JPS5865737A - Method for producing synthetic resin with excellent anti-static and anti-fog properties - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a thermoplastic synthetic resin that has both electrical resistance and antifogging properties.

Synthetic resins are generally poor conductors of electricity, and are used as electrical insulators by taking advantage of their properties. On the other hand, due to its insulating properties, once charged, electricity does not easily escape.1. 1. Dust damage occurs due to friction and peeling, and as a result, problems due to static electricity appear during processing, and in practical terms, the static electricity attracts dirt and dust in the air, causing it to stick to the surface. There are many problems caused by charging, such as:

As a method to solve this drawback of synthetic resins, it is effective to reduce the electrical resistance of the synthetic resin surface, that is, to give the synthetic resin surface conductivity with water absorbency. A pre-static agent is used.

In addition, synthetic resins have extremely hydrophobic surfaces, making them water resistant; however, because they are hydrophobic, if moisture adheres to the surface, the moisture will be absorbed by both surfaces of the resin. It does not show any phenomenon and only stays as water droplets.

For example, when polyethylene film or polypropylene film is used to package foods containing moisture (fruits, vegetables, meat, etc.), moisture condenses on the inner surface of the film, clouding the film surface and causing the packaging to deteriorate. This is manifested in the fact that the product becomes visible and becomes K<. In addition, when polyvinyl chloride film is used to cover agricultural greenhouses and thermal tunnels, water vapor that evaporates from the ground surface condenses on the inside of the film, making it opaque and impairing the penetration of sunlight. It causes a nuisance that reduces the growth of cultivated crops.

As a means to prevent surface fogging caused by the hydrophobic nature of synthetic resins, a method of imparting hydrophilicity to the resin surface is generally adopted. There is.

In this way, antistatic agents and antifogging agents are used to solve various problems caused by the static charge and fogging properties of synthetic resins.For example, polyoxyethylene alkyl is used as an antistatic agent. Amine, polyoxyethylene alkylamine is commonly known.

As heavy antifogging agents, sorbitan high WIW acid esters and higher fatty acid glycerides are generally used.

However, the commonly known antistatic agents do not exhibit the desired antifogging properties when used as antifogging agents.

In addition, commonly known antifogging agents are effective in both antistatic and antifogging properties, such as not showing anti-soldering properties on the furnace shaft W.
nothing is known.

As mentioned above, synthetic resin products are often required to have both electrical resistance and antifogging properties from a practical standpoint, and in this case, attempts have been made to use a combination of antistatic agents and antifogging agents.

However, in order to achieve the performance of both, antistatic agents and antifogging agents must be mixed into the synthetic resin in the amounts necessary to achieve each performance.As a result, synthetic resin molded products In many cases, paper that has blooming, paper that has decreased blocking resistance, and the original properties of the resin are impaired.
A synthetic resin molded product with effective anti-electricity and anti-fogging properties has not yet been obtained.

As a result of intensive research, the present inventors have arrived at the invention of a method for producing a synthetic resin that has both excellent electrical resistance and antifogging properties without impairing the original performance and characteristics of the resin. In other words, the present invention provides stearylamine 1 represented by 2RNH,
1 mole of polyoxyethylene stearylamine obtained by addition reaction with 2.5 to 40 moles of ethylene oxide, 50 to 80% by weight of stearic acid, and 50 to 20% by weight of palmitic acid. α9~1
It is characterized by adding α1-No by weight to a thermoplastic synthetic resin (hereinafter referred to as polyolefin resin or polyvinyl chloride resin) by carrying out a dehydration reaction in the range of 3 moles, and The present invention provides a method for producing a synthetic resin having excellent properties and antifogging properties.

In other words, the composite according to the present invention has the properties of both an antistatic agent and an antifogging agent.

In order to obtain the compound according to the present invention, 1 mole of ska-lylamine is first subjected to an addition reaction of 18 to 10 moles of ethylene oxide. 15G-180 in the presence of catalyst
At a temperature of 0.degree. C., 25 to 0 moles of ethylene oxide are added to stearylamine and subjected to an addition reaction with a pressurizer.

(2) 14 to 1 mole of stearylamine without addition of catalyst
Addition reaction of 1 mol of ethylene oxide under pressure at a temperature of 0 to 180°C (3) Addition reaction of 24 mol of ethylene oxide to 71 mol of stearyl ane at a temperature of 1150 to 180°C under pressure without addition of catalyst or catalyst. Then, an addition reaction such as 6 is employed in which 5 to 1.0 mol of the remaining ethylene oxide α is added under pressure at a temperature of 100 to 120°C.

Among these methods (1) to (3), method (2) is the most preferable method because it does not cause coloring of the addition reaction product and does not involve the presence of catalyst. Further, the composition of the polyoxyethylene stearylamine obtained by methods (1) to (3) was analyzed by gas chromatography, and the composition was as follows.

