JP3379140B2 - 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 polyurethane and polychloride.
Composite resin composition comprising vinylVibration absorbing material consisting of
About. [0002] 2. Description of the Related Art Conventionally, load-bearing variation of a polyvinyl chloride resin has been improved.
As a method for improving the formability, that is, the compression set,
Nzoyl peroxide, dicumyl peroxide, t
Organic peroxides such as -butyl peroxide;
Tramethylenediamine, 1,6-hexamethylenediami
Diamine compounds such as sulfur, sulfur, tetramethylchuura
Sulfur compounds such as mudisulphide and triazinedithiol
Of vinyl chloride resin with materials, diallyl phthalate
G, components such as crosslinkable polyurethane or epoxy resin
Cross-linking method, or cross-linking salt previously cross-linked during polymerization
Crosslinking with good compatibility with vinyl chloride resin or vinyl chloride resin
Method of blending NBR with vinyl chloride resin,
Using vinyl chloride resin having such reactive groups
There is a method of forming a crosslinked body with an anate or the like. [0003] In these methods, vinyl chloride resin
When cross-linking, a composition with good compression set
It is possible to obtain, but the problem is that the melt viscosity
Significantly increases, resulting in a material having poor moldability. Other
(1) Poor thermal stability and easy to color (2) Residual crosslinking agent
(3) If the degree of cross-linking is increased,
There is a problem such as having a large amount of plasticizer to control the temperature. When a reactive plasticizer is used, the radical reaction
Since they are often reactive, the same problems as described above occur. [0005] Cross-linked vinyl chloride resin or cross-linked NBR
When blending with vinyl chloride resin, (1) vinyl chloride
Tensile strength, elongation, related to their dispersibility in resin
(2) Large amount due to hardness adjustment
(3) Moldability is poor if a large amount is added
(4) Weather resistance due to butadiene component in cross-linked NBR
And poor heat aging resistance. Further, salts having a reactive group such as a hydroxyl group
Crosslinked with diisocyanate using vinyl chloride resin
In this method, the reactivity is inferior, so that the improvement effect is small. [0007] In recent years, polyvinyl chloride resin and polyurethane
Attention has been paid to compounding, and various methods have been proposed. example
If polyurethane is dissolved in vinyl chloride monomer (VCM)
And the vinyl chloride resin and polyurethane by polymerization of VCM
Of VCM in the presence of polyol
Producing hydroxyl-containing vinyl chloride resin by polymerization
And the like by a urethanization reaction of However, the vinyl chloride obtained by these methods has
The composite of nylon and polyurethane has poor rubber elasticity.
Therefore, it is not suitable for applications requiring these characteristics. On the other hand, large injection molding, precision injection molding, etc.
Improve the required molding workability, as well as compression set and
In recent years, demand for rubber-like properties such as
Material with low compression set and excellent moldability
Fees are desired. [0010] DISCLOSURE OF THE INVENTION The present invention is intended to improve the moldability.
A thermoplastic elastomer that maintains and has excellent compression setFrom
Becomes a vibration absorbing materialThe purpose is to provide. [0011] Means for Solving the Problems The present inventors have made the above-mentioned description.
In view of the current situation, the components of polyurethane that form a crosslinked body
As a result of intensive studies, the present invention was completed.
Was. That is, the present invention relates to a polyvinyl chloride resin,
Resin composition consisting of urethane and plasticizer(However, poly
PVC resin, polyurethane, plasticizer, and stone
Oil resin, cumarone resin and / or rosin resin.
Excluding the resin composition. )And as polyurethane
Has a crosslinked structure, linear region, tensile mode
Loss tangent obtained from temperature dependence of dynamic viscoelasticity in steel
(Tanδ) is estimated from the maximum value of tanδ
Has a value of 0.3 or more at 30 ° C higher than the transition temperature
Using polyurethaneWasThermoplastic elastomer resin set
AdultA vibration absorbing material characterized by comprisingAbout.
The details of the present invention are described below. The polyvinyl chloride resin used in the present invention and
Is a vinyl chloride homopolymer resin, a chlorinated vinyl chloride resin,
Of all monomers copolymerizable with vinyl chloride monomer
Random or block copolymerization with one or more
The resulting vinyl chloride copolymer resin (for example, vinyl acetate-salt
Vinyl copolymer, ethylene-vinyl chloride copolymer
Etc.) and grafting functional groups such as hydroxyl groups to the above resins
The resulting resin and the functional group and reactive compound
Reacted and graft-bonded resin.
