JP3141504B2 - 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 relates to a polyvinyl chloride resin composition having excellent compression set and excellent vibration energy absorption 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 ')). In order to design as a vibration energy absorbing material, the larger the loss coefficient is, the more the storage modulus has an optimum value depending on the form used.

[0004] 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.

[0005] Therefore, conventionally, as a criterion required for such a vibration energy absorbing material, a high loss coefficient is firstly obtained 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 elastomers, and the like have a maximum loss coefficient 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.

Further, polyvinyl chloride resin has a long history as one of the five major general-purpose resins, and most molding processes 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.

However, the glass transition temperature of the vinyl chloride resin is about 80 ° C., and it cannot be used alone because it falls outside the practical use temperature range (-30 to 70 ° C.) of the vibration energy absorbing material. There is a plasticizer that lowers the glass transition temperature of this vinyl chloride resin. For example, when DOP, which is the most common plasticizer, is added, the glass transition temperature decreases, but the maximum value of the loss coefficient also decreases. Vibration energy absorption performance is poor. As a result of our recent investigations, it was found that the addition of a very limited type of plasticizer, such as dicyclohexyl phthalate, to vinyl chloride resin increased the peak value of the loss coefficient. Was about 30 ° C. at which the value of 0.5 or more was maintained.

In addition, since the vibration energy absorbing material is often used as a foot of a relatively heavy precision instrument, the vibration energy absorbing material is deformed after a long time, and the initial shape is not maintained. There was a drawback that it could not be demonstrated.

[0010] Therefore, there is a demand for a vibration energy absorbing material having low load deformation resistance, that is, low compression set.

[0011]

DISCLOSURE OF THE INVENTION The present invention provides a high vibration coefficient or a relatively high loss coefficient over a wide temperature range while utilizing the characteristics of a polyvinyl chloride resin, and a vibration having a small compression set. An object is to provide a polyvinyl chloride resin composition having energy absorption performance.

[0012]

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, a polyvinyl chloride resin, a polymer polyol having a molecular weight of 300 to 10,000, a compound having three or more isocyanate groups, a phthalic ester having the following structure (1), and a structure having the following structure (2) The present invention relates to a polyvinyl chloride resin composition obtained by heating and mixing a phosphate ester and at least one resin selected from the following groups (a) to (h).

[0014]

Embedded image R ₁ and R ₂ each represent a monocyclic hydrocarbon.

[0015]

Embedded image R _{3 to} R ₅ each represent an aromatic monocyclic hydrocarbon.

(A) Petroleum resin (b) Coumarone resin (c) Ketone resin (d) Low molecular weight polystyrene (e) Maleic resin (f) Rosin resin (g) Terpene resin (h) Xylene resin The present invention relates to a vibration energy absorbing material made of a resin.

The polyvinyl chloride resin used in the present invention includes vinyl chloride homopolymer resin, chlorinated vinyl chloride resin,
A vinyl chloride copolymer resin obtained by random copolymerization or block copolymerization with one or more of all monomers copolymerizable with the vinyl chloride monomer (for example, vinyl acetate-vinyl chloride copolymer, ethylene- Vinyl chloride copolymer)
And a single resin or a mixture of two or more of the above resins.

The polymer polyol used in the present invention has two or more hydroxyl groups and has a molecular weight of 300 or more and 1 or more.
0000 or less, preferably 1000 or more and 5000 or less. Such polymer polyols are, for example,
It can be obtained by condensation polymerization of an aliphatic dicarboxylic acid having 4 to 10 carbon atoms and an aliphatic glycol having 2 to 10 carbon atoms and / or a glycol having 5 or less repeating units obtained by ring-opening polymerization of an epoxy group. it can.

In the present invention, the molecular weight refers to a number average molecular weight, which can be measured by gel permeation chromatography (GPC) or the like.

The aliphatic glycol having 2 to 10 carbon atoms used in the production of the polymer polyol includes, for example, 1, 1
2-ethanediol, 1,2-propanediol, 1,
4-butanediol, butenediol, 3-methyl-
1,5-pentanediol, 1,6-hexanediol, 1,10-decamethylenediol, 2,5-dimethyl-2,5-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol and the like. .

