JP2621431B2 - Surfactant-containing resin composition with excellent thermal stability - Google Patents

Description

The present invention relates to a surfactant-containing resin composition. More specifically, the present invention relates to a surfactant-containing resin composition having improved thermal stability.

<Conventional Technology> Surfactants have been actively added to resins for the purpose of enhancing the functionality of the resins. Specifically, functions such as antistatic properties, antifogging properties, and dispersibility when filling an inorganic compound can be imparted to the resin by adding a surfactant. Japanese Patent Application Laid-Open No. 60-36545 discloses a resin composition in which a surfactant is added to a polyolefin-based resin and which has an antifogging function.

<Problems to be Solved by the Invention> However, a surfactant-containing resin composition can impart high functionality to a resin due to a surfactant, but lowers the thermal stability of the resin composition itself. Such a decrease in thermal stability pellets, films, burning and gelation in a processing machine when processing the surfactant-containing resin composition into molded products,
It causes discoloration immediately after processing, and also causes deterioration due to poor thermal stability depending on use conditions not only at the time of processing but also after the end of the product, resulting in a significant reduction in commercial value.

SUMMARY OF THE INVENTION An object of the present invention is to provide a surfactant-containing resin composition which significantly improves thermal stability and does not reduce the function imparted by a surfactant to a practically problematic level. is there.

<Means for Solving the Problems> The present inventors have continued research on a surfactant-containing resin composition, particularly a surfactant-containing resin composition containing an inorganic compound. As a result, they have found that the addition of a specific inorganic compound to a surfactant-containing resin composition significantly improves the thermal stability of the composition, thereby completing the present invention.

That is, the present invention provides (A) a surfactant, (B) a BET surface area of 10 m ² / g or more, a maximum acid strength of the surface of -8.2 to -3.0 in pKa, and a pKa of -3.
A surfactant-containing resin composition comprising an inorganic compound having an acid amount of 0 or less and 1 μmol / g or more.

In the present invention, an inorganic compound added to improve thermal stability has an BET surface area of 10 m ² / g or more, and an acid having a maximum acid strength of -8.2 to -3.0 at pKa and -3.0 or less at pKa. The amount is 1 μmol / g or more and can be represented by the following general formula.

(SiO ₂ ) _x · (Al ₂ O ₃ ) _y · (M ¹ _α1 O _β1 ) _z1 · (M ²
_{α2 O β1) Z2 ...... (M} m αm O βm) zm (M 1, M 2, M m represents various metals, specifically, Ti, Zr, B,
Be, Mg, Ca, Ba, Zn, Pb, Sn and the like. α ₁ , α ₂ , α _m , β
₁ , β ₂ and β _m are natural numbers. x, y, z ₁ , z ₂ , zm are zero or positive numbers. Specific examples of these inorganic compounds include metal oxides of natural minerals such as acid clay, montmorillonite, kaolinite and bentonite, and Al ₂ O ₃ —SiO ₂ , Al ₂ O ₃ —TiO ₂ ,
Examples include composite oxides such as TiO ₂ -ZrO ₂ and Al ₂ O ₃ -ZrO ₂ and oxides supporting a sulfate group and the like.These inorganic compounds contain a small amount of impurities and water. You may.

When the maximum acid strength of the surface of the inorganic compound is smaller than -8.2 in pKa, the solid acid catalytic activity of the inorganic compound becomes strong and the resin is deteriorated. Conversely, the maximum acid strength of the surface is -3.0 in pKa.
In the case described above, the effect of improving the thermal stability of the resin composition is significantly reduced.

When the BET surface area of the inorganic compound is 10 m ² / g or less or the acid content is 1 μmol / g or less, the effect of improving the thermal stability is not sufficient.

Inorganic compounds used in the present invention can be prepared by known methods other than natural products (Suzaki Ozaki et al., Catalyst Engineering Lecture 10, Catalyst Handbook by Element, Jinjinshokan (Showa 42): Naoto Todo et al., Catalyst Preparation, Kodansha (Showa 49): It can also be synthesized according to Kobe Tabe et al., Acid-base Catalyst, Sangyo Tosho (Showa 41). For example,
The amount of acid and the maximum acid strength can be changed by changing the pH in the washing step, and the BET surface area and the amount of acid can be changed by changing the concentration during the reaction.

The BET surface area, the amount of acid, and the maximum acid strength can also be changed by firing the inorganic compound.