Alternatively, it is a mixture of two or more. The degree of polymerization of the polyvinyl chloride resin is particularly limited.
But not more than 400 and less than 8000 from the viewpoint of moldability,
More preferably 500 or more and 5000 or less, still more preferably
It is preferably 800 or more and 4000 or less. Also, the above
Any amount can be added to a polyvinyl chloride resin having a polymerization degree in the range.
May be blended with polyvinyl chloride resin
No. The polyurethane used in the present invention is a polyfunctional iso-
Crosslinked type consisting of cyanate compound and polymer polyol
Polyurethane in the linear region, tensile mode
Tangent measured from temperature dependence of dynamic viscoelasticity in steel
(Tanδ) is a gas estimated from the maximum value of tanδ.
A value of 0.3 or more at a temperature 30 ° C higher than the lath transition temperature
Must have. If the value is less than 0.3,
Dispersibility in polyvinyl chloride resin is poor and
No. This phenomenon is described below. Materials having a crosslinked structure are represented by vulcanized rubber.
Once it is crosslinked so that it can not be molded
You. However, very loosely crosslinked materials are not
Even if the size is reduced by freezing and pulverization,
Molding can be performed again by the action of long and long side chains
It becomes possible. The material obtained by molding again in this way
Consists of a crosslinked product even at temperatures above the glass transition temperature.
Entangled long long side chains, or long side chains and other
The time it takes for the entanglement with the crosslinked product of
The longest relaxation time) exists in the long-term region,
It does not impair physical properties such as comparative strength.
Material. The long side chain described here is a bullet
Of free molecular chains at one end that do not contribute to the
A substance having a molecular weight greater than the molecular weight between intermeshing points.
You. Such a phenomenon is described in Ferry, J. et al. D. Details by
(Ferry, JD "Visc"
oerastic Properties of Po
lymers "3rd Ed., John Wiley
  & Sons, Inc. (1980) p. 419),
De Gennes makes the end-chain Reptatio
It is also explained from molecular theory as n motion. (De Genenes "Scaling"
  Concepts in Polymer Phys
ics ", Cornell Univ. Press,
(1979), p. 232) Now, the existence of a long side chain having such a long-term relaxation exists.
The presence can be evaluated by measuring the relaxation time distribution. Loose
The measurement of the sum time distribution can be performed in various ways. An example
For example, dynamic relaxation represented by dynamic viscoelasticity measurement,
Electric relaxation, magnetic relaxation, etc.
The orientation of the vibrated molecular chains is measured using an optical system.
It is also possible. We describe this behavior as dynamic viscoelasticity.
It was evaluated from the temperature dispersion in the tension mode. Like this
In measurement, long-term relaxation mode appears on high temperature side
And evaluate as the magnitude of loss tangent (tan δ)
Can be. That is, the relaxation of a molecular chain having an average relaxation time
The sum is (mainly, the network components that contribute to the elasticity forming the
The glass transition temperature of the material
Can be evaluated as the maximum of tan δ
The relaxation of the side chains is due to the large tan δ above the glass transition temperature.
It is evaluated as magnitude. Here, as the value of tan δ is larger,
It can be considered that the relaxation of long side chains is strongly exhibited. ideal
Complete crosslinked product (has no long side chains that do not contribute to elasticity)
Tanδ in the temperature range above the glass transition temperature is
Usually, it is 0.1 or less. Such materials are once broken into pieces.
Once crushed, it cannot be processed again. Our inspection
According to the discussion, the dynamic viscoelasticity measurement
At a temperature 30 ° C. higher than the lath transition temperature, tan δ
If it is 0.3 or more, once the crosslinked product is crushed, it is molded again
It turned out to be possible. [0018] Such a loosely crosslinked product that can be formed and processed is
Used as a thermoplastic elastomer even when used alone
Is possible, but the strength is not sufficient.
