JPH05247302A - Polyvinyl chloride resin composition - Google Patents

Abstract

(57) [Summary] [Constitution] Polyvinyl chloride resin, molecular weight of 300 or more 1
Polymer polyols of 0000 or less, compounds having 3 or more isocyanate groups, phthalates having the structure of (1) below, phosphates having the structure of (2) below, and groups of (a) to (h) below. A polyvinyl chloride resin composition obtained by heating and melting and mixing at least one resin selected from the above, and a vibration energy absorbing material comprising the composition. [Chemical 1] R ₁ and R ₂ each represent a monocyclic hydrocarbon. [Chemical 2] R _{3 to} R ₅ each represent an aromatic monocyclic hydrocarbon. (A) Petroleum resin (b) Coumaron resin (c) Ketone resin (d) Low molecular weight polystyrene (e) Maleic acid resin (f) Rosin resin (g) Terpene resin (h) Xylene resin [Effect] Compression set Excellent in vibration energy absorption performance.

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 which is excellent in compression set and vibration energy absorption.

[0002]

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

The primary evaluation of these vibration energy-absorbing materials is the storage elastic modulus (E ') and loss coefficient (tan δ = loss elastic modulus (E ") / determined by viscoelasticity measurement of the material.
Storage modulus (E ')). For designing as a vibration energy-absorbing material, the larger the loss factor is, and the storage elastic modulus has an optimum value depending on the form used.

These two factors are usually highly temperature dependent. That is, the storage elastic modulus gradually decreases as the temperature rises, and usually sharply decreases from the temperature range exceeding the glass transition point. Further, the loss coefficient shows the highest value in the temperature range exceeding the glass transition point, but generally tends to decrease in the temperature range before and after that.

Therefore, the standard conventionally required for such a vibration energy absorbing material has been to have a high loss coefficient in the 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 in a considerable range by adding an inorganic or metallic filler, a softening agent, or rubber. .. Therefore, butyl rubber, polynorbornene, special urethane elastomer, etc. have maximum loss factors of tan δ = 1.4, 2.
It shows an excellent value of 81.3. However, these materials were difficult to process and form, and their use range was limited.

Further, polyvinyl chloride resin has a long history as one of the five major general-purpose resins, and most molding processing methods have been established as well as economical efficiency. In addition, it has advantages such as being an amorphous resin and being easily compounded with an inorganic / metal filler or a softening agent.

However, the glass transition temperature of vinyl chloride resin is about 80 ° C., and this alone cannot be used because it is outside the practical use temperature range (−30 to 70 ° C.) of the vibration energy absorbing material. A plasticizer is used to lower 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 is lowered but the maximum loss coefficient is also lowered. The vibration energy absorption performance becomes poor. As a result of our recent studies, it has been found that the addition of a very limited number of plasticizers represented by dicyclohexyl phthalate to vinyl chloride resin increases the peak value of the loss coefficient, but its temperature dependence is large and the loss coefficient is large. Was about 30 ° C. for maintaining a value of 0.5 or more.

Further, since the vibration energy absorbing material is often used as a foot of a relatively heavy precision equipment, the vibration energy absorbing material is deformed after a long time and the initial shape is not maintained and the performance is deteriorated. There was a drawback that it could not be exhibited.

Therefore, there is a demand for a vibration energy absorbing material having a low load-bearing deformation property, that is, a low compression set.

[0011]

DISCLOSURE OF THE INVENTION The present invention makes use of the characteristics of polyvinyl chloride resin while maintaining a high loss coefficient or maintaining a relatively high loss coefficient in a wide temperature range, and further, vibration with less compression set. It is an object to provide a polyvinyl chloride resin composition having energy absorption performance.

[0012]

SUMMARY OF THE INVENTION In view of the present situation as described above, the inventors of the present invention have made extensive 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 or more and 10000 or less, a compound having 3 or more isocyanate groups, a phthalate ester having the structure of (1) below, and a structure of (2) below. The present invention relates to a polyvinyl chloride resin composition obtained by heating and melting and mixing a phosphoric acid ester and at least one resin selected from the groups (a) to (h) below.

[0014]

[Chemical 3] R ₁ and R ₂ each represent a monocyclic hydrocarbon.

[0015]

[Chemical 4] R _{3 to} R ₅ each represent an aromatic monocyclic hydrocarbon.

(A) Petroleum resin (b) Coumaron resin (c) Ketone resin (d) Low molecular weight polystyrene (e) Maleic acid resin (f) Rosin resin (g) Terpene resin (h) Xylene resin Vibration energy absorber made of the above resin.

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

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.
It is 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 a glycol having 5 or less repeating units obtained by ring-opening polymerization of an aliphatic glycol having 2 to 10 carbon atoms and / or an epoxy group. it can.

The term "molecular weight" as used in the present invention means 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 for producing the polymer polyol is, for example, 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 can be mentioned. ..

On the other hand, examples of the compound having an epoxy group include ethylene oxide, propylene oxide, and cyclic ethers such as tetrahydrofuran (THF). Those obtained by ring-opening polymerization of these to give glycols 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 acid having 4 to 10 carbon atoms used for producing the polymer polyol include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, etc., and one of them may be used. Two or more kinds are used.

