JP3321815B2 - 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. The primary evaluation of these vibration energy absorbing materials is a storage elastic modulus (E ') and a loss coefficient (tan δ = loss elastic modulus (E ") / storage elastic modulus (E')) obtained by measuring the viscoelasticity of the material. Done.

[0003] 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 changes depending on the form used. These two
The 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.

[0004] Therefore, as a standard conventionally required for such a vibration energy absorbing material, first, a material having a high loss coefficient in a temperature range in which the material is used. On the other hand, the storage elastic modulus can be adjusted to an optimum value because the value can be adjusted within a considerable range by adding an inorganic or metal filler, a softening agent, rubber, or the like. Therefore, butyl rubber, polynorbornene, special urethane-based elastomer, and the like exhibit excellent loss coefficients of tan δ = 1.4, 2.8, and 1.3 at maximum. However, these materials have difficulties in workability and formability, and their use range is limited.

[0005] The demand for higher performance and higher quality of various kinds of transportation equipment such as recent precision electronic equipment and automobiles does not stop, and not only the value of the loss coefficient is large in a specific temperature range but also a wide temperature range. That is, it is desired to maintain a high tan δ value from room temperature to about 60 ° C., or from −20 ° C. to about 100 ° C. depending on the use.

[0006] Incidentally, 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 has advantages such as being an amorphous resin and being ready for complexing with an inorganic / metal filler or a softener. The loss coefficient of polyvinyl chloride alone has a peak value of about 1.1 at about 90 ° C., which is represented by di-2-ethylhexyl phthalate (hereinafter abbreviated as DOP) which is a typical plasticizer. Is added to 100 parts by weight of the polyvinyl chloride resin, the peak temperature of the loss coefficient is about 5 ° C., and the peak value is about 0.7.
To a degree. 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, the addition of a very limited type of plasticizer to polyvinyl chloride lowers the peak temperature of the loss factor, but increases the peak value to about 1.8. That was found. However, the plasticizer used here is expensive in comparison with ordinary plasticizers, and its performance is still inferior to that of existing high-performance vibration absorbers.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a vibration energy absorbing material which has a high loss coefficient and is economically excellent while utilizing the characteristics of a polyvinyl chloride resin.

[0008]

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, the phthalic acid ester having the following structure (I) or the phthalic acid ester and the phosphoric acid ester having the following structure (II) are 5 to 200 parts by weight based on 100 parts by weight of the polyvinyl chloride resin. Parts, and 5 to 200 parts by weight of at least one resin selected from the group consisting of the following (a) to (e) , and a polyvinyl chloride resin composition in the composition. Resin 10
The present invention relates to a polyvinyl chloride resin composition containing 5-200 parts by weight of a petroleum resin with respect to 0 parts by weight, and a vibration energy absorbing material comprising these compositions.

[0010]

Embedded image

[0011]

Embedded image (Wherein R ₁ and R ₂ are monocyclic hydrocarbons consisting of C _{3 to} C ₈ ,
R _{3 to} R ₅ are an aromatic monocyclic hydrocarbon composed of C _{6 to} C ₉ . (A) Ketone resin (b) Low molecular weight polystyrene (c) Maleic resin (d) Rosin-based resin (e) Terpene-based resin The details will be described below.

The polyvinyl chloride resin used in the present invention is not limited to a vinyl chloride homopolymer, but may be a vinyl chloride resin such as a copolymer with vinyl acetate, ethylene, or a graft polymer with polyurethane. Is shown.

The phthalic acid ester represented by the structural formula (I) used in the present invention shows a maximum loss coefficient of 1.4 to 1.8 even when it is used alone and mixed with a polyvinyl chloride resin.

Specific examples of such a compound include dicyclohexyl phthalate (DCHP), dimethylcyclohexyl phthalate, diphenyl phthalate and the like.

Further, the phosphate ester represented by the structural formula (II) used in the present invention has a maximum loss coefficient of 0.8-1.
3 is shown.

Specific examples include tricresyl phosphate and trixylenyl phosphate (TXP).

In particular, the phthalic acid ester used in the present invention has a poor plasticizing efficiency, so that even if it is added in a considerable amount, the temperature range showing the maximum loss coefficient is hardly lowered to the room temperature range most frequently used as a vibration energy absorbing material. There are drawbacks,
This disadvantage can be compensated for by using a phosphate ester in combination.

Further, the phthalic acid ester used in the present invention has a drawback that it is easy to bleed after molding.
It is an advantage that the bleed can be suppressed by adding a phosphate ester.

The addition amount of these two ester-based plasticizers cannot be specified unconditionally depending on the application. Less than parts by weight is appropriate. If the addition amount is less than 5 parts by weight, the improvement of the loss coefficient cannot be expected much. On the other hand, if it is added in excess of 200 parts by weight, the stickiness of the plasticizer increases, which is not preferred.