Although the workability is possible, it is a remarkably poor material. There
So we are going to make urethane gel with such loose crosslinking
Polyvinyl chloride resin with good compatibility with urethane
To improve strength and add plasticizer
That a material with excellent moldability can be obtained
did. Also, by using such urethane gel,
Can be blended with polyvinyl chloride resin
The amount of possible urethane gel can be significantly improved,
As a result, the compression set resistance characteristic showing the properties of a crosslinked rubber is
The present inventors have found that a significantly improved composition can be obtained, and
Was completed. By the way, do not have long side chains
When the cross-linked product is polyurethane, polyurethane
Polyvinyl chloride tree which is said to be excellent in compatibility with
Even in blends with fats, large amounts of polyurethane
It becomes difficult to render. This is a polyvinyl chloride type
Entanglement of resin and polyurethane, or polyurethane
Because the entanglement of comrades is hardly formed
I have. The present inventionFor obtaining vibration absorbing materialComposition
Of Polyvinyl Chloride Resin Containing Polyurethane and Polyurethane
Is not particularly limited, but has improved compression set resistance.
In order to achieve this, 100 parts by weight of polyvinyl chloride resin
100 parts by weight or more of polyurethane, preferably 120 parts by weight.
It is desirable to use at least part by weight. In addition, cost performance
-The amount of polyurethane added from the viewpoints of performance, processability, etc.
Is preferably based on 100 parts by weight of the polyvinyl chloride resin.
Is 900 parts by weight or less, more preferably 600 parts by weight or less
It is desirable that The present inventionFor obtaining vibration absorbing materialComposition
Used as a polyurethane material constituting
-Polyol and polyvinyl chloride resin as described above
Good compatibility is desirable, and polyester
All, polycaprolactone polyol, polycarbonate
Polyol, castor oil-based polyol, saponified EVA
(Ethylene-vinyl acetate copolymer) and the like. In addition, this
The polyester polyols shown here include, for example,
As obtained from the condensation polymerization of glycol and adipic acid
Also includes ether ether type polyester polyol
And multifunctionalized with trimethylolpropane, etc.
Also included are polyester polyols. Also here for
The molecular weight of the polymer polyol used is easy to handle
Saya, 300 or more 10 for the purpose of giving long side chains effectively
000 or less, preferably 500 or more and 8000 or less
It is desirable. The tan δ constituting the composition of the present invention is
0.3% higher than the transition temperature
To obtain urethane, the isocyanate index (I
Number of cyanate groups / number of hydroxyl groups) Should be controlled.
Specifically, the average number of functional groups per molecule is 3.6.
When using socyanate compound and polymer diol as materials
If the isocyanate index is 0.3 or more and 0.8 or less
Full, preferably 0.4 or more and 0.75 or less. 0.3
If it is less than the above, it becomes difficult to exhibit rubber-like properties.
When it is 0.8 or more, tan δ is 0.3 in the measurement temperature range.
Less long side chains that do not contribute to elasticity
When blended with polyvinyl chloride resin,
May cause scattering. However, the isotype shown here
Cyanate index is the average of isocyanate compounds
Number of functional groups, and average number of functional groups in polymer polyol
The properties of the material obtained will change greatly,
Inter-entangled molecules depending on the molecular weight of the polymer polyol
Differences in the formation of long side chains with molecular weights greater than
Appropriate adjustment according to the number of functional groups and molecular weight of the material used
There is a need to continue to. The polyurethane used in the present invention is
Isocyanate compound, which is a material for obtaining, is particularly limited
Not receive. For example, 2,4- and 2,6-tolylene
Isocyanates, m- and p-phenylenediisocyanes
1-chlorophenylene-2,4-diisocyanate
G, 1,5-naphthalenediisocyanate, methylene bi
Suphenylene 4,4'-diisoanate, m- and p-
Xylene diisocyanate, hexamethylene diisocyanate
, Lysine diisocyanate, 4,4'-methylenebi
Scyclohexyl diisocyanate, isophorone diiso
Cyanate, trimethylhexamethylene diisocyanate
Trimer of diisocyanate such as 1,6,11-un
Decane triisocyanate, lysine ester triisocyanate
Anate, 4-isocyanatomethyl-1,8-octa
Triisocyanates such as methyl diisocyanate
Polyfunctional such as polyphenylmethane polyisocyanate
Isocyanates; one or two of these isocyanates;
The above is used. In addition, the above diisocyanates
It is also possible to use them together. In the present invention, a plasticizer may be added.
