JPS61250044A - Production of polyvinyl chloride-polyurethane molding composition - Google Patents

Abstract

PURPOSE:To readily obtain the titled composition highly resistant to wear, oil, freeze, etc., by blending powdery polyvinyl chloride, isocyanate compound, polyol, and, if needed additive, in the presence of a liquid plasticizer. CONSTITUTION:First, the following materials are prepared: (A) powdery polyvi nyl chloride with a polymerization degree >=600, (B) 2-120wt%, based on the component (A), of a liquid plasticizer such as diethyl phthalate or DOP, (C) an isocyanate compound such as 2,4- or 2,6-tolylene diisocyanate and (D) a polyol such as 1,4-butanediol in a NCO/OH ratio 0.5-10 for the components (C) and (D). A mixture of the components (B) and (C) is added to the component (A) while agitating the latter in a mixer to effect impregnation followed by incorporating another mixture of the components (B) and (D) to effect impregna tion and, if needed, blending an additive, thus obtaining the objective composi tion.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a molding composition for obtaining a composite of a vinyl chloride polymer (hereinafter referred to as PvC) and a polyurethane polymer (hereinafter referred to as PU).

More specifically, the urethanization reaction is allowed to proceed at the same time as heat molding, and PvC and PU are blended homogeneously in the presence of a plasticizer, or molded products in the form of composites in which chains are entangled with each other can be efficiently produced. The object of the present invention is to provide a method for producing a molding composition that can be obtained with good quality.

[Industrial application field]

PvC is a versatile thermoplastic resin with excellent processability, and is widely used in pipes, corrugated plates, sashes, films, sheets, leather, electric movable covers, hoses, boots, and daily miscellaneous goods. There is.

However, so-called hard polyvinyl chloride, which does not use much plasticizer such as dioctyl phthalate (hereinafter referred to as DOP), has a drawback in impact resistance, especially brittleness at low temperatures.

On the other hand, polyvinyl chloride uses a large amount of low-molecular-weight plasticizers such as DOP, resulting in poor flexibility, cold resistance, and solvent resistance due to volatilization, migration, and elution of the plasticizer with solvents. There is a drawback.

In addition, PU has excellent abrasion resistance, low-temperature properties, oil resistance, gun stain resistance, etc., and it is easy to obtain any physical property from soft to hard by combining the constituent raw materials, so it can be used for a variety of purposes. It is used in various fields.

The present invention prevents the migration and elution of the plasticizer by forming a homogeneous blend of PvC and PU or by forming a complex in which a plasticizer such as DOP is present in the chain structure. Furthermore, due to the synergistic effect with the original physical properties of PU, physical properties such as abrasion resistance, oil resistance, and cold resistance are improved.Moreover, it can be processed using general PvC processing methods without any troublesome pretreatment. The present invention provides a molding composition that can be easily processed.

Therefore, it can be used in many industrial fields, and applications that take advantage of its main characteristics include leather, hose materials, special wire sheath materials, flooring materials, automobile parts, boots for cold regions,
Examples include oil-resistant work boots and shoe soles.

[Prior art] Composites of PVC and PU have been proposed, and tubes,
Used for hoses, sheets, industrial parts, etc.

For example, the following methods are known for compounding, but all of them are limited in terms of processability and range of application, and require many complicated steps to prepare the compound. It also has disadvantages such as complicated pretreatment during molding.

α) Blending of PvC and Thermoplastic Polyurethane In order to obtain a mixture that is inexpensive and has excellent physical properties, it has been proposed to blend thermoplastic polyurethane (hereinafter referred to as TPO) and PvC, but it has not been actually used in some fields. There is.

However, since TPU is usually in the form of flakes or pellets, it has poor workability when blended with PvC powder, and when mixing additives such as stabilizers,
Since the particle sizes are different, they are non-uniform, and there are problems such as insufficient mechanical strength and poor appearance of the molded product.

There is also a method of powdering TPO and blending it with PVC powder, but it is often difficult to powder TPU, which is relatively soft and matches the physical properties required for ordinary mixed resins.