On the other hand, examples of the compound having an epoxy group include cyclic ethers such as ethylene oxide, propylene oxide, and tetrahydrofuran (THF). Those obtained by subjecting these to ring-opening polymerization to form a glycol having a repeating unit of 5 or less are also suitably used as the glycol of the present invention. One or more of these are used.

Examples of the aliphatic dicarboxylic acids having 4 to 10 carbon atoms used in the production of the polymer polyol include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and the like. Two or more are used.

The addition amount of the polymer polyol is preferably from 10 to 180 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 10 parts by weight, rubber elasticity is not improved,
If it exceeds 180 parts by weight, processing may not be possible.

The compound having three or more isocyanate groups used in the present invention includes, for example, 2,4- and 2,6-
Tolylene diisocyanate, m- and p-phenylene diisocyanate, 1-chlorophenylene-2,4-diisocyanate, 1,5-naphthalene diisocyanate,
Methylenebisphenylene-4,4′-diisocyanate, m- and p-xylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate,
Triisomer of diisocyanate such as 4,4'-methylenebiscyclohexyl diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, lysine ester triisocyanate, 4-isocyanatomethyl-1,8-octa Examples include triisocyanates such as methyl diisocyanate and polyfunctional isocyanates such as polyphenylene methane polyisocyanate, and one or more of these are used. It is also possible to use the above diisocyanates in combination.

However, the number of moles of NCO groups of triisocyanate to the number of moles of NCO groups of all isocyanates is 0.
25 or more is desirable. If it is less than 0.25, sufficient performance may not be obtained due to insufficient crosslinking density.

The compound having an isocyanate group has a molar ratio (NCO / OH (molar ratio)) of the isocyanate group to the hydroxyl group in the polymer polyol.
It is preferable to use it in the range of 0.3 to 1.3. If it is less than 0.3, even if only triisocyanate is used as the isocyanate, sufficient performance may not be exhibited due to insufficient crosslinking density, and if it exceeds 1.3, processing may be difficult.

The phthalic acid ester having the structure of the general formula (1) used in the present invention means that R ₁ and R ₂ are C ₃
It is a compound consisting of monocyclic hydrocarbons -C _8. R ₁ ,
R ₂ may be the same or different, and hydrogen on the ring may be substituted with another substituent. Specifically, dicyclohexyl phthalate (DCHP), dimethyl cyclohexyl phthalate, diphenyl phthalate and the like can be mentioned.
Preferably, dicyclohexyl phthalate is used.
The addition amount is preferably 5 parts by weight or more and 200 parts by weight or less, more preferably 10 parts by weight or more and 100 parts by weight or less with respect to 100 parts by weight of the polyvinyl chloride resin from the viewpoint of processability and economy.

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.

The petroleum resin (a) in the present invention is C ₅ to
It is obtained by polymerizing leave olefins mixed state of C _9. However, the addition of petroleum resin improves the maximum value of the loss coefficient, but the degree of the effect varies considerably depending on the composition and the molecular weight. That is, as a petroleum resin, C ₉
Preferably, the composition contains at least 50% by weight of indene and styrene, and more preferably, the ratio of indene to styrene is at least half. Further, it is preferable that the number average molecular weight is 500 or more and 1500 or less. Outside of these ranges, the value of the loss coefficient may decrease.

The coumarone resin (b) in the present invention is a polymer comprising a coumarone-indene copolymer. This is a complex mixed resin such as a homopolymer of each monomer, a copolymer of any two of these, or a copolymer of three of them, and preferably has a softening point of 70 to 150 ° C.

The ketone resin (c) 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.

The low molecular weight polystyrene (d) 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 the molecular weight is preferably 3000 or less.

