JPH07304918A - Vinyl chloride paste resin composition - Google Patents

Abstract

PURPOSE:To obtain a vinyl chloride paste resin compsn. excellent, in heat- meltability at a low temp. of about, 130 deg.C by blending a vinyl chloride paste resin with a specific mixed plasticizer. CONSTITUTION:100 pts.wt. vinyl chloride paste resin is blended with (l) 50-150 pts.wt. mixed plasticizer comprising 95-50 wt.% didecyl phthalate mainly comprising di-2-propylheptyl phthalate and 5-50wt.% glycerol diacetate monolaurate, or (2) 50-150 pts.wt. mixed plasticizer comprising 95-50wt.% didecyl phthalate mainly comprising di-2-propylheptyl phthalate and 5-50wt.%, triphenyl phosphate or tricresyl phosphate. The average degree of polymn. of the vinyl chloride paste resin to be used is in the range of 2,500 to 4,000.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride paste resin composition excellent in low-temperature heat melting property and viscosity stability over time.

[0002]

2. Description of the Related Art A vinyl chloride paste resin composition is used to prepare a paste of vinyl chloride resin for use in a plastisol state.
It is prepared by mixing a plasticizer and other additives.
At present, vinyl chloride paste resin compositions that are widely used industrially have a vinyl chloride paste resin and a plasticizer having an average particle size of about 0.2 to 10 μm, usually about 1 to 3 μm as a basic composition, and further, if desired. , Heat stabilizer, filler,
It is obtained by mixing and stirring with a pigment and other compounding agents, and defoaming.

The above vinyl chloride paste resin composition is
The viscosity of the prepared plastisol is stable over time, it has excellent low-temperature heating and melting properties, and it has excellent fluidity and is easy to process and mold under conditions from the low shearing force range to the high shearing force range that it receives during processing. Is required.

The above vinyl chloride paste resin composition includes
As a plasticizer, di-2-ethylhexyl phthalate (DOP) has been generally used from the viewpoint of the balance between performance and price. However, when DOP is used, the stability over time of viscosity is poor, and there is a problem that the viscosity increases over time and molding becomes difficult.

Further, the vinyl chloride paste resin composition is usually heated and melted at 140 to 200 ° C. for use. However, in recent years, particularly in the case of heat molding of sealing materials for automobiles, underbody coating materials, etc., they are melted at a low temperature of about 130 ° C. in a short time, and the molded product also exhibits sufficient physical properties. I have been asked. Therefore, for the purpose of improving the meltability,
A vinyl chloride-vinyl acetate copolymer has come to be used as a resin. However, when such a resin having a good meltability is used, the plasticizer is absorbed by the resin even when left at room temperature, and the plasticizer becomes DOP. If so, the viscosity stability becomes worse.

In order to solve the above problems, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) and the like were used as plasticizers. However, the viscosity stability of DINP is not sufficient and the viscosity stability of DIDP is low. Although effective for improvement, there was a problem that the meltability was poor and it was difficult to develop sufficient physical properties when melted at low temperature in a short time.

Japanese Unexamined Patent Publication (Kokai) No. 6-9842 discloses a technique for solving this problem by using di-2-propylheptyl phthalate as a plasticizer. However, by using this plasticizer alone, plastisol The required performance, elongation, was inferior to DINP, and could not solve the problem.

[0008]

SUMMARY OF THE INVENTION In view of the above, the present invention provides a plasticizer containing di-2-propylheptyl phthalate as a main component, which has good viscosity stability over time.
It is an object of the present invention to provide a vinyl chloride paste resin composition having excellent heat melting property at a low temperature of about 0 ° C.

[0009]

The gist of the present invention is to provide 100 parts by weight of vinyl chloride paste resin and di-phthalate.
Didecyl phthalate 9 mainly composed of 2-propylheptyl 9
The vinyl chloride paste resin composition is composed of 50 to 150 parts by weight of a mixed plasticizer composed of 5 to 50% by weight and glycerin diacetomonolaurate of 5 to 50% by weight.

The vinyl chloride paste resin of the present invention is obtained by emulsion-polymerizing vinyl chloride or a mixture of vinyl chloride and a comonomer copolymerizable therewith in an aqueous medium in the presence of a water-soluble polymerization catalyst. , A fine suspension polymerization in the presence of an oil-soluble polymerization catalyst.

The comonomer copolymerizable with the vinyl chloride is not particularly limited, and examples thereof include vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; acryl such as methyl acrylate and ethyl acrylate. Acid esters; methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; maleic acid esters such as dimethyl maleate and diethyl maleate; fumaric acid esters; vinyl ethers such as isobutyl vinyl ether and phenyl vinyl ether; acrylonitrile, styrene , Vinylidene chloride and the like.