[0020]

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

Low molecular weight polystyrene in the present invention
(B) 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 the molecular weight is preferably 3000 or less.

The maleic acid resin (c) in the present invention is also referred to as a rosin-modified maleic acid resin and is a kind of polyester resin which is 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 resin (d) in the present invention is 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. Resin (d)
Although there are many kinds including modified products, rosin esters are particularly preferred.

In the present invention, the terpene resin (e) 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.

[0026]

The amount of addition of at least one resin selected from the resin group (a) to (e) is 5 to 200 parts by weight, preferably 10 to 100 parts by weight of the polyvinyl chloride resin. The amount is preferably not less than 100 parts by weight and not more than 100 parts by weight. Below 5 parts by weight, the loss factor does not improve much,
Further, if it is added in excess of 200 parts by weight, the processability is extremely reduced.

Further, the petroleum resin 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 a C5 fraction and a C6 to C11 fraction, and their polymerization methods include, but are not particularly limited to, cationic polymerization, thermal polymerization, and radical polymerization. Further, a petroleum resin modified by the introduction of a functional group such as addition of a polar group such as maleic anhydride or the introduction of a carboxyl group or the addition of a monomer is also included in the resin. Although the maximum value of the loss coefficient is greatly improved by adding a petroleum resin, in the present invention, a so-called C9 petroleum resin obtained by polymerizing a BTX extraction residue is preferable, and particularly, a resin containing 50% by weight or more of indene and styrene of the C9 component is preferable. In addition, the ratio of indene to styrene is preferably such that styrene accounts for more than half. 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 petroleum resin is from 5 to 200 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.
Further, the amount is preferably from 10 parts by weight to 100 parts by weight.
If the amount is less than 5 parts by weight, the loss factor does not improve much,
If added in excess of 0 parts by weight, the processability will be extremely deteriorated.
In addition, the resin (a) to (e) and the petroleum resin
More than 100 parts by weight is more preferable.

The vibration energy absorbing material according to the present invention includes:
Inorganic fillers such as calcium carbonate and talc which are usually added to polyvinyl chloride resins, flame retardants such as antimony trioxide and zinc borate, and flake-like fillers such as mica and graphite And the like can be added as needed.

If necessary, acrylonitrile-butadiene rubber, ethylene-vinyl acetate copolymer, acrylic resin and the like which are usually used for modifying polyvinyl chloride resin can be blended.

The vibration energy absorbing material according to the present invention is a calender made by a conventional polyvinyl chloride resin molding method.
It can be formed freely by a method such as processing, extrusion, injection molding, foam molding, compression molding and the like.

The vibration energy absorbing material obtained according to the present invention has high accuracy in the manufacturing process of a support member or an electronic component manufacturing line where the accuracy is affected by vibration, such as precision electronic equipment and precision measuring equipment. It can be used as a vibration-proof material for equipment as required, a fixing member such as packing and gasket, and a laminated member such as audio equipment. Furthermore, it can be directly attached to highly vibrating parts such as automobiles and industrial equipment to suppress vibrations, or used in combination with other materials such as metal materials such as stainless steel plates and aluminum plates, wood, inorganic materials, etc. it can.

[0034]

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

[0035]

[0036]

Example 1 Ethylene-vinyl chloride copolymer resin (Ryuron E-2)
800, manufactured by Tosoh Corporation) 100 parts by weight, phthalic acid S
Dicyclohexyl phthalate (DCHP, large
Osaka Organic Chemical Co., Ltd.) 40 parts by weight, phosphate ester
Trixylenyl phosphate (TXP, Daihachi Chemical
70 parts by weight, ketone resin (ketone resin K-
90, Arakawa Chemical Industry Co., Ltd.) 20 parts by weight, as stabilizer
OG-756 (manufactured by Mizusawa Chemical Co., Ltd.) 5 parts by weight, flame retardant
As antimony trioxide (ATOX-S, Nippon Concentrate)
7 parts by weight) and mixed at a temperature of 150 ° C for about 5 minutes.
Roll kneading was performed to obtain a sheet having a thickness of 0.2 mm.

Example 2 In Example 1, low molecular weight polystyrene (Hymer ST95, manufactured by Sanyo Chemical Industries, Ltd.) was used instead of the ketone resin.
The desired composition was obtained by exactly the same operation except that 0 parts by weight was used.

Examples 3 and 4 Instead of the low molecular weight polystyrene used in Example 2 , low molecular weight polystyrenes having different softening points (Hymer ST
120, Hymer SB150, manufactured by Sanyo Chemical Industry Co., Ltd.)
A target composition was obtained by exactly the same operation except that 20 parts by weight was used.

