JPH0515753B2 - - Google Patents

Description

[Detailed description of the invention]

Conventionally, surfactants have a wide range of properties such as emulsification, dispersion, cleaning, wetting, and foaming, and these properties have been used to improve materials such as fibers, paper, rubber, plastics, metals, and paints. It is used in various fields such as pigments, civil engineering and architecture. Particularly recently, there has been an active movement toward improving the performance of end products using surfactants, and along with this, secondary drawbacks of surfactants have also been pointed out. For example, paints, printing inks, adhesives, pressure-sensitive adhesives, etc. are used during the manufacturing of the product, or during product stabilization.
Furthermore, it is indispensable in terms of workability and the like. When these products are used in applications such as coating, printing, adhesion, and adhesion, surfactants are not necessary; rather, the surfactants present are responsible for forming coatings, printed surfaces, and adhesive films. In many cases, performance such as water resistance and oil resistance may be deteriorated. As a countermeasure to these problems, efforts have been made to reduce the amount of surfactants blended and to use polymeric surfactants, but these problems have not yet been fully resolved in terms of product stability and workability. It's not on. On the other hand, in order to provide new types of surfactants, there are many patents for polymerizable, reactive, or degradable surfactants. For example, as an anionic surfactant,
No. 34894, Special Publication No. 56-29657, Japanese Patent Publication No. 51-30285
No. 49-46291, JP-A No. 56-127697, etc. As a nonionic surfactant, JP-A-56
-28208, JP-A-50-98484, etc. The present invention is based on the general formula: [However, in the above formula, R is an alkyl group having 8 to 30 carbon atoms, an alkenyl group, an alkylaryl group, or an aralkylaryl group, A is an alkylene group having 2 to 4 carbon atoms, or a substituted alkylene group, and n is 0 to 100 , m is an integer from 1 to 200, and M is an alkali metal atom, NH ₄ , or an alkanolamine residue. ] Provided is a synthetic resin antistatic agent characterized by comprising a compound represented by the following. In the general formula, R is an alkyl group, alkenyl group, alkylaryl group, or aralkylaryl group having 8 to 30 carbon atoms, and examples of the alkyl group include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, and tetradecyl. ,
Examples include pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, and the like. Examples of alkenyl groups include octenyl,
Examples include nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, and the like. Examples of the alkylaryl group include monobutylphenol, dibutylphenol, sec-butylphenol, disec-butylphenol, tert-butylphenol, octylphenol, nonylphenol, dinonylphenol, dodecylphenol, and didecylphenol. Examples of aralkyl phenols include mono-, di-, and tri-styrene phenols, benzyl phenols, cumyl phenols, and the like, or mixtures thereof, and may be mixtures of these alkyl groups. Further, A is an alkylene group or substituted alkylene group having 2 to 4 carbon atoms, such as ethylene, propylene, butylene, isobutylene, etc., and may be a single group or a block or random mixture thereof. n is an integer of 0 to 100, m is an integer of 1 to 200, more preferably n is 0 or 1 to 50, m is 2
~100 range. Furthermore, the antistatic agent of the present invention can be easily manufactured industrially, and can be manufactured, for example, as follows. That is, nonylphenol or lauryl alcohol is used as a raw material, alkylene oxide is added if necessary, and allyl glycidyl ether is heated and reacted in the presence of a catalyst.
An alkylene oxide is further added to the obtained reaction composition in a conventional manner. Next, it can be obtained by sulfating with a sulfating agent such as sulfuric acid or sulfamic acid, and neutralizing with a basic substance if necessary. EXAMPLES Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not limited thereto. (%, parts and parts are based on weight.) Production Example 1 220g (1.0 mol) of nonylphenol and 1.5g of triethylamine as a solvent were charged into a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, and then allylglycidyl was added. Add 114 g (1.0 mol) of ether dropwise to 100
The mixture was stirred at ℃ for 5 hours. Next, the obtained reaction composition was transferred to an autoclave, and caustic potassium was used as a catalyst to
10 mol, 30 mol, and 100 mol of ethylene oxide were added to the reaction composition under conditions of cm ² and temperature of 130° C. to obtain compositions. Next, 387 g (0.5 mol) of the 10 mol ethylene oxide adduct of the above reaction composition and 58.2 g (0.6 mol) of sulfamic acid were placed in a reaction vessel equipped with a stirrer and a thermometer, and the temperature was raised to 120°C. The reaction was stirred for a period of time and sulfation was carried out. The composition obtained by removing unreacted sulfamic acid by filtration was designated as the surfactant of the present invention [A]. The ammonium sulfate ester of an adduct of 30 moles of ethylene oxide obtained in the same manner was used as the surfactant of the present invention [B], and the ammonium sulfate of an adduct of 100 moles of ethylene oxide was used as the surfactant of the present invention [B]. C]. Production Example 2 Into a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, 186 g (1.0 mol) of lauryl alcohol and 0.6 g of boron trifluoride ether complex as a catalyst were charged, and then 228 g (2.0 mol) of allyl glycidyl ether was added dropwise. After stirring at 80°C for 5 hours, the mixture was heated to 120°C and excess allyl glycidyl ether was removed under reduced pressure. Next, the obtained reaction composition was transferred to an autoclave, and caustic potassium was used as a catalyst to reduce pressure.
