JP3409409B2 - Wear resistant material - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wear resistant material composed of a polyvinyl chloride resin composition having both good wear characteristics and rubber elastic properties such as compression set, and liquids, powders, etc. The present invention relates to a wear-resistant material which can be used for a hose / tube for transportation, a packing for sealing, a gasket, a boot, a seat and a sole of a sports shoe.

[0002]

2. Description of the Related Art Conventionally, as a polyvinyl chloride-based thermoplastic elastomer using a blending method, a blend of a polyvinyl chloride resin and a partially crosslinked NBR (acrylonitrile-butadiene rubber) has been commercially available. However, the polyvinyl chloride-based thermoplastic elastomer blended with the partially crosslinked NBR is effective for modifying rubber elastic properties such as compression set, but on the other hand, material strength characteristics represented by tensile strength, tensile breaking elongation, etc. For properties regarding
Since the partially crosslinked NBR in the blend acts as a structural defect, it tends to be deteriorated with the addition amount of the partially crosslinked NBR, and the compression set and the material strength property are generally incompatible. Moreover, the polyvinyl chloride-based thermoplastic elastomer generally has poor wear resistance, and the fact is that it is not improved even if the partially crosslinked NBR is added. Therefore, a polyvinyl chloride-based thermoplastic elastomer having both good rubber elasticity and excellent wear properties is desired.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a wear resistant material having both good wear resistance properties and rubber elastic properties such as compression set.

[0004]

SUMMARY OF THE INVENTION The present inventors have completed the present invention as a result of earnestly studying an abrasion resistant material made of a polyvinyl chloride resin composition in view of the above-mentioned situation. That is, in the present invention, with respect to 100 parts by weight of the polyvinyl chloride resin (1), the tensile elastic modulus in linear viscoelasticity measurement is 7 × 10 in the range of 20 ° C. to 70 ° C.
20 parts by weight or more and 180 parts by weight or more of the crosslinkable polyurethane (2) having ⁶ dyne / cm ² or more and 8 × 10 ⁷ dyne / cm ² or less
Less than 20 parts by weight and more than 20 parts by weight of plasticizer (3) 180
A resin composition comprising a resin composition (A) (hereinafter, appropriately referred to as component A) containing less than parts by weight and a resin composition (B) (hereinafter, appropriately referred to as component B) containing a non-crosslinking thermoplastic polyurethane. Then, the mixing ratio of the component A and the component B is 95/5 to 5/95 by weight, and in the component A, a sea-island type phase separation structure is observed by a transmission electron microscope observation,
In addition, the size of the separation structure is 0.01 micron or more and 500
It is an abrasion resistant material composed of a polyvinyl chloride resin composition having a size of not more than micron. Hereinafter, the present invention will be described in detail.

The polyvinyl chloride resin (1) used in the present invention is a vinyl chloride homopolymer resin, a chlorinated vinyl chloride resin, or a monomer which can be copolymerized with a vinyl chloride monomer and a vinyl chloride monomer. Vinyl chloride copolymer resin (for example, vinyl acetate-vinyl chloride copolymer, ethylene-vinyl chloride copolymer, etc.) obtained by random copolymerization or block copolymerization of one or more of the above monomers, and the above resins Examples of the resin include a resin obtained by grafting a functional group such as a hydroxyl group on the resin, a resin obtained by reacting the functional group with a reactive compound and graft-bonding the resin, and the resin can be used alone or as a mixture of two or more kinds.

The degree of polymerization of the polyvinyl chloride resin (1) is not particularly limited, but 400 or more and 800 or more from the viewpoint of molding processability.
It is 0 or less, more preferably 500 or more and 5000 or less, and further preferably 800 or more and 4000 or less. A blend of a polyvinyl chloride resin having a polymerization degree in the above range and a polyvinyl chloride resin having an arbitrary molecular weight can also be used.