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

The compounds having three or more isocyanate groups used in the present invention include, 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,
Trimer of diisocyanate such as 4,4′-methylenebiscyclohexyl diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, lysine ester triisocyanate, 4-isocyanate methyl-1,8-octa Examples thereof 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 together.

However, the number of moles of NCO groups in the triisocyanate 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.

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

Further, 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
To C ₈ monocyclic hydrocarbon compounds. R ₁ ,
R ₂ may be the same or different, and the hydrogen on the ring may be substituted with another substituent. Specific examples thereof include dicyclohexyl phthalate (DCHP), dimethyl cyclohexyl phthalate, diphenyl phthalate, and the like.
Dicyclohexyl phthalate is preferably used.
From the viewpoint of processability and economic efficiency, the amount of addition is preferably 5 parts by weight or more and 200 parts by weight or less, and 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.

The phosphoric acid ester 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 the hydrogen on the ring may be substituted with another substituent. Specifically, tricresyl phosphate (TCP),
Examples thereof include trixylenyl phosphate (TXP), and preferably trixylenyl phosphate is used. From the viewpoint of processability and economical efficiency, the amount of addition is 5 parts by weight or more and 200 parts by weight or more per 100 parts by weight of 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-
It is obtained by polymerizing a C ₉ olefin in a mixed state. However, the addition of petroleum resin improves the maximum value of the loss coefficient, but the degree of its effect varies considerably depending on the composition and the molecular weight. That is, as a petroleum resin, C ₉
It is preferable that the indene and styrene components are contained in an amount of 50% by weight or more. Further, it is desirable that the ratio of indene and styrene is styrene occupying more than half. The number average molecular weight is preferably 500 or more and 1500 or less. If the value is out of these ranges, the value of loss factor may decrease.

The coumarone resin (b) in the present invention is a polymer composed of 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 these, and the one having a softening point of 70 to 150 ° C. is preferable.

The ketone resin (c) in the present invention is a resin obtained by condensation of ketone and formaldehyde. The ketones used here are classified into anone series (using cyclohexanone, methylcyclohexanone, etc.) and acetophenone series (using acetophenone, ethylphenylketone, etc.), but when used in the present invention, anone series is particularly preferable and softening 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 resin or α
-Methylstyrene resin. The composition and manufacturing 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, which is a kind of polyester resin and is an ester formed with a polyhydric alcohol by forming an acid-base acid adduct from rosin and maleic anhydride. Is.
Although various properties such as softening point and solubility can be obtained depending on the addition amount of maleic anhydride, the type of polyhydric alcohol, and the degree of esterification, those having a softening point of 80 to 150 ° C are preferable.

The rosin-based resin (f) used in the present invention is a gum rosin containing abietic acid as a main component, wood rosin, tall oil rosin (hereinafter referred to as rosin), hydrogenated rosin obtained by reacting rosin with hydrogen, and a molecule of fatty acid. Mainly consists of dimer of disproportionated rosin and rosin obtained by reaction of dehydroabietic acid with stable aromatic ring and hydrogenated dihydroabietic acid which are dehydrogenated by hydrogen transfer between molecules They are polymerized rosins and rosin esters obtained by esterifying these rosins and modified rosins with glycerin, pentaerythritol and the like. The resin (f) includes a wide variety including modified products, and rosin ester is particularly preferable.

The terpene resin (g) in the present invention is α
-A resin using turpentine as a raw material, which contains pinene as a main component and a cyclic terpene such as β-pinene, camphene, and dipentene. This is classified into α-pinene type, β-pinene type, and terpene phenol obtained by cationically polymerizing α-pinene and phenol, depending on the composition, but α-pinene type or terpene phenol is particularly preferable.

The xylene resin (h) in the present invention is m-
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 (novolac or resole), and a phenol-modified xylene resin (novolac) is particularly preferable.

The amount of at least one resin selected from the resin groups (a) to (h) is 3 parts by weight or more and 200 parts by weight or less, and more preferably 10 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin. It is preferably not less than 100 parts by weight and not more than 100 parts by weight. If it is less than 3 parts by weight, the loss factor does not improve so much,
If it is added in an amount of more than 200 parts by weight, workability may be extremely reduced.

The polyvinyl chloride resin composition according to the present invention contains antimony trioxide, an inorganic filler typified by calcium carbonate, talc, etc., which is usually added to polyvinyl chloride resins to the extent that the performance thereof is not extremely deteriorated. A flame retardant typified by zinc borate, a flaky filler often used as a vibration energy absorbing material typified by mica and graphite, and the like can be added as necessary.

Vibration energy obtained by the present invention
Absorbing materials are used for supporting members of equipment such as precision electronic equipment and precision measuring equipment whose accuracy is affected by vibration, fixing members such as packing and gaskets, laminated members such as audio equipment and chassis. it can. In addition, it is used to suppress vibration by directly attaching it to areas with severe vibration such as automobiles and industrial equipment, and to prevent the propagation of vibration from the floor by using it on the legs of precision equipment. It can also be used in combination with other materials such as wood and inorganic materials including metal materials such as aluminum plates.