Furthermore, due to the physical properties required of the mixed resin, the melting temperatures of TPU and PvC are often different, which makes mixing difficult and has the disadvantage of poor workability.

(2) Graft polymer of PVC and thermoplastic polyurethane JP-A-58-40312, 58-4-2611, 5
TPU soluble in vinyl chloride monomer (hereinafter referred to as VCM) as described in publications such as No. 8-37019
Grafting by suspension polymerization of VCM and VCM has been proposed, and compositions have been provided. These compositions combine TPU with VCM
Since it is necessary to dissolve the PU and mix it uniformly, the composition and amount of PU to be added must be restricted. For example, PU is a thermoplastic and has a low softening point. For this reason, they are limited to special types that do not contain hard segments in their molecular chains.

A method has been proposed for preparing a polyurethane composition by reaction in the presence of G() PVC powder, as described in Japanese Patent Application Laid-Open No. 58-5357. In this case, a difficult process is required to obtain a uniform dispersion state of PvC powder in the composition, and if the amount of PvC powder added increases significantly, the viscosity of the reaction mixture increases, making it difficult to manufacture the composition. It is. Furthermore, since the reaction mixture is unstable, its pot life is short and it is difficult to store it in this state.

(4) Production of polyurethane in PVC A method for producing PU during mixing with pvc'
A method such as that described in Publication No. 9464 has been proposed.
I'm here. In this case, a plasticizer for polyvinyl chloride is not used, so there is no need to worry about elution of the plasticizer. However, since polyol and polyisocyanate are impregnated into PvC at the inner end and difficult to disperse uniformly, gelled polyurethane tends to occur in some areas.
There are problems such as defects in the mechanical strength of the molded product and poor appearance.

! ? ,: In order to obtain the desired flexibility, it is necessary to add a large amount of urethane component. This makes it more difficult to impregnate polyol and polyisocyanate into PvC, and the resulting material does not turn into powder. It tends to be clay-like semi-gel-like.

This tendency is particularly noticeable in polyether polyols.

[Problems to be solved by the present invention]

The present inventors have faced this situation and obtained a composite resin that has improved wear resistance, low temperature resistance, and oil resistance without impairing the processability of PVC, and at the same time has improved tensile properties due to the reinforcing effect. As a result of extensive research into the method, we found that we could easily obtain a high-performance, highly processable composite of PvC and PU than by conventional methods, and we also found that it was a thermosetting type with a high crosslinking density that had better physical properties. We have discovered a method to obtain PU by combining it with PvC, and have completed the present invention.

Powdered PvC, apart from so-called paste PvC used as plastisols or organosols, is usually used for calendering, extrusion, injection molding, etc. in as porous a manner as possible to improve the absorption of plasticizers. Manufactured to quality.

Therefore, substances capable of providing a plasticizing effect other than those used as normal PVC plasticizers can also be absorbed into the pores of the PvC powder.

The present invention takes advantage of this property and utilizes the reactivity of isocyanate compounds to encapsulate the polyurethane component in a stable state in the PVCA pores, or uses PvC as a carrier.
By adjusting a composition impregnated with a polyurethane component, and then proceeding with a urethanization reaction simultaneously with heat molding, or by making a certain molecular arrangement take place, it is possible to obtain a composite of PvC and PU in a so-called one-shot process during molding. That is.

The degree of absorption of the absorbent into the pores of the PvC powder depends on (1) compatibility of the absorbent with PvC (2) liquid properties (viscosity) of the absorbent.

Most of the PU acid component is absorbed into the pores,
If it is not present on the PVC surface, the PvC powder remains free-flowing, but if the absorbent is not sufficiently absorbed and remains in a large amount on the surface, it is difficult to obtain a powder with good fluidity. I can't.

