JPH06263838A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To obtain a vinyl chloride resin compsn. having improved resistances to migration and extraction with gasoline. CONSTITUTION:This resin compsn. is obtd. by compounding 100 pts.wt. paste- forming vinyl chloride resin produced by emulsion or microsuspension polymn. with 30-70 pts.wt. mixture of a blocked polyisocyanate with a polyisocyanate in an equivalent ratio of 0.9-1.1 and, if necessary, 30 pts.wt. or lower plasticizer, and further a stabilizer, a filler, a blowing agent, etc. The compsn. is applied to a substrate, molded, and thermally cured to give a PVC-polyurethane composite molding.

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 which can be used as a substitute for plastisol or organosol, and a composite molded article obtained from the composition.

[0002]

2. Description of the Related Art Plastisols containing paste resins and plasticizers as main components, organosols containing diluents, and molded articles obtained from them are widely used in the paint industry, automobile industry, etc., and as building materials. ing. However, coating film molded articles and the like obtained from plastisol and organosol have many inconveniences due to the inclusion of a 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, there is a problem that if it is used for a long period of time, the plasticizing ability is lowered and the molded product becomes hard.

Further, plastisol in which polyvinyl chloride and polyurethane are mixed, plastisol in which polyisocyanate or polyisocyanate prepolymer and polyols are mixed with polyvinyl chloride, etc.
No. 24989, Japanese Patent Application Laid-Open No. 58-5357, Japanese Patent Application Laid-Open No. 3-9916, etc., all of these plastisols contain a plasticizer and have the above-mentioned various drawbacks. There is.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention are keen to find a vinyl chloride resin composition which can adopt a molding method similar to that of plastisol while avoiding the above-mentioned adverse effects caused by a plasticizer. As a result of repeated studies, they have found that a sol composition can be formed by using a paste resin, a blocked polyisocyanate and a polyol without using a plasticizer substantially, and have reached the present invention. That is, an object of the present invention is to use a molding method similar to that of plastisol without substantially using a plasticizer, and a vinyl chloride resin composition and oil resistance obtained from the composition, which is excellent in non-migration property. Another object is to provide a composite molded body.

[0005]

The gist of the present invention is, therefore, a paste-forming vinyl chloride resin (hereinafter referred to as a paste resin) obtained by an emulsion polymerization method or a fine suspension polymerization method, a blocked polyisocyanate. And a polyvinyl chloride-based resin composition containing a polyol as a main component, and a polyvinyl chloride-polyurethane-based composite molded body obtained by shaping the composition and then heating and solidifying the composition. Hereinafter, the present invention will be described in detail.

The paste resin, which is the first component of the composition of the present invention, is a fine vinyl chloride-based resin having a particle size of 3 μm or less, preferably 0.1 to 2 μm, produced by an emulsion polymerization method or a fine suspension polymerization method. Examples thereof include those obtained by usually spray-drying an aqueous dispersion liquid containing coalesced particles. The emulsion polymerization method includes, for example, vinyl chloride or a comonomer copolymerizable therewith, for example, a mixture of vinyl acetate, an alkyl (meth) acrylate, ethylene, propylene, etc., for polymerization of sodium lauryl sulfate, sodium dodecylbenzenesulfonate, etc. It is a method of polymerizing in the presence of an emulsifier and a water-soluble polymerization catalyst. Further, the fine suspension polymerization method, for example, a vinyl chloride or a mixture with a comonomer copolymerizable therewith, together with an emulsifier or a suspending agent and a vinyl chloride-soluble polymerization catalyst finely dispersed uniformly in a disperser such as a homogenizer. It is a method of polymerizing after stabilizing.

The blocked polyisocyanate, which is the second component of the composition of the present invention, is a known method using a polyisocyanate monomer with a blocking agent such as alcohols, phenols, oximes and lactams. Stabilized by blocking reaction with. Examples of the polyisocyanate monomer include tolylene-
2,4-diisocyanate, tolylene-2,6-diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 1-chlorophenylene-
2,4-diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-bistoluene-4,4'-diisocyanate, methylenebisphenylene-4,4'-diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc. These are used alone or in combination of two or more.

As the polyol which is the third component of the composition of the present invention, various polyols which are liquid at the time of heating can be used. The polyol preferably exhibits a liquid state at a temperature equal to or lower than the dissociation temperature of the blocked polyisocyanate, and is a normal temperature (25
It is more preferable that the liquid form is exhibited in the vicinity of (° C.). Even when a polyol that is not liquid at around room temperature is used, the composition can be easily prepared by using a composition preparation device equipped with appropriate heating equipment.

Examples of the type of the polyol include monomer polyols and polymer polyols such as polyether polyols and polyester polyols, and these can be used alone or in combination. Examples of the monomer polyol include 1,2-propanediol, 1,
2-butanediol, 1,3-butanediol, 1,4
-Butanediol, 3-methyl-1,5-pentanediol, trimethylolpropane and the like.

