CN1070311A

CN1070311A - A kind of fruit antirust agent and preparation method thereof

Info

Publication number: CN1070311A
Application number: CN 91108817
Authority: CN
Inventors: 何玉如; 宋锦玉; 赵永鹤; 王延河; 林民
Original assignee: Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 1991-09-11
Filing date: 1991-09-11
Publication date: 1993-03-31
Anticipated expiration: 2006-09-11
Also published as: CN1033202C

Abstract

The present invention proposes and be used to prevent that fruit from producing a kind of fruit antirust agent and the preparation thereof of rust staining.By pertroleum wax, dispersant, modified resin, gelating agent, compound emulsifying agent and water in proportion this fruit antirust agent of making of emulsification can reduce due to illness insect pest, wind and rain and sunshine effectively excessively or factor affecting such as applying pesticides and the fruit russeting that produces on the fruits such as the apple that causes, pears, thereby improve the commodity value of fruit significantly.

Description

A kind of fruit antirust agent and preparation method thereof

The present invention relates to a kind of fruit of forming by pertroleum wax, dispersant, resin, gelating agent, compound emulsifying agent and water that prevents and produce fruit antirust agent of rust staining and preparation method thereof.

Fruit cell division is rapid within behind the fruit tree fallen flowers 10-25 days, growth of young is rapid, grow different at the cuticula of fruit different parts, when being subjected to the influence that humidity changes (as the dew effect), cuticula can produce be full of cracks and come off, epidermal cell is exposed, run into damage by disease and insect this moment, wind and rain and sunshine are excessively or the effect of environmental factor such as applying pesticides, on young fruit, can form cork layer and then generate the cork cell, make fruit face peritheliumization, become fruit russeting, the area of high humidity (as: coastal area, rivers two sides), this kind situation is particularly serious.

For preventing the generation of fruit russeting, employing puts paper bag to each young fruit and solves this problem mostly.But the bagging method is not only taken a lot of work but also uneconomical.It is the generation that the poly emulsion replacement bagging method of 500-3000 suppresses fruit russeting that Japan Patent J46-241 proposes with mean molecule quantity, though pre-preventing disease and pest of its energy and the fruit russeting that excessively causes sunshine thereof, but because of its film that on young fruit, forms, gas permeability is bad, especially can not be to the moisture of the very strong young fruit surface evaporation of metabolism to external diffusion, these moisture are condensed in film, caused the fruit russeting identical with the rain and dew water generates.Japan Patent J47-32543 proposes to add inorganic matter as zinc with Heveatex or synