JP3427109B2 - Plumbing materials - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plumbing material comprising a composite resin composition containing a polyurethane, a polyvinyl chloride resin and a plasticizer, and the material is rubber. Materials, waterproof sheets, hoses, tubes,
It is a material that can be used for water supplies such as mats, malls, and automobile exteriors represented by weather strips. 2. Description of the Related Art Conventionally, as a method for improving the load resistance of polyvinyl chloride resin, ie, the compression set, benzoyl peroxide, dicumyl peroxide, t
Chloride with organic peroxides such as -butyl peroxide, diamine compounds such as 1,4-tetramethylenediamine and 1,6-hexamethylenediamine, and sulfur compounds such as sulfur, tetramethylturum disulfide and triazinedithiol. Cross-linking of vinyl resin, component cross-linking of diallyl phthalate, cross-linkable polyurethane or epoxy resin, and blending of pre-cross-linked cross-linked vinyl chloride resin or cross-linked NBR with good compatibility with vinyl chloride resin into vinyl chloride resin A known method is a method of using a vinyl chloride resin having a reactive group such as a hydroxyl group to form a crosslinked product with diisocyanate or the like. In these methods, when a vinyl chloride resin is crosslinked, a composition having good compression set can be easily obtained, but on the other hand, the melt viscosity of the obtained composition is low. It increased significantly, making injection molding impossible. In addition, (1) poor heat stability and easy coloring, (2) residual odor due to the residue of the crosslinking agent, and (3) a high degree of crosslinking has a large amount of plasticizer to achieve a predetermined hardness. , Etc. When a reactive plasticizer is used, it is often a radical reaction system, so that the same problem as described above occurs. [0005] When a crosslinked polyvinyl chloride resin or a crosslinked NBR is blended with a polyvinyl chloride resin, it is necessary to (1) relate to their dispersibility in the polyvinyl chloride resin; Remarkable decrease in physical properties,
(2) A large amount of plasticizer is required for adjusting the hardness. (3)
(4) Cross-linked NBR
There are problems such as poor weather resistance and heat aging resistance due to the butadiene component therein. Further, in the method of using a vinyl chloride resin having a reactive group such as a hydroxyl group to form a crosslinked product with diisocyanate or the like, the reactivity is poor, so that the improvement effect is small. Therefore, in recent years, a composite of a polyvinyl chloride resin and a polyurethane has attracted attention, and various methods have been proposed. For example, polyurethane is converted to a vinyl chloride monomer (VC
M) to obtain a composite of a vinyl chloride resin and a polyurethane by polymerization of VCM, a method of producing a hydroxyl group-containing vinyl chloride resin by polymerization of VCM in the presence of a polyol, and a method of obtaining these by a urethanization reaction. is there. However, the composite of the polyvinyl chloride resin and polyurethane obtained by these methods has poor rubber elasticity and is not suitable for applications requiring these properties. On the other hand, demands for rubber-like properties such as compression set have recently increased in water-stopping materials, waterproof sheets, hoses, tubes, mats, and even water-related products such as automobile exteriors such as moldings and weather strips. However, a material having a low compression set is desired. [0010] An object of the present invention is to provide a plumbing material excellent in compression set. Means for Solving the Problems The present inventors have made intensive studies in view of the above-mentioned current situation, and as a result, have completed the present invention. That is, the present invention relates to a resin composition comprising a polyvinyl chloride resin (1), a polyurethane (2) and a plasticizer (3), wherein a sea-island type phase-separated structure is observed with a transmission electron microscope. And the size of the polyurethane dispersed phase, which is the island portion of the separation structure, is 0.01 μm or more and 100 μm or less, and the polyurethane (2) is the following compound 1
One or more polymer polyols described in
Reaction with a compound having two or more isocyanate groups
And the tensile elastic modulus in the linear viscoelasticity measurement is 20 ° C.