Is important for the purpose of improving moldability. In the present invention
As a plasticizer that can be used, for example, phthalic acid
Di-n-butyl, di-2-ethylhexyl phthalate (D
OP), di-n-octyl phthalate, diisode phthalate
Sil, diisooctyl phthalate, octyl decyl phthalate
Butyl benzyl phthalate, di-2-e-isophthalate
Phthalic acid plasticizers such as tylhexyl, and adipate di-2
-Ethylhexyl (DOA), di-n-decyl adipate
Diisodecyl adipate, dibutyl sebacate,
Aliphatic esters such as di-2-ethylhexyl basinate
Plasticizer, trioctyl trimellitate, trimellit
Pyromellitic acid plasticizers such as tridecyl acid, phosphate
Libutyl, tri-2-ethylhexyl phosphate, phosphoric acid 2
-Ethylhexyl diphenyl, tricresyl phosphate, etc.
Epo such as phosphate ester plasticizer and epoxy soybean oil
Xy plasticizer, chlorinated paraffin, polyester
Polymer plasticizers, such as polymer plasticizers, have glass transition temperatures
Lower than polyvinyl chloride resin and polyvinyl chloride resin
High molecular weight compounds having plasticizing ability for fats
One or two or more of these can be used. The above plasticizer is appropriately selected according to the purpose.
You. For example, to improve heat resistance and non-migratory properties,
It is advisable to use a
Glycol adipate or the like may be used. Also, liquidity
Adipate plasticizer,
It is preferable to add a basic ester plasticizer. The amount of the plasticizer to be added is as follows.
10 parts by weight or more and 200 parts by weight or less with respect to 00 parts by weight,
Preferably not less than 25 parts by weight and not more than 150 parts by weight
Is desirable. Less than 10 parts by weight impairs moldability.
Bleed out when the amount exceeds 200 parts by weight
May occur. The present inventionTo obtain a vibration absorbing materialPoly salt
The performance of vinyl chloride resin compositions is extremely reduced.
To the extent that carbon dioxide is normally added to polyvinyl chloride resin
Inorganic fillers such as lucium, talc, etc.
Flame retardants such as antimony and zinc borate, partially crosslinked
Polyvinyl chloride, partially crosslinked acrylonitrile-butadiene
Modifiers such as rubber (NBR), represented by acrylic resin
Processing aids, metal salts, hydrotalcite, etc.
The heat stabilizer can be added as needed. Ma
Also, add mica etc. which is often added to the vibration absorbing material.
It is also possible. In addition, this resin composition can be used for other resins.
It is also possible to blend. In this case, the third component
Use a compatibilizer between the resin composition and another resin
Is also possible. The present inventionFor obtaining vibration absorbing materialResin group
As a method for producing a product, for example, a polyurethane
After finely crushing the tongue by freezing and crushing,
Examples include methods of blending with vinyl resins and plasticizers
In this case, a roll or ba
A device such as an inventory mixer or an extruder is used.
Furthermore, the polyurethane prepared in advance is mixed with a roll kneader or the like.
After forming the sheet, polyvinyl chloride resin, plastic
The resin composition by the method of blending with the agent
Can be. The resin composition thus obtained is subjected to compression
It becomes a thermoplastic elastomer with excellent strain. Also here
By manipulating the polyurethane and plasticizer used in
It is also possible to provide a vibration absorber with little change in elastic modulus.
is there. This is from the glass transition temperature at which the elastic modulus changes significantly.
Higher tan δ at higher temperatures
You. Materials with large tan δ are given by vibration
Converts the mechanical energy into thermal energy and dissipates it
It has vibration absorption performance. In general, tan δ
Takes a large value near the glass transition temperature.
Is not suitable as a material because the elastic modulus changes drastically
However, the thermoplastic elastomer obtained here has a glass transition
Temperature range higher than the temperature (rubber-like area: little change in elastic modulus)
Region) also has a large tan δ, so that suitable vibration
It becomes an absorbent. When used as a vibration absorber,
To demonstrate performance in the temperature and frequency range of use
Select the structure of plasticizer or polymer polyol,
It is possible to adjust the transfer temperature. [0030] EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these examples. Embodiment 1 3-methyl-1,5-pentanediol and adipic acid
Polyester polyol obtained by condensation polymerization (Co., Ltd.)