In the present invention, didecyl phthalate, which is mainly composed of di-2-propylheptyl phthalate, is used as a plasticizer. The di-2-propylheptyl phthalate is obtained by subjecting phthalic acid or phthalic anhydride and 2-propylheptanol to a dehydration condensation esterification reaction in the presence of a catalyst. In addition, the above-mentioned phthalic acid di-2-
Didecyl phthalate mainly containing propylheptyl can be obtained as a mixture of di-2-propylheptyl phthalate and didecyl phthalate other than di-2-propylheptyl phthalate. Didecyl phthalate other than di-2-propylheptyl phthalate can be obtained by an esterification reaction of phthalic acid or phthalic anhydride with decyl alcohol.

Examples of the decyl alcohol include:
4-methyl-2-propylhexanol, 2-methyl-
2-ethylheptanol, 5-methyl-2-propylhexanol, 2-isopropylheptanol, 4,4-
Dimethyl-2-propylheptanol and the like can be mentioned.

The above-mentioned mixture of decyl alcohols is obtained, for example, by preparing a mixture of n-valeraldehyde and 2-methylbutyraldehyde by an oxo reaction using butene-1, and subjecting these aldehydes to an aldol condensation and subsequent dehydration reaction. It can be synthesized by a hydrogenation reaction of the mixture. It is also possible, for example, to prepare the decyl alcohols separately and mix them.

Glycerin diacetomonolaurate used in the present invention is a kind of glycerin fatty acid ester,
It is an edible plasticizer that is also recognized as a food additive. The above-mentioned glycerin diacetomonolaurate has good penetrability into a vinyl chloride resin and has an effect of promoting low-temperature heat-meltability of plastisol.

The mixed plasticizer component which is a constituent of the vinyl chloride paste resin composition of the present invention comprises didecyl phthalate 95 to 5 mainly composed of di-2-propylheptyl phthalate.
0 wt% and glycerin diacetomonolaurate 5-5
It consists of 0% by weight.

If the amount of glycerin diacetomonolaurate is less than 5% by weight, sufficient physical properties cannot be obtained and 50% by weight is not obtained.
When it exceeds, the stability with time of viscosity is extremely deteriorated, so that the content is limited to the above range. Didecyl phthalate, which is mainly composed of di-2-propylheptyl phthalate, is preferably contained in an amount of 90 to 60% by weight.

The vinyl chloride paste resin composition of the present invention is prepared by uniformly mixing a vinyl chloride paste resin as a resin, didecyl phthalate mainly containing di-2-propylheptyl phthalate as a plasticizer, and glycerin diacetomonolaurate. Obtained. The mixing ratio is 50-150 mixed plasticizer with respect to 100 parts by weight of vinyl chloride paste resin.
Parts by weight. When the amount of the mixed plasticizer is less than 50 parts by weight, the meltability is insufficient, and when it exceeds 150 parts by weight, the viscosity stability is lost, and neither of the objects of the present invention can be achieved. It The blending amount of the mixed plasticizer is preferably in the range of 70 to 120 parts by weight.

In the vinyl chloride paste resin composition of the present invention, other plasticizers can be used in combination as long as 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 examples thereof include dibutyl phthalate (DBP), diheptyl phthalate (DHP), DOP, DINP, DIDP, diundecyl phthalate (DUP), dibutyl. Examples thereof include phthalic acid esters such as benzyl phthalate (BBP), adipic acid esters such as di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), and diisodecyl adipate (DIDA). The amount of the plasticizer used is preferably within 5% by weight of the total amount of the plasticizer.

If desired, various additives such as fillers, stabilizers, diluents, thickeners, adhesion promoters and pigments can be added to the vinyl chloride paste resin composition of the present invention. Further, other additives can be added as required. The vinyl chloride paste resin composition of the present invention can be used as a resin raw material that is heated and melted after being applied on a substrate.

The present invention 2 comprises a vinyl chloride paste resin composition, 100 parts by weight of a vinyl chloride paste resin having an average degree of polymerization of 2500 to 4000, and didecyl phthalate 95-containing mainly di-2-propylheptyl phthalate. Fifty
50 to 150 parts by weight of a mixed plasticizer consisting of 5 to 50% by weight of triphenyl phosphate or tricresyl phosphate.

If the average degree of polymerization of the vinyl chloride paste resin composition is less than 2500, the low-temperature heat-meltability is excellent, but the viscosity stability over time is poor, and if it exceeds 4000, the low-temperature heat-meltability is poor, so that it falls within the above range. Limited. It is preferably 3000 to 3500.

If the mixed plasticizer contains triphenyl phosphate or tricresyl phosphate in an amount of less than 5% by weight, sufficient physical properties cannot be obtained, and if it exceeds 50% by weight, the stability with time of viscosity is extremely poor. Is limited to the above range.