From a plumbing materials consisting of 7 × 10 ⁶ dyne / cm ² or more 8 × 10 ⁷ dyne / cm ² or less der Ru resin composition in the range of 70 ° C.. Compound 1 (A) 1,4-butanediol, diethylene glycol, 3-methyl-1,5-pentanediol, 1,6-
Polycaprolactone obtained by ring-opening polymerization of polyester polyol (B) β-methyl-δ-valerolactone obtained by polycondensing one or more diols selected from hexanediol and neopentyl glycol with adipic acid Polyol (C) Polycarbonate Polyol The details of the present invention are described below. The polyvinyl chloride resin (1) used in the present invention is at least one of a vinyl chloride homopolymer resin, a chlorinated vinyl chloride resin, and all monomers copolymerizable with 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 with the above-mentioned monomer. Examples of the resin include a resin obtained by grafting a functional group, a resin obtained by reacting a reactive compound with the functional group and graft-bonding the resin, and may be a single resin or a mixture of two or more resins. The degree of polymerization of the polyvinyl chloride resin (1) is not particularly limited, and is from 400 to 8000, preferably from 500 to 6000, more preferably from 800 to 5,000 from the viewpoint of moldability. Further, a polyvinyl chloride resin having an arbitrary molecular weight may be blended with a polyvinyl chloride resin having a polymerization degree in the above range. The polyurethane (2) used in the present invention has a tensile modulus in the range of 20 ° C. to 70 ° C. in a linear viscoelasticity measurement of 7 × 10 ⁶ dyne / cm ² or more and 8 × 10 ⁷ d.
yne / cm ² or less, more preferably 1 × 10 ⁷ dyne
/ Cm ² or more and 7 × 10 ⁷ dyne / cm ² or less are used. By using such a polyurethane, the compression set of the present invention is improved and the moldability is also improved. In order to further improve the compression set of the material of the present invention, the compression set of the polyurethane (2) used alone is preferably 40 or less, more preferably 35 or less. The compression set referred to here is
This is a value measured according to the method of JIS K6301 compression set, the measurement temperature is 70 ° C., and the time for giving strain is 22 hours. The use of a polyurethane having a network structure as the polyurethane (2) is effective from the viewpoint of improving the compression set of the material of the present invention. That is, it is desirable to use a polyurethane (2) having a THF content of 10% or less in a good solvent such as tetrahydrofuran (THF). Such a polyurethane is obtained by reacting a polymer polyol with a compound having three or more isocyanate groups. In order to further improve the compression set of the material of the present invention, the ratio of the compressive modulus of the matrix phase to the compressive modulus of the dispersed phase at 70 ° C. is desirably 0.4 or more and 1.8 or less. . In order to improve the tensile strength of the material of the present invention, it is preferable to use a polyurethane (2) having excellent compatibility with the polyvinyl chloride resin (1) to be used. Examples of such polyurethane (2) include polyester-based polyurethane, polycaprolactone-based polyurethane, and polycarbonate-based polyurethane. However, in order to be used as a water-around material, there is a problem of hydrolyzability derived from an ester bond, so that there is a limit to what can be used as a polymer polyol which is a constituent component of the polyurethane (2). Examples of the polymer polyol having excellent hydrolysis resistance and cost performance include the compounds shown in the following compound 1, and one or more of these compounds are used. Compound 1 (A) 1,4-butanediol, diethylene glycol, 3-methyl-1,5-pentanediol, 1,6-