Kuraray product name, Kurapol P2010, number average molecular weight
2000) 100 parts by weight as an isocyanate compound
Isocyanurate transformation of hexamethylene diisocyanate
(Polyfunctional isocyanate compound, average number of functional groups
3.6 per molecule) (manufactured by Nippon Polyurethane Co., Ltd.)
12.9 parts by weight (NCO / OH (a
Socyanate index) = 0.65)
DBTDL (dibutyltin dilaurate) as a medium 26.
Mix 7PPM and release in oven at 120 ° C for 2 hours
To make a polyurethane. Thickness from this sample
0.5mm, width 5mm, length 25mm strip type test piece
Was cut out to obtain a sample for measuring dynamic viscoelasticity. Again
Reduce the surface temperature of the polyurethane obtained separately to 50 ° C
Set the material of the composite as a sheet with the set roll kneader.
did. The thus obtained polyurethane sheet 50
0 g of ethylene-vinyl chloride with a surface temperature of 150 ° C
Copolymer (Rulon E-2800, average degree of polymerization: 2)
750, manufactured by Tosoh Corporation).
Barium arate 2g, zinc stearate 1g, amine
Nissan Ferro-Organic Chemical Co., Ltd. product name BP-
331, 1.5 g, di-2ethylhexyl phthalate
(DOP) 67 g was charged and kneaded. Kneading time is 15 minutes
And After completion of kneading, the obtained composite is roll-formed.
After slicing into a sheet, JIS K6301 compression permanent
So that the thickness is 12.70 ± 0.13 mm for strain,
Press molded. Embodiment 2 Instead of the polyester polyol used in Example 1
Having the same composition and a number average molecular weight of 500
Ester polyol (Kuraray Co., Ltd., trade name Kurapo)
100 parts by weight of isocyanate compound in 5 parts by weight.
Except for 2.0 parts by weight (NCO / OH = 0.65)
The target composition was obtained by the same operation. Embodiment 3 Instead of the polyester polyol used in Example 1
Of the same composition and a number average molecular weight of 4000
Riester polyol (Kuraray Co., Ltd., trade name Kurapo)
P4010) 100 parts by weight, isocyanate compound
To 6.6 parts by weight (NCO / OH ratio = 0.65)
Aside from this, the same composition was used to obtain the desired composition. Embodiment 4 Instead of the polyester polyol used in Example 1
For condensation polymerization of 1,4-butanediol and adipic acid
The resulting polyester polyol (Nippon Polyure
Manufactured by Tan Co., Ltd., Nipporan 4010, number average molecular weight 20
00) and 100 parts by weight of the isocyanate compound.
Same except for 6 parts by weight (NCO / OH ratio = 0.65)
The desired composition was obtained in the same manner. Embodiment 5 In Example 1, a roll forming machine with a surface temperature of 150 ° C.
200g of polyurethane to be charged, polyvinyl chloride tree
The same operation was carried out except that the fat and the plasticizer were 100 g and 100 g, respectively.
The desired composition was obtained by cropping. Embodiment 6 100% by weight of the polyester polyol in Example 3
Parts, 5.5 parts by weight of an isocyanate compound (NCO / O
The objective is the same operation except that the H ratio is 0.55).
Was obtained. Embodiment 7 100% by weight of the polyester polyol in Example 3
Parts, 7.2 parts by weight of an isocyanate compound (NCO / O
H ratio = 0.70)
Was obtained. Embodiment 8 The polyester polyol used in Example 3 was 50
Parts by weight, having the same composition, trimethylolpropane
Trifunctional polyester polyols
(Kuraray Co., Ltd., trade name Kurapole F3010, Sappei)
50 parts by weight, isocyanate compound
To 15.1 parts by weight (NCO / OH ratio = 0.5)
Aside from this, the same composition was used to obtain the desired composition. Comparative Example 1 Example 1 is the same except that no polyurethane is used.