Ethylene oxide was added to the reaction composition at a rate of 1.5Kg/cm ² and a temperature of 130°C at 5 moles, 20 moles, and 50 moles.
The composition obtained by the molar addition was sulfated according to Production Example 1, and the obtained sulfate ester ammonium salt of the 5 mol ethylene oxide adduct was added to the surfactant of the present invention [D] and 20 mol ethylene oxide. The ammonium sulfate ester salt of the adduct was designated as the surfactant of the present invention [E], and the ammonium sulfate ester salt of the 50 mole ethylene oxide adduct was designated as the surfactant of the present invention [F]. Production Example 3 In a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, add 10 moles of distyrenated phenol ethylene oxide and 2 moles of propylene oxide block adduct.
856 g (1.0 mol) and 2 g of boron trifluoride ether complex as a catalyst were added, and then 228 g (2.0 mol) of allyl glycidyl ether was added dropwise. After stirring at 80°C for 5 hours, the mixture was heated to 120°C and reduced pressure. Excess allyl glycidyl ether was removed. Next, the obtained reaction composition was transferred to an autoclave, and caustic potassium was used as a catalyst at a pressure of 1.5 Kg/cm ² and a temperature of 130°C.
The composition obtained by adding 15 moles and 40 moles of ethylene oxide to the reaction composition under the conditions of The ester ammonium salt was used as the surfactant of the present invention [G], and the sulfuric acid ester ammonium salt of a 40 mol ethylene oxide adduct was used as the surfactant of the present invention [H]. Production Example 4 Into a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, 1588 g (1.0 mol) of 30 mol adduct of oleyl alcohol ethylene oxide and 3 g of boron trifluoride ether complex as a catalyst were charged, and then 228 g of allyl glycidyl ether ( 2.0 mol) was added dropwise and the mixture was heated at 80°C.
After stirring for an hour, the mixture was heated to 120°C and excess allyl glycidyl ether was removed under reduced pressure. Next, the obtained reaction composition was transferred to an autoclave, and caustic potassium was used as a catalyst at a pressure of 1.5 Kg/cm ² and a temperature of 130°C.
A composition obtained by randomly adding 40 moles of ethylene oxide and 10 moles of propylene oxide to the reaction composition at An equivalent amount of caustic soda to the sulfamic acid is added to the obtained sulfate to remove ammonia, and the obtained sulfate ester sodium salt is used as the surfactant of the present invention []
And so. Production Example 5 A reaction vessel equipped with a stirrer, a thermometer, and a reflux tube was charged with 385 g (1.0 mol) of a 2-mol adduct of stearyl alcohol propylene oxide and 1.5 g of boron trifluoride ether complex as a catalyst, and then allyl glycidyl ether was charged. 228 g (2.0 mol) was added dropwise, and 80
After stirring at ℃ for 5 hours, the mixture was heated to 120 ℃ and excess allyl glycidyl ether was removed under reduced pressure. Next, the obtained reaction composition was transferred to an autoclave, and a pressure of 1.5 kg/kg was added using caustic potassium as a catalyst.
The composition obtained by adding 2 moles or 5 moles of ethylene oxide at a temperature of 130° C. was sulfated using sulfamic acid according to Production Example ¹ , and the resulting sulfated product was An equivalent amount of monoethanolamine to sulfamic acid was added to remove ammonia. Sulfate ester monoethanolamine salt,
This was designated as the surfactant of the present invention [K]. Production Example 6 A reaction vessel equipped with a stirrer, a thermometer, and a reflux tube was
278 g (1.0 mol) of sec-butylphenol butylene oxide 3 mol adduct and 1 g of boron trifluoride ether complex as a catalyst were charged, and then 228 g (2.0 mol) of allyl glycidyl ether was added dropwise to the mixture, and the mixture was heated at 80°C.
After stirring for 5 hours, the mixture was heated to 120°C, and excess allyl glycidyl ether was removed under reduced pressure.
Next, the obtained reaction composition was transferred to an autoclave, and a pressure of 1.5 Kg/cm ² was applied using caustic potassium as a catalyst.
At a temperature of 130℃, propylene oxide 2
15 moles of ethylene oxide were added to the reaction composition, the resulting composition was sulfated according to Production Example 1, and the obtained sulfate ester ammonium salt was added to the surfactant of the present invention [L]. And so. Production Example 7 Into a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, 1244 g (1.0 mol) of a 20 mol adduct of tribenzylphenol ethylene oxide and 4 g of boron trifluoride ether complex as a catalyst were charged, and then 228 g of allyl glycidyl ether was charged. (2.0 mol) was added dropwise, and after stirring at 80°C for 5 hours, the mixture was heated to 120°C, and excess allyl glycidyl ether was removed under reduced pressure. Next, the obtained reaction composition was transferred to an autoclave,
Using caustic potassium as a catalyst, 5 mol of propylene oxide was added to the reaction composition at a pressure of 1.5 Kg/cm ² and a temperature of 130°C, and the resulting composition was sulfated according to Production Example 1. The sulfuric acid ester ammonium salt obtained was designated as the surfactant of the present invention [M]. Example 1 The surface tensions of aqueous solutions of the surfactants [A] to [M] of the present invention obtained in Production Examples 1 to 7 were measured. In addition, the surface tension of a conventional surfactant is also shown as a comparative product. (Surface tension was measured by the Traube method.) The results are shown in Table 1.

