JPH06145501A - Production of composite material of poly@(3754/24)vinyl chloride) resin with polyurethane - Google Patents

Abstract

PURPOSE:To obtain the title material which has satisfactorily low compression set, a low melt viscosity, and excellent moldability by using specific conditions in producing the composite. CONSTITUTION:The title method comprises melt-kneading a polymerpolyol (e.g. a polyesterpolyol obtained from 3-methyl-1,5-pentanediol and adipic acid) with an isocyanate compound (e.g. a hexamethylene diisocyanate modified with isocyanurate) and a PVC resin (e.g. an ethylene/vinyl chloride copolymer), the conversion of the NCO groups being heightened to 50% or above before the melting and gelation of the PVC resin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a composite resin composition comprising polyurethane and polyvinyl chloride.

[0002]

2. Description of the Related Art Conventionally, benzoyl peroxide, dicumyl peroxide, and t have been known as methods for improving the load-bearing deformability of polyvinyl chloride resins, that is, the compression set.
-Chlorination with organic peroxides such as butyl peroxide, diamine compounds such as 1,4-tetramethylenediamine and 1,6-hexamethylenediamine, and sulfur compounds such as sulfur, tetramethylthiuram disulfide and triazinedithiol Cross-linking of vinyl resin, method by cross-linking of components such as diallyl phthalate, cross-linkable polyurethane or epoxy resin, and further, cross-linked vinyl chloride resin pre-cross-linked during polymerization or cross-linked NBR having good compatibility with vinyl chloride resin is blended with vinyl chloride resin There is a method, a method of forming a crosslinked body with diisocyanate or the like using a vinyl chloride resin having a reactive group such as a hydroxyl group.

In these methods, when a vinyl chloride resin is cross-linked, it is possible to easily obtain a composition having a good compression set, but on the other hand, the problem is that the melt viscosity is remarkably increased and It becomes a material with poor workability. In addition, (1) Poor heat stability and easy coloring, (2) Odor is left due to the residue of the cross-linking agent, (3) When the degree of cross-linking is increased, a large amount of plasticizer is used to obtain a predetermined hardness. There's a problem.

When a reactive plasticizer is used, it is often a radical reaction system, so that the same problem as described above occurs.

When a crosslinked vinyl chloride resin, crosslinked NBR or the like is blended with a vinyl chloride resin, (1) it is related to their dispersibility in the vinyl chloride resin, and the physical properties such as tensile strength and elongation are remarkably deteriorated ( 2) A large amount of plasticizer is required for adjusting the hardness. 3) Addition in a large amount deteriorates moldability. 4) There are problems such as poor weather resistance and heat aging resistance due to the butadiene component in the crosslinked NBR. .

Further, the method of forming a cross-linked product by using a vinyl chloride resin having a reactive group such as a hydroxyl group with diisocyanate or the like is inferior in reactivity, so that the improvement effect is small.

In recent years, attention has been paid to a composite of vinyl chloride resin and polyurethane, and various methods have been proposed. For example, a method of dissolving polyurethane in a vinyl chloride monomer (VCM) and polymerizing VCM to obtain a composite of a vinyl chloride resin and polyurethane, a method of polymerizing VCM in the presence of a polyol to produce a hydroxyl group-containing vinyl chloride resin, and There is a method of obtaining it by a urethanization reaction.

However, the composites of vinyl chloride resin and polyurethane obtained by these methods are inferior in rubber elasticity and are not suitable for applications requiring these properties.

On the other hand, easy moldability required for large-scale injection molding, precision injection molding, etc., particularly improvement of moldability represented by a decrease in melt viscosity, and further rubber properties such as compression set and creep resistance. In recent years, there has been an increasing demand for a material, and a material having a low compression set and an improved moldability, particularly a material having a low melt viscosity is desired.

[0010]

DISCLOSURE OF THE INVENTION The present invention simplifies the manufacturing process without impairing the balance between the excellent compression set and moldability of the composite of polyvinyl chloride resin and polyurethane, and simplifies the manufacturing process. The purpose is to provide excellent materials.

[0011]

The inventors of the present invention have completed the present invention in view of the above-mentioned current situation.