Crosslinkable polyurethane used in the present invention (2)
Has a tensile modulus of 20 to 70 in linear viscoelasticity measurement.
7 × 10 ⁶ dyne / cm ² or more in the range of ℃ 8 × 1
0 ⁷ dyne / cm ² or less, more preferably 1 × 10 ⁷ dyne / cm ² or more and 7 × 10 ⁷ dyne / c
m ² or less is used, and the compression set of the material of the present invention is improved by using such a crosslinkable polyurethane (2). Further, polyurethane (2) used for further improving the compression set characteristics of the material of the present invention
The compression set alone is preferably 40 or less, and more preferably 35 or less. The compression set referred to here is JI.
It is a value measured according to the method for measuring compression set described in SK6301, the measurement temperature is 70 ° C., and the time for giving strain is 22 hours. Further, it is effective to use a polyurethane having a network structure as the crosslinkable polyurethane (2) from the viewpoint of improving the compression set of the material of the present invention. Polyurethane having such a network structure can be defined, for example, as having a tetrahydrofuran (THF) dissolved content of 10% or less. Such cross-linkable polyurethane can be obtained, for example, by reacting a polymer polyol with a compound having three or more isocyanate groups, or by reacting a high molecular weight linear compound having an isocyanate group at the polymer end with a compound having three or more hydroxyl groups. However, it is desirable to obtain according to the method from the viewpoint of cost performance.

Further, in order to improve the compression set of the material of the present invention, the ratio of the compression elastic modulus of the polyvinyl chloride resin to the compression elastic modulus of the crosslinkable polyurethane used at 70 ° C. is set to 0.4 or more and 1.8 or less. It is desirable to do.

The polymer polyol as a raw material of the crosslinkable polyurethane (2) for exhibiting compression set and wear characteristics has two or more hydroxyl groups, and is a polyester polyol, a polyether polyol, a polycarbonate polyol or a vinyl type. Examples thereof include polyols, diene-based polyols, castor oil-based polyols, silicone polyols, polyolefin-based polyols and copolymers thereof. Among these polyols, it is particularly preferable to use polyester polymer polyols, polyether polyols, and polycarbonate polyols that have good compatibility with vinyl chloride resins, in order to exhibit compression set and wear resistance of the obtained material. The molecular weight of these polymer polyols is 300 or more and 10,000 or less, particularly 50.
Those of 0 or more and 5000 or less are preferably used.

It is also possible to control the isocyanate index (the number of isocyanate groups / the number of hydroxyl groups = NCO / OH) of the crosslinkable polyurethane (2). The isocyanate index is preferably 0.6 or more and 1.2 or less. Isocyanate index is 0.
If it is less than 6, sufficient abrasion properties and compression set may not be obtained, or the molded product may feel when molded, while if it exceeds 1.2, the material may be colored such as yellowing. .

The ratio of the polyvinyl chloride resin (1) to the crosslinkable polyurethane (2) in the component A used in the present invention is not particularly limited, but in order to improve the compression set characteristics of the obtained material, the ratio of Vinyl chloride resin (1) 100
The crosslinkable polyurethane (2) must be contained in an amount of 20 parts by weight or more, preferably 30 parts by weight or more, and more preferably 45 parts by weight or more, based on parts by weight. From the viewpoint of cost performance, the addition amount of the crosslinkable polyurethane (2) is 1 with respect to 100 parts by weight of the polyvinyl chloride resin (1).
It is less than 80 parts by weight, more preferably less than 150 parts by weight, still more preferably less than 120 parts by weight.

The present invention is a wear-resistant material comprising a resin composition containing component A containing polyvinyl chloride resin (1) and component B containing thermoplastic polyurethane. Is 95/5 to 5/95 by weight,
It is preferably 90/10 to 40/60, more preferably 80/20 to 50/50. 95% of ingredient A
If it exceeds, the effect of improving the wear resistance of the obtained material is not remarkable, while if the proportion of the component B exceeds 95%, it is effective in improving the wear resistance, but the compression set is significantly impaired.

The plasticizer (3) used in the present invention is not particularly limited, and examples thereof include di-n-butyl phthalate, di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, Phthalic acid plasticizers such as diisodecyl phthalate, diisooctyl phthalate, octyldecyl phthalate, butylbenzyl phthalate, di-2-ethylhexyl isophthalate, di-2-ethylhexyl adipate (DOA), di-n-adipate Decyl, diisodecyl adipate, dibutyl sebacate, di-sebacate
Aliphatic ester plasticizers such as 2-ethylhexyl, trioctyl trimellitate, pyromellitic acid plasticizers such as tridecyl trimellitate, tributyl phosphate, tri-2-ethylhexyl phosphate, 2-ethylhexyl diphenyl phosphate, phosphorus Phosphate ester-based plasticizers such as acid tricresyl, epoxy-based plasticizers such as epoxy-based soybean oil, polyester-based polymer plasticizers, and the like can be used, and one or more of these can be used. Among these plasticizers, a plasticizer having a good compatibility with the polyvinyl chloride resin is preferably used.

