JPH05295251A - Vinyl chloride-based resin composition and complex molded product - Google Patents

Abstract

PURPOSE:To obtain a vinyl chloride-based resin composition capable of adopting a molding method similar to that of plastisol without substantially using a plasticizer and a complex molded product obtained from this composition and excellent in migration resistance, etc. CONSTITUTION:The objective vinyl chloride-based resin composition consists essentially of a vinyl chloride-based resin obtained by an emulsion-polymerization method or a fine suspension-polymerization method, a blocked urethane prepolymer and a polyol capable of exhibiting a liquid state at a temperature lower than the block dissociation temperature of the blocked urethane prepolymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition containing substantially no plasticizer for vinyl chloride resin and used as a substitute for plastisol or organosol, and a composite formed by molding the composition. ..

[0002]

2. Description of the Related Art Plastisols and organosols containing paste resin and a plasticizer as main components or molded articles obtained from them are widely used in the paint industry, the automobile industry and as a building material. However, coating film molded articles and the like obtained from plastisol and organosol have many inconveniences due to the plasticizer. For example, there is a drawback that the plasticizer bleeds onto the surface of a molded product, contaminates the molded product itself, and reduces the adhesive strength, and when used in an automobile or the like, it causes fogging. Further, if it is used for a long period of time, the plasticizing ability is lowered and the molded product becomes hard. Further, the inventions of plastisols in which polyvinyl chloride and polyurethane are mixed and plastisols in which polyvinyl chloride is mixed with polyisocyanate prepolymer and polyol are disclosed in Japanese Patent Publication No. 50-24989.
Although disclosed in JP-A-5357 and JP-A-3-9916, all of these inventions contain a plasticizer and have the above-mentioned various drawbacks.

[0003]

DISCLOSURE OF THE INVENTION The present inventor has made earnest studies on a vinyl chloride resin composition which can avoid the above-mentioned adverse effects caused by a plasticizer and can adopt a molding method similar to that of plastisol. The inventors have found that a sol composition can be formed by using a paste resin, a blocked urethane prepolymer and a liquid polyol without using a plasticizer, and arrived at the present invention. That is, the object of the present invention is to
(EN) It is an object to provide a vinyl chloride resin composition capable of adopting a molding method similar to that of plastisol without substantially using a plasticizer, and an oil-resistant and non-migrating excellent composite molded article obtained from the composition. ..

[0004]

Therefore, the gist of the present invention is to provide a vinyl chloride resin, a blocked urethane prepolymer and a block of the blocked urethane prepolymer obtained by an emulsion polymerization method or a fine suspension polymerization method. A vinyl chloride-based resin composition containing a polyol as a main component, which is in a liquid state at a temperature equal to or lower than a dissociation temperature, and a polyvinyl chloride-polyurethane composite molded article obtained by shaping the composition into a gel after heating. To explain the present invention in detail, a vinyl chloride resin is
Particle size 3μ manufactured by emulsion polymerization method or fine suspension polymerization method
Hereinafter, the so-called paste resin is usually obtained by spray-drying an aqueous dispersion containing 0.1 to 2 μm of fine vinyl chloride polymer particles.

The emulsion polymerization method includes, for example, vinyl chloride or a comonomer copolymerizable therewith, specifically vinyl acetate.
A method of polymerizing a mixture of alkyl (meth) acrylate, ethylene, propylene, etc. in the presence of an emulsifier for polymerization such as sodium lauryl sulfate, sodium dodecylbenzene sulfonate, etc. and a water-soluble polymerization catalyst. The legal method is to stabilize, for example, by finely dispersing a mixture of vinyl chloride or a comonomer copolymerizable therewith together with an emulsifying agent or a suspending agent and a vinyl chloride-soluble polymerization catalyst in a homogenizer or the like in a disperser such as a homogenizer. After that, it is a method of polymerizing. The blocked urethane prepolymer, which is one component of the composition of the present invention, is obtained by reacting a polyfunctional isocyanate with a polyol to form a terminal isocyanate compound, and the isocyanate compound is used as a blocking agent such as phenols, oximes, and lactams. It is one which is stabilized by performing a blocking reaction by a known method.

As the polyfunctional isocyanate, tolylene diisocyanate, phenylene diisocyanate, 1-
Chlorophenylene-2,4-diisocyanate, 1,5
-Naphthalene diisocyanate, 8,8'-bistoluene-4,4'-diisocyanate, methylenebisphenylene-4,4'-diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and the like, and one of these or Use two or more types together.

Examples of the polyol to be reacted with the above polyfunctional isocyanate include 1,2-butanediol, 2-methyl-1,3-propanediol and 3-methyl-1,5-.
Pentanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol and the like are used as glycol components, and succinic acid, glutaric acid,
Adipic acid, azelaic acid, polyester polyol reacted with a dibasic acid component such as sebacic acid, γ-valerolactone, γ-caprolactone, δ-valerolactone,
Examples thereof include ester polyols obtained by ring-opening polymerization of δ-caprolactone and the like, but are not particularly limited to the above, and these may be used alone or in combination. It is preferable that these polyols are liquid at room temperature (25 ° C.) and have a low viscosity, and the average molecular weight thereof is preferably about 500 to 5,000.