Usually, in the case of polyols used as PU acid components, D
Compared to PVC plasticizers such as OP, it is poorly absorbed into PvC, so it easily adheres to the 270 surface, making it difficult to obtain a powder that maintains satisfactory fluidity. In this state, Tokuko Sho 59-3946
As in the invention No. 4, if polyisocyanate is added and the urethanization reaction is carried out, the polyisocyanate becomes P.
It is difficult to be absorbed into VC, so the polyurethanization reaction occurs on the 270 surface, and the PvC powder hardens as a clay-like semi-gelled material due to the PU generated on the surface. This is extremely disadvantageous for subsequent processing steps. In addition, since the added polyisocyanate is not uniformly dispersed, the blending ratio of polyol and polyisocyanate within the pores of PvC or on the surface is partially different, and for this reason, the PUg component has sufficient chain extension. Otherwise, a side reaction may occur partially and a gelled product of PU may be generated. As a result, there are many problems such as blurring of physical properties, poor appearance, and occurrence of fish marks when the obtained molded powder is molded.

In order to obtain a powder with good fluidity in which the PU acid component is stably encapsulated in PVC, it is necessary that the polyol and isocyanate compound to be absorbed be sufficiently absorbed into the PvC pores.

In addition, in order to obtain a composite of PvC and PU that is better in aged form, it is necessary that the polyol and isocyanate compound be uniformly dispersed, and that the highly reactive isocyanate groups be stably protected from external factors. be.

The present invention is completed by solving these points.

[Means to solve the problem]

That is, the gist of the present invention is to impregnate powdered polyvinyl chloride with an isocyanate compound and a polyol in the presence of a liquid plasticizer, and the liquid plasticizer is used in the method of the present invention. Possibly PVC and PU
In the combination of the above, a significant effect can be obtained compared to the conventional techniques described above.

That is, one embodiment of the implementation is as follows: α) Isocyanate compound mixed with a liquid plasticizer (Liquid A) (2) Polyol mixed with a liquid plasticizer (BWI) 6)
While stirring powdered PvC with a mixer, first add liquid A to impregnate it, then add liquid B to impregnate it, and add additives as necessary to form polyvinyl chloride-polyurethane. The present invention provides a spherical composition.

In this method, by mixing isocyanate compounds with liquid plasticizers, Q By increasing the amount (liI dilution) with a liquid plasticizer and adding it, the isocyanate compound is uniformly absorbed into the PVCJI pores. Next, a polyol component is added, but the polyol normally used as a PU acid component is difficult to be efficiently absorbed by PVC. This is due to the high compatibility between Pvc and polyol and the high viscosity of polyol, but by mixing a liquid plasticizer with polyol, the 9B solution improves its compatibility with PVc and has a lower viscosity. The system becomes viscous, and Pv
Absorption into C is performed efficiently.

At the stage when liquid B is absorbed following liquid A, the isocyanate compound and polyol come into contact with each other in the PVC pores and a partial urethanization reaction takes place, but generally the proportion of polyol is large near the surface of PvC. It is thought that the powder molding composition is obtained in a state in which the isocyanate compound is protected from the outside by the polyol.

In preparing this molding composition, additives such as stabilizers and lubricants may be added as necessary.

This molding composition is made of ordinary PVC:! It can be molded using exactly the same processing method as that used for molding, and the urethanization reaction proceeds at the same time during heat molding, resulting in a completely homogeneous blend or mutual entanglement of chains. A composite of PVC and PU can be obtained as a molded article.

Although the molded product according to the present invention uses a low molecular weight plasticizer such as D()P, the plasticizer is present in the molecule between PVC and PU, so it is not plasticized. Migration and elution of the agent are small, and it is possible to obtain a molded product with performance comparable to that of so-called unplasticized PVc.

The liquid plasticizer used in Zero M-light is phthalate, which is normally used as a plasticizer for PVC. esters, dibasic acid esters, inorganic esters, and glycol esters, such as diethyl phthalate\7dipyl thalate,
DOP, butyl lauryl phthalate, di-2-ethylhexyl 7-dipate, di-2-ethylhexyl 7-gelate, tricresyl phosphate, diethyl tryptopate, dibutyl diglyfur adipate, and the like.

Furthermore, in the molded product according to the present invention, water resistance, which is the biggest drawback of composites of PVc and PU, has been greatly improved.

This is thought to be due to the effect of the strongly hydrophobic plasticizer wrapping the molecular chain and protecting the PU chain, and even the presence of a small amount of plasticizer has a large effect.