[0024]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 Vinyl chloride paste resin (straight, polymerization degree 110
0, ZEON 22, manufactured by Nippon Zeon Co., Ltd.), as a compounding plasticizer, 65 parts by weight of didecyl phthalate mainly containing di-2-propylheptyl phthalate, glycerin diacetomonolaurate (Poem G-002, Riken Vitamin Co., Ltd.) 15 parts by weight, a total of 80 parts by weight, and as a stabilizer, 2 parts by weight of Ba-Zn stabilizer (LTL-272, Nissan Ferro Co., Ltd.), epoxidized soybean oil (O-130).
P, manufactured by Asahi Denka Kogyo Co., Ltd.) was mixed, and the mixture was uniformly stirred and mixed by a raker machine, and then defoamed under vacuum to prepare a plastisol. The tensile test and viscosity measurement of this plastisol were carried out as follows, and the viscosity stability is shown in Table 1.

Physical Properties Test Plastisol was applied on a glass plate to a thickness of about 0.5 mm, heated and melted in a dryer kept at a temperature of 130 ° C. for 20 minutes, taken out, and cooled to obtain a test piece. A tensile test was performed on this test piece. Tensile test Viscosity measurement according to JIS K 6771 After preparing plastisol, immediately after leaving it in a constant temperature room at 23 ° C for 2 hours (hereinafter referred to as initial viscosity) and after leaving it at 40 ° C for 6 days, a B-type viscometer The viscosity was measured by (unit: centipoise). Viscosity stability (AI) [rotation speed 20 rpm, 40 ° C. × 6]
Viscosity after day] / [initial viscosity at 20 rpm].

Examples 2 and 3, Comparative Examples 1 to 6 Plastisols were prepared in the same manner as in Example 1 except that the mixing ratios and amounts of the compounding plasticizers shown in Table 1 were changed, and their physical properties were measured. It was shown to.

Example 4 100 parts by weight of a vinyl chloride paste resin having an average degree of polymerization of 3500 (straight, Zeon 43H, manufactured by Nippon Zeon Co., Ltd.), and didecyl phthalate 65 mainly containing di-2-propylheptyl phthalate as a plasticizer. 1 part by weight and 15 parts by weight of TPP (manufactured by Daihachi Chemical Industry Co., Ltd.) are added, and further, as a stabilizer, 2 parts by weight of a Ba-Zn stabilizer (LTL-272, manufactured by Nissan Ferro Co., Ltd.), epoxidized soybean oil (O 2 parts by weight (-130P, manufactured by Asahi Denka Kogyo Co., Ltd.), and the mixture was uniformly stirred and mixed by a raker machine, and then defoamed under vacuum to prepare a plastisol. The tensile test and viscosity measurement of this plastisol were carried out in the same manner as in Example 1, and the viscosity stability is shown in Table 2.

Examples 5 to 7 and Comparative Examples 7 to 13 Plastisols were prepared in the same manner as in Example 4 except that the mixing ratios and amounts of the compounding plasticizers shown in Table 2 were changed, and their physical properties were measured. It was shown to. In Table 2, a vinyl chloride paste resin having an average degree of polymerization of 3500 is ZEON 43 manufactured by Nippon Zeon Co., Ltd.
H, vinyl chloride paste resin with an average degree of polymerization of 3000
Kaneka Chemical Co., Ltd., Kaneka PSH-17, average degree of polymerization 2
The vinyl chloride paste resin of 800 is Kaneka PSH-24 manufactured by Kaneka Chemical Co., Ltd., and the vinyl chloride paste resin of average polymerization degree 1600 is ZEON 121 manufactured by Nippon Zeon.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

INDUSTRIAL APPLICABILITY According to the present invention, di-2 phthalate is used as a plasticizer.
-By using a plasticizer mainly composed of propylheptyl, and further using glycerin diacetomonolaurate as an additive, a vinyl chloride paste resin composition excellent in low-temperature heat melting property and viscosity stability over time is obtained as compared with the conventional one. be able to.

Claims (2)

[Claims] 1. A vinyl chloride paste resin 100 parts by weight,
And 50 to 150 parts by weight of a mixed plasticizer consisting of 95 to 50% by weight of didecyl phthalate mainly composed of di-2-propylheptyl phthalate and 5 to 50% by weight of glycerin diacetomonolaurate. Vinyl chloride paste resin composition. 2. 100 parts by weight of a vinyl chloride paste resin having an average degree of polymerization of 2500 to 4000 and di-phthalic acid
Didecyl phthalate 9 mainly composed of 2-propylheptyl 9
Mixed plasticizers 50 to 15 consisting of 5 to 50% by weight and triphenyl phosphate or tricresyl phosphate 5 to 50% by weight
A vinyl chloride paste resin composition comprising 0 parts by weight.