C,H,OR The compound according to the present invention is obtained by dehydrating polyoxyethylene stearylamine having the above-mentioned composition with higher fatty acids, and when this compound is added to a synthetic resin, it has excellent properties. The reason why the compound exhibits electrical resistance and antifogging properties is that the compound is not a single compound, but there is a distribution of moles in the added part of ethylene oxide, and the distribution of the number of moles is moderate. Therefore, it is considered to be effective.

Similarly, because the reaction mode between higher aliphatic amines and ethylene oxide is specific, for example, it is practically impossible to obtain polyoxyethylene stearylamine having the above composition according to the present invention.

In addition, when adding ethylene oxide to polyoxyethylene stearyl obtained by addition reaction of more than 3 moles of ethylene oxide, which is outside the scope of the present invention, to 1 mole of stearylamine, compared to the compound according to the present invention, , poor in both electrical resistance and antifogging properties, especially poor in electrical resistance.

Furthermore, the amount of ethylene oxide per mole of stearyl acin is outside the scope of the present invention. When the dehydration reaction product of polyoxyethylene stearylamine obtained by addition reaction and higher fatty acid is added to a synthetic resin, the electrical resistance is lower than that of the composite according to the present invention. It is inferior in both anti-fog properties, especially in anti-fog properties.

When 1 mole of stearylamine is subjected to an addition reaction of 2 moles of ethylene oxide at a temperature of 150 to 180°C without the addition of a catalyst, the added mole of ethylene oxide having the structure of Although a product with no distribution in number can be obtained almost quantitatively, the dehydration reaction product of stearylgetanolamine and higher fatty acid is also inferior in effectiveness, like the above-mentioned addition reaction product.

Next, the higher fatty acid used to obtain the composite according to the present invention is a mixed fatty acid of stearic acid and valmitic acid having a composition of stearic acid SO ~80% by weight and valmitic acid SO 50-20% by weight. % stearic acid 60~
The composition 1c) obtained using a mixed fatty acid having a composition of 70 by weight and 40 to 30 by weight of barmitic acid is preferred in terms of effectiveness when carrying out the present invention.

The compositions obtained using mixed fatty acids whose stearic acid content is less than that of the SO type (valmitic acid content 50 wt. - thicker) compare in terms of effectiveness with the compositions according to the invention. , the heat resistance is the same but the electric resistance is inferior, and the composition obtained using mixed fatty acids with a stearic acid content of more than 80% by weight (valmitic acid content less than 20% by weight) Compared to the composite according to the present invention in terms of effectiveness, the anti-static property is almost the same, but the anti-fog property is considerably inferior.
Moreover, in this case, a blooming phenomenon occurs on the surface of the synthetic resin.

Furthermore, the compound according to the present invention can be obtained by dehydrating 1 mole of polyoxyethylene stearylamine in a range of 9 to 13 moles of higher fatty acid α, but when the number of moles of higher fatty acid is outside this range, It is inferior in terms of effectiveness,
This is not preferable because the resulting synthetic resin surface product exhibits bleeding and bluish phenomena.

The dehydration reaction is mostly an esterification reaction, but C,
H,OR Amidation reaction also occurs partially (Csa HsvN <
The compound obtained by the dehydration reaction of +R is an amide compound, unreacted polyoxyethylene stearylamine, monofatty acid ester of polyoxyethylene stearylamine, difatty acid ester of polyoxyethylene stearylamine, etc., and has the following structure. (However, R and R are stearic acid or palmitic acid residues) Although the mixture has the above structure, it acts in a complex manner and gives synthetic resins excellent electrical resistance and antifogging properties. Conceivable.

Further, the amount of the compound according to the present invention added to the synthetic resin is preferably αl to 3vi. The amount added is (L1 weight -
When the amount is less than 3, the desired anti-electricity and anti-fogging properties are not exhibited, and even if more than 3 weight is used, the effect remains the same and the cost becomes high economically, which is not preferable.

In carrying out the present invention, antioxidants, ultraviolet absorbers, anti-blocking agents, pigments, etc. may be added as necessary without interfering with the present invention.

In addition, the compound according to the present invention and antistatic agents such as polyoxyethylene amide, polyoxyethylene alkylamine, and quaternary ammonium compounds, or sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, and Antifogging agents such as oxyethylene alkyl ethers have been used in combination without impairing the effects of the present invention, but it is difficult to achieve effects exceeding those of the present invention in terms of electrical protection and antifogging properties.

The present invention can be applied to 11 processing methods commonly used industrially.

Hereinafter, the present invention will be explained in detail with reference to Examples.

Synthesis Example 1 140-150 to 1 mole of stearylamine of 95%
Reaction temperature in °C,! Under pressure of ~4 noodles/-, 1 mole of ethylene oxide was reacted, then cooled to 110°C, and 1
Ethylene oxide 1 under pressure at a reaction temperature of 00”-110°C
．． 5 moles were reacted. The obtained polyoxyethylene stearylamine had the following composition as a result of GLC analysis.

