JPH08100098A - Organoplastisol composition - Google Patents

Abstract

PURPOSE: To prepare an organoplastisol which has good flame retardancy, is less likely to evolve hydrochloric acid gas and has good pot life and good curability by blending an acrylic resin with a triaryl ester of phosphoric acid. CONSTITUTION: The organoplastisol compsn. comprises (A) an acrylic resin and (B) a triaryl ester of phospohric acid. The blending ratio of the components A to B is pref. 0.3 to 10.0. The triary ester of phosphoric acid is particularly pref. a compd. represented by the formula (wherein 0<=1<=3, 0<=m<=3, 0<=n<=3, and 0.5<=1+m+n<=5.0) because the use of such a compd. can impart a particularly excellent pot life to the organoplastisol.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an organoplastisol having excellent storage stability.

[0002]

2. Description of the Related Art It is a well known fact that molded articles made of organoplastisol using a vinyl chloride resin generate a large amount of highly toxic hydrogen chloride gas upon combustion. As one means for solving this, it is known to suppress the amount of hydrogen chloride generated by incorporating fine particle calcium carbonate as a filler. However, in this case, the effect is not obtained unless a large amount of fine particle calcium carbonate is blended, and in that case, there is a drawback that mechanical properties and other properties are inevitably deteriorated.

As a fundamental solution, it is described in JP-A-6-115015 that the use of an acrylic resin instead of a vinyl chloride resin can suppress the generation of highly toxic hydrogen chloride gas. However, according to the additional test by the present inventors, it was found that the pot life of the compound was very bad and not suitable for practical use.

[0004]

The object of the present invention is to provide good flame retardance, generate a very small amount of hydrogen chloride gas, and
It is an object of the present invention to provide an organoplastisol composition having a good pot life and a good curability.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, an organoplastisol composed of an acrylic resin as a resin and a triaryl phosphate phosphate as a plasticizer has good storage stability and is very practical. The present invention has been completed by finding out that it is excellent in. That is, the organoplastisol of the present invention is an organoplastisol composition which produces a small amount of hydrogen chloride gas, has a good pot life, and has good curability.

The acrylic resin used in the organoplastisol of the present invention is a general term for resins obtained by polymerizing acrylic acid and its derivatives, and specifically, homopolymers or copolymers of the monomers shown in the following examples. Polymerization. Examples of acrylic resin monomers include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, hydroxylethyl acrylate, dimethyl. Aminoethyl acrylate, glycidyl acrylate, allyl acrylate, (poly) alkylene glycol acrylate, trimethylolpropane triacrylate, acrylic acid metal salt and other acrylates, methacrylic acid, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate,
Lauryl methacrylate, stearyl methacrylate,
Methoxyethyl methacrylate, butoxyethyl methacrylate, hydroxylethyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, glycidyl methacrylate, allyl methacrylate, (poly) alkylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and other methacrylates. Also, for the purpose of resin modification with these monomers, vinyl halides such as vinyl chloride and vinylidene chloride; vinyl esters such as vinyl acetate vinyl propionate; copolymers with styrene derivatives such as styrene and chlorostyrene. May be. Further, it may be a blend of two or more of these acrylic resins.
The shape of the acrylic resin used in the present invention does not matter as long as the mixture is a paste, but the primary particle size is preferably 100 μm or less from the viewpoint of workability at the time of compounding.

The triaryl phosphates used in the present invention act as plasticizers in the organoplastisols.
Specifically, tricresyl phosphate, cresyl diphenyl phosphate, phenyl dicresyl phosphate, trixylenyl phosphate, xylenyl diphenyl phosphate, phenyl dixylenyl phosphate, (ethylphenyl) diphenyl phosphate, bis (ethylphenyl) Phenylphosphate, triisopropylphenyldiisopropylphenylphenylphosphate, dicumenyltriisopropylphenylphosphate, cumenyltriisopropylphenylphenylphosphate, triisopropylphenyldiphenylphosphate, cumenylbis (diisopropylphenyl) phosphate, bis (diisopropylphenyl) phenylphosphate, dicumenyldiisopropyl Phenyl phosphate, cumenyl di Sopropylphenylphenylphosphate, diisopropylphenyldiphenylphosphate, tricumenylphosphate, dicumenylphenylphosphate, cumenyldiphenylphosphate, tris (t-butylphenyl) phosphate, (t-butylphenyl) diphenylphosphate, bis (t-butylphenyl) Examples include phenyl phosphate. These may be used alone or in a mixture.

It has been found that when the phosphoric acid triaryl ester represented by the following general formula is used among the above phosphoric acid triaryl esters, the pot life of the compounded organoplastisol is particularly excellent.