【table】

[Table] Example 2 Charge 5 g of the surfactant shown in Table 2, 50 g of methyl acrylate, 0.5 g of benzoyl peroxide, and 200 g of toluene into a flask, and heat to 80°C while stirring.
The polymerization reaction was carried out by heating for 10 minutes. The obtained polymer solution was poured onto a glass plate to a dry film thickness of 0.5 mm, dried at room temperature for 1 day, and then dried in an oven at 80° C. for 3 hours. The resulting film was tested for appearance, water resistance and surface resistivity. The results are shown in Table 2.

[Table] Example 3 Low density polyethylene containing 0.5% of the surfactant shown in Table 3 (film grade M 1.0g/
A film with a thickness of 0.3 mm was prepared using the T-die method (10 min.), and the surface resistivity and frictional charge were measured and compared with those without the addition of surfactant.

[Table] Example 4 ABS resin (general grade MI 14g/10min.)
2 parts of the surfactant shown in Table 4 was kneaded into 100 parts by roll kneading, and a sheet having a thickness of 1 mm was formed by press working. The surface resistivity and frictional charging voltage of the sheet were measured and compared with those without any surfactant added.

[Table] Example 5 0.5 parts of 2,2'-azobisisobutyronitrile and 12.5 parts of the surfactant shown in Table 5 were dissolved in 250 parts of methyl methacrylate and immersed in an oil bath heated to 200°C. After 60 minutes, remove from the oil bath and cool quickly. Next, 0.05% of 2,2'-azobisisobutyronitrile was added and mixed to this prepolymerized product, and then poured between two glass plates, immersed in an aqueous solution at 60°C for 20 minutes, and then heated to 120°C. A polymethyl methacrylate plate was prepared by heating in an air bath for 60 minutes, and its surface resistivity was measured and compared with one without the addition of surfactant.

【table】

Claims (1)

[Claims] 1 General formula, [However, in the above formula, R is an alkyl group having 8 to 30 carbon atoms, an alkenyl group, an alkylaryl group, or an aralkylaryl group, A is an alkylene group having 2 to 4 carbon atoms, or a substituted alkylene group, and n is 0 to 100 , m is an integer from 1 to 200, and M is an alkali metal atom, NH ₄ , or an alkanolamine residue. ] A synthetic resin antistatic agent characterized by comprising a compound represented by the following.