It goes without saying that the addition of a plasticizer greatly contributes to processability (lowering processing temperature, improving appearance, etc.).

Isocyanate compounds used in the present invention a include 2,4- and 2,6-) lylene diisocyanate, m- and p-7 enylene diisocyanate, 1
- Rikurophenylene-2,4-diisocyanate,
5-S7tale diisocyanate, methylenebisphenylene-4,4'-diisocyanate, m- and p-
Xylene diisocyanate, same ethylene diisocyanate 7
lysine diisocyanate), 4,4'-methylenebis(cyclohexyl isocyanate), isophorone diisocyanate*), )limethylhexamethylene diisocyanate, and the like. Diisocyanates, triisocyanates such as 1,6.11-undecane triisocyanate, lysine ester triisocyanate, 4-isocyanate methyl-1,8-octamethyl diisocyanate,
or polyfunctional isocyanates such as polyphenylmethane polyisocyanate, dimers or dimers of these isocyanate compounds, the short-chain and long-chain polyols, or water and active hydrogen compounds such as amino compounds; An isocyanate compound such as an isocyanate compound having a terminal isocyanate group obtained by reaction with an isocyanate compound is used.

In addition, as for isocyanate compounds, the above-mentioned isocyanate compounds are stabilized with boot kinging agents such as active methylene compounds, oximes, lactams, phenols, alkylphenols, and basic nitrogen-containing compounds, and the isocyanate groups are regenerated by heating. Also included are printed isocyanate compounds.

Furthermore, as the isocyanate compound, it is also possible to use a mixture of several types of the above-mentioned isocyanate compounds, and it is also possible to use a mixture of the above-mentioned isocyanate compounds dissolved in a solvent.

The polyols used in the present invention include short chain polyols such as aliphatic, alicyclic, aromatic, substituted aliphatic or heterocyclic dihydroxy compounds, trihydroxy compounds,
Tetrahydroxy compounds, such as 1,2-ethanediol, 1,2-propanediol, 1,4-butanediol, butynediol, 1,6-ethanediol,
1.10-decamethylene diol, 2.5-dimethyl-
2,5-hexanediol, neopentyl glycol,
Diethyleneglyfur, 1,4-cyclohexane dimetatool, bis(β-human-xyethoxy)benzene, p
-xylene diol, dihydroxyethyltetrahytophthalate, trimethylolpropane, glycerin,
2-methylpropane-1,2,3-) diol, 1
, 2,6-hexanetriol, pentaerythritol, etc.

Long chain polyols include polyester polyol, polyether polyol, polycarbonate polyol,
Vinyl polyols, diene polyols, castor oil polyols, silicone polyols, polyolefin polyols, copolymers thereof, and the like are used.

These long chain polyols are preferably used in a molecular weight range of 3oo to 10,000, more preferably in a molecular weight range of 500 to 8,000.

Examples of polyester polyols include succinic acid, geltaric acid, 7-divic acid, azetuic acid, sebacic acid,
A dicarboxylic acid selected from dodecanoic acid, phthalic anhydride, inphthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, fumaric acid, itaconic acid, etc. and a hydroxy compound selected from the short chain polyols mentioned above. The product obtained by the reaction is used.

Another method for obtaining polyester polyols is β-propiolactone-1, Viva-p-tetra, δ-valerolactone, -1-caprolactone, methyl-C-caprolactone, dimethyl-1-caprolactone, trimethyl-1-
It is also possible to react a lactone compound such as caprolactone with a human-oxy compound selected from the short chain polyols mentioned above.

As the polyether polyol, polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polypropylene glycol, etc. are used.

As the polycarbonate polyol, one obtained by a transesterification method from a hydroxy compound selected from the short chain polyols mentioned above and diallyl carbonate, dialkyl carbonate, or ethylene carbonate is used. For example, poly-1,6-hexamethylene carbonate, poly-2,2'-bis(4-human-oxyhexyAe)propane carbonate, etc. are industrially produced and can be easily produced by nine people.

Another method to obtain polycarbonate polyol is
The so-called phosgene method (or solvent method) can be used.