The maleic acid resin (e) 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 acid-base acid adduct 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 different 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 (f) in the present invention includes gum rosin, wood rosin, tall oil rosin (hereinafter referred to as rosin) containing abietic acid as a main component, hydrogenated rosin obtained by reacting rosin with hydrogen, and molecules of fatty acids. The main component is a disproportionated rosin or rosin dimer obtained by a reaction that generates dehydroabietic acid having a stable aromatic ring and hydrogenated dihydroabietic acid by being dehydrogenated by the transfer of hydrogen between them. Polymerized rosin and rosin esters obtained by esterifying these rosins and modified rosins with glycerin, pentaerythritol and the like. The resin (f) includes various types including modified products, and rosin esters are particularly preferable.

In the present invention, the terpene resin (g) 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 (h) 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 and a phenol-modified xylene resin (novolak, resol), and particularly preferably a phenol-modified xylene resin (novolak).

The amount of addition of at least one resin selected from the resin groups (a) to (h) is 3 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. If less than 3 parts by weight, the loss factor does not improve much,
If it is added in excess of 200 parts by weight, workability may be extremely reduced.

The polyvinyl chloride resin composition according to the present invention contains an inorganic filler, such as calcium carbonate and talc, which is usually added to the polyvinyl chloride resin to such an extent that its performance is not extremely reduced, and antimony trioxide. Flame retardants such as zinc and borate, and flake fillers often used as vibration energy absorbing materials such as mica and graphite can be added as necessary.

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.

[0040]

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

Example 1 An ethylene-vinyl chloride copolymer (Rulon E-2800, Toso-Tokyo Co., Ltd.) obtained by suspension polymerization in a Banbury mixer having an internal volume of 1700 cc and a casing temperature of 150 ° C.
100 parts by weight, 4 parts of barium stearate, 2 parts of zinc stearate as a stabilizer, Nissan Ferro-Organic Chemical Co., Ltd. product name BP-331 as an amine supplement
1.5 parts were charged and stirred at a constant rotation speed. Separately from this, 80 parts by weight of polymer polyol (Kuraray Co., Ltd., trade name: Kurapol P2010, number average molecular weight: 2000) 80 parts by weight and DMCHP (dimethylcyclohexyl phthalate) "Osaka Organic Chemical Co., Ltd." (stock)
100 parts by weight and petroleum resin (trade name PETCOL LX
40 parts by weight of Tosoh Corporation and 20 parts by weight of TXP (trixylenyl phosphate, manufactured by Daihachi Chemical Co., Ltd.) were mixed and mixed with a trimer of hexamethylene diisocyanate (trade name, manufactured by Nippon Polyurethane Co., Ltd.). Coronate EH) 1
3.4 parts by weight (NCO / OH ratio = 1) and 0.0078 parts of dibutyltin dilaurate as a catalyst were charged, mixed for 1 minute, and then poured from the Banbury mixer inlet. The reaction and mixing time was 15 minutes.

After completion of the reaction, the obtained composite was rolled into a sheet by a roll forming machine, and the thickness was set to 12.70 ± 0.13 mm for JIS K6301 compression set.
Press molded. In addition, a sheet having a thickness of 0.5 mm was separately press-molded as a sample for measuring dynamic viscoelasticity.

Example 2 Coumarone resin (Nippon Steel Coumaron T-105, manufactured by Nippon Steel Chemical Co., Ltd.) was used in place of the petroleum resin used in Example 1.
The desired composition was obtained by exactly the same operation except that 0 parts by weight was used.

Example 3 In place of the petroleum resin used in Example 1, a ketone resin (Ketone Resin K-90, manufactured by Arakawa Chemical Industry Co., Ltd.) 40
The desired composition was obtained by exactly the same operation except that parts by weight were used.

Example 4 Instead of the petroleum resin used in Example 1, a low molecular weight polystyrene (Hymer ST95, Sanyo Chemical Industries, Ltd.)
The intended composition was obtained by exactly the same operation except that 40 parts by weight of the product was used.

Examples 5 and 6 Instead of the low molecular weight polystyrene used in Example 4, 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 40 parts by weight was used.

Example 7 A maleic acid resin (traffics 4102P, Arakawa Chemical Industries, Ltd.) was used in place of the petroleum resin used in Example 1.
The intended composition was obtained by exactly the same operation except that 40 parts by weight of the product was used.