In the present invention, the amount of the plasticizer (3) used is 20 parts by weight or more and less than 180 parts by weight, more preferably 30 parts by weight, per 100 parts by weight of the polyvinyl chloride resin (1).
The amount is not less than 150 parts by weight and more preferably not less than 40 parts by weight and less than 120 parts by weight. When the amount used is less than 20 parts by weight, the material of the present invention may lack flexibility, while when it is 180 parts by weight or more, bleeding may occur although the flexibility is excellent.

Component B used in the present invention is a resin composition containing a non-crosslinking thermoplastic polyurethane. The reason why the material of the present invention exhibits wear resistance is that the component B is selectively compatibilized in the sea phase (matrix phase) mainly composed of the polyvinyl chloride resin (1) and the plasticizer (3). It is considered that this is due to the fact that

Examples of the component B include thermoplastic polyurethane simple substance having good compatibility with polyvinyl chloride, resin composition of thermoplastic polyurethane having good compatibility with polyvinyl chloride and polyvinyl chloride resin, polyvinyl chloride resin with polyurethane. A resin composition containing a block-copolymerized or graft-copolymerized copolymer is used. The resin composition used as the component B is preferably one in which a sea-island type phase separation structure is not observed by observation with a transmission electron microscope or the like. As the resin composition that can be used as the component B, urethane / vinyl chloride graft copolymer (Dominus manufactured by Tosoh Corporation), thermoplastic polyurethane (Miractran manufactured by Nippon Miractolane Co., Ltd.) and the like are currently commercially available. The compatibility of the polyvinyl chloride resin and the thermoplastic polyurethane referred to here is determined by a spectroscopic method (peak shift amount in infrared absorption (IR) measurement), a scattering method (small angle X-ray scattering, correlation in light scattering measurement). (Length and concentration fluctuations), differential scanning calorimetry (glass transition temperature or melting point shift and unity) and dynamic viscoelasticity (loss tangent peak narrowness and unity) .

The resistance material of the present invention is a polyester elastomer (for example, Hytrel manufactured by DuPont Co., Ltd., Toyobo Co., Ltd.) to the extent that the compatibility with the polyvinyl chloride resin is not impaired in order to impart further abrasion resistance. ), Which is commercially available under the trade name of Perprene, etc.) or chloroprene rubber, etc. may be added. Also, to reduce frictional resistance, ultra high molecular weight high density polyethylene (UHMW
HDPE), a fluororesin such as tetrafluoroethylene (PTFE), polyacetal, solid wax, molybdenum disulfide and the like can also be added to the material of the present invention.
Furthermore, calcium carbonate that is usually added to polyvinyl chloride resin to the extent that the performance of other materials is not significantly reduced,
Inorganic filler typified by talc, flame retardant typified by antimony trioxide and zinc borate, partially crosslinked polyvinyl chloride, partially crosslinked acrylonitrile-butadiene rubber (NB
A modifier such as R) and a processing aid typified by an acrylic resin can be added to the material of the present invention as required. Further, hydrolysis-resistant inhibitors represented by carbodiimide, which are usually added to polyurethane, chlorine-based, nitrogen-based,
It is also possible to add a mildew proofing agent represented by a silver-zeolite system, a UV stabilizer and the like, if necessary.

Further, the abrasion resistant material of the present invention can be blended with another resin to improve the abrasion resistance of the other resin. In this case, a compatibilizing agent of the material of the present invention and another resin can be used together as the third component.

The method for obtaining the component A in the method for producing the material of the present invention is not particularly limited, and any method can be adopted. Specifically, the following method is exemplified. A method in which polyurethane (2) is finely crushed by freeze pulverization or the like, and then blended with polyvinyl chloride resin (1).
In this case, the device used for blending is optional and rolls, Banbury mixers, extruders and the like can be mentioned. A method in which a polyvinyl chloride resin (1), a polyol and an isocyanate compound are added to a solvent such as tetrahydrofuran (THF) to cause a urethane reaction in the solvent, and then the solvent is evaporated. A method of obtaining a composite material by heating and melting a polyvinyl chloride resin (1), a plasticizer (3), a polymer polyol, and an isocyanate compound under shearing force. Of these, the use of the above method is particularly preferable for the material of the present invention because the strength represented by tensile strength is improved.

Further, the component A used in the present invention is a sea-island type phase-separated structure when observed with a transmission electron microscope (TEM) after dyeing with a staining agent such as osmumic acid, and The size of the polyurethane dispersed phase, which is the part of (1), must be 0.01 micron or more and 500 micron or less. When the size of the dispersed phase exceeds this range, the formability of the material of the present invention is significantly deteriorated. When improving moldability, the size of the dispersed phase is preferably 0.03 micron or more and 400 micron or less, more preferably 0.05 micron or more and 300 micron or less.