That is, the present invention provides a method for producing a composite material comprising a polyvinyl chloride resin and polyurethane by mixing the polyvinyl chloride resin, a polymer polyol and a compound having an isocyanate group under melt shearing. A method for producing a polyvinyl chloride-based resin-polyurethane composite material, characterized in that an isocyanate group consumption rate of the resin-based resin before being melted and gelled is 50% or more. The details of the present invention will be described below.

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.), a resin obtained by grafting a functional group such as a hydroxyl group onto the above resin, or a resin obtained by reacting such a functional group with a reactive compound and graft-bonding, and a single or two types of the above resins. It is a mixture of the above.

The polyvinyl chloride resin may have any degree of polymerization, but in view of moldability, it is 400 or more and 8000 or less,
It is more preferably 500 or more and 5000 or less, and further preferably 800 or more and 4000 or less. Further, a polyvinyl chloride resin having an arbitrary molecular weight may be blended with the polyvinyl chloride resin having a polymerization degree in the above range.

The polymer polyol used in the present invention has two or more hydroxyl groups and a molecular weight of 300 or more and 1 or more.
0000 or less, preferably 300 or more and 5000 or less. Such a polymer polyol is obtained, for example, by condensation polymerization of a dicarboxylic acid having 4 to 10 carbon atoms and a glycol having a repeating unit of 5 or less obtained by ring-opening polymerization of a glycol having 2 to 10 carbon atoms and / or an epoxy group. be able to. The molecular weight referred to in the present invention means a number average molecular weight, which can be measured by gel permeation chromatography (GPC) or the like.

The glycol having 2 to 10 carbon atoms used for producing the polymer polyol includes, for example, 1,2-ethanediol, 1,2-propanediol, 1,4-butanediol, butenediol and 3-methyl-. 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decamethylenediol, 2,5-dimethyl-2,5- Hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol 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.
4 to 10 carbon atoms used for producing polymer polyol
Examples of the dicarboxylic acid include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, and the like, and one or more of them are used. The polymer polyol may of course be a ring-opening polymer of a lactone compound.

Further, polycarbonate polyol, acrylic polyol and the like can also be used.

It is also possible to use a polymer polyol having three or more functional groups. In order to produce such a polymer polyol, it can be obtained, for example, by using trimethylolpropane or the like when producing a polyester polyol.

One kind or two or more kinds of the polyol thus obtained is used.

The addition amount of the polymer polyol is 20 parts by weight or more and 800 parts by weight or less, more preferably 25 parts by weight or more and 250 parts by weight or less, further preferably 30 parts by weight or more and 150 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. Less than or equal to parts by weight is desirable. If it is less than 20 parts by weight, the rubber elasticity will not be improved, and if it exceeds 150 parts by weight, processing may not be possible.

The compound having an isocyanate group used in the present invention is a compound having three or more isocyanate groups, such as 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, 4,4 ' -Trimer of diisocyanate such as methylenebiscyclohexyl diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, 1,6,11
-Undecane triisocyanate, lysine ester triisocyanate, 4-isocyanatomethyl-1,8-
Triisocyanates such as octamethyldiisocyanate, or polyfunctional isocyanates such as polyphenylene methane polyisocyanate may be mentioned.
One kind or two or more kinds are used. It is also possible to use the above diisocyanates together. However, the number of NCO groups of triisocyanate is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.25 or more with respect to the number of NCO groups of all isocyanates. If it is less than 0.1, sufficient performance may not be obtained due to insufficient crosslink density.

In order to improve the flex fatigue resistance of the composition, the reaction ratio of the polyurethane used (number of hydroxyl groups /
It is also possible to control the number of isocyanate groups).
Generally, polyurethane is obtained by a polyaddition reaction between a compound having a hydroxyl group and a compound having an isocyanate group, but the number of functional groups in each compound is not fixed and there are various types. For example, when the number of branch points in the polyester molecular structure is increased with trimethylolpropane or the like, a large number of hydroxyl groups are contained in one molecule, so that the gel point generated by the reaction with an isocyanate compound becomes a considerably low reaction ratio. It is difficult to unambiguously determine the optimum reaction ratio depending on the number of functional groups of the compound used, but the reaction ratio of polyurethane is preferably 0.1 or more and 2 or less,
It is more preferably 0.1 or more and 1.2 or less, and even more preferably 0.1 or more and 0.9 or less.

