JPS62104842A - Antiblocking agent for raw rubber - Google Patents

Abstract

PURPOSE:An antiblocking agent, obtained by incorporating a specific phosphoric acid ester compound with specific higher fatty acid/polyalkylene polyamine condensate and having good wetting property and remarkably improved antiblocking effect without any cissing on the surface of rubber sheets. CONSTITUTION:An antiblocking agent for raw rubber obtained by incorporating (A) 100pts.wt. phosphoric acid ester compound expressed by formula I (R1 is nonylphenyl, octylphenyl, dinonylphenyl, 8-24C alkyl or alkenyl; R2 is C2H4 or C3H6; m is an integer 4-20; x is 1 or 2) with (B) 5-200pts.wt. condensate of a higher fatty acid with an alkyleneamine or amino-alcohol expressed by formula II (R3 is 9-23C alkyl or alkenyl; R4 is C2H4 or C3H6; R5 is NH2 or NHOCR3; n is 0 or an integer 1-4) or a compound prepared by condensing the condensate with urea, etc. 0-500pts.wt., based on 100pts.wt. total of the components (A) and (B), calcium carbonate or talc may be further incorporated.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an anti-adhesive agent for raw rubber, the main component of which is a blend of a phosphate ester surfactant and a condensate of a higher fatty acid and a polyalkylenepolamine.

Generally, when storing raw comb in the form of sheets, so-called unvulcanized rubber sheets, blocking occurs during storage unless an anti-adhesive agent is applied to the surface of the rubber sheets to be stacked r'+jf.

There are two types of anti-adhesive treatment methods used to prevent blocking: a wet method and a dry method. In the latter dry method, powders such as calcium carbonate, talc, and clay are applied directly to the surface of the unvulcanized rubber sheet to prevent the rubber from sticking, but the scattering of the powder contaminates the working environment and poses a health hazard. In addition, the former wet method is generally preferable because there are undesirable problems in terms of machine maintenance. Conventionally, as anti-adhesion agents for wet processing, inorganic powders such as calcium carbonate, talc, clay, magnesium carbonate, or powdered metal soaps have been suspended in water to prevent rubber from adhering. However.

The anti-adhesive agent attached to the rubber sheet will scatter when the moisture is removed. In addition, the sheets may peel off and scatter when handled, causing environmental pollution due to dust as in the dry method, and damaging mechanical equipment, which is undesirable.

Recently, silicone-based compositions and higher fatty acid metal salts have been used as anti-adhesive agents. Although these have good adhesion-preventing properties, when a rubber sheet is immersed in an anti-adhesive bath, the surface of the rubber sheet will repel and become wet. This is not good, and when the moisture is gone, the adhering powder will scatter. Moreover, it has the disadvantage that the physical properties of the vulcanized rubber are deteriorated considerably.

As a result of intensive research to improve the drawbacks of conventional anti-adhesion agents, the present inventors used a mixture of a compound represented by general formula (1) and a compound represented by general formula (II) as an anti-adhesion agent. In this case, there is no repellency on the surface of the rubber sheet, the wetting is good, and the adhesion prevention effect is particularly excellent. Alternatively, by using a powdered inorganic substance such as calcium carbonate or talc in combination with the mixture of the compounds of general formulas (1) and (n) of the present invention.

Furthermore, it was discovered that the anti-adhesion effect is improved, and the redispersibility of the powder is also excellent, so that there is no scattering of the adhering powder, which led to the present invention.

That is, the composition of the present invention has the general formula (1) (wherein R1 is a nonylphenyl group, an octylphenyl group, a dinonylphenyl group, an alkyl group or an alkenyl group having 8 to 24 carbon atoms, and R2 is an alkylene group. ,C,H
, or and C, H, , m represents an integer from 4 to 20,
X is 1 or 2)) based on 100 parts by weight of at least one phosphoric acid ester compound represented by the general formula (II) R3 is an alkyl group or alkenyl group having 9 to 23 carbon atoms, R4 is C, H4 or C, R5 is NH,
A condensate of a higher fatty acid represented by NHOCR, or OH (n is an integer of 0 or 1 to 4) and alkylene amines or amino alcohols, or a compound obtained by condensing the above condensate with urea or thiourea. at least one of
It is characterized in that the main component is a blend containing 5 to 200 parts by weight of seeds.

The compounds represented by the general formulas (1) and (II) according to the present invention can be obtained by the following method. First, nonylphenol, octylphenol, dinonylphenol, or octyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol,
Carbon number 8 such as oleyl alcohol and behenyl alcohol
A polyoxyalkylenated alkylphenol and a polyoxyalkylenated alcohol can be obtained by a known method of adding a basic catalyst or an acidic catalyst to the higher alcohol of ~24 and adding ethylene oxide or propylene oxide at a high temperature. Further, addition of alkylene oxide may be carried out by mixing ethylene oxide and propylene oxide and reacting the mixture.