As the resin used in the present invention, polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-
Homopolymer of olefin such as pentene, ethylene-propylene block copolymer, ethylene-propylene random copolymer, ethylene-1-butene copolymer, ethylene-1-hexane copolymer, ethylene-4-methyl-1 −
Pentene copolymer, ethylene-1-octene copolymer,
Copolymer of olefin such as propylene-1-butene copolymer, ethylene-vinyl acetate copolymer, copolymer of olefin and polar vinyl compound such as ethylene-methyl methacrylate copolymer, polymethyl methacrylate and the like Acrylic resin, ionomer resin, polyester resin, polyamide resin, polycarbonate resin, phenol resin,
Examples thereof include a polyvinyl chloride resin and a polyurethane resin.

The surfactant used in the present invention varies depending on the function to be imparted to the resin, and is not particularly limited.
Preferably, a nonionic surfactant is used.

Specifically, as a polyethylene glycol derivative,
Higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, fatty acid ethylene oxide adduct, higher alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, etc. And polyglycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitan and sorbitol fatty acid ester, sucrose fatty acid ester, fatty acid amine of ethanolamine, and polyethyleneimine derivative.

The mixing ratio of the surfactant in the fat composition of the present invention is generally used in the range of 0.01 to 30 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the resin. 0.01
When the amount is less than 30 parts by weight, the performance of the surfactant is not sufficiently exhibited. Bleeding occurs on the surface of the composition, causing adverse effects such as lowering the appearance.

The compounding ratio of the inorganic compound in the resin composition of the present invention is generally used in the range of 0.01 to 300 parts by weight, preferably 0.1 to 100 parts by weight, per 1 part by weight of the surfactant. When the amount is less than 0.01 part by weight, the effect of improving the thermal stability is poor. There is a problem that the change is remarkable as compared with the case where no compound is blended.

The resin composition of the present invention is a heat stabilizer within a range not impairing the object of the present invention, a light stabilizer, an ultraviolet absorber, various stabilizers such as an antioxidant and an antifogging agent, an antistatic agent, a lubricant, Fillers, flame retardants, pigments and the like can be included as components.

The method of compounding each component described above is not particularly limited, and can be compounded by a general method such as a Banbury mixer, a mixing roll, and an extruder.

<Effect of the Invention> According to the present invention, in the surfactant-containing resin composition,
By adding a specific inorganic compound, a surfactant-containing resin composition having significantly improved thermal stability can be obtained.

<Examples> Hereinafter, examples of the present invention will be described, but the present invention is not limited thereto.

 The test methods in the examples are as follows.

Thermal stability test: After a test piece having a thickness of 1 mm was aged in an oven at 180 ° C. for 3 hours, the degree of discoloration (color difference) of the test piece and the rate of change of the melt index (MI deviation)
The thermal stability was evaluated. The smaller the value of each of the dye and the MI deviation, the better the thermal stability of the test piece.

Color difference: SM color computer manufactured by Suga Test Machine Co., Ltd. so
It was measured.

MI deviation: Under the conditions of 190 ° C and a load of 2.16 kg, the melt index of the test piece before and after the above-mentioned thermal stability test was measured, and the melt index before the test was MI. When the melt index after the test is set to MI ₃₀ , it is expressed by equation (1).
MI was taken as MI deviation.

 The smaller the MI deviation, the better the thermal stability of the test piece. Mineralization
BET area measurement method of compound: Monosorb manufactured by Quantachrome
(Specific surface area measuring device), sample amount 100mg,
Carrier gas: mixed gas of 30% nitrogen, 70% helium, degassing
The measurement was performed using the BET-point method under the condition of air time of 15 minutes.

Maximum acid strength of inorganic compound: Take 5-10 cm ² of benzene in a 50 cm ² sample bottle, and quickly add about 100 mg of test powder into it. Subsequently, a Hammett indicator solution shown in the following table was added in order of 0.1 cm ^{3 in} ascending order of the pKa, and the maximum acid strength was determined from the pKa of the indicator which initially showed an acidic color.

Method for measuring acid content of inorganic compound (acid content of pKa of -3.0 or less):
Weigh 100-200 mg (the exact mass is W) of the inorganic compound of the sample into a test tube equipped with a three-way cock, and place at 250 ° C.
For 1 hour under air. Thereafter, the mixture is allowed to cool to room temperature while flowing nitrogen, and 5 ml of benzene and 3 drops of a 0.1% dicinnamal ascent solution (benzene solvent) are added to color the sample in an acidic color. A 1/10 or 1/100 normal n-butylamine solution (benzene solvent) is slowly added dropwise with sufficient stirring until the acidic color disappears.

Assuming that the amount of the n-butylamine solution was 1/10 N, which was required until the acidic color disappeared, and the amount of the n-butylamine solution was X ml, the acid amount A (m
mol / g) is determined by the following equation.