Examples of the polyether polyols include polyoxyalkylenes obtained by addition-polymerizing alkylene oxides such as ethylene oxide and propylene oxide with polyvalent active hydrogen compounds such as propylene glycol, glycerin, trimethylolpropane, pentaerythritol and diglycerin. In addition to polyols, polytetramethylene ether glycol and the like can be mentioned.

As the polyester polyol, for example, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5- Pentanediol, 2-ethyl-1,3-hexanediol, 2,2
Polyester polyol obtained by polycondensing glycol such as 4-trimethyl-1,3-pentanediol and dibasic acid such as succinic acid, glutaric acid, adipic acid, azelaic acid and sebacic acid, γ-butyrolactone, δ−
Examples thereof include polyester polyols obtained by ring-opening polymerization of lactones such as valerolactone and ε-caprolactone. Among the above polyols, polymer polyols are preferable, and polyester polyols are more preferable. It is preferable that these polymer polyols are liquid at room temperature (25 ° C.) and have low viscosity, and further, the average molecular weight thereof is preferably about 500 to 5,000.

The use ratio of the paste resin, the blocked polyisocyanate and the polyol in the composition of the present invention is usually 30 to 70 in total with respect to 100 parts by weight of the paste resin.
It is 0 part by weight, preferably 50 to 500 parts by weight. Then, the use ratio of the blocked polyisocyanate and the polyol is such that the equivalent ratio of the polyisocyanate monomer obtained by dissociation of the blocked polyisocyanate and the polyol is in the range of 0.9 to 1.1. Is desirable.

In the composition of the present invention, the above-mentioned first to third components are mixed in a known manner with auxiliary agents such as stabilizers, fillers and foaming agents which are usually added to vinyl chloride resins, if necessary. It can be prepared by uniformly mixing with a machine such as a pony mixer, a Hobart mixer, an internal mixer, a change can mixer, a kneader, and a crusher. 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 is volatilized during the molding process of the composition, it is possible to use a relatively large amount within the range where the performance of the molded product is not impaired. It is usually used in the range of 30 parts by weight or less per 100 parts by weight of the paste resin.

For the composition of the present invention, a molding method similar to that for plastisol or organosol can be adopted. For example, when the composition of the present invention is in the form of a sol, a polyvinyl chloride-polyurethane composite molded article is obtained by coating and shaping the composition on a substrate and then heating and heating to solidify.
The obtained composite molded article is preferably used for the same applications as molded articles obtained from plastisols and organosols.

[0015]

EXAMPLES Next, specific embodiments of 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 was tested as follows.

(1) Non-migration test Acrylonitrile-butadiene-styrene resin (hereinafter,
The composite molded body (sheet) is brought into close contact with the plate of ABS) and polystyrene resin (hereinafter referred to as PS), and a load of 1 is applied.
After applying kg / cm ² , the degree of contamination on each plate after standing for 4 days at a temperature of 70 ° C. was visually judged. The judgment result is displayed as follows. ○: 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 was shown as a percentage.

Examples 1 to 5 Each component having the composition shown in Table 1 was uniformly mixed to prepare a sol composition, which was defoamed and then coated on a release paper to a thickness of 0.5 mm at 180 ° C. After solidifying by heating for 10 minutes and cooling this, a test piece (sheet) of the composite molded body was obtained. The performance is shown in Table-2. Comparative Example 1 The same procedure as in Example 1 was carried out except that unblocked polyisocyanate monomer was used. The results are also shown in Table-2.

[0018]

[Table 1]

[0019]

[Table 2]

[0020]

INDUSTRIAL APPLICABILITY The vinyl chloride resin composition of the present invention can be formed by a molding method similar to that of plastisol or organosol even though it does not substantially contain a plasticizer. The molded product obtained by shaping and then heating and solidifying becomes a polyvinyl chloride-polyurethane composite molded product, which is non-migratory, resistant to gasoline extraction, etc. as compared to a vinyl chloride resin molded product containing a large amount of plasticizer. It has excellent properties and can be effectively used as a vehicle part molded product, an electric device part, or a building material.

Claims (4)

[Claims] 1. A vinyl chloride resin composition comprising a paste-forming vinyl chloride resin obtained by an emulsion polymerization method or a fine suspension polymerization method, a blocked polyisocyanate, and a polyol as main components. 2. The vinyl chloride resin composition according to claim 1, wherein the polyol is liquid at a temperature not higher than the dissociation temperature of the blocked polyisocyanate. 3. The vinyl chloride resin composition according to claim 1, wherein the composition is a sol. 4. A polyvinyl chloride-polyurethane composite molding, which is obtained by shaping the vinyl chloride resin composition according to any one of claims 1 to 3 and then solidifying it by heating.