JPS6136533B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a chemical foaming aid that can appropriately, reliably, and quickly adjust and control the decomposition temperature of a resin foaming agent. Conventionally, an important point in the production of foams of various resins, especially thermoplastic resins, is to prevent the decomposed gas of the blowing agent from escaping by lowering the melt viscosity during heating. In the case of PVC (hereinafter abbreviated as PVC), a plasticizer is added to make it gel, and in the case of polyolefin, methods such as adding a crosslinking agent or crosslinking with electron beams are used. It has become important to adjust and control the decomposition temperature of the blowing agent appropriately, reliably, and quickly in addition to adjusting the viscosity of the resin to effectively generate decomposed gas. For this purpose, conventional foaming aids include urea-based agents such as urea and urea derivatives, organic acid-based agents such as salicylic acid, stearic acid, lauric acid, and phthalic acid, and zinc salts, calcium salts, lead salts, and barium salts of the aforementioned organic acids. metal salts such as zinc white, metal oxides such as litharge, and
Glycerin, ethanolamine, ethylene glycol, etc. are used. However, although these aid in the decomposition of the blowing agent, they have many other drawbacks; for example, urea-based blowing aids are nitrosopentamethylenetetramine (hereinafter referred to as DPT), which is a nitroso-based blowing agent.
It is used in combination with the azo foaming agent azodicarbonamide (hereinafter referred to as ADC), but it has high hygroscopicity. It has major drawbacks such as poor compatibility with resins and a tendency to cause blooming, which poses problems for use in practical products. Further, when zinc white is used, thermal stability decreases, when calcium salts and barium salts of organic acids are used, there is a problem with plate-out, and when ethanolamine is used, bubbles become coarse. Salicylic acid is used in conjunction with DPT for rubber, but it has a strong odor, and stearic acid has drawbacks such as the tendency to bleed onto the product surface. Therefore, the present inventors (a) General formula () (In the formula, R ₁ and R ₂ are alkyl groups of 5 to 19 and 1 to 10, respectively) or a branched chain fatty acid with a total of 8 to 22 carbon atoms and the general formula () R ₃ -CH ₂ A mixed fatty acid containing 10% by weight or more of the former in a mixture with a straight chain fatty acid having a total carbon number of 8 to 22 represented by -COOH () (in the formula, R ₃ is an alkyl group of 6 to 20). (b) The fatty acids in (b), magnesium, calcium,
Salts with barium, zinc, tin, lead or alkyltin. By using one or more selected from (a) and (b) above in combination with a foaming agent, the drawbacks of conventional foaming aids such as high hygroscopicity, poor compatibility with resins, and blooming can be avoided. It has been found that it has improved the problems of easy bleeding, decreased thermal stability, and unpleasant odor, and has excellent performance such as low migration and extractability. The fatty acid used in the present invention is obtained by using α-olefin or n-olefin as a raw material, converting it into an aldehyde by the oxo method using carbon monoxide and hydrogen as auxiliary raw materials, and then oxidizing it.
Metals constituting the above fatty acid salts include magnesium, calcium, barium, zinc, tin, and lead, and alkyl groups include monomethyltin, monobutyltin, monooctyltin, monocyclohexyltin, monophenyltin, and monobenzyltin. tin,
Examples include dimethyltin, dibutyltin, dioctyltin, dicyclohexyltin, diphenyltin, dibenzyltin, trimethyltin, tributyltin, trioctyltin, and the like. As blowing agents used in combination with the blowing aid of the present invention,
For example, DPT, ADC, P・P′-oxybis(benzenesulfonylhydrazide), N・N′-dimethyl-N・N′-dinitrosoterephthalimide, benzenesulfonylhydrazide, P-toluenesulfonylhydrazide, azobisisobutyronitrile,
Nitrourea, acetone-P-toluenesulfonylhylazone, P-toluenesulfonyl azide,
2,4-Toluene disulfonyl hydrazide, P-
Methyl urethane benzenesulfonyl hydrazide,
Examples include trinitrosotrimethylenetriamine, P-toluenesulfonyl semicarbazide, oxalylhydrazide, nitroguanidine, hydrazocarboniamide, trihydrazinotriazine, and the like. The foaming aid of the present invention may include other foaming aids, blowing agents, pigments, dyes, fluorescent whitening agents, fillers, reinforcing agents, foam stabilizers, antistatic agents, antifogging agents, lubricants, plasticizers, and antioxidants. various additives such as UV absorbers, chelating agents, flame retardants, flame retardants, electrical insulation improvers, stabilizers, bactericidal agents, colorants, crosslinking agents, fragrances, petroleum softeners, and anti-aging agents. Even if you use it depending on the purpose and use,
The effects of the present invention are not impaired in any way. The foaming aid is produced by the following method.
That is, salts of magnesium, calcium, barium, zinc, etc. and fatty acids are obtained by precipitation of fatty acids or their esters obtained by the olefin oxo method and metal hydroxides, oxides, and weak acid salts (metathesis method);
It can be obtained by a melting method, a direct method of reacting a fatty acid with a metal powder, or the like. Salts of tin, salts, etc. and fatty acids can be obtained by reacting metal alcoholates or chlorides with fatty acids in an anhydrous organic solvent. The reaction product of a fatty acid and an alkyltin can be obtained by a dehydration reaction or an exchange reaction between an alkyltin oxide or an alkyltin lower fatty acid ester and a fatty acid. The above manufacturing method is merely an example, and manufacturing is possible by other methods, but the present invention is not limited in any way by these manufacturing methods. Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. Examples 1 to 8 Vinyl chloride resin (hereinafter abbreviated as PVC) was blended with the composition shown below, thoroughly mixed using a Henshil mixer, and further defoamed for 1 hour under reduced pressure of 5 mm/Hg. Next, the defoamed sol was applied onto a ferro plate and allowed to gel in an oven at 150°C for 5 minutes. This gelled sheet was foamed at 190°C at regular intervals, and the foaming ratio of the foam was measured at regular intervals. The results are shown in Table 1. Resin composition PVC (Nippon Zeon #25) 100 parts by weight Dioctyl phthalate (DOP) 80 parts by weight Stabilizer (Envirizer T-508) 3 Parts by weight Stabilizer (Envirizer SB-24) 0.5 parts by weight ADC 3 Parts by weight Foaming Auxiliary agent (Table 1) Listed in Table 1