Thus, the obtained polyoxyalkylenated alkylphenol and polyoxyalkylenated alcohol are phosphoric esterified by a known method using a phosphorylating agent such as phosphorus pentoxide or phosphorus oxychloride, thereby producing the general product of the present invention. A compound represented by formula (1) is obtained. Further, the phosphoric acid ester compound thus obtained is usually a mixture containing a phosphoric acid monoester compound and a phosphoric acid diester compound as main components, but a phosphoric acid triester compound may be partially included.

Next, the compound represented by the general formula (II) according to the present invention is obtained by mixing 1 mol to 4 mol of higher fatty acids and 1 mol of alkylene amines or amino alcohols, and heating the mixture at 100°C to 200°C, preferably. is a condensate that can be easily obtained by carrying out an amidation reaction sufficiently at 150°C to 200°C by a known method.

The higher fatty acids used here have 10 to 2.1 carbon atoms.
Specific examples of saturated or unsaturated fatty acids include lauric acid, myristic acid, valmitic acid, stearic acid, 12-human tetearic acid, oleic acid, ricinoleic acid, erucic acid, and behenic acid. , alkyleneamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, and dipropylenetriamine, and aminoalcohols include aminoethylethanolamine, monoethanolamine, and motuprobanol. Examples include amines.

In addition, 2 moles of a condensate of higher fatty acids and alkylene amines or amino alcohols and 1 mol of urea or 1,000 urea
A condensate obtained by mixing mol to 2 mol and sufficiently carrying out a bisamidation reaction at 1 OQ'C to 200°C, preferably 120°C to 150°C by a known method can also be used.

The anti-adhesion agent composition for unvulcanized rubber according to the present invention has the general formula (
5 to 20 parts of at least one compound of general formula (II) to 100 parts by weight of at least one compound of formula (1)
0 parts by weight, preferably 30 to 150 parts by weight.

The anti-fouling liquid is prepared by emulsifying or dispersing a mixture of the compound of general formula (1) and the compound of general formula (2) (hereinafter referred to as the composition of the present invention) in water, and then adjusting the mixture to a predetermined concentration. Dilute. Waterproof liquid concentration is 1-15%, especially 1-6%
is preferred. If it exceeds 15%, the peel strength will decrease, but the rubber surface will remain sticky and the physical properties of the rubber will deteriorate, which is not preferable.

Next, based on 100 parts by weight of the composition of the present invention, 0 to 500 parts, preferably 5 parts by weight, of a powdered inorganic substance such as calcium carbonate, talc, clay, mica, magnesium carbonate, etc.
By using 0 to 300 parts by weight, the adhesion prevention effect is further improved, and the powder has excellent redispersibility.
It is possible to obtain an anti-adhesion liquid with no powder scattering at all.

Rubber substances targeted by the anti-adhesive agent of the present invention include natural rubber, butadiene styrene rubber, butadiene acrylonitrile rubber, chloroprene rubber, and the like.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

Example 15 Example (1) Production example of anti-adhesive agent according to the present invention (anti-adhesive agent A) 1 mol (8 mol) of nonylphenol was placed in an autoclave reactor.
80 parts) and caustic potash (2 parts), and after vacuum dehydration, 15
10 moles (1760 parts) of ethylene oxide are introduced at 0 to 170°C, and addition polymerization is carried out at a pressure of 5 kg/- or less to obtain poly(10) oxyethylene nonylbuenyl ether. Furthermore, 1 mol (2640 parts) of the obtained poly(10)oxyethylene nonylphenyl ether was added with 0 phosphorus pentoxide.
4 mol (227 parts) was reacted to obtain a liquid substance containing 60% phosphoric acid monoester and 34% phosphoric diester. It is referred to as compound (1) of anti-adhesive agent A.

Next, 1 mol (282 parts) of oleic acid and 1 mol (146 parts) of triethylenetetraamine were charged into a four-bottle flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a cooling tube.
A dehydration reaction was carried out at 70°C for 5 hours to obtain a liquid substance of monoamide (410 parts) of oleic acid and triethylenetetramine. It is referred to as compound (II) of anti-adhesive agent A.

100 parts of compound (I) and 60 parts of compound (II) were mixed and stirred to obtain a viscous liquid substance. It is referred to as anti-adhesive agent A according to the present invention.

(Anti-adhesion agent B) Using the same equipment and method as compound (I) of anti-adhesion agent A, 3 mol of propylene oxide was added to 1 mol of lauryl alcohol, and then 3 mol of ethylene oxide was added to form poly(3)oxypropylene. - Obtain poly(3)oxyethylene lauryl ether. Next.