Polycaprolactone obtained by ring-opening polymerization of polyester polyol (B) β-methyl-δ-valerolactone obtained by polycondensing one or more diols selected from hexanediol and neopentyl glycol with adipic acid Polyol (C) Polycarbonate Polyol It is also possible to control the isocyanate index (number of isocyanate groups / number of hydroxyl groups) of polyurethane (2) in the material of the present invention. Although it is difficult to uniquely determine the optimal isocyanate index according to the number of functional groups of the compound, it is desirable that the index be 0.6 or more and 1.2 or less. Is prevented. When the polyurethane (2) to be used is obtained by urethane reaction of a polymer polyol with a compound having three or more isocyanate groups, the molecular weight of the polyol which is one of the components of the polyurethane is not particularly limited. However, a material obtained by using a polymer polyol having an average molecular weight of 300 or more and 4000 or less has excellent compression set and is preferable. The ratio of the polyvinyl chloride resin (1) to the polyurethane (2) used in the present invention is not particularly limited. However, in order to improve the compression set characteristics of the obtained material, the polyvinyl chloride resin (1) is used. The amount of the polyurethane (2) is preferably at least 20 parts by weight, preferably at least 30 parts by weight, and more preferably at least 45 parts by weight with respect to 100 parts by weight. From the viewpoint of cost performance, the amount of the polyurethane (2) is preferably 900 parts by weight or less, more preferably 300 parts by weight or less, and further preferably 150 parts by weight or less based on 100 parts by weight of the polyvinyl chloride resin (1). It is desirable to do. The plasticizer (3) used in the material of the present invention is not particularly limited, and any plasticizer that is generally used for a polyvinyl chloride resin may be used. However, polyvinyl chloride resin (1) 100
It is desirable to add the plasticizer (3) in an amount of 30 parts by weight or more and 180 parts by weight or less based on parts by weight. If the amount is less than 30 parts by weight, flexibility may be impaired. If the amount exceeds 180 parts by weight, the plasticizer may bleed. In order to improve the water resistance of the material of the present invention, that is, the hydrolysis resistance, it is desirable to add a hydrolysis resistance inhibitor represented by carbodiimide, since the effect is remarkably exhibited. . Also, calcium carbonate, talc, mica,
The addition of fillers typified by carbon, barium sulfate and the like also improves the hydrolysis resistance, so these additions are preferred. The material of the present invention includes a flame retardant, such as antimony trioxide and zinc borate, which is usually added to a polyvinyl chloride resin to such an extent that its performance is not extremely deteriorated, a partially crosslinked polyvinyl chloride, a partially crosslinked polyvinyl chloride. A modifier such as acrylonitrile-butadiene rubber (NBR) and a processing aid represented by an acrylic resin can be added as needed. In addition, antifungal agent usually added to polyurethane, UV
It is also possible to add a stabilizer and the like as needed. 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) A method in which a polyurethane (2) is finely crushed by freeze pulverization or the like and then blended with a polyvinyl chloride resin (1). In this case, an apparatus used for blending is arbitrary, and examples thereof include a roll, a Banbury mixer, and an extruder. (B) 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. (C) 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 a shearing force. In particular, by using the method (C), the material of the present invention is preferable because strength represented by tensile strength is improved. Further, the material of the present invention has a sea-island type phase-separated structure when observed with a transmission electron microscope (TEM) after staining with a staining agent such as OsO ₄ , and The size of the polyurethane dispersed phase, which is an island portion, must be 0.01 μm or more and 100 μm or less. If the size of the dispersed phase exceeds this range, the moldability of the resulting material will be significantly reduced. When the formability is improved, the size of the dispersed phase is preferably from 0.03 to 80 μm, more preferably from 0.05 to 60 μm. As a molding method of the material of the present invention, any molding method usually used for thermoplastic resin, such as press molding, extrusion molding and calender molding, can be used. And the molded article obtained in this way is excellent in compression set. EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these examples. Example 1 Polyester polyol obtained by condensation polymerization of 3-methyl-1,5-pentanediol and adipic acid (Co., Ltd.)