Example 8 The same procedure as in Example 1 was repeated except that 40 parts by weight of disproportionated rosin (Longis R, manufactured by Arakawa Chemical Industry Co., Ltd.) was used instead of the petroleum resin used in Example 1. I got

Example 9 Except that the petroleum resin used in Example 1 was replaced by 40 parts by weight of a hydrogenated rosin ester (ultra-light rosin ester KE-311, manufactured by Arakawa Chemical Industry Co., Ltd.) As a result, a target composition was obtained.

Example 10 The intended composition was obtained in exactly the same manner except that 40 parts by weight of rosin ester (Superester A-100, manufactured by Arakawa Chemical Industries, Ltd.) was used in place of the petroleum resin used in Example 1. I got something.

Example 11 The intended composition was obtained by the same procedure except that 40 parts by weight of rosin (Gum Rosin CG-WW, manufactured by Arakawa Chemical Industries, Ltd.) was used in place of the petroleum resin used in Example 1. Obtained.

Example 12 Terpene resin (YS resin TO-105, manufactured by Yasuhara Yushi Co., Ltd.) 40 instead of the petroleum resin used in Example 1
The desired composition was obtained by exactly the same operation except that parts by weight were used.

Example 13 The same procedure as in Example 1 was repeated except that 40 parts by weight of a phenol-modified xylene resin (Nicalol NP-100, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used instead of the petroleum resin. A composition was obtained.

Example 14 The same procedure as in Example 2 was repeated except that the amount of the cumarone resin was changed to 60 parts by weight to obtain a target composition.

Example 15 A target composition was obtained in exactly the same manner as in Example 2 except that 20 parts by weight of the low-molecular-weight polystyrene used in Example 4 was added.

Example 16 A target composition was obtained in the same manner as in Example 7 except that 20 parts by weight of the disproportionated rosin used in Example 8 was further added.

Comparative Example 1 The target product was obtained in exactly the same manner as in Example 1, except that no petroleum resin was added.

Comparative Example 2 The desired product was obtained in the same manner as in Example 1, except that the polyester polyol, hexamethylene diisocyanate trimer and the catalyst were not added. The desired composition was obtained by one operation.

The composition obtained above was evaluated by the following method. Table 1 shows the results.

(Evaluation of compression set) Measurement was performed in accordance with JIS K6301.

(Evaluation of Loss Factor (tan δ)) Using a viscoelasticity analyzer RSAII (Rheometrics Far East), which is a measuring device based on a non-resonant type forced vibration method, a temperature rising rate of 2 ° C./min. , Measurement frequency 10
The maximum value of the loss coefficient (tan δ) and the temperature region where the loss coefficient was 0.5 or more were measured in Hz.

[0062]

[Table 1]

[0063]

As is clear from the above description, the composite obtained by the present invention becomes an excellent vibration energy absorbing material having a small compression set and a high loss coefficient.

Continuation of the front page (51) Int.Cl. ⁷ identification code FI C08L 93/00 C08L 93/00 F16F 7/00 F16F 7/00 B (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 27 / 06 C08K 5/12 C08K 5/29-5/31 C08K 5/521-5/523 C08L 57/02 C08L 93/00-93/04 F16F 7/00-7/14

Claims (2)

(57) [Claims] 1. A polyvinyl chloride resin, a polymer polyol having a molecular weight of 300 or more and 10,000 or less, a compound having three or more isocyanate groups, a phthalic acid ester having the structure of the following (1), and a structure of the following (2): A polyvinyl chloride resin composition obtained by heat-melting and mixing the phosphoric acid ester and at least one resin selected from the following groups (a) to (h). Embedded image R ₁ and R ₂ each represent a monocyclic hydrocarbon. Embedded image R _{3 to} R ₅ each represent an aromatic monocyclic hydrocarbon. (A) Petroleum resin (b) Coumarone resin (c) Ketone resin (d) Low molecular weight polystyrene (e) Maleic resin (f) Rosin resin (g) Terpene resin (h) Xylene resin 2. A vibration energy absorbing material comprising the polyvinyl chloride resin composition according to claim 1.