The wear resistant material of the present invention can be obtained by appropriately mixing and kneading the above-mentioned components A and B.

The material of the present invention can be molded by a molding method such as extrusion molding, injection molding, calender molding, blow molding or press molding which can be used for ordinary thermoplastic resins. The molded product thus obtained becomes a material having excellent wear characteristics and compression set, and is used for transportation of fuel oil and lubricating oil such as hoses and tubes, packing for sealing, gaskets, boots, seats, and shoes for sports shoes. Can be used for the bottom etc.

[0023]

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

Example 1 Polyester polymer polyol obtained by condensation polymerization of 1,4 butanediol and adipic acid (Nipporan 4010, manufactured by Nippon Polyurethane Co., Ltd., number average molecular weight 2)
000) 77.92 parts by weight and an isocyanurate modified product of hexamethylene diisocyanate (trifunctional isocyanate compound) (manufactured by Nippon Polyurethane Co., Ltd., trade name Coronate HX) 15.48 parts by weight (NCO / OH ratio = 1 ．
02) and further 100 ppm of DBTDL (dibutyltin dilaurate) as a catalyst were mixed and left in an oven at 120 ° C. for 2 hours to prepare a crosslinkable polyurethane (2). And from this sample, thickness 0.5mm, width 5
mm, and a 25 mm long strip-shaped test piece was cut out and used as a sample for dynamic viscoelasticity measurement. Also, apart from this,
The obtained crosslinkable polyurethane (2) was finely crushed by freeze pulverization and used as a raw material of the material of the present invention.

93.4 parts by weight of the crosslinkable polyurethane (2) fine powder obtained above, polyvinyl chloride resin (1) (manufactured by Tosoh Corp., ethylene-vinyl chloride copolymer, Luron E-2800, Average degree of polymerization: 2750)
100 parts by weight, 2 parts by weight of barium stearate as a stabilizer, 1 part by weight of zinc stearate, amine scavenger (Nissan Ferro Organic Chemical Co., Ltd., trade name BP-331) 1.5
15 parts by weight of plasticizer (3) DOP (di-2-ethylhexyl phthalate) 100 parts by weight using an 8-inch roll.
Component A was obtained by kneading at 0 ° C. for 5 minutes. Subsequently, as component B, a urethane / vinyl chloride graft copolymer (Tosoh Corporation)
Manufactured by Dominus 550F), and the ratio of the component A and the component B is 90/10 by weight and the same roll is used for 150
The material of the present invention was obtained by kneading at 5 ° C. for 5 minutes. This was molded into each test molded body and evaluated. The results are shown in Table 1.

Example 2 A material was obtained and evaluated in the same manner as in Example 1 except that the weight ratio of the components A and B was 70/30. The results are shown in Table 1.

Example 3 A material was obtained and evaluated in the same manner as in Example 1 except that a commercially available thermoplastic polyurethane (Miractran E580 manufactured by Nippon Miractolan Co., Ltd.) was used as the component B. The results are shown in Table 1.

Example 4 A material was obtained and evaluated in the same manner as in Example 3 except that the weight ratio of the components A and B was 70/30. The results are shown in Table 1.

Example 5 As the crosslinkable polyurethane (2), the diol component was 1,
6 hexadiol, the acid component is a mixture of adipic acid and phthalic acid, and the polyester-based polymer polyol obtained by condensation polymerization of both components (Adeka New Ace F1212-29, manufactured by Asahi Denka Co., Ltd., number) Average molecular weight = 1
500) 80 parts by weight and isocyanurate modified product of hexamethylene diisocyanate (trifunctional isocyanate compound) (Nippon Polyurethane Co., Ltd., trade name Coronate HX) 15.3 parts by weight (NCO / OH ratio = 0.85) Material was obtained and evaluated in the same manner as in Example 1 except that the material manufactured by (4) was used. The results are shown in Table 1.

Example 6 A material was obtained and evaluated in the same manner as in Example 5 except that the weight ratio of the components A and B was 70/30. The results are shown in Table 1.

Comparative Example 1 Only the component A used in Example 1 was molded into each test molded article and evaluated. The results are shown in Table 1.

Comparative Example 2 Only the component A used in Example 5 was molded into each test molded body and evaluated. The results are shown in Table 1.