In addition, vinyl polyols such as acrylic polyols obtained by copolymerizing acrylic esters with acrylic monomers having hydroxyl groups such as β-hydroxyethyl acrylate and β-human p-xylethyl methacrylate; 4-butadiene), poly(1,2-
Polybutadiene polyols such as (butadiene), castor oil polyols such as polypropylene glycol lysyllate, silicone polyols, polyolefin polyols, and the like are used.

It is also possible to use any number of the above-mentioned short-chain and long-chain polyols in combination.

Vinyl chloride used in the present invention is a vinyl chloride-containing polymer, such as a polyvinyl chloride homopolymer with a degree of polymerization of 600 or more, or a copolymer whose main component is beer chloride, such as vinyl chloride-vinyl acetate polymer, vinyl chloride- Examples include ethylene φ vinyl acetate copolymer. Additives such as stabilizers, lubricants, and colorants can be added to the polyvinyl chloride and the like in advance, if necessary.

In addition, in the present invention, a thermoplastic resin or rubber other than polyurethane that is compatible with the polyvinyl chloride, such as acrylic resin, styrene [1], ABS resin, nitrile rubber, etc., is blended with polyvinyl chloride in advance. You can also use

The amount of softener used in the present invention is generally P.
Preferably, the amount is 2 to 120% by weight relative to VC.

If the plasticizer as a whole exceeds 1205 by weight relative to PvC, it is important to obtain a powder with good flowability, depending on the amount and type of isocyanate compound and polyol used.

When using a sufficiently large amount of hexamethylene diisocyanate, which has good liquid properties, as an isocyanate compound, or when using an appropriate amount of poly-diethylene glyfur adipate, which has good compatibility with PvC and low viscosity, as a polyol, use A. It is also possible to omit the use of either the EWil agent when preparing the liquid or the B liquid.

The amount of isocyanate compound used in the present invention is determined by a ratio of NGO10H to the polyol added next.
The ratio is between 5 and 100, and the use varies depending on the required physical properties. For normal use, NGO10H ratio is 0.9
-1.2 is preferable, but when the NC010H ratio is 1.3 or more, excess NGO groups cause a crosslinking reaction and a structure similar to that of a thermosetting resin is obtained. NGO10H ratio: 10 or more Specific gravity: 0 or more Reactive NGO groups remain, which is undesirable
It is 0% or less. If it exceeds 100% by weight based on PvC, it will depend on the type of polyol used, but PvC will increase.
Adsorption to VC is incomplete, making it difficult to obtain powder with good fluidity.

In this III, PvC is impregnated with the above-mentioned liquids A and B, and additives such as stabilizers, lubricants, and in some cases, colorants and fillers are added using a glue pump blender, a Warner type Nygoo, and a Pony ξ Kisser. - A mixer such as a Henschel mixer can be used.

Powdered PvC is put into a mixer, and while stirring, the temperature of the powdered material is raised to 50 to 70°C, and Solution A is added. 50~
Stirring is carried out at 70° C. for 5 to 10 minutes, and after liquid A is completely absorbed, liquid B is added, and stirring is further carried out for 10 to 20 minutes.

Liquid B is impregnated to obtain a fluid powder. Next, additives such as stabilizers, lubricants, and in some cases colorants and fillers are added.

and mix evenly.

When adding liquids A and B, it is more convenient to keep them warm in advance;
Preferably, the temperature is 50 to 60°C and 70 to 90°C for each liquid.

100 to 12 if dry-up is slow after adding liquid B.
It is preferable to stir for about 10 minutes at a temperature of 0°C.

It is also possible to mix a urethane reaction catalyst such as dibutyltin dilaurate, a stabilizer for polyurethane, etc. in the B liquid in advance.

The thus obtained polyvinyl chloride composition of the present invention contains a polyurethane compound filled with an isocyanate compound as a polyurethane component and further sealed with a polyol that is the other polyurethane component and is stable against external factors. It is a powder with good fluidity that uses PVC as a carrier to contain ingredients.

The additives used in the present invention and added as necessary include stabilizers, lubricants, colorants, urethanization reaction catalysts, fillers, extenders, and the like.