[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 (Luron E-2800, Tosoh Corporation) 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, Stabilate 4 parts barium stearate, zinc stearate 2 parts, amine scavenger Nissan Ferro Organic Chemical Co., Ltd. trade name BP-331,
1.5 parts was charged and stirred at a constant rotation speed. Separately from this, 80 parts by weight of a polymer polyol (Kuraray Co., Ltd., trade name: CLAPOL P2010, number average molecular weight 2000) preliminarily kept at 70 ° C. and DMCHP (dimethylcyclohexyl phthalate) “Osaka Organic Chemistry” (stock)
100 parts by weight and petroleum resin (trade name Petcole LX
40 parts by weight of Tosoh Co., Ltd. and 20 parts by weight of TXP (trixylenyl phosphate, manufactured by Daihachi Chemical Co., Ltd.) were mixed, and 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 a Banbury mixer charging port. The reaction and mixing time was 15 minutes.

After the completion of the reaction, the obtained composite was put into a sheet by a roll forming machine, and then the thickness was adjusted to 12.70 ± 0.13 mm for JISK6301 compression set.
Press molded. In addition, a 0.5 mm-thick sheet was separately press-molded as a sample for measuring dynamic viscoelasticity.

Example 2 Instead of the petroleum resin used in Example 1, coumarone resin (Nippon Steel Coumaron T-105, manufactured by Nippon Steel Chemical Co., Ltd.) 4
The target composition was obtained by exactly the same operation except that 0 part by weight was used.

Example 3 Instead of the petroleum resin used in Example 1, a ketone resin (ketone resin K-90, manufactured by Arakawa Chemical Industry Co., Ltd.) 40 was used.
The target composition was obtained by the same procedure except that the parts by weight were used.

Example 4 Instead of the petroleum resin used in Example 1, low molecular weight polystyrene (Haimer ST95, Sanyo Kasei Co., Ltd.)
The target 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 (Himmer ST
120, Hymer SB150, manufactured by Sanyo Kasei Co., Ltd.
The target composition was obtained by the completely same operation except that 40 parts by weight was used.

Example 7 Instead of the petroleum resin used in Example 1, a maleic acid resin (Traffus 4102P, Arakawa Chemical Industry Co., Ltd.) was used.
The target composition was obtained by exactly the same operation except that 40 parts by weight of the product) was used.

Example 8 The composition of interest was obtained by the same procedure except that 40 parts by weight of disproportionated rosin (Longis R, manufactured by Arakawa Chemical Industry Co., Ltd.) was used in place of the petroleum resin used in Example 1. Got

Example 9 Exactly the same operation except that 40 parts by weight of hydrogenated rosin ester (ultra-light rosin ester KE-311, manufactured by Arakawa Chemical Industry Co., Ltd.) was used in place of the petroleum resin used in Example 1. The desired composition was obtained.

Example 10 The target composition was obtained by the same procedure except that 40 parts by weight of rosin ester (Super Ester A-100, manufactured by Arakawa Chemical Industry Co., Ltd.) was used in place of the petroleum resin used in Example 1. I got a thing.

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

Example 12 Instead of the petroleum resin used in Example 1, a terpene resin (YS resin TO-105, manufactured by Yasuhara Yushi Co., Ltd.) 40
The target composition was obtained by the same procedure except that the 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., Inc.) was used instead of the petroleum resin used in Example 1. A composition was obtained.

Example 14 A target composition was obtained by the same procedure as in Example 2 except that 60 parts by weight of coumarone resin was used.

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

Example 16 The object composition was obtained by the same procedure 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 desired product was obtained by the same procedure as in Example 1 except that the petroleum resin was not added.

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

The composition obtained above was evaluated by the following methods. The results are shown in Table 1.

(Evaluation of compression set) The compression set was measured according to JIS K6301.

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

[0062]

[Table 1]

[0063]

As is clear from the above description, the composite obtained according to the present invention is an excellent vibration energy absorber having a small compression set and a high loss coefficient.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI technical display location C08L 57/02 LMJ 7167-4J 93/00 LSK 7415-4J F16F 7/00 B 9240-3J

Claims (2)

[Claims] 1. A polyvinyl chloride resin, a polymer polyol having a molecular weight of 300 or more and 10000 or less, a compound having 3 or more isocyanate groups, a phthalate ester having a structure of (1) below, and a structure of (2) below. A polyvinyl chloride resin composition obtained by heating, melting and mixing the phosphoric acid ester and at least one resin selected from the groups (a) to (h) below. [Chemical 1] R ₁ and R ₂ each represent a monocyclic hydrocarbon. [Chemical 2] R _{3 to} R ₅ each represent an aromatic monocyclic hydrocarbon. (A) Petroleum resin (b) Coumaron resin (c) Ketone resin (d) Low molecular weight polystyrene (e) Maleic acid 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.