JPH083401A - Plastisol composition - Google Patents

Abstract

PURPOSE:To improve long-term stability of viscosity, melting ability by low- temperature heating, tensile strength and elongation by incorporating a vinyl chloride paste resin and a specific plasticizer and penetration accelerator. CONSTITUTION:Phthalic acid (anhydride) and a mixed decyl alcohol composed mainly of 2-propylheptanol are subjected to dehydration condensation/ esterification in the presence of an acid to obtain a plasticizer (B) comprising a didecyl phthalate composed primarily of di-2-propylheptyl phthalate. This composition is prepared by mixing 100 pts.wt. vinyl chloride paste resin (A), 50-120 pts.wt. component (B), and 5-30 pts.wt. at least one penetration accelerator (C) selected from among N,N-dimethylformamide, diethyl sulfate and an ethyleneamine of the formula, H2N(CH2CH2NH)nH (wherein n is 2-5).

Description

Detailed Description of the Invention

[0001]

This invention relates to plastisol compositions.

[0002]

2. Description of the Related Art Generally, a plastisol comprising a vinyl chloride paste resin and a plasticizer, and a compounding agent such as a heat stabilizer, a filler and a pigment is widely used as a sealing material for automobiles. ) It has excellent fluidity and can be easily molded, (2) its viscosity is stable over time,
(3) Performance such as excellent low temperature heating and melting property is required.

Conventionally, as a plasticizer used for plastisols, di-2-ethylhexyl phthalate (DOP) has been generally used because of its excellent balance between performance and price. However, the plastisol using DOP has a problem that the stability with time is poor, the viscosity increases with time, and molding becomes difficult.

Further, in recent years, heat molding tends to be carried out at low temperature and in a short time, so that a molded product is also required to have sufficient physical properties. Therefore, a vinyl chloride-vinyl acetate copolymer is often used for the purpose of improving the meltability, but even in this case, when left at room temperature, the plasticizer is absorbed by the resin and the DOP
Then, the temporal stability is further reduced. Therefore, diisononyl phthalate, diisodecyl phthalate, and the like were used as plasticizers replacing DOP. These also improved the stability over time, but did not have sufficient heat-meltability at low temperatures.

In order to solve the above problems, it is disclosed that di-2-propylheptyl phthalate is used as a plasticizer (Japanese Patent Laid-Open No. 9842/1994), but only di-2-propylheptyl phthalate is used. However, it was still insufficient to improve the low-temperature heat-meltability, and the physical properties were not good, such as poor plastisol elongation.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks, and an object thereof is to have good viscosity stability over time, excellent low-temperature heat melting property, tensile strength and elongation. An object is to provide a plastisol composition having excellent physical properties.

[0007]

The plastisol composition of the present invention comprises a vinyl chloride paste resin, a plasticizer made of didecyl phthalate mainly containing di-2-propylheptyl phthalate, and a penetrating additive.

The above vinyl chloride paste resin is, for example,
Obtained by a method such as emulsion polymerization of vinyl chloride or a mixture with a comonomer copolymerizable therewith in an aqueous medium in the presence of a water-soluble polymerization catalyst, fine suspension polymerization in the presence of an oil-soluble polymerization catalyst, and the like. .

Examples of the comonomer include vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; acrylic acid esters such as methyl acrylate and ethyl acrylate; methyl methacrylate and ethyl methacrylate. Methacrylic acid esters such as;
Examples thereof include 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.

The above-mentioned didecyl phthalate can be obtained by subjecting phthalic acid or phthalic anhydride and mixed decyl alcohol mainly containing 2-propylheptanol to dehydration condensation esterification reaction in the presence of a catalyst.

Other decyl alcohols other than the mixed decyl alcohol containing 2-propylheptanol phthalate as a main component include, for example, 4-methyl-2-propylhexanol, 5-methyl-2-propylhexanol and 2-methyl-2-propylhexanol.
Methyl-2-ethylheptanol, 2-isopropylheptanol, 4,4-dimethyl-2-propylheptanol and the like can be mentioned.

The method for producing the mixed decyl alcohol is
The mixture is not particularly limited, and for example, a mixture of n-valeraldehyde and 2-methylbutyraldehyde is produced by an oxo reaction using butene-1, and the mixture obtained by aldol condensation of these aldehydes and the subsequent dehydration reaction. Examples thereof include a method of synthesizing by hydrogenation reaction, a method of separately preparing and mixing each, and the like.

In the composition of the present invention, when the amount of didecyl phthalate, which is mainly composed of di-2-propylheptyl phthalate, decreases, the fluidity of plastisol decreases, and when the amount of didecyl phthalate increases, the physical properties, particularly tensile strength, decrease. It is limited to 50 to 120 parts by weight, preferably 60 to 100 parts by weight, relative to 100 parts by weight of the paste resin.

The above-mentioned penetrating additive is at least one selected from the group consisting of N, N-dimethylformamide, diethyl sulfate and ethyleneamines represented by the following general formula (I). It has good penetrability and has the effect of promoting the low-temperature heat-meltability of plastisol.