〔Effect of the invention〕

The reactive molding composition thus prepared can be processed and molded in the same manner as ordinary PvC compounds, such as extrusion molding, injection molding, and calendering. It can also be used in blends with other PvC compounds and thermoplastic elastomers.

As is clear from the above description, the following effects can be obtained according to the present invention.

(Since gpvc and PU are homogenized and have a partially entangled chain structure, a composite with excellent heat-resistant shape retention, abrasion resistance, and low-temperature impact resistance can be obtained.

(2) Despite using a plasticizer such as DOP, it is possible to obtain a product that exhibits non-migration properties comparable to non-plastic mpvc.

0) Since the polyurethanization reaction progresses and is completed at the same time as molding, the process is simplified and the product can be provided at low cost.

(4) By using polyols or isocyanate compounds with a large number of functional groups, PvC and thermosetting PU
A complex with can also be obtained.

(5) Sem1-IPN formed by PVC and PU
(A structure in which linear polymers are intertwined in cross-linked poly(i)), it is possible to exhibit strong physical properties.

Utilizing these properties, the molding composition of the present invention can be used in many industrial fields as described above, but more specifically, for example, in the field of electric wire coating, the molding composition of the present invention can be used to improve the conventional molding composition. With this equipment, electric wires with excellent wear resistance, oil resistance, etc. can be manufactured, and moving electric wires or sheathed wires can be manufactured at low cost.

Furthermore, in the manufacture of shoe soles, there is a field in which a blend resin of PVC and PU is used, and since this process can be labor-saving, a product can be manufactured at a low total cost. Furthermore, as a thermoplastic elastomer that has both cold resistance and oil resistance, it is ideal for industrial use, for example, in the production of boots for slaughtering meat.

Furthermore, in the field of flooring materials and automobile parts, by using a thermosetting composition of the PU acid component, it is possible to provide a material with a high heat distortion temperature.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 (1) 1. Same ethylene diisocyanate (
A by mixing 20 parts by weight of HDI and 20 parts by weight of DOP.
All the liquid.

(2) 250 parts by weight of Niraporan-4010 (trade name manufactured by Nippon Polyurethane Industries KK, 1,4-butanediol adipate MW=2000) as a polyol and DOP80
30 parts by weight of organic tin malate and 0.3 parts by weight of dibutyltin dilaure were further added and mixed to prepare Solution B.

(3) 1000 parts by weight of polyvinyl chloride powder with a degree of polymerization of 1300 was added to the content of 2I! Pour the contents into a Warner Base Nigu and keep the temperature of the contents at 60°C while stirring. Solution A heated to about 55°C was added and stirred for 5 minutes.

The mixture became an easily flowable powder.

Further, while stirring this powder mixture, Solution B heated to 80° C. was added and mixed with stirring for 20 minutes.

The contents were then cooled to room temperature, 10 parts of powdered barium stearate were added, and stirred for 1 minute to obtain a powdered compound.

This compound was kneaded for 10 minutes with a heated roll at 150°C to form a sheet with a thickness of about 0.8 cm.

The compounding ratio of the compound, the temperature of the hot roll, and the measurement results of physical properties are summarized in Table 1 together with those of other Examples.

Example 2 42 parts by weight of MDI was used as liquid A, and DOP was used as liquid B.
A compound obtained in the same manner as in Example 1 using 200 parts by weight and 500 parts by weight of Niraporan-4070 (trade name, manufactured by Nippon Polyurethane Industry KK, 1,6-hexamethylene glycol 7 dipate type = ester MW = 2000) was prepared. A sheet was prepared using this material, and its physical properties were measured. Table 1 shows the results.
Shown below.

Example 3.4 A compound was prepared and a sheet was prepared in the same manner as in Example 1 except for using PvC with a degree of polymerization of 700 and changing the type of isocyanate compound and polyol.

The results are shown in Table 1.

The following isocyanate compounds and polyols were used.