80 parts by weight of Kuraray (trade name: Kurapol P2010, number average molecular weight: 2,000) and isocyanurate modified product of hexamethylene diisocyanate (trifunctional isocyanate compound) (trade name: Coronate HX, manufactured by Nippon Polyurethane Co., Ltd.) 13 0.4 parts by weight (NCO / OH ratio = 0.8
5) Further, 26.7 PPM of DBTDL (dibutyltin dilaurate) was mixed as a catalyst, and the mixture was left in an oven at 120 ° C. for 2 hours to produce a polyurethane. 0.5mm thick, 5mm wide, 25mm long from this sample
Was cut out and used as a sample for measuring dynamic viscoelasticity. In addition, the obtained polyurethane was finely crushed by freeze pulverization to obtain a composite material. The thus obtained polyurethane fine powder 9
3.4 parts by weight, and an ethylene-vinyl chloride copolymer (Rulon E-2800,
Average polymerization degree: 2750, 100 parts by weight of Tosoh Corporation; 2 parts of barium stearate, 1 part of zinc stearate as a stabilizer; amine scavenger (BP-331 manufactured by Nissan Ferro-Organic Chemical Co., Ltd.) ) 1.5 parts and di-2ethylhexyl phthalate (DOP) 100 parts by weight were sufficiently mixed at room temperature. This was kneaded with a roll forming machine having a surface temperature set at 150 ° C. for 15 minutes to obtain a composition. After completion of the kneading, the obtained roll sheet is subjected to JI
SK6301 12.70 ± thickness for compression set measurement
It was press-molded to a thickness of 0.13 mm. In addition, as a sample for the hydrolysis resistance test, it was extruded into a sheet having a thickness of 2 mm. The extrusion temperature was 180 ° C. Example 2 In place of DOP, a polyester plasticizer (made by Asahi Denka Kogyo Co., Ltd., trade name: ADEKASIZER-U)
L-80) Except for using the desired composition, it was obtained in the same manner as in Example 1 and molded. Example 3 The desired composition was prepared in the same manner as in Example 1 except that 100 parts by weight of calcium carbonate (trade name: Whiten P-10, manufactured by Shiraishi Industry Co., Ltd.) was charged into a roll kneader. This was molded. Example 4 A target composition was obtained and molded in the same manner as in Example 3 except that 5 parts by weight of a carbodiimide compound (manufactured by Bayer, trade name: Stabacol 1) was added as a hydrolysis resistance inhibitor. Example 5 Polyester polyol obtained by polycondensation of 1,4-butanediol and adipic acid (Nippon Polyurethane Co., Ltd.)
Manufactured by Nipporan 4010, number average molecular weight 200)
Except that 80 parts by weight and 16.1 parts by weight of the isocyanate compound (NCO / OH ratio = 1.02) were used, the target composition was obtained and molded by the same operation as in Example 4. Example 6 Example 1 was repeated except that a polycaprolactone polyol obtained from ring-opening polymerization of β-methyl-δ-valerolactone (Kuraray Co., Ltd., trade name: Clapol L2010, number average molecular weight: 2,000) was used. A target composition was obtained by the same operation as described above, and was molded. Example 7 The same operation as in Example 1 was carried out except that a vinyl chloride homopolymer (Rulon TH-1300, average degree of polymerization: 1300, manufactured by Tosoh Corporation) was used as the polyvinyl chloride resin. The desired composition was obtained and molded. Example 8 An ethylene-vinyl chloride copolymer (Rulon E-2200, average degree of polymerization: 2200) was used as the polyvinyl chloride resin.
A target composition was obtained and molded by the same operation as in Example 1 except that Tosoh Corporation was used. Comparative Example 1 A composition was obtained and molded by the same operation as in Example 1 except that no polyurethane was used. Comparative Example 2 438 g of the polyvinyl chloride resin used in Example 1 in a Banbury mixer, 12 g of barium stearate and 5.4 g of zinc stearate as stabilizers, an amine supplement (Nissan Ferro-Organic Chemical Co., Ltd.) Product name BP-331)
7.5 g was charged and stirred at a constant rotation speed. Separately from this, a polymer polyol (Nipporan 406 manufactured by Nippon Polyurethane Co., Ltd.) which has been previously kept at 70 ° C.
7, number average molecular weight 2000) 350 g and DOP 438 g
Is mixed with 3 ml of hexamethylene diisocyanate.