[0009]

Embedded image

(However, l, m, and n are 0 ≦ l ≦
3, 0 ≦ m ≦ 3, 0 ≦ n ≦ 3 and 0.5 ≦ l + m + n
It satisfies ≦ 5.0. )

The mixing ratio of acrylic resin / triaryl phosphate is preferably 0.3 to 10.0 when the organoplastisol is prepared. When the compounding ratio is more than 10.0, the viscosity of the compounded organoplastisol is so high that it is not suitable for practical use. On the other hand, if the compounding ratio is less than 0.3, the plasticizer bleeds out from the compound when the compounded organoplastisol is cured, which is also not practical.

Other additives to the organoplastisol of the present invention, for example, various fillers such as calcium carbonate, aluminum hydroxide, magnesium hydroxide and talc, various flame retardants such as antimony trioxide and zinc borate, titanium white and carbon. Pigments such as black, cadmium yellow, phthalocyanine blue and chrome red, and stabilizers such as stearic acid metal salt may be added. However, the addition of these additives does not affect the effect of the present invention.

To prepare the organoplastisol of the present invention, a planetary mixer, a kneader, a triple roll,
A Hobart mixer, a butterfly mixer, a dissolver, a grinder, a ribbon blender, a Henschel mixer, etc. can be used. However, the kneading method is not limited to this.

The organoplastisol of the present invention is widely used as a sealing material or underbody coating material for automobiles, wallpaper, flooring material, gloves, etc., but is not limited thereto.

[0015]

The present invention will be specifically described below with reference to examples.

(Preparation Example 1) An experiment was carried out in the same manner as in Example 5 of Japanese Examined Patent Publication No. 51-10236 to prepare a phosphoric acid ester consisting of triphenyl phosphate and isopropylated phosphate. The isopropylation degree (l + m + n) of this product was 1.5. (Hereinafter referred to as compound A)

(Preparation Example 2) The same experiment as in Example 6 of JP-B-51-10236 was carried out to prepare a phosphoric acid ester consisting of triphenyl phosphate and isopropylated phosphate. The isopropylation degree (l + m + n) of this product was 2.0. (Hereinafter referred to as compound B)

Example 1 Compounds A and 6 of Preparation Example 1
2.5 g and 50 g of acrylic paste resin (F320 manufactured by Nippon Zeon Co., Ltd.) were pre-kneaded in an automatic mortar (ANM-1000 type manufactured by Nitto Kagaku Co., Ltd.) at room temperature for 20 minutes, and further vacuum crusher ( Ishikawa Type Stirrer Type 18
In step Z), degassing was performed by stirring for 30 minutes.

The viscosity of the acrylic plastisol composition thus obtained was measured immediately after the compounding and 1 to 3 weeks after the compounding (using a B8L type viscometer No. 3 rotor manufactured by TOKIMEC CORPORATION, rotation speed 6 rpm). ) Was used for the measurement. Further, the curability of the acrylic plastisol of the compound immediately after the kneading is cured in a gear oven (Tabay Espec Corp. GPS-112 type) at 140 ° C. for 5 minutes to determine the hardness of the cured product and the presence of tack on the surface. It was observed and judged. The results obtained by the above measurement are shown in Table 1.

Example 2 Instead of the compound A of Example 1, the compound B of Preparation Example 2 was used. The results are shown in Table 1 below.

Example 3 Compound A in Example 1
Table 1 shows the results of the same measurement using TCP (tricresyl phosphate: manufactured by Junsei Kagaku Co., Ltd.) instead of.

(Comparative Example 1) Compound A in Example 1
Was measured in the same manner using DOP (dioctyl phthalate: manufactured by Junsei Kagaku Co., Ltd.) instead of. The results are shown in Table 1.

(Comparative Example 2) Compound A in Example 1
DBP (dibutyl phthalate: manufactured by Junsei Kagaku Co., Ltd.) was used instead of the above, and the same measurement was performed. The results are shown in Table 1.

[0024]

[Table 1]

[0025]

As described in detail above, when the triaryl phosphate ester of the present invention is used as a plasticizer, the organoplastisol compound of acrylic resin has a very good pot life and can be actually used. I knew that. Further, unlike the PVC molded product, the cured product of the present organoplastisol compound produces an extremely small amount of hydrogen chloride gas upon combustion, and therefore produces less toxic gas when a fire occurs.

Claims (2)

[Claims] 1. An organoplastisol composition comprising a triaryl phosphate and an acrylic resin. 2. The organoplastisol composition according to claim 1, wherein the triaryl phosphate ester is a phosphate ester represented by the following general formula. Embedded image (However, l, m, and n are 0 ≦ l ≦ 3 and 0 ≦ m ≦, respectively.
3, 0 ≦ n ≦ 3 and 0.5 ≦ l + m + n ≦ 5.0 are satisfied. )