To 1 mol of the obtained poly(3) oxypropylene-poly(3)-oxyethylene lauryl ether was added 0.0 phosphorus pentoxide.
4 moles were reacted to obtain an oily substance containing 65% phosphoric acid monoester and 31% phosphoric diester. It is referred to as compound (1) of anti-adhesive agent B.

Next, 1 mol of stearic acid and aminoethyl airmite (
410 parts) of a liquid substance was obtained. Compound of anti-adhesion agent A ([1
).

100 parts of compound (1) and 60 parts of compound (b) were mixed and stirred to obtain a viscous liquid substance. It is referred to as anti-adhesive agent A according to the present invention.

(Anti-adhesive agent B) Using the same equipment and method as for compound (I), 3 mols of propylene oxide was added to 1 mol of lauryl alcohol, and 3 mols of ethylene oxide was added by blowing. Propylene-poly(3)oxyethylene lauryl ether is obtained. 1 Next, 1 mole of the obtained poly(3)oxypropylene-poly(3)-oxyethylene lauryl ether was reacted with 0.4 mole of phosphorus pentoxide to obtain a phosphoric acid monoester content of 65% and a phosphoric acid diester content of 31%. An oily substance containing . It is referred to as compound (1) of anti-adhesive agent B.

Next, 1 mole of stearic acid and 1 mole of aminoethylethanolamine were reacted using the same apparatus and method as for compound (II) of anti-adhesive agent A to form a monoafide of stearic acid and aminoethylethanolamine (stefuramide ethylethanol). A solid substance (at room temperature) of amine) was obtained. Furthermore, 2 moles of the obtained stefuramidoethylethanolamine and 1 mole of urea were reacted to form a solid substance (at room temperature) of N,N'-distearoamidoethyl-N,N'-dihydroxyethyl urea. Obtained. Compound of anti-adhesion agent B (11
).

Compound (1) loop part and 50 parts of compound ([1)] were heated and mixed to obtain a paste-like substance. It is referred to as anti-adhesive agent B according to the present invention.

(Deposition preventive agent C-H of the present invention and comparative antideposition agents I and J) Deposition preventive agent C-H of the present invention synthesized using the same apparatus and method as Compound (I) and (B) of the deposit preventive agent A (2) Anti-adhesion test The raw rubber used in the anti-adhesion test had the composition shown in Table 2.

Table 2 Composition of Raw Rubber (Test Method) The rubber dough shown in Table 2 is kneaded again and made into a sheet with a thickness of 3 to 5 mm. 3.0X the sheeted com fabric
A test piece was cut into a rectangular shape of IO, Ors.

Next, Test No. 1 was immersed in each anti-adhesive treatment bath and air-dried. After air-drying, the two combs were put together and a load of LOOG/A was applied and left for 2.1 hours.

Thereafter, the force required for peeling was measured using a Schopper type tensile tester. In addition, the state of adhesion of powder on the peeled surface was observed.

The composition of the anti-adhesive treatment method is summarized in Table 3.

(Adhesion resistance test results) The anti-adhesion test results are shown in Table 3.

5・-1t9 The control was made of rubber fabric that had not been treated with an anti-adhesive agent.

From the results of the adhesion prevention test in Table 3, it was found that the products of the present invention (anti-adhesion agents A to old) had significantly better anti-adhesion effects than the comparative products (anti-adhesion agents I and J), and there was no powder scattering. Old-fashioned.

Claims (2)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) (However, R_1 is a nonylphenyl group, octylphenyl group, dinonylphenyl group, or an alkyl group having 8 to 24 carbon atoms. or an alkenyl group, R_2 is an alkylene group, and C
_2H_4 or and C_3H_4, m represents an integer from 4 to 20, and x is 1 or 2. ) of the general formula (II) R_3CONH(R_4NH)nR_4R_5...
・・・・・・(II) (However, in the formula, R_3 has a carbon number of 9 to 23
alkyl or alkenyl group, R_4 is C_2H_
4 or C_3H_4, R_5 is NH_2, NHOCR
At least one of a condensate of a higher fatty acid represented by _3 or OH (n is an integer of 0 or 1 to 4) and alkylene amines or amino alcohols, or a compound obtained by condensing the condensate with urea or thiourea. Seeds 5-200
An anti-adhesive agent for raw rubber, characterized in that the main component is a product blended with parts by weight. (2) Compound 100 of compounds of general formulas (I) and (II)
The anti-adhesion agent for raw rubber according to claim 1, which contains 0 to 500 parts by weight of a powdered inorganic substance such as calcium carbonate or talc.