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When the number of n in the general formula (I) of the above-mentioned ethyleneamines is small, it has a low boiling point, so that it is volatilized when it is heated and melted, and when it is large, the compatibility with the plasticizer deteriorates. Limited to ~ 5. Examples of the ethyleneamines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like.

In the composition of the present invention, the penetrating additive is
When the amount is too small, sufficient physical properties cannot be obtained, and when the amount is too large, the stability with time of viscosity is extremely lowered. is there.

The plastisol composition of the present invention comprises a vinyl chloride paste resin, didecyl phthalate mainly composed of di-2-propylheptyl phthalate as a plasticizer, and N, N-dimethylformamide and diethyl sulfate as a penetrating additive. And at least one member selected from the group consisting of ethyleneamines represented by the general formula (I) are uniformly mixed.

Further, the composition of the present invention may be used in combination with other plasticizers as long as the effects of the present invention are not impaired. The plasticizer is not particularly limited, for example,
DOP, dibutyl phthalate, diheptyl phthalate,
Phthalic acid esters such as diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, dibutylbenzyl phthalate; di-2-ethylhexyl adipate,
Examples thereof include adipic acid esters such as diisononyl adipate and diisodecyl adipate. The plasticizer used in combination is preferably within 5% by weight of didecyl phthalate, which is mainly composed of di-2-propylheptyl phthalate.

Further, if necessary, the composition of the present invention contains a stabilizer such as a Ba--Zn stabilizer or an epoxidized soybean oil.
Additives such as fillers, diluents, thickeners, tackifiers and contents may be used. The pustizol composition of the present invention can be used as a resin raw material that is heated and melted after being applied on a substrate.

[0020]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. (Example 1) Vinyl chloride paste resin (manufactured by Zeon Corporation: Zeon 121, straight, polymerization degree 1600) 10
0 parts by weight, 70 parts by weight of didecyl phthalate mainly composed of di-2-propylheptyl phthalate as a plasticizer, 10 parts by weight of N, N-dimethylformamide (manufactured by Nitto Chemical Co., Ltd.) as a penetrating agent, and a stabilizer. As a Ba-Zn stabilizer (Nissan Ferro Co., Ltd .: LTL-272) 2 parts by weight and epoxidized soybean oil (Asahi Denka Kogyo Co., Ltd.) 2 parts by weight are blended and uniformly mixed with a raker machine, and then vacuumed. A plastisol composition was prepared by defoaming underneath. The physical properties and viscosity stability of the above composition were evaluated according to the following methods, and the results are shown in Table 1.

Example 2 A composition was prepared in the same manner as in Example 1 except that the plasticizer was 50 parts by weight and the penetrating additive was 30 parts by weight, and the composition was evaluated. The results are shown in Table 1.

Example 3 A composition was prepared in the same manner as in Example 1 except that the plasticizer was 100 parts by weight and the penetrating additive was 30 parts by weight, and the composition was evaluated. The results are shown in Table 1.

Example 4 A composition was prepared in the same manner as in Example 1 except that diethyl sulphate was used instead of N, N-dimethylformamide as the penetrating additive, and the composition was evaluated. The results were shown in Table 1.

Example 5 A composition was prepared in the same manner as in Example 4 except that the plasticizer was 50 parts by weight and the penetrating additive was 30 parts by weight, and the composition was evaluated. The results are shown in Table 1.

Example 6 A composition was prepared in the same manner as in Example 4 except that the plasticizer was 100 parts by weight and the penetrating additive was 30 parts by weight, and the composition was evaluated. The results are shown in Table 1.

(Example 7) In Example 1, diethylenetriamine (manufactured by Tosoh Corp., n = in the general formula (I)) was used instead of N, N-dimethylformamide as the penetrating additive.
A composition was prepared in the same manner except that 2) was used, the composition was evaluated, and the results are shown in Table 1.

(Example 8) In Example 1, 50 parts by weight of a plasticizer was added, and triethylenetetramine (manufactured by Tosoh Corp., in the general formula (I) as n = N = N-dimethylformamide as a penetrating agent was used). A composition was prepared in the same manner except that the amount of 3) was changed to 30 parts by weight, and the composition was evaluated. The results are shown in Table 1.

(Example 9) In Example 1, 100 parts by weight of a plasticizer was used, and tetraethylenepentamine (manufactured by Tosoh Corporation, n in the general formula (I) in place of N, N-dimethylformamide as a penetrating agent was used). = 4) was changed to 30 parts by weight, a composition was prepared in the same manner, the composition was evaluated, and the results are shown in Table 1.

Comparative Example 1 A composition was prepared in the same manner as in Example 1 except that the plasticizer was 20 parts by weight and the penetrating additive was 70 parts by weight, and the composition was evaluated. The results are shown in Table 1.

Comparative Example 2 A composition was prepared in the same manner as in Example 1 except that the plasticizer was 80 parts by weight and no other penetrating additive and stabilizer were added. The results are shown in Table 1.