Example 5 A maleic acid resin (traffics 4102P, manufactured by Arakawa Chemical Industries, Ltd.) was used instead of the ketone resin in Example 1.
A target composition was obtained by exactly the same operation except that 20 parts by weight was used.

Example 6 The same procedure as in Example 1 was repeated except that 20 parts by weight of disproportionated rosin (Longis R, manufactured by Arakawa Chemical Industry Co., Ltd.) was used instead of the ketone resin to obtain the desired composition. Was.

Example 7 The procedure was performed in exactly the same manner as in Example 1 except that 20 parts by weight of hydrogenated rosin ester (ultra-light rosin ester KE-311, manufactured by Arakawa Chemical Industry Co., Ltd.) was used instead of the ketone resin. Was obtained.

Example 8 A rosin ester (Superester A-100, Arakawa Chemical Industries, Ltd.) was used in Example 1 in place of the ketone resin.
Except for using 20 parts by weight) to obtain the target composition.

Example 9 The same procedure as in Example 1 was repeated, except that 20 parts by weight of rosin (gum rosin CG-WW, manufactured by Arakawa Chemical Industry Co., Ltd.) was used instead of the ketone resin to obtain a target composition. .

Example 10 The same procedure as in Example 1 was repeated, except that 20 parts by weight of a terpene resin (YS Resin TO-105, manufactured by Yasuhara Yushi Co., Ltd.) was used instead of the ketone resin. Was.

[0046]

[0047]

[0048]

Example 11 A target composition was obtained in exactly the same manner as in Example 5, except that 20 parts by weight of the disproportionated rosin used in Example 6 was added.

[0050]

Example 12 The same procedure as in Example 7 was repeated except that dicyclohexyl phthalate was used in an amount of 20 parts by weight and petroleum resin (Petokol LX-T, manufactured by Tosoh Corporation) was added in an amount of 20 parts by weight. I got something.

Comparative Example 1 The same procedure as in Example 1 was carried out except that no ketone resin was added, to obtain a target composition.

Comparative Example 2 The same procedure as in Comparative Example 1 was repeated except that the amount of dicyclohexyl phthalate was changed to 60 parts by weight, to obtain a target composition.

Comparative Example 3 The same procedure as in Comparative Example 1 was repeated except that the amount of dicyclohexyl phthalate was changed to 90 parts by weight to obtain a target composition.

[Evaluation of Loss Factor (tan δ)]
A sheet of the composition obtained in the comparative example was subjected to a viscoelastic analyzer RSAI, which is a measuring device based on a non-resonant type forced vibration method.
I (manufactured by Rheometrics Fast Company) was used to measure the loss coefficient at a heating rate of 2 ° C./min and a measurement frequency of 10 Hz. Table 1 shows the peak value of the loss coefficient at this time and the temperature at that time.

[0056]

[Table 1]

[0057]

As is apparent from the above description, according to the present invention, a polyvinyl chloride resin is combined with a specific phthalate, or a phthalate and a phosphate, and a specific resin. Thus, a vibration energy absorbing material having excellent economic efficiency and a high loss coefficient can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 45:02) C08L 45:02) (C08L 27/06 (C08L 27/06 61:00) 61:00) (C08L 27 / 06 (C08L 27/06 93:00) 93:00) (C08L 27/06 (C08L 27/06 25:06) 25:06) (56) References JP-A-4-117455 (JP, A) JP-A JP-A-61-192753 (JP, A) JP-A-3-70758 (JP, A) JP-A-4-57835 (JP, A) JP-A-4-153208 (JP, A) JP-A-4-81444 (JP JP-A-3-59055 (JP, A) JP-A-59-1557 (JP, A) JP-A-53-121847 (JP, A) JP-A-58-208016 (JP, A) JP-A-58-208016 49-90335 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 27/06 C08L 57/02

Claims (3)

(57) [Claims] 1. A phthalic acid ester having the following structure (I), or a phthalic acid ester and a phosphoric acid ester having the following structure (II): 5 to 200 parts by weight based on 100 parts by weight of a polyvinyl chloride resin. And the following (a) to
(E) at least one resin selected from the group consisting of 5-2
A polyvinyl chloride resin composition comprising 00 parts by weight. Embedded image Embedded image (Wherein R ₁ and R ₂ are monocyclic hydrocarbons consisting of C _{3 to} C ₈ ,
R _{3 to} R ₅ are an aromatic monocyclic hydrocarbon composed of C _{6 to} C ₉ . (A) Ketone resin (b) Low molecular weight polystyrene (c) Maleic resin (d) Rosin resin (e) Terpene resin 2. The polyvinyl chloride resin composition according to claim 1, comprising 5 to 200 parts by weight of a petroleum resin based on 100 parts by weight of the polyvinyl chloride resin. 3. A vibration energy absorbing material comprising the composition according to claim 1 or 2.