JPH0616888A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To obtain a vinyl chloride resin compsn. which can gel at a low temp. and has an improved balance between the stability of viscosity during aging and melting properties by compounding a vinyl chloride resin with 2- propylheptyl benzyl phthalate which has a good compatibility with the resin. CONSTITUTION:100 pts.wt. vinyl chloride resin is compounded with 30-400 pts.wt. 2-propylheptyl benzyl phthalate to give the compsn. The phthalate is obtd. by the esterification of a mixture of about equimolar amts. of phthalic acid (anhydride), 2-propylheptanol, and benzyl chloride in the presence of an amine catalyst.

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 having good compatibility with a vinyl chloride resin and containing a novel plasticizer suitable for a vinyl chloride paste resin.

[0002]

2. Description of the Related Art Conventionally, di-2-ethylhexyl phthalate (DOP) has been widely and generally used as a plasticizer for soft vinyl chloride resins from the viewpoint of performance and price balance. However, the soft vinyl chloride resin using DOP is
If it is not molded at a heating temperature of 180 ° C. or higher, sufficient physical properties cannot be exhibited. Particularly in the case of vinyl chloride plastisol, it is desired that the viscosity stability with time is good and that sufficient physical properties be exhibited by molding at a lower heating temperature.

For example, a so-called plastisol, in which a vinyl chloride paste resin is uniformly dispersed in a plasticizer, is widely used for molding a sealing material or an underbody coating material for automobiles, wallpaper, flooring material, gloves and the like. .
The plastisol is heated and melted after being spray-applied to a base material in a sealing material or an underbody coating material for automobiles by a spray or the like. Further, in wallpaper, flooring, etc., a mold is soaked in plastisol to form a shape in boots, gloves, etc. by a spread coating method, and then heated and melted.

When DOP is used as a plasticizer, the melting property of the resin upon heating is poor, so that 1 is required for the development of sufficient physical properties.
It requires a heating temperature of 80 ° C. or higher, and has a drawback that the burden of energy cost is large. In order to reduce the energy cost, that is, in order to exhibit sufficient physical properties even at low temperature, a vinyl chloride / vinyl acetate copolymer is used in recent years to improve the meltability of the resin when heated. .

However, even when a vinyl chloride / vinyl acetate copolymer is used, the object cannot be sufficiently achieved. For the purpose of improving the meltability, for example, dibutyl phthalate (DBP), isononylbenzyl phthalate (I
NBP) and other benzyl group-containing plasticizers such as alkylbenzyl phthalate are used. However, in plastisols using these plasticizers, the viscosity stability becomes poor and the viscosity increases with time, and However, a plasticizer satisfying both viscosity stability and meltability could not be found.

[0006]

DISCLOSURE OF THE INVENTION The present invention has good compatibility with a vinyl chloride resin, can be gelated at a relatively low temperature during molding, and has various physical properties such as strength as gelled at high temperature. As a result of diligent studies on a vinyl chloride resin composition exhibiting the above, it was found that the above-mentioned object can be achieved by using 2-propylheptylbenzyl phthalate as a plasticizer, and the plasticizer is particularly effective when used in plastisol. I knew it was.

That is, the object of the present invention is to have a good compatibility with vinyl chloride resins, to be able to gel at low temperatures, and to have a good balance of viscosity stability with time and meltability when used in plastisols. A vinyl-based resin composition is provided.

[0008]

The gist of the present invention resides in a vinyl chloride resin composition containing vinyl chloride resin and 2-propylheptylbenzyl phthalate as main components. The present invention will be described in detail. The vinyl chloride resin, which is the resin component of the vinyl chloride resin composition of the present invention, is, for example, a mixture of vinyl chloride or a comonomer copolymerizable therewith in an aqueous medium in the presence of a dispersant and an oil-soluble polymerization initiator. Is a polymer obtained by suspension polymerization, or a so-called vinyl chloride paste resin obtained by emulsion polymerization or fine suspension polymerization in the presence of an emulsifier and a water-oil polymerization initiator or an oil-soluble polymerization initiator. . The polymer obtained by suspension polymerization is a polymer having a porous particle size of several tens of μm to several hundreds of μm and has good plasticizer absorbability, and even if the same amount of plasticizer as the polymer is mixed at room temperature. It exists in powder form. On the other hand, the paste resin usually has a particle size of 5 μm or less, mainly 2 μm or less, does not absorb the plasticizer so much at room temperature, and exhibits a sol state with a small amount of the plasticizer.

Examples of the comonomer copolymerizable with vinyl chloride include vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate, acrylic acid esters such as methyl acrylate and ethyl acrylate, and methacrylic acid. Methyl acid, methacrylic acid esters such as ethyl methacrylate, dimethyl maleate, maleic acid esters such as diethyl maleate, fumaric acid esters, vinyl ethers such as isobutyl vinyl ether, phenyl vinyl ether, acrylonitrile, styrene, vinylidene chloride, etc. Can be mentioned.

The plasticizer, which is one of the components of the present invention, is subjected to an esterification reaction in a substantially equimolar mixture of phthalic acid or phthalic anhydride, 2-propylheptanol and benzyl chloride in the presence of an amine catalyst according to a conventional method. 2-propylheptylbenzyl phthalate produced by carrying out. 2-Propylheptanol is, for example, butene-1.
Is converted into n-valeraldehyde by oxo reaction, and n
It can be produced by hydrogenating 2-propylheptenal obtained by aldol condensation of valeraldehyde and dehydration reaction of the reaction product.