Antifogging test: A 100 μm thick film was used as a test piece.
After aged at 0 ° C for 10 days, one side of the test piece was exposed to saturated steam at 50 ° C, and the other was air-conditioned at room temperature, and the degree of haze (degree of water droplet adhesion) of the test piece was visually observed. Observed.

Evaluation criteria ◎ No water droplets adhered ○ Water droplets adhered to 10% or less of the entire area of the film △ 〃 30% or less × 〃 50% or more In addition, the production of the inorganic compounds used in Examples was carried out, for example, as described below. .

Synthesis of Inorganic Compound a 1850 g of a liquid sulfuric acid band containing 8% of Al ₂ O ₃ was used as solution A. Measure the No. 3 water glass so that the molar ratio of SiO ₂ / Al ₂ O ₃ is 4.5, measure the aqueous sodium hydroxide solution so that the mono ratio of Na ₂ O / Al ₂ O ₃ is 3.6, and mix both solutions into a raw material mixing tank And mix well.
Water is added so as to have the same volume as the solution, and this is designated as solution B.

1100 ml of water is weighed into the reaction tank, and the solution A and the solution B are simultaneously dropped while stirring at 100 rpm. After the completion of the dropping, stirring is further continued for 1 hour. The resulting slurry is centrifuged, 2000
Wash with ml of water (pH of the solution during washing is adjusted to 5). The wet cake obtained by centrifugation was dried by heating at 250 ° C. to obtain an inorganic compound a.

Synthesis of inorganic compound b Inorganic compound A except that the pH at the time of washing the slurry was set to 9.
In the same manner as in the synthesis method, inorganic compound b was obtained.

Synthesis of Inorganic Compound f Inorganic Compound b is calcined at 250 ° C. for 3 hours to obtain inorganic compound f.
I got

Example 1 Melt index 1.5 g / 10, density 0.922 g / cm^ThreeLow density
Polyethylene (Sumikasen manufactured by Sumitomo Chemical Co., Ltd.) F2
08-1) 100 parts by weight, diglycerinse as surfactant
2 parts by weight of squiolate, aluminosil
Kate (composition SiO_Two 63%, Al_TwoO_Three 24%, Na_TwoO13%) 8
Parts by weight and as an antioxidant, Sumitomo Chemical Co., Ltd.
Sumilyzer BP1010.3 parts by weight Banbury mixer
After kneading at 150 ° C for 5 minutes, granulate with an extruder
Thus, a pellet was obtained.

The pellet was press-molded at 160 ° C. to obtain a sheet having a thickness of 1 mm.

The sheet was subjected to a thermal stability test. As a result, the color difference was 10, and the MI deviation was 47%. Thus, the sheet was excellent in thermal stability. Also obtained by press molding from this pellet
When the antifogging test was performed on the 100 μm film, it was still good on the 15th day.

Examples 2 to 8 A sheet having a thickness of 1 mm and a film having a thickness of 100 μm were obtained in the same manner as in Example 1 except that the resins and inorganic compounds shown in Table 1 were used.

Both the thermal stability and the antifogging property of this sheet were excellent.

Comparative Example 1 As an inorganic compound, the amount of acid having a pKa of −3.0 or less is zero.
Snow mark SP-10 (made by Kinsei Kogyo Co., Ltd.)
A sheet having a thickness of 1 mm was obtained in the same manner as in Example 1 except for
Was. The thermal stability of this sheet was poor.

Comparative Examples 2 to 5 In the same manner as in Example 1, a sheet having a thickness of 1 mm was obtained using the resins and inorganic compounds shown in Table 1. The thermal stability of each of these sheets was inferior.

Comparative Examples 6 to 9 Without using an inorganic compound, using the resins shown in Table 1,
In the same manner as in Example 1, a sheet having a thickness of 1 mm was obtained. The results of the thermal stability test of this sheet were inferior as shown in Table 1.

Comparative Example 10 A sheet having a thickness of 1 mm was obtained in the same manner as in Example 1, except that the inorganic compound and the surfactant were not used. Table 1 shows the results of the heat stability test and the antifogging test of this sheet. The antifogging property was extremely poor.

Claims (1)

(57) [Claims] (1) a surfactant having (A) a surfactant and (B) a BET surface area of 1
0m ² / g or more, the maximum acid strength of the surface is -8.2 to -3.0 in PKa, PK
A surfactant-containing resin composition comprising: an inorganic compound having an acid amount of 1 μmol / g or more, wherein a is −3.0 or less.