Comparative Example 3 A composition was prepared in the same manner as in Example 1 except that the plasticizer was 80 parts by weight and the penetrating additive was 2 parts by weight, and the composition was evaluated. The results are shown in Table 1.

(Comparative Example 4) A composition was prepared in the same manner as in Example 1 except that DOP was used instead of didecyl phthalate mainly containing di-2-propylheptyl phthalate as a plasticizer. Evaluate the composition,
The results are shown in Table 1.

Comparative Example 5 A composition was prepared in the same manner as in Example 1 except that the plasticizer was 24 parts by weight and the penetrating additive was 6 parts by weight, and the composition was evaluated. The results are shown in Table 1.

Comparative Example 6 A composition was prepared in the same manner as in Example 1 except that the plasticizer was 140 parts by weight and the penetrating additive was 30 parts by weight, and the composition was evaluated. The results are shown in Table 1.

Comparative Example 7 A composition was prepared in the same manner as in Example 4 except that the plasticizer was 20 parts by weight and the penetrating additive was 70 parts by weight, and the composition was evaluated. The results are shown in Table 1.

Comparative Example 8 A composition was prepared in the same manner as in Example 4 except that the plasticizer was 80 parts by weight and the penetrating additive was 2 parts by weight, and the composition was evaluated. The results are shown in Table 1.

(Comparative Example 9) A composition was prepared in the same manner as in Example 4 except that DOP was used instead of didecyl phthalate mainly containing di-2-propylheptyl phthalate as a plasticizer. Evaluate the composition,
The results are shown in Table 1.

Comparative Example 10 A composition was prepared in the same manner as in Example 4 except that the plasticizer was 24 parts by weight and the penetrating additive was 6 parts by weight, and the composition was evaluated. The results are shown in Table 1.

Comparative Example 11 A composition was prepared in the same manner as in Example 4 except that the plasticizer was 140 parts by weight and the penetrating additive was 30 parts by weight, and the composition was evaluated. The results are shown in Table 1.

Comparative Example 12 A composition was prepared in the same manner as in Example 7 except that the plasticizer was 20 parts by weight and the penetrating additive was 70 parts by weight, and the composition was evaluated. The results are shown in Table 1.

(Comparative Example 13) A composition was prepared in the same manner as in Example 7 except that the plasticizer was 80 parts by weight, the penetrating additive was 2 parts by weight, and no other stabilizer was added. The composition was evaluated and the results are shown in Table 1.

(Comparative Example 14) A composition was prepared in the same manner as in Example 7 except that DOP was used instead of didecyl phthalate mainly containing di-2-propylheptyl phthalate as a plasticizer. The composition was evaluated and the results are shown in Table 1.

(Comparative Example 15) A composition was prepared in the same manner as in Example 7 except that the plasticizer was 24 parts by weight and the penetrating additive was 6 parts by weight, and the composition was evaluated. The results are shown in Table 1.

Comparative Example 16 A composition was prepared in the same manner as in Example 7 except that the plasticizer was 140 parts by weight and the penetrating additive was 30 parts by weight, and the composition was evaluated. The results are shown in Table 1.

[Evaluation of Physical Properties] The plastisol composition was applied on a glass plate to a thickness of about 0.5 mm and heated and melted in a dryer kept at 130 ° C. for 20 minutes. Then, this was taken out and cooled to obtain a test piece. JIS for this test piece
A tensile test was performed according to K 6771 to determine elongation and tensile strength.

[Evaluation of Viscosity Stability] Immediately after preparing the plastisol composition, it was left in a thermostatic chamber at 23 ° C. for 2 hours, and then the viscosity at a rotation speed of 20 rpm was measured by a B-type viscometer (initial viscosity). Also, after preparing the plastisol composition, 4
The sample was allowed to stand in a thermostatic chamber at 0 ° C. for 6 days, then the viscosity was measured in the same manner, and the viscosity stability (AI) was determined by the following formula. AI = 40 ° C, viscosity after 6 days / initial viscosity

[0047]

[Table 1]

[0048]

The plastisol composition of the present invention is as described above, and contains vinyl chloride paste resin and di-2 phthalate.
-Plastic heptyl-based plasticizer, further N, N
-Since it comprises at least one penetrating additive selected from the group consisting of dimethylformamide, diethyl sulfate, and ethyleneamines represented by the general formula (I), it has good viscosity stability over time, and also has low-temperature heat-meltability, Has excellent physical properties such as tensile strength and elongation.

Claims (1)

[Claims] 1. 100 parts by weight of a vinyl chloride paste resin, 50 to 120 parts by weight of a plasticizer consisting of didecyl phthalate mainly composed of di-2-propylheptyl phthalate, N, N-dimethylformamide, diethyl sulfate and general. A plastisol composition comprising 5 to 30 parts by weight of at least one penetrating additive selected from the group consisting of ethyleneamines represented by formula (I). Embedded image