Other ash Next, a temperature needle, N, gas inlet tube, and water test tube were installed in the 972 Sco, 1 mole equivalent of polyoxyethylene stearyl ain, 1 mole phase of mixed fatty acid with a composition of 40% by weight of baluntic acid and 60% by weight of stearic acid. Prepare the volume and introduce N2 gas, 1
The resulting product, which was subjected to dehydration reaction at so%tso°C for 7 hours, was a pale yellow solid with a melting point of 42°C and an acid value of 21.

Synthesis Example 2 1 mole of 95% pure stearylamine! IO<17
Reaction temperature of 0℃,! 0 then Zoo'-10 in which 2 moles of ethylene oxide were reacted under a pressure of 1 to aIcf/-
At a reaction temperature of 0° C., 1 mole of ethylene oxide was subjected to an addition reaction under pressure to obtain polyoxyethylene stearylamine having the following composition.

Others Fist... tSS A dehydration reaction was carried out in the same manner as in Synthesis Example 1 using a 1 molar phase amount of this polyoxyethylene stearylamide and a 114 molar phase amount of mixed fatty acids having the composition of palmitic acid tO*S stearic acid son. This yielded a yellow solid with a melting point of 43°C.

Synthesis Examples 3 to 7 In the same manner as in Synthesis Example 1, the following compounds according to the present invention were obtained.

Comparative Example 1 1 mole of stearic acid with a purity of 95 KIISO ~ 170°C
2 moles of ethylene oxide were reacted at a reaction temperature of 2 to 4 −/− and a pressure of 2 to 4 −/−.

C, H, OR Others 7- Next, an amount equivalent to 1 mole of this reactant and 40-
A comparative compound which does not correspond to the scope of the present invention was obtained by comparing a 1 molar phase of a mixed fatty acid having a composition of 60% stearic acid with an electromagnetic acid.

Nine points.

Example 1 Polypropylene pellets (Mitsui Toatsu Chemical, Mitsui Noprene J8-957) if (Synthesis example, comparative example and conventional product were added with LOPHR and mixed thoroughly, then extruded using a 36cm extruder at an extrusion temperature of 210°C A 50 μm blown film was made.

The electrical resistance, antifogging properties, and film properties of the nine films prepared were investigated. The results are shown in Table IK.

Table 1 The method and criteria for performance evaluation were as follows.

(1) l! l! The surface resistance value was measured using a new super megohmmeter made by Kawaguchi Electric Co., Ltd. under the conditions of 20℃ and 65-RH.
The surface resistivity was determined using the following formula 1 & 7M surface resistance value.

The awards and measurements were made at 8th and 9th place after the film was created.

(2) Pour 40° C. hot water 50° into an anti-fogging 2QO beaker, cover the beaker opening with the prepared film, and secure with a rubber band.

This beaker was fixed in a constant temperature bath at 40° C., and the state of water droplets adhering to the inner surface of the film was observed to evaluate the antifogging property.

5......No water droplets observed 4...
...Status 3 where slight water droplets are observed...
・・・・・・Situation where water droplets are observed...
...Condition 1 where a considerable amount of water droplets are observed...
...Condition where water droplets are attached to the entire surface (3) During the bleed state, hang the film made with Dart Champamhi, and
・・・・・・Those who show bleaching...
・Procedural amendment in which a significant whitening phenomenon is observed (voluntary) June 77, 1932 Patent Office Director General Indication of the incident 1982 Patent Application No. 163444 2 Name of the invention Electrical resistance and protection Relationship with the case of the person making the λ amendment to the method for producing a synthetic resin with excellent cloudiness Patent applicant address: 1-14-94 Kakigara-cho, Nihonbashi, Chuo-ku, Tokyo Patent Shimizu of the specification subject to the amendment (D@@C) Column 2, Claims 2〇, 1 mole of polyoxyethylene stearylamine obtained by adding 15 to 10 moles of ethylene oxide to 1 mole of stearylamine represented by H□NH, Stearic acid 5G-80 weight, Valmitic acid 50-
Electrical protection and anti-static property characterized by adding 1-No weight of a compound obtained by dehydrating a higher fatty acid consisting of 40 mols in the range of α9 to 1.3 mols to a synthetic resin. A method for producing synthetic resin with excellent cloudiness.

Claims (1)

[Claims] Formula C1aH8? 1 mole of polyoxyalyl amine obtained by addition reaction of 25 to 10 moles of ethylene oxide to 1 mole of stearylamine represented by NH1, 80 to 80% by weight of stearic acid, and palmitic acid sO~! O weight-
Synthesis of 9 synthetic products obtained by dehydrating higher fatty acids in the range of a9 to L3 moles