or more, it becomes hard, and when it is 7% by weight or less, it swells in oil. Therefore, it is a rubbery oil-resistant copolymer having an acrylonitrile amount of 15 to 50% by weight , and more preferably 25 to 40% by weight. The polymerization reaction is carried out by emulsion polymerization, and the polymerization temperature can be used without any problem from a cold rubber obtained at a low temperature to a hot rubber obtained at a normal temperature or higher. The Mooney viscosity (ML _{1 + 4} (10
0 °)) is from 20 to 90, more preferably from 50 to 80.

The ethylene-vinyl acetate copolymer (c) used in the present invention is a copolymer formed by general industrial production of ethylene and vinyl acetate, such as high-pressure polymerization, emulsion polymerization, and solution polymerization. It is a polymer. Also,
In addition to ethylene and vinyl acetate, polar monomers such as acrylic acid and acrylic acid ester may be contained as the third component. Usually, those vinyl acetate is about 7-80 wt% ethylene - but called vinyl acetate copolymer, ethylene used in the composition - vinyl acetate copolymer intended content of vinyl acetate is not less than 20 wt% There is . When the content of vinyl acetate is less than 20% by weight, the loss coefficient is lowered in view of compatibility with vinyl chloride.

The amount of addition of at least one selected from the groups (a) to (c) is
The amount is 5 parts by weight or more and 100 parts by weight or less, preferably 5 parts by weight or more and 50 parts by weight or less with respect to 0 parts by weight. When the amount is less than 5 parts by weight, the effect of reducing the stickiness is not so significant and 1
When the amount exceeds 00 parts by weight, the loss coefficient is significantly reduced.

Further, by combining the resins (d) to (k) in addition to the phthalic acid ester and the phosphoric acid ester, the loss factor can be further increased.

The coumarone resin (d) in the present invention is also referred to as a coumarone-indene copolymer and is a polymer composed of three types of styrene, coumarone and indene in the composition of heavy gas oil. This is a complex mixed resin such as a homopolymer of each monomer, any two of these copolymers, or three copolymers, but has a softening point of 70 to 150.
° C is preferred.

The ketone resin (e) in the present invention is a resin obtained by condensation of a ketone and formaldehyde. The ketones used here are classified into anone-based (using cyclohexane, methylcyclohexane, etc.) and acetophenone-based (using acetophenone, ethylphenylketone, etc.). In the case of using in the present invention, anone-based is particularly preferable, and softening is preferred. The point is preferably 70 to 120 ° C.

The low molecular weight polystyrene (f) in the present invention is also called oligostyrene, and has a number average molecular weight of 300.
~ 5000 liquid or solid styrene resins or α
-A methylstyrene resin. The composition and production method are not particularly limited, but those having a molecular weight of 3000 or less are preferably used.

The maleic acid resin (g) in the present invention is also referred to as a rosin-modified maleic acid resin, and is a kind of polyester resin obtained by forming an adduct of tribasic acid from rosin and maleic anhydride and esterifying it with a polyhydric alcohol. It is.
Depending on the amount of maleic anhydride added, the type of polyhydric alcohol, and the degree of esterification, various properties such as softening point and solubility can be obtained, but those having a softening point of 80 to 150 ° C are preferred.

The rosin-based resin (h) in the present invention includes gum rosin, wood rosin, tall oil rosin (hereinafter referred to as rosin) whose main component is abietic acid, hydrogenated rosin obtained by reacting rosin with hydrogen gas, and fatty acid The main component is a disproportionated rosin and rosin dimer obtained by the reaction of dehydrobietic acid having a stable aromatic ring and hydrogenated dihydroabietic acid being dehydrogenated by the transfer of hydrogen between molecules. And rosin esters obtained by esterifying these rosins and modified rosins with glycerin, pentaerythritol and the like. These include various types including modified products, and rosin esters are particularly preferable.

In the present invention, the terpene resin (i) is α
-A resin made from turpentine as a raw material, the main component being pinene, and the cyclic terpene such as β-pinene, camphene and dipentene. These are classified into α-pinene-based, β-pinene-based, and terpene phenols obtained by cationic polymerization of α-pinene and phenol, and α-pinene-based or terpene phenols are particularly preferred.

The xylene resin (j) in the present invention is m-
It is a 100% xylene resin obtained from xylene and formaldehyde, or a modified xylene resin such as an alkylphenol-modified xylene resin or a phenol-modified xylene resin (novolak, resol), and particularly preferably a phenol-modified xylene resin (novolak).