The vinyl chloride resin composition of the present invention is obtained by uniformly mixing a vinyl chloride resin and 2-propylheptylbenzyl phthalate. The mixing ratio of the vinyl chloride resin and 2-propylheptylbenzyl phthalate is selected from the range of 30 to 400 parts by weight, preferably 50 to 200 parts by weight with respect to 100 parts by weight of the former. When the vinyl chloride resin composition is plastisol, a part of the vinyl chloride paste resin having a particle size larger than that of the paste resin is used, for example, to reduce the viscosity of the plastisol.
It may be replaced with a so-called vinyl chloride cleansing resin of about 40 μm.

Further, the composition of the present invention can be used in combination with other plasticizers within the range where the effects of the present invention are not impaired. The plasticizer is not particularly limited as long as it is used for vinyl chloride resins, and specifically includes dibutyl phthalate (DBP) and diheptyl phthalate (DH).
P), DOP, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), BBP, phthalate esters such as di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA). ), Isodecyl adipate (D
Examples thereof include adipic acid esters such as IDA), phosphoric acid esters, and the like.

Further, various additives such as fillers, stabilizers, diluents, thickeners, colorants, adhesion promoters and the like can be added to the composition of the present invention as required. Of course, other additives can be added as required. The vinyl chloride resin composition of the present invention is prepared by uniformly mixing the vinyl chloride resin, 2-propylheptylbenzyl phthalate and, if necessary, the above-mentioned various additives by a conventional method. For example, when 2-propylheptylbenzyl phthalate is mixed with a vinyl chloride resin produced by the suspension polymerization method with a high-speed mixer, 2-propylheptylbenzyl phthalate is absorbed by the vinyl chloride resin and becomes drylen. May be directly used as a raw material for molding such as injection molding, extrusion molding, calendering, or the dry blended product may be once pelletized and subjected to the above-mentioned various molding methods. When 2-propylheptylbenzyl phthalate is mixed with paste resin, it easily becomes plastisol,
The plastisol is applied to an automobile and melted by heating to be used as an automobile sealing material or an underbody coating material,
Alternatively, it can be used as a resin raw material for wallpaper, flooring, etc., which is applied on a substrate by various methods and then heated and melted, or as a resin raw material for immersion processing of boots, gloves, etc.

[0014]

EXAMPLES Next, the vinyl chloride resin composition of the present invention will be described in detail with reference to Examples.
The present invention is not limited to the following examples. The composition of the present invention was evaluated by plastisol. The test method for plastisol is as follows.

Viscosity of plastisol: After preparing plastisol, the viscosity at the time of standing at 40 ° C. for 3 hours and 3 days is B
Measured with a viscometer (unit: poise). Viscosity stability (AI): viscosity after 3 days / viscosity after 3 hours
Expressed as Measurement of physical properties: Plastisol was applied on a glass plate to a thickness of about 1 mm, and then heated and melted for 20 minutes in a dryer kept at 140 ° C and 160 ° C, taken out and cooled to obtain a test piece. About this test piece, JIS K 7
A tensile test was performed based on 113.

Of 2-propylheptylbenzyl phthalate
2-Propylheptanol 1.0 per mole of synthetic phthalic anhydride
1 mol and 1.01 mol of benzyl chloride are mixed,
1.03 mol of triethylamine was added dropwise in about 5 minutes.
During this time, the temperature was naturally raised to 80 ° C. Then, when heated up to 100 ° C., spontaneous heat is generated again, and after reaching 120 ° C., the mixture is kept at 120 ° C. for 2 hours while being cooled and reacted. Water was poured into the reaction completed liquid (slurry) to dissolve the solid (triethylamine hydrochloride), oil-water separation was performed, and then alkali washing and water washing were performed, and then excess alcohols were removed by steam distillation. Then, it was dehydrated and filtered to produce 2-propylheptylbenzyl phthalate.

Example 1 and Comparative Examples 1 to 3 100 parts by weight of vinyl chloride paste resin (trademark Vinca P-500, manufactured by Mitsubishi Kasei Vinyl Co., Ltd.) was added to the above-mentioned 2-propylheptylbenzyl phthalate and phthalic acid 2 respectively.
80 parts by weight of ethylhexylbenzyl and isononylbenzyl phthalate were blended, uniformly stirred and mixed by a crusher, and then defoamed under vacuum to prepare a plastisol. The viscosities of these plastisols and the tensile test were measured and shown in Table 1 together with the viscosity stability.

[0018]

[Table 1]

As is clear from these Examples and Comparative Examples, the plastisol of the present invention has better viscosity stability over time than those using a plasticizer having an alkyl group other than 2-propylheptyl group, and It can be seen that the tensile strength in low-temperature melting is also significantly superior to that using DOP.

[0020]

INDUSTRIAL APPLICABILITY The vinyl chloride resin composition of the present invention uses novel 2-propylheptylbenzyl phthalate as a plasticizer, and the plasticizer has good compatibility with the vinyl chloride resin, The resin composition can be melt-gelled at a low temperature, and the obtained molded product has the same strength as the molded product obtained by melt-gelling at a high temperature using a general-purpose plasticizer such as DOP. Further, the plastisol using the plasticizer has a low viscosity and is excellent in viscosity stability over time.

Claims (3)

[Claims] 1. A vinyl chloride resin composition comprising a vinyl chloride resin and 2-propylheptylbenzyl phthalate as main components. 2. The vinyl chloride resin composition according to claim 1, wherein the vinyl chloride resin is a vinyl chloride paste resin. 3. The vinyl chloride resin composition according to claim 1, which is a plastisol or an organosol.