6) Niraporan-4009 (Japan Polyurethane Industry KK
Product name: Polybutylene Glyfur 7 Dibate MW = 1000) (b) MTL-C (Japan Polyurethane Kogyo K11K product name: Liquefied methylene bisphenylene-4,4'-diincyane) NGO content 28.6% by weight) (→ Coronet)-EH ('Japan Polyurethane Industry KK
Product name: incyanurate trimer of hexamethylene diisocyanate; NCO content 21% by weight) (6) MDI (trade name, manufactured by Nippon Polyurethane Industries KK;
Hexamethylene diisocyanate) [Example 5] 11,000 tt of polyvinyl chloride powder with a degree of polymerization of 1,300 was put into a Henschel mixer, and the rotation speed was 1,000 rp.
While stirring and mixing at m, 30 parts by weight of organic tin malate was added, followed by 0 parts by weight of DOP IQ. Next, while maintaining the temperature of the mixture at 80°C, 150 weight of Tsunate-4048 (trade name manufactured by Nippon Polyurethane Kogyo KK; NGO content 6.1% by weight), which is a prepolymer for cast urethane elastomer, was heated to 80°C in advance. The mixture was mixed and stirred for 10 minutes. Next, Niraporan-150 (product name: diethylene glycol adipe, manufactured by Nippon Polyurethane Industries), which had been heated to SO'c in advance, was used. MW=l 00
0> was added in an amount of 110 parts by weight, and stirring and mixing were continued for 20 minutes. Next, after cooling the mixture to room temperature, 10 parts by weight of barium stearate was added and mixed with stirring to obtain a powdery compound. This powder was heat-sealed at 145° C. to prepare a sheet with 14 tR of tO molecules, and its physical properties were measured.

The results are shown in Table 1.

Comparative Examples 1 to 3 General vinyl chloride powder (Toyo Soda Kogyo KK brand name,
The stabilizer and the mobilizable agent were triblended using a Leune 8008K), a sheet was prepared using a heated roll, and the physical properties were measured. Table 1 shows the physical property measurement results along with the blending ratio and hot roll temperature.

[Comparative Example 4] 1000 parts by weight of polyvinyl chloride powder with a degree of polymerization of 1300 was added to an internal amount of 2I! 10 parts by weight of barium stearate and 30 parts by weight of organic tin malate were added while stirring at high speed, and the mixture was heated to 70°C. Next, 250 portions of Niraporan-4010 heated to 70°C was added, and the mixture was stirred and mixed for 10 minutes while maintaining the temperature of the mixture at 100°C. The mixture became an easily flowable powder mixture. Further, 22 parts by weight of tolylene diisocyanate was added to this powdered mixture while stirring, the temperature of the contents was raised to 110°C, stirring and mixing was continued for about 1 hour, and then the contents were cooled to obtain a powder. Ta. Brown particles, which appeared to be gelled urethane, were partially observed in the powder.

An attempt was made to make a sheet using idP gingerol at 170° C. using the obtained dung powder, but appropriate softening did not occur and a sheet could not be obtained.

Although a sheet was finally formed by raising the temperature of the mixing μm to 190° C., the resulting sheet turned black and had many cracks, making it impossible to measure its tensile properties.

Table 1 shows the measurement results of hardness, oil resistance weight change, and water absorption.

[Comparative Example 5] Polyvinyl chloride powder with a degree of polymerization of 700 was placed in a Henschel mixer and mixed by stirring at a rotational speed of 1000 rpffl for 2 minutes.

Next, 30 parts by weight of organic tin malate and stearic acid)
10 parts by weight of lithium was added.

The mixture in the mixer was then heated to 70°C with N-4
After adding 250 parts by weight of 010, the mixture was stirred and mixed for 100 minutes while keeping the temperature of the mixture at 100°C.

An easily flowable powder mixture was obtained. Furthermore, 20 parts by weight of hexamethylene diisocyanate was added to this powdered mixture while stirring, the temperature of the contents was raised to 110° C., and stirring and mixing were continued for about 1 hour.

The contents are then cooled to room temperature and powdered feces/(r)
I got an index. Brown particles thought to be urethane gel were observed in the middle of the powder.

Using the obtained compound, a sheet was prepared in a single molten glass at 170°C. A partially discolored gelled product (so-called fish eyes) was observed in the obtained sheet.

