JPH07304920A - Vinyl chloride paste resin composition - Google Patents

Abstract

PURPOSE:To provide a vinyl chloride paste resin compsn. having an excellent heat meltability at a temp. of as low as about 130 deg.C while utilizing a good viscosity stability even after the elapse of time of a plasticizer composed mainly of di-2-propylheptyl phthalate. CONSTITUTION:A vinyl chloride paste resin compsn. comprising: 100 pts.wt. mixed vinyl chloride paste resin comprising 70 to 5wt.% vinyl chloride paste resin having an average particle diameter of 0.1 to 0.5mum and 30 to 95wt.% vinyl chloride paste resin having an average particle diameter of 1 to 3mum; and 50 to 150 pts.wt. didecyl phthalate composed mainly of di-2-propylheptyl phthalate.

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 a vinyl chloride paste resin 70 having an average particle diameter of 0.1 to 0.5 μm.
To 5 wt% and 30 to 95 wt% of a vinyl chloride paste resin having an average particle size of 1 to 3 μm, and 100 parts by weight of a mixed vinyl chloride paste resin, and didecyl phthalate 50 mainly containing di-2-propylheptyl phthalate. ~ 15
This is because the vinyl chloride paste resin composition is composed of 0 parts by weight.

The mixed vinyl chloride paste resin which is a constituent of the vinyl chloride paste resin composition of the present invention is a vinyl chloride paste resin 70 having an average particle diameter of 0.1 to 0.5 μm.
˜5% by weight and 30 to 95% by weight of vinyl chloride paste resin having an average particle size of 1 to 3 μm.

If the vinyl chloride paste resin having an average particle diameter of 0.1 to 0.5 μm exceeds 70% by weight, the stability with time of viscosity is poor, and if it is less than 5% by weight, sufficient physical properties cannot be obtained. If the vinyl chloride paste resin having an average particle diameter of 1 to 3 μm is less than 30% by weight, the stability with time of viscosity is poor, and if it exceeds 95% by weight, the physical properties are deteriorated, so that the content is limited to the above range. Preferably, the average particle size is 0.1 to 0.
The vinyl chloride paste resin of 5 μm is 40 to 10% by weight,
Vinyl chloride paste resin with an average particle diameter of 1 to 3 μm is 60
Is about 90% by weight.

The vinyl chloride paste resin of the present invention is prepared 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 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 whose main component is 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.

Didecyl phthalate, which is mainly composed of di-2-propylheptyl phthalate, is di-2 phthalate.
It can be obtained as a mixture of propylheptyl 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, other decyl alcohol, etc. are mentioned.

The 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.

The vinyl chloride paste resin composition of the present invention comprises the above-mentioned mixed vinyl chloride paste resin as a resin, didecyl phthalate mainly containing di-2-propylheptyl phthalate as a plasticizer, glycerin diacetomonolaurate and the like. Obtained by mixing uniformly. The mixing ratio is 50 to 150 parts by weight of the mixed plasticizer with respect to 100 parts by weight of the mixed vinyl chloride paste resin. The mixed plasticizer is 50
If it is less than 1 part by weight, the meltability will be insufficient, and if it exceeds 150 parts by weight, the viscosity stability will be lost, and the object of the present invention cannot be achieved in either case, so the content is limited to the above range. 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 other than didecyl phthalate used is 20% by weight of the total amount of the plasticizer.
It is preferably within.

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 has an average particle diameter of 0.1 to 0.5 μm.
m vinyl chloride paste resin 45 to 10% by weight, average particle diameter 1 to 3 μm vinyl chloride paste resin 40 to 60% by weight, and average particle diameter 10 to 50 μm vinyl chloride paste resin 5 to 30% by weight mixed vinyl chloride It is a vinyl chloride paste resin composition containing 50 to 150 parts by weight of didecyl phthalate, which is mainly composed of di-2-propylheptyl phthalate, based on 100 parts by weight of the paste resin.

If the vinyl chloride paste resin having an average particle diameter of 0.1 to 0.5 μm of the vinyl chloride paste resin composition exceeds 45% by weight, the stability with time of viscosity is poor, and if it is less than 10% by weight, it is sufficient. If the vinyl chloride paste resin having an average particle diameter of 1 to 3 μm is less than 40% by weight, sufficient physical properties cannot be obtained, and if it exceeds 60% by weight, viscosity stability with time is poor, and , Average particle size 10-5
If the vinyl chloride paste resin of 0 μm is less than 5% by weight, the stability with time of viscosity is poor, and if it exceeds 30% by weight, the physical properties are deteriorated, so the content is limited to the above range. Preferably,
Vinyl chloride paste resin having an average particle diameter of 0.1 to 0.5 μm is 40 to 30% by weight, vinyl chloride paste resin having an average particle diameter of 1 to 3 μm is 45 to 55% by weight, and an average particle diameter is 10
The vinyl chloride paste resin of ˜50 μm is 10 to 20% by weight.