Comparative Example 3 Ethylene-vinyl chloride copolymer (Leuron E-280
0, manufactured by Tosoh Corporation, 100 parts by weight, partially crosslinked NBR
(NPC-38 manufactured by Japan Synthetic Rubber Co., Ltd., acrylonitrile content = 40%) 93.4 parts by weight, 100 parts by weight of DOP were roll-kneaded at 150 ° C. for 10 minutes, and the resin composition obtained was molded into a molded body for each test. evaluated. The results are shown in Table 1.

Comparative Example 4 A resin composition obtained in Comparative Example 3 and a urethane / vinyl chloride graft copolymer (Dominus 550F, manufactured by Tosoh Corporation) were used at a weight ratio of 90/10 by using an 8-inch roll.
A resin composition was obtained by kneading at 50 ° C. for 5 minutes, and the resin composition was molded into a test molded body and evaluated. The results are shown in Table 1.

Comparative Example 5 The resin composition obtained in Comparative Example 3 and a urethane / vinyl chloride graft copolymer (Dominus 550F manufactured by Tosoh Corporation) were used at a weight ratio of 70/30 using an 8-inch roll.
A resin composition was obtained by kneading at 50 ° C. for 5 minutes, and the resin composition was molded into a test molded body and evaluated. The results are shown in Table 1.

The obtained molded body was evaluated by the following method.

(Evaluation of Wear Resistance) In accordance with JIS K6301, wear wheel H-22 was evaluated by weight loss (mg) after 1000 rotations.

(Evaluation of compression set) JIS K6301
(70 ° C, 22 hours).

(Confirmation of phase structure) The sample was exposed to the vapor of osmumic acid, stained, and finished into a 0.1 micron ultrathin section in an atmosphere of -100 ° C with an ultramicrotome. Next, use an electron microscope (J, manufactured by JEOL Ltd.)
EOL JEM-2000FX) and accelerating voltage 20
It was observed at 0 kV. By this observation, the component of polyurethane dyed with osmumic acid was 0.1 micron (μ
It was confirmed that the dispersed phase had a size of m) to 100 microns (μm).

(Measurement of Dynamic Viscoelasticity) Using a viscoelasticity measuring and measuring apparatus (RSA II manufactured by Rheometrics Far East Co., Ltd.) which is a measuring apparatus based on the non-resonant type forced vibration method, a measuring frequency is 10 Hz, and a measuring mode is tensile. , By 2
The tensile storage elastic modulus (E ′) at 3 ° C. was measured.

[0041]

[Table 1]

[0042]

As described above, the material of the present invention is a wear resistant polyvinyl chloride type thermoplastic elastomer material having both good wear resistance and compression set.

Continuation of front page (56) Reference JP-A-7-2007096 (JP, A) JP-A-7-173386 (JP, A) JP-A-7-173357 (JP, A) JP-A-7-166016 (JP , A) JP 7-166015 (JP, A) JP 7-157618 (JP, A) JP 7-41626 (JP, A) JP 6-87999 (JP, A) JP 4-164913 (JP, A) JP-A-4-164912 (JP, A) JP-A-4-149225 (JP, A) JP-A-4-149224 (JP, A) JP-A-3-294326 (JP, A) A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 75/04-75/12 C08K 5/00-5/12 C08L 27/00-27/08

Claims (2)

(57) [Claims] 1. A cross-linkable polyurethane (2) according to item 1 above 20 parts by weight and less than 180 parts by weight and a plasticizer (3) 20 parts by weight with respect to 100 parts by weight of a polyvinyl chloride resin (1). Resin composition (A) containing at least 180 parts by weight
And a resin composition (B) containing a non-crosslinkable thermoplastic polyurethane, wherein the resin composition (A) and the resin composition (B) are mixed in a weight ratio of 95.
/ 5 to 5/95, and a sea-island type phase-separated structure is observed in the resin composition (A) by a transmission electron microscope.
In addition, the size of the separation structure is 0.01 micron or more and 500
An abrasion resistant material comprising a polyvinyl chloride resin composition having a size of not more than micron. (Title 1) Tensile elastic modulus in linear viscoelasticity measurement is 20 ° C.
To 70 ° C., a crosslinkable polyurethane having a density of 7 × 10 ⁶ dyne / cm ² or more and 8 × 10 ⁷ dyne / cm ² or less. 2. A thermoplastic polyurethane-containing resin composition (B) comprises a polyvinyl chloride resin-polyurethane block-copolymerized or graft-copolymerized copolymer or a composition of a polyvinyl chloride resin and polyurethane. The wear resistant material according to claim 1, which is a resin composition.