Physical properties were measured avoiding the fisheye area.

The measurement results are shown in Table 1.

The sheet physical properties shown in each example and comparative example were measured according to JIS-6301. [Example 6] α) Prepare liquid A by mixing 75 parts by weight of HDI and 100 parts by weight of DOP. did.

(2) Plaxel-L-220 (
Daicel Chemical Industries KK product name, polycarbonate polyol MW = 2000) 250 weight tS and trimethy-
A liquid B was prepared by mixing 30 parts by weight of lube bread and 700 parts by weight of DOP, and further adding 30 parts by weight of organic tin laurate and 0.3 parts by weight of dibutyltin dilaurate.

(3) A powder mixture was obtained in the same manner as in Example 1 using 1000 parts of polyvinyl chloride powder with a degree of polymerization of 1300. 100 parts by weight of light calcium carbonate was blended with this to prepare a powdered dung pound.

Using this compound, injection molding machine (Yamae Seiki K)
A sheet with a thickness of 3 m was prepared from 5AY-100B) manufactured by K.

Each physical property was measured using this sheet. The measurement results of physical properties are summarized in Table 2.

[Injection molding conditions]

The injection molding conditions are shown below.

Comparative example 6 Polyvinyl chloride powder ioo used in Example 6.

The weight part is the content lid 21! Pour into the Warner mold 2~Goo,
While stirring at about 100°C, 30 parts by weight of organotin malate, barium stearate totti, DOP 100
Blending is performed by sequentially adding 0 parts by weight. After drying up, 100 parts by weight of light calcium carbonate was added to obtain a soft PvC dung pound.

A sheet with a thickness of 3 cm was prepared in the same manner as in Example 3, and its physical properties were measured. Table 2 compares the measurement results of physical properties with Example 3.
(Note) xA5h7a: Resin 1118 (1℃, injection pressure 35~(tt2)) Difference between hardness at -20℃ and hardness at 25℃ (Note 3) JIS K 6301;
40°C x 22h = 7 Tori oil procedural amendment (voluntary) July 22, 1985 Michibe Uga, Commissioner of the Patent Office 1, Indication of the case 1985 Patent head @ 91243 2, Name of the invention Polyvinyl chloride -Production method of polyurethane molding composition 3, Relationship with the case of the person making the amendment Patent applicant address 2-8-5, Toranomon-chome, Minato-ku, Tokyo Number of inventions increased by the amendment None 6, Contrast of the amendment Scope of Claims and Detailed Explanation of the Invention Column 7 of the Specification, Contents of the Amendment As shown in the attached sheet, Amendment 1, page 7, line 6 of the specification, "...It was difficult to obtain..." Correct it to ``...it became difficult, but it was achieved...''.

λ Specification, page 14, lines 18 to 20, "4,4'-methylenebis(cyclohexyl isocyanate)" is corrected to "l,1'-methylenebis(4isocyanatocyclohexyl)."

3. In the first line of page 15 of the specification, "...etc. diisocyanate..." is corrected to "...etc. diisocyanate...".

4. Specification page 34, line 3 "Example 3..." is corrected to "Example 6...".

5. Specification page 34, line 1lJ, line 4 "...Example 3" is corrected to "...Example 6".

Claim 1: A polyvinyl chloride-polyurethane molding composition characterized in that powdered polyvinyl chloride, an isocyanate compound, a polyol, and optionally additives are blended in the presence of a liquid plasticizer. manufacturing method.

2. The method according to claim 1, wherein the mixing of the powdered polyvinyl chloride and the isocyanate compound and/or the powdered polyvinyl chloride and the polyol is carried out in the presence of a liquid plasticizer.

Claims (1)

[Scope of Claims] 1. A polyvinyl chloride-polyurethane molding composition characterized in that powdered polyvinyl chloride, an isocyanate compound, a polyol, and optionally additives are blended in the presence of a liquid plasticizer. How things are manufactured. 2. The method according to claim 1, characterized in that the mixing of powdered polyvinyl chloride and an isocyanate compound and/or powdered polyvinyl chloride and polyol is carried out in the presence of a liquid plasticizer.