[Table] Examples 9 to 14 From 100 parts by weight of PVC, 80 parts by weight of DOP, 3 parts by weight of ADC, 3 parts by weight of barium-zinc liquid stabilizer, and foaming aid (composition and amount added are shown in Table 2). The formulation was processed in the same manner as in Examples 1 to 8 and then foamed at 220°C for 3 minutes. The obtained foam was sliced thinly and the size of the bubbles was observed under a microscope, and the results are shown in Table 2.

【table】

[Table] Examples 15 to 22 A mixture of ABS resin and the composition shown below was uniformly stirred using a Henschel mixer, and the cylinder temperature was 150°C and 160°C, and the head temperature was
Extrusion foaming was carried out using a 30 mm diameter extruder with a die temperature of 160° C. and a screw rotation speed of 50 rpm. The surface and internal foam layer of the obtained foamed molded product were observed, and the results are shown in Table 3. Resin composition ABS (Cycolac) 100 parts by weight Stabilizer (Enbilizer P#55) 2 parts by weight ADC 0.5 parts by weight Foaming aid Listed in Table 3

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[Table] Examples 23 to 30 Addition amount PVC (Nippon Zeon 103EP) 100 parts by weight DOP 50 parts by weight Stabilizer (Enbilizer P#55) 2 parts by weight DPT 2 parts by weight Foaming aid Listed in Table 4 Above formulation After dry blending with a Henshil mixer, 0.5% with two calendar rolls at 160℃
A m/m sheet was prepared, and the following tests were conducted on this sheet. The results are shown in Table 4. Test method 1 Bleeding test (i) Ultraviolet irradiation: irradiation with 2 x 10W germicidal lamps at 30℃ constant temperature with a distance of 15cm from the sample piece for 6 hours (ii) High humidity: 40℃ x 98% RH x 120 hours◎ The results were judged and displayed in three stages: no bleed △; slight bleed ×; severe bleed. 2 Heat resistance stability test Time (minutes) until sample piece changes color to yellowish brown in 190℃ gear oven

【table】

【table】

Claims (1)

[Claims] 1 (a) General formula () (In the formula, R ₁ and R ₂ are alkyl groups of 5 to 19 and 1 to 10, respectively) or a branched chain fatty acid with a total carbon number of 8 to 22 and the general formula () R ₃ -CH ₂ - COOH...() (in the formula, R ₃ is an alkyl group of 6 to 20) is a mixture with a straight chain fatty acid having a total of 8 to 22 carbon atoms.
Mixed fatty acids containing 10% or more by weight. (b) The fatty acids in (b), magnesium, calcium,
Salts with barium, zinc, tin, lead or alkyltin. A foaming aid characterized by using one or more selected from (a) and (b) above.