The polyurethane used is a polymer polyol having two or more hydroxyl groups and two isocyanate groups.
In the case of obtaining by reacting a compound having at least one with a urethane, the molecular weight of the polyol, which is one of the components of the polyurethane, is not particularly limited, but an average molecular weight of 300 or more 50
Molding processability is better when a polymer polyol of 00 or less is used.

The use of the plasticizer in the present invention includes
No restrictions. Examples of the plasticizer that can be used in the present invention include di-n-butyl phthalate, di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisodecyl phthalate, diisooctyl phthalate, and phthalate. Phthalic acid-based plasticizers such as octyldecyl acid salt, butylbenzyl phthalate, and di-2-ethylhexyl isophthalate, di-2-ethylhexyl adipate (DO
A), di-n-decyl adipate, diisodecyl adipate, dibutyl sebacate, di-2-ethylhexyl sebacate, and other aliphatic ester plasticizers, trioctyl trimellitate, tridecyl trimellitate, and pyromellitic acid. Plasticizer, tributyl phosphate, tri-phosphate
Polymers typified by phosphoric ester plasticizers such as 2-ethylhexyl, 2-ethylhexyl diphenyl phosphate, tricresyl phosphate, epoxy plasticizers such as epoxy soybean oil, chlorinated paraffins and polyester polymer plasticizers Examples of the plasticizer include a high molecular weight compound having a glass transition temperature lower than that of the polyvinyl chloride resin and having a plasticizing ability for the polyvinyl chloride resin.
Alternatively, two or more kinds can be used.

The above-mentioned plasticizer is appropriately selected according to the purpose, and for example, a high molecular weight plasticizer is used to improve heat resistance and non-migration property. To improve oil resistance, dibutyldiglycol adipate or the like may be used. Further, in order to improve the fluidity, an adipic acid ester plasticizer,
A sebacate ester plasticizer or the like is added.

The polyvinyl chloride-based composite material obtained according to the present invention includes an inorganic filler such as calcium carbonate or talc, which is usually added to a polyvinyl chloride resin to the extent that the performance is not extremely deteriorated, and trioxide. Flame retardant typified by antimony and zinc borate, partially crosslinked polyvinyl chloride,
Partially cross-linked acrylonitrile-butadiene rubber (NBR)
A modifier such as the above and a processing aid typified by an acrylic resin can be added as necessary. It is also possible to blend the obtained material with another resin. In this case, a compatibilizing agent for the material obtained as the third component and another resin can be used together.

The present invention provides the above-mentioned polyvinyl chloride resin,
When producing a composite material by mixing a polymer-polyol and a compound having an isocyanate group under melt shearing, the isocyanate group consumption rate, which is a measure of the urethane reaction during the melt gelation of the polyvinyl chloride resin, is 50%. % Or more. This means that the crosslinking reaction of polyurethane proceeds and a polyurethane gel structure insoluble in the solvent is generated. When the polyurethane gel is formed before the polyvinyl chloride resin is melted and gelled, the final material has a sea-island structure with polyurethane as the dispersed phase. As a result, the obtained material has a low melt viscosity and is excellent in moldability. The fact that urethane gel is formed can be confirmed by dissolving it in a solvent such as tetrahydrofuran (THF) and measuring the insoluble content.

The melt gelation of the polyvinyl chloride resin used in the present invention means a state in which at least secondary particles of the polyvinyl chloride resin are disintegrated. Polyvinyl chloride resin generally has a very complicated structure, and particles called secondary particles of about 1 to 3 microns are aggregated to form one particle. The secondary particles are also finer than 200-5.
It is an aggregate of primary particles having a size of about 00 angstrom. Melt gelation in the present invention means a state in which at least the secondary structure of such particles is collapsed, and when observing the structure with an electron microscope or the like, a particle structure of 1 micron or more is observed. It represents the state of disappearance.

The consumption of isocyanate groups, which is a measure of the urethane reaction, can be easily measured by a Fourier transform infrared spectroscope or the like. Here, the consumption rate of the isocyanate groups must be 50% or more, preferably 55% or more, and more preferably 60% or more before the melt gelation of the polyvinyl chloride resin occurs. If it is less than 50%, good rubber elasticity may not be exhibited.