The vinyl chloride paste resin composition of the present invention 2 is a mixed vinyl chloride paste resin as a resin, didecyl phthalate mainly containing di-2-propylheptyl phthalate as a plasticizer, glycerin diacetomonolaurate, etc. Is evenly mixed to obtain. The mixing ratio is 50 to 150 parts by weight of the mixed plasticizer with respect to 100 parts by weight of the mixed vinyl chloride paste resin. The mixed plasticizer is 50
If it is less than 1 part by weight, the meltability will be insufficient, and if it exceeds 150 parts by weight, the viscosity stability will be lost, and the object of the present invention cannot be achieved in either case, so the content is limited to the above range. The blending amount of the mixed plasticizer is preferably in the range of 70 to 120 parts by weight.

[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 80 parts by weight of didecyl phthalate, which is mainly composed of di-2-propylheptyl phthalate, was mixed with a vinyl chloride paste resin (straight, degree of polymerization 1000, trademark ZEON trademark) having an average particle diameter of 0.20 μm as a compounding resin. 43F, made by Nippon Zeon Co., Ltd.) and 33.3 parts by weight of vinyl chloride paste resin having an average particle diameter of 1.70 μm (straight, polymerization degree 1100,
Trademark Zeon 22, manufactured by Nippon Zeon Co., Ltd.) Resin mixed with 67.7 parts by weight, a total of 100 parts by weight, and as a stabilizer, 2 parts by weight of Ba-Zn stabilizer (trademark LTL-272, manufactured by Nissan Ferro Co., Ltd.) Part, epoxidized soybean oil (trademark O-13
2 parts by weight (0P, 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. Tensile tests and viscosity measurements were performed on these plastisols, 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, the one left for 2 hours in a constant temperature room at 23 ° C (hereinafter referred to as initial viscosity) and the one left for 6 days at 40 ° C were measured with a B-type viscometer. Measure viscosity with (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, 2, 3, 4 and 5 Plastisols were prepared in the same manner as in Example 1 except that the compounded resin agents and plasticizers shown in Table 1 were used, and their physical properties were measured. The results are shown in Table 1.

Example 4 80 parts by weight of didecyl phthalate mainly consisting of di-2-propylheptyl phthalate was mixed with a vinyl chloride paste resin (straight, degree of polymerization 1000, trademark ZEON under the trade name of ZEON as a compounding resin and an average particle diameter of 0.20 μm). 43F, manufactured by Zeon Corporation), 35 parts by weight, 50 parts by weight of vinyl chloride paste resin (straight, polymerization degree 1100, trademark Zeon 22, manufactured by Nippon Zeon) having an average particle diameter of 1.70 μm, and chloride having an average particle diameter of 20 μm. Vinyl paste resin (straight,
Polymerization degree 1200, trademark ZEON 52, manufactured by ZEON CORPORATION) 1
Resin mixed with 5 parts by weight, a total of 100 parts by weight was added, and as a stabilizer, a Ba-Zn stabilizer (trade name LTL-2
72, manufactured by Nissan Ferro Co., Ltd.) and 2 parts by weight of epoxidized soybean oil (trademark O-130P, manufactured by Asahi Denka Kogyo Co., Ltd.) were mixed and uniformly mixed with a raider machine, and then defoamed under vacuum. Then, plastisol was prepared. Tensile test and viscosity measurement of these plastisols were carried out to determine the viscosity stability in Example 1.
The measurement was carried out in the same manner as above, and the results are shown in Table 2.

Examples 5, 6 and 7, Comparative Examples 6, 7, 8
9 and 10 A plastisol was prepared in the same manner as in Example 4 except that the compounded resin agent and the plasticizer shown in Table 1 were used, and the physical properties thereof were measured.

As is clear from these Examples and Comparative Examples, it was found that the vinyl chloride paste resin composition of the present invention has improved physical properties as compared with the plastisol containing only di-2-propylheptyl phthalate. .

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

INDUSTRIAL APPLICABILITY The present invention uses vinyl chloride paste resins having different average particle sizes and uses di-2-phthalic acid as a plasticizer.
Since a plasticizer containing propylheptyl as a main component is used, a vinyl chloride paste resin composition having better low-temperature heat melting property than before can be obtained.

Claims (2)

[Claims] 1. 70 to 5% by weight of a vinyl chloride paste resin having an average particle size of 0.1 to 0.5 μm and an average particle size of 1 to 3.
100 parts by weight of a mixed vinyl chloride paste resin consisting of 30 to 95% by weight of a vinyl chloride paste resin of μm, and
A vinyl chloride paste resin composition comprising 50 to 150 parts by weight of didecyl phthalate, which is mainly composed of di-2-propylheptyl phthalate. 2. A vinyl chloride paste resin having an average particle size of 0.1 to 0.5 μm, 45 to 10% by weight, and an average particle size of 1 to 3.
40 to 60% by weight of vinyl chloride paste resin of 5 μm and 5 to 5 μm of vinyl chloride paste resin of 10 to 50 μm average particle diameter
Mixed vinyl chloride paste resin 100 consisting of 30% by weight
A vinyl chloride paste resin composition comprising 50 parts by weight and 50 to 150 parts by weight of didecyl phthalate mainly composed of di-2-propylheptyl phthalate.