The proportion of the polyfunctional isocyanate and the polyol used for producing the blocked urethane prepolymer is in the range of 1.8 to 2.2 in terms of equivalent ratio, and the proportion of the blocking agent used is It may be a ratio that completely blocks free isocyanate groups. The obtained blocked urethane prepolymer is preferably liquid and has a block dissociation temperature of 80 ° C. or higher for the preparation of the composition of the present invention. The reason for using a blocked urethane prepolymer is that the isocyanate block is generally solid and difficult to sol, and when an unblocked urethane prepolymer is used, it reacts with the polyol to keep the sol viscosity constant. There is something that cannot be done.

Further, as the polyol which is in a liquid state at a temperature not higher than the block dissociation temperature of the blocked urethane prepolymer, which is another component of the composition of the present invention, the above-mentioned various polyols used in the production of the urethane prepolymer are used as they are. .. The melting point of the polyol added at the time of preparing the composition needs to be lower than the temperature in view of the block dissociation temperature of the blocked urethane prepolymer, and it is particularly desirable that it is liquid at around room temperature (25 ° C). By adding the liquid polyol, the blocked urethane prepolymer can be dissolved and the composition can be made into a sol. In addition, when using a composition preparation device having a heating facility, a polyol that is in a liquid state when heated can also be used. The use ratio of the vinyl chloride resin, the blocked urethane prepolymer and the polyol in the composition of the present invention is 30 to 30 parts by weight in total of the blocked polyurethane and the polyol with respect to 100 parts by weight of the vinyl chloride resin.
It is 700 parts by weight, preferably 50 to 500 parts by weight.
The ratio of the blocked polyurethane to the polyol used is preferably in the range of 0.9 to 1.1 in terms of equivalent ratio.

The composition of the present invention contains, in addition to the above-mentioned three components, a stabilizer, a filler, a foaming agent, and other auxiliary agents which are usually added to vinyl chloride resins, if necessary, in a known mixer, for example. It is prepared by uniformly mixing with a Banbury mixer, an intensive mixer, an intermix, a kneader, a continuous mixer, a V-type mixer, a twin-screw kneader, an extruder, a super mixer and the like. At the time of preparation, an organic solvent or a small amount of a plasticizer may be used together for the purpose of reducing the viscosity of the composition. Since the organic solvent volatilizes during the molding process of the composition,
A relatively large amount of the plasticizer can be used as long as the performance of the molded product is not impaired, but the plasticizer is limited in its use ratio in order to achieve the object of the present invention. For the composition of the present invention, a molding method similar to that for vinyl chloride resin can be adopted. For example, when the composition of the present invention is a sol, it is coated and shaped on a substrate, and then heated and heated to form a gel, whereby a polyvinyl chloride-polyurethane composite molded body is obtained.

[0011]

EXAMPLES Next, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist. The performance of the composite molded body produced from the composition of the present invention was tested as follows.

(1) Non-migratory test A composite molded body (sheet) is brought into close contact with an ABS and polystyrene (PSR) plate, a load of 1 kg / cm ² is applied, and a temperature of 70 ° C
The degree of contamination on each plate after being left at the temperature of 4 days was visually determined. ○: No pollution ○ ^x : Slightly polluted (2) Extraction amount of gasoline After immersing the composite molded article in gasoline at 23 ° C for 1 day,
It was dried at 80 ° C. for 4 hours, and the weight change of the composite molded article before and after the test was shown in percentage.

Examples 1 to 6 The compositions shown in the following Table 1 were prepared, defoamed, coated on a release paper to a thickness of 0.5 mm, melted and gelled at 180 ° C. for 10 minutes, and then cooled to form a composite. Molded specimen (sheet)
And The performance is shown in Table 2.

[0014]

[Table 1]

Comparative Example 1 Example 1 was repeated except that an unblocked urethane prepolymer was used. The results are also shown in Table 2.

[0016]

[Table 2]

[0017]

[Table 3] * 1 The polyol (A) of each Example is used as the raw material polyol * 2 1,2-BG: 1,2-butanediol 1,4-BG: 1,4-butanediol MPD: 3- Methyl-1,5-pentanediol NPG: Neopentyl glycol 1,6-HG: 1,6-hexanediol EHD: 2-Ethyl-1,3-hexanediol * 3 TDI: Tolylene diisocyanate HDI: Hexamethylene diisocyanate * 4 HBAE: 2-ethylhexyl P-hydroxybenzoate MEKO: Methylethylketoxime * 5 Urethane reaction proceeds when (A) and (B) are mixed, and cannot be operated thereafter

[0018]

INDUSTRIAL APPLICABILITY The vinyl chloride resin composition of the present invention can employ the same molding method as that of plastisol or organosol even though it does not contain a plasticizer, and the composition is heated after shaping. The molded product obtained by gelling becomes a polyvinyl chloride-polyurethane composite molded product, which is superior in properties such as non-migratory property and resistance to gasoline extraction to vinyl chloride resin molded products, and can be used as a molded product for vehicle parts such as electrical products. It can be effectively used as a device part or a building material.

Claims (4)

[Claims] 1. A main component is a vinyl chloride resin obtained by an emulsion polymerization method or a fine suspension polymerization method, a blocked urethane prepolymer, and a polyol which is in a liquid state at a temperature not higher than the block dissociation temperature of the blocked urethane prepolymer. And a vinyl chloride resin composition. 2. The vinyl chloride resin composition according to claim 1, wherein the polyol is liquid at a temperature of 25 ° C. 3. The vinyl chloride resin composition according to claim 1, which is a sol composition. 4. A polyvinyl chloride-polyurethane composite molded article obtained by shaping the vinyl chloride resin composition according to claim 1, 2 or 3 into a gel after heating.