The product was obtained by operation. Comparative Example 2 The polyester polyol used in Example 1 was 10
0 parts by weight, and 13.4 parts by weight of an isocyanate compound (N
CO / OH = 0.85) to make polyurethane,
A sample for measuring dynamic viscoelasticity was cut out. Also with this
Separately, roll the polyurethane obtained at a surface temperature of 50 ° C.
I tried to make a sheet with a molding machine, but it was impossible
Then, crush the polyurethane finely with a roll forming machine,
The material of the composite was used. The polyurethane obtained in this way
500 g, other compositions and blending amounts are the same as in Example 1.
With a roll forming machine set to a surface temperature of 150 ° C.
Tried to do. Comparative Example 3 Polyester polyol 100 used in Example 3
Parts by weight and 10 parts by weight of an isocyanate compound (NCO /
OH = 1.0) by the same method as in Comparative Example 2.
Thus, a composition was obtained. Comparative Example 4 The same as Comparative Example 1 except that the DOP was changed to 100 g.
A composition was prepared by operation. (Evaluation of compression set) According to JIS K6301
Measured accordingly. Initial strain is 25%, temperature is 70 ℃, 22:00
After a lapse of time, the strain was released and the residual strain was measured. (Measurement of Dynamic Viscoelasticity) Non-Resonant Forced Vibration Method
-Based viscoelasticity analyzer RSA
II (Rheometrics Far East)
Constant frequency 10 Hz, measurement mode: pulling, heating rate:
The temperature dependence of dynamic viscoelasticity was measured at 2 ° C./min.
The applied strain was performed in a linear region of 0.1% or less. this
Loss tangent (tan δ), storage modulus in measurement
(E ') was measured. Table 1 shows the results.
Is the maximum glass transition temperature of tan δ of polyurethane.
And tan δ at 30 ° C. higher temperature side
Also described. [0047] [Table 1] The purpose of evaluating the effect as a vibration absorber is
Then, the dynamic viscoelasticity was measured. Measurements are in Example 1 and comparison
The composition of Example 4 was prepared with a thickness of 0.5 mm, a width of 5 mm, and a length of 25 m.
m into a strip-shaped sheet for measuring dynamic viscoelasticity
And the measurement conditions were as described above. That
The results are shown in FIGS. As is clear from the measured values shown in Table 1,
The composite obtained according to the invention has excellent heat resistance and excellent compression set.
It becomes a plastic elastomer. Also, the vibration absorbing material shown in FIG.
As a result, the complex obtained in the present invention was
It is a measure of vibration absorption performance even in the temperature range exceeding the transition temperature.
Is relatively large, and the temperature dependence of the elastic modulus is
It turns out that it is excellent also as a small vibration absorbing material. [0050] As described above, the resin composition of the present invention
A thermoplastic elastomer with excellent compression set resistance
It should be a vibration-absorbing material with a small temperature change in elastic modulus.
I understand.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing the measurement results of dynamic viscoelasticity of the resin composition of the present invention produced according to Example 1. FIG. 2 is a view showing the measurement results of dynamic viscoelasticity of a resin composition produced according to Comparative Example 4.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-87999 (JP, A) JP-A-4-117455 (JP, A) JP-A-56-115342 (JP, A) JP-A-60-1985 92345 (JP, A) JP-A-51-28135 (JP, A) JP-A-52-63252 (JP, A) JP-A-2-120349 (JP, A) JP-A-4-85353 (JP, A) (58) Surveyed field (Int.Cl. ⁷ , DB name) C08L 27/06 C08L 75/04-75/16 F16F 15/02-15/08

Claims (1)

(57) [Claims] (1) A resin composition comprising a polyvinyl chloride resin, a polyurethane, and a plasticizer (however, a polyvinyl chloride resin
Fats, polyurethanes, plasticizers, petroleum resins, cumaro
A resin composition comprising a resin and / or a rosin resin.
except. ) , Wherein the polyurethane has a crosslinked structure and the loss tangent (tan δ) obtained from the temperature dependence of the dynamic viscoelasticity in the linear region and the tensile mode is t.
3 from the glass transition temperature estimated from the maximum value of anδ
Made of a thermoplastic elastomer resin composition using a polyurethane having a 0.3 or more values at 0 ℃ higher temperatures
A vibration absorbing material characterized by the above .