The petroleum resin (k) used in the present invention is a resin obtained by polymerizing a cracked oil fraction containing a large number of unsaturated hydrocarbons by-produced by thermal decomposition of naphtha or the like. The cracked oil fraction is a BTX extraction residue of C ₅ fraction and C ₆ -C ₁₁ fraction, these polymerization methods are cationic polymerization, thermal polymerization, as the like radical polymerization and the like, to be particularly restricted is not. Further, a petroleum resin modified by introducing a functional group such as adding a polar group such as maleic anhydride or introducing a carboxyl group to the resin, or adding a monomer is naturally included. The maximum value of the loss factor by the addition of petroleum resin is improved significantly, those containing preferably a so-called C ₉ petroleum resins obtained by polymerizing BTX extraction residue in the present invention, particularly indene and styrene C ₉ or more components 50 wt% It is more preferable that the ratio of indene to styrene be at least half that of styrene. Also,
It is preferable that the number average molecular weight is 500 or more and 1500 or less. However, the petroleum resin used in the present invention is not limited to this description.

The amount of the resin (d) to (k) is preferably 3 to 200 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin. If the amount is less than 3 parts by weight, the loss coefficient is not so much improved, and if it exceeds 200 parts by weight, the processability is extremely reduced.

The polyvinyl chloride resin composition according to the present invention contains DOP and dioctylsebacate which are usually added to the polyvinyl chloride resin to such an extent that the performance is not extremely reduced.
(DOS), inorganic fillers such as calcium carbonate and talc, flame retardants such as antimony trioxide and zinc borate, and vibration energy absorbers such as mica and graphite. Flake fillers and the like to be used can be added as needed.

The polyvinyl chloride resin composition of the present invention can be freely formed by a conventional method such as calendering, extrusion, injection molding, foam molding, compression molding, etc. be able to.

The vibration energy obtained by the present invention
Absorbents are used for supporting members of equipment such as precision electronic equipment and precision measuring equipment, etc., whose accuracy may be affected by vibration, fixing members such as packing and gaskets, laminated members and chassis of audio equipment, etc. it can. It is also used to control vibration by attaching it directly to highly vibrating parts such as automobiles and industrial equipment.It is also used on the legs of precision equipment to prevent vibration transmission from the floor. It can be used in combination with other materials such as a metal material such as an aluminum plate, wood, an inorganic material, and the like.

[0035]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

Example 1 Ethylene-vinyl chloride copolymer (Rulon E-280)
0, 100 parts by weight, manufactured by Tosoh Corporation; 50 parts by weight of dicyclohexyl phthalate (DCHP, manufactured by Osaka Organic Chemical Co., Ltd.); 50 parts by weight of trixylenyl phosphate (TXP, manufactured by Daihachi Chemical Industry Co., Ltd.) Part, OG-75 as stabilizer
6 (manufactured by Mizusawa Chemical Co., Ltd.), 7 parts by weight of antimony trioxide (ATOX-S, manufactured by Nippon Seimitsu Co., Ltd.) as a flame retardant, chlorosulfonation (polyethylene (TOSO-CS)
20 parts by weight of MTS-320, ML _{1 + 4} (100 ° C.) = 37, manufactured by Tosoh Corporation were mixed and roll-kneaded at a temperature of 150 ° C. for 5 minutes to obtain a target composition.

Example 2 In Example 1, nitrile rubber (PN20HA, Nippon Synthetic Rubber Co., Ltd.) was used instead of chlorosulfonated polyethylene.
Except for using 20 parts by weight) to obtain the target composition.

Example 3 In Example 1, an ethylene-vinyl acetate copolymer (Ultracene 76) was used instead of the chlorosulfonated polyethylene.
0, manufactured by Tosoh Corporation) to obtain the desired composition by the exact same operation except that 20 parts by weight were used.

Example 4 The procedure of Example 2 was repeated, except that the nitrile rubber was used in an amount of 40 parts by weight to obtain a target composition.

Example 5 In Example 1, a coumarone resin (Nippon Steel Coumaron T) was added.
-105, manufactured by Nippon Steel Chemical Co., Ltd.), except that 20 parts by weight were added to obtain the target composition.

Example 6 In Example 1, a ketone resin (ketone resin K-
90, manufactured by Arakawa Chemical Industry Co., Ltd.) except that 20 parts by weight were added to obtain the desired composition.

Example 7 A target composition was obtained in exactly the same manner as in Example 1, except that 20 parts by weight of low-molecular-weight polystyrene (Hymer ST95, manufactured by Sanyo Chemical Industries, Ltd.) was added.

Example 8 A target composition was obtained in exactly the same manner as in Example 1, except that 20 parts by weight of maleic acid resin (traffics 4102P, manufactured by Arakawa Chemical Industry Co., Ltd.) was added.

Example 9 In Example 1, rosin (gum rosin CG-W) was added.
W, Arakawa Chemical Industry Co., Ltd.) except that 20 parts by weight were added to obtain the target composition.