The consumption amount of such isocyanate group can be adjusted as appropriate. For example, (1) a method of operating the concentration of the urethane reaction catalyst, (2) a method of operating the temperature, and (3) adding a plasticizer. The method of (4) operating the shearing force,
(5) Method of preliminarily impregnating a polymer polyol, a compound having an isocyanate group, or a plasticizer with a porous polyvinyl chloride resin, (6) Adding a gelation accelerator for the polyvinyl chloride resin, etc. Method, (7) a method of operating a pH that affects the urethane reaction, (8) a method of adding an external plasticizer typified by stearic acid, (9) an internal plasticity typified by an ethylene copolymer vinyl chloride, etc. A method of using a modified polyvinyl chloride resin, (10) a method of controlling a urethane reaction by using polymer polyols having different reactivity, and the like.
It is also possible to operate these in combination.

The resin composition obtained by the production method of the present invention exhibits good rubber elasticity and is excellent in fluidity, and is compared with a production process of blending a pre-reacted polyurethane with a polyvinyl chloride resin. Since it is possible to omit processes such as freeze-grinding of polyurethane, the material has excellent cost performance.

[0033]

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

Example 1 Ethylene-vinyl chloride copolymer obtained by suspension polymerization method (Leuron E-2800, average degree of polymerization: 2750,
100 parts by weight of Toso Corporation, 2 parts of barium stearate as a stabilizer, 1 part of zinc stearate, an amine scavenger (trade name BP-331 manufactured by Nissan Ferro Organic Chemical Co., Ltd.)
1.5 parts, di-2 ethylhexyl phthalate (DOP)
100 parts by weight of a polyester polyol obtained by condensation polymerization of 3-methyl-1,5-pentanediol and adipic acid (Kuraray P201, manufactured by Kuraray Co., Ltd.)
0, number average molecular weight 2000) 80 parts by weight, isocyanurate-modified hexamethylene diisocyanate (trifunctional isocyanate compound) (Nippon Polyurethane Co., Ltd.)
Made, product name Coronate HX) 13.4 parts by weight (NCO /
An OH ratio = 0.85) and 0.078 parts of DBTDL (dibutyltin dilaurate) as a catalyst were mixed at room temperature, and the pasty raw material was put into a roll kneader having a surface temperature of 150 ° C. While kneading with a sheet thickness of 1 mm, 1
Sampling was performed at intervals of minutes to prepare samples for infrared spectroscopy and for transmission electron microscope observation. After kneading for 15 minutes, the obtained composite was press-molded to have a thickness of 12.70 ± 0.13 mm for JISK6301 compression set. Further, this pressed product was cut into 5 mm squares to obtain samples for measuring melt viscosity.

Example 2 Instead of the polyester polyol used in Example 1, a polyester polyol having the same composition and a number average molecular weight of 500 (manufactured by Kuraray Co., Ltd., trade name CLAPOL P510) 56.8 parts by weight, hexa 36.6 parts by weight of trimer of methylene diisocyanate (NCO / OH ratio =
0.85), and the target composition was obtained by the completely same operation except that the catalyst was 0.0156 parts.

Example 3 Among the raw materials used in Example 1, DOP was previously mixed with polyvinyl chloride resin and dried up with a Henschel mixer. The target composition was obtained by the same operation except that the raw material thus obtained and the other raw materials used in Example 1 were stirred at room temperature and then charged into a roll kneader.

Example 4 A target composition was obtained by the same method except that the catalyst was changed to 0.043 part in Example 2.

Example 5 The raw materials used in Example 1 were mixed at room temperature into a Labo Plastomill (manufactured by Toyo Seiki Seisakusho, Ltd.) having an internal volume of 60 cc and a preset temperature of 100 ° C., and then added. Rotation speed is 60
r. p. m. After kneading for 30 minutes, the mixture was taken out, formed into a sheet by a roll forming machine, and then press-formed according to Example 1. Further, during the kneading, sampling was performed at intervals of 2 minutes to obtain a sample for infrared spectroscopic measurement.

Example 6 A polyester polyol obtained by condensation polymerization of adipic acid, butanediol, and ethylene glycol in place of the polyester polyol used in Example 1 (Nipporan 404, manufactured by Nippon Polyurethane Co., Ltd.)
2, the target composition was obtained by the completely same operation except that the number average molecular weight of 2000) was used.