58.6 g of a monomer (NCO / OH ratio = 0.85) and 0.03 g of dibutyltin dilaurate as a catalyst were mixed, mixed for 1 minute, and then poured from a Banbury mixer inlet. The reaction and mixing time were carried out for 15 minutes, and a composition was obtained. The composition obtained was molded in the same manner as in Example 1. Comparative Example 3 Polyester polyol obtained by polycondensation of ethylene glycol and adipic acid (manufactured by Nippon Polyurethane Co., Ltd.)
A composition was obtained and molded in the same manner as in Example 1, except that Nipporan 4040 (trade name, number average molecular weight 2000) was used. Comparative Example 4 A composition was obtained and molded in the same manner as in Example 1 except that a pulverized product of polyurethane which had been mechanically pulverized and did not pass a 2 mm mesh was blended. Comparative Example 5 A composition was obtained in the same manner as in Example 1 except that 1000 parts by weight of a freeze-ground polyurethane was blended.
This was molded. Comparative Example 6 Polyether thermoplastic polyurethane (Milactran P-39, manufactured by Nippon Miractran Co., Ltd.) was used as the polyurethane.
A composition was obtained and molded in the same manner as in Example 1 except that (RSOP) was used. Comparative Example 7 64.9 parts by weight of a polyester polyol and 28.5 parts by weight of an isocyanate compound (NCO / OH ratio: 0.5
8) A desired composition was obtained and molded by the same operation as in Example 1 except that the composition was used. 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. After an initial strain of 25% and a temperature of 70 ° C. for 22 hours, the strain was released and the residual strain was measured. (Evaluation of hydrolysis resistance) A dumbbell for tensile test (JIS K630) was extruded from a sheet extruded to a thickness of 2 mm.
(No. 1, 3 dumbbells). This is brought to a temperature of
Tensile strength retention was measured after standing for 6 weeks in a thermo-hygrostat at 95% humidity. The tensile test was performed at a tensile speed of 200.
mm / min. (Confirmation of phase structure) The sample was exposed to the vapor of OsO ₄ and stained, and this was subjected to −10 with an ultramicrotome.
Finish in 0.1 micron ultra-thin section at 0 ° C. This was taken with an electron microscope JEOL JEM-2.
Observation was performed at an acceleration voltage of 200 kV using 000FX. At the time of this observation, it was confirmed that the component of the polyurethane dyed into OsO ₄ was a dispersed phase having a size of 0.1 to 100 μm. (Measurement of dynamic viscoelasticity) Viscoelasticity measuring device DV
Using E-V4 (manufactured by Rheology Co., Ltd.), the tensile storage elastic modulus (E ′) at 23 ° C. was measured at a measurement frequency of 10 Hz, a measurement mode of tensile, and a strain of 1% or less in a linear region. [Table 1] As described above, the material of the present invention is a plumbing material excellent in compression set, workability and hydrolysis resistance.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 27/06 C08L 75/04-75/16 B60R 13/06 C08G 18/42-18/46

Claims (1)

(57) [Claims] 1. A resin composition comprising a polyvinyl chloride resin (1), a polyurethane (2) and a plasticizer (3). islands phase separation structure is observed in, and the island size of the polyurethane dispersed phase is a portion of the isolation structure is 100 microns or less than 0.01 microns, polyurethane (2) is referred to the following compounds 1
One or more polymer polyols and three or more
By reaction with a compound having an isocyanate group
Is, tensile modulus in the linear viscoelastic measurement from 20 ° C. 7
7 × 10 ⁶ dyne / cm ² or more and 8 × in the range of 0 ° C.
Plumbing materials consisting of 10 ⁷ dyne / cm ² or less der Ru resin composition. Compound 1 (A) 1,4-butanediol, diethylene glycol, 3-methyl-1,5-pentanediol, 1,6-
Polyester polyol (B) obtained by polycondensation of one or more diols selected from hexanediol and neopentyl glycol with adipic acid (B) Polycaprolactone obtained by ring-opening polymerization of β-methyl-δ-valerolactone Polyol (C) Polycarbonate polyol