Example 10 A hydrogenated rosin ester (ultra-light rosin ester KE-311, manufactured by Arakawa Chemical Industries, Ltd.) in Example 1 was added.
The desired composition was obtained by exactly the same operation except that 0 parts by weight was added.

Example 11 A target composition was obtained in the same manner as in Example 1 except that 20 parts by weight of rosin ester (Superester A-100, manufactured by Arakawa Chemical Industries, Ltd.) was further added.

Example 12 In Example 1, a terpene resin (YS Resin TO
-105, manufactured by Yasuhara Yushi Co., Ltd.) to obtain the target composition by exactly the same operation except that 20 parts by weight were added.

Example 13 In Example 1, a phenol-modified xylene resin (Nicalol NP-100, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 2
The desired composition was obtained by exactly the same operation except that 0 parts by weight was added.

Example 14 A target composition was obtained in exactly the same manner as in Example 1 except that 20 parts by weight of petroleum resin (Petokol LX, manufactured by Tosoh Corporation) was added.

Example 15 In Example 14, 70% of dicyclohexyl phthalate was added.
A desired composition was obtained by exactly the same operation except that the amount of trixylenyl phosphate was changed to 80 parts by weight, and 20 parts by weight of the coumarone resin used in Example 5 was further added.

Comparative Example 1 A target composition was obtained in exactly the same manner as in Example 1, except that chlorosulfonated polyethylene was not added.

Comparative Example 2 A target composition was obtained in exactly the same manner as in Example 5 except that chlorosulfonated polyethylene was not added.

Comparative Example 3 A target composition was obtained in the same manner as in Example 15 except that chlorosulfonated polyethylene was not added.

[Evaluation of Loss Factor (tan δ)]
The composition obtained in the comparative example was pressed at 180 ° C.
A sheet having a thickness of mm was prepared. Using this sheet, a viscoelastic analyzer RSAII (manufactured by Rheometrics Fast Co., Ltd.), which is a measuring device based on the non-resonant type forced vibration method, heats up at a rate of 2 ° C./min and a measuring frequency of 10 Hz.
Was used to measure the loss factor. Table 1 shows the peak value of the loss coefficient at this time and the temperature at that time.

[Evaluation of Surface Condition] The compositions obtained in Examples and Comparative Examples were pressed at 180 ° C., and were 90 mm in length and 6 in width.
Sheets having a thickness of 0 mm and 2 mm were prepared. The two sheets were superposed on each other and sandwiched by two smooth glass plates 60 mm in length and width each along one side of the width of the press sheet. The height and width of the bottom are 60 mm each, and the mass is 3
kg, put in a 70 ° C. atmosphere for 24 hours, remove the weight, and let it cool at room temperature for 1 hour.
When the sheets were gently peeled off, the contact surface was examined for any damage or other abnormalities. Table 1 shows the results.

[0056]

[Table 1]

[0057]

As is apparent from the above description, according to the present invention, a specific phthalate ester, a phosphate ester, or a phthalate ester, a phosphate ester, a specific resin and a CSM, By combining at least one of NBR and EVA, vibration energy having a non-sticky surface and a high loss coefficient in an arbitrary temperature range is obtained.
An absorbent is obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 31/04 C08L 31/04 57/00 57/00 93/04 93/04 (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 27/06 C08L 23/34 C08L 31/04 C08L 57/00-57/12 C08L 93/04

Claims (3)

(57) [Claims] 1. A phthalic ester represented by the following general formula (1) is added to a polyvinyl chloride resin in an amount of 5 to 100 parts by weight.
200 parts by weight, 5 to 200 parts by weight of a phosphoric acid ester represented by the following general formula (2), and 5 to 100 parts of at least one resin selected from the following groups (a) to (c):
A polyvinyl chloride resin composition comprising parts by weight. Embedded image Embedded image R ₁ , R ₂ : monocyclic hydrocarbon R _{3 to} R ₅ : aromatic monocyclic hydrocarbon (a) Chlorosulfonated polyethylene having a chlorine content of 25 to 45% by weight (b) 15 to 50% by weight Of acrylonitrile,
Mooney viscosity (ML _{1 + 4} (100 ℃)) is 20 ~ 90
Certain nitrile rubber (c) Ethylene-vinyl acetate copolymer having a vinyl acetate unit content of 20% by weight or more 2. The polyvinyl chloride resin composition according to claim 1, wherein at least one selected from the group consisting of the following (d) to (k) based on 100 parts by weight of the polyvinyl chloride resin. A polyvinyl chloride resin composition comprising 3 to 200 parts by weight of the above resin. (D) Coumarone resin (e) Ketone resin (f) Low molecular weight polystyrene (g) Maleic resin (h) Rosin resin (i) Terpene resin (j) Xylene resin (k) Petroleum resin 3. A vibration energy absorbing material comprising the polyvinyl chloride resin composition according to claim 1.