Example 7 A polyester polyol obtained by condensation polymerization of adipic acid and ethylene glycol in place of the polyester polyol used in Example 1 (manufactured by Nippon Polyurethane Co., Ltd., trade name Nipporan 4040, number average molecular weight 2)
000) was used to obtain the target composition by the completely same operation.

Example 8 A polyester polyol obtained by condensation polymerization of adipic acid and butanediol instead of the polyester polyol used in Example 1 (Japan Polyurethane Co., Ltd.)
Made, brand name Nipporan 4010, number average molecular weight 200
The target composition was obtained by exactly the same operation except that 0) was used.

Example 9 A polyester polyol obtained by condensation polymerization of adipic acid and diethylene glycol in place of the polyester polyol used in Example 1 (Asahi Denka Kogyo Co., Ltd.)
A target composition was obtained by exactly the same operation except that the product, F15-22, trade name, number average molecular weight 2000) was used.

Example 10 Polycaprolactone polyol obtained by ring-opening polymerization of β-methyl-δ-valerolactone instead of the polyester polyol used in Example 1 (Kuraray Co., Ltd., trade name Clapol L2010, number average) Molecular weight 200
The target composition was obtained by the completely same operation except that 0) was used.

Example 11 Instead of the ethylene-vinyl chloride copolymer used in Example 1, a polyvinyl chloride resin (Luron P.V.
C. TH-1300, average degree of polymerization: 1300, manufactured by Tosoh Corp. was used to obtain the target composition by exactly the same operation except that it was used.

Comparative Example 1 The target composition was obtained in exactly the same manner as in Example 1 except that the amount of the catalyst used was 0.0078 parts.

Comparative Example 2 The target composition was obtained in the same manner as in Example 5, except that the set temperature was 150 ° C.

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

(Evaluation of Melt Viscosity) The melt viscosity was measured by Toyo Seiki Seisakusho Capirograph (die: φ = 1.0 m).
m, L = 60 mm) at 180 ° C. Hereinafter, the melt viscosity means that the shear rate measured under the above conditions is 120.
It means the value at 0 (1 / sec).

(Evaluation of Isocyanate Consumption) The measurement was carried out using a Fourier transform infrared spectroscope. The device is Nicolet FT-IR 5DX Spectratech, Sca
The number n was 100 times, the measurement range was 80 μm × 80 μm, the detector was MCT, the measurement method was the transmission method, and the sample holding plate was barium fluoride. The sample taken out from the kneading machine was immediately subjected to infrared absorption spectrum measurement using this apparatus to detect the absorption at 2277 cm ^-1 , which is the characteristic absorption of the isocyanate group. At this time, the absorption at 1600 cm originating from the benzene ring of the plasticizer (DOP) was also detected as a reference peak at the same time. Before starting the reaction, the peak intensity at 2277 cm ^-1 was set to 16
The value obtained by dividing the peak intensity at 00 cm ^-1 was taken as the isocyanate consumption amount of 0%, and the value obtained for each sample after the reaction was initiated was standardized to obtain the isocyanate consumption amount.

The OsO ₄ (transmission electron microscope) sample
Is exposed to the steam of the above and dyed, and this is finished into an ultra-thin section of 0.1 micron in an atmosphere of -100 ° C with an ultramicrotome. This is an electron microscope DEOL JEM-2000F
Using X, the accelerating voltage was 200 KV, and the observation magnification was set to 1000 to 200,000 times according to the size of the dispersed phase. At the time of this observation, a sample in which particles of 0.1 μm or more were not observed was made into polyvinyl chloride melt-gelled, and the isocyanate consumption rate (value obtained by FI-IR) at this time is shown in Table 1.

[0051]

[Table 1]

[0052]

As described above, the composite produced by the method of the present invention becomes a thermoplastic elastomer having a low melt viscosity and excellent moldability while maintaining a good compression set.

Claims (1)

[Claims] 1. A polyvinyl chloride resin, a polymer polyol and a compound having an isocyanate group are melt-sheared,
A method for producing a polyvinyl chloride-based resin and a polyurethane composite material by mixing, wherein the isocyanate group consumption rate of the polyvinyl chloride-based resin before melt gelation is 50% or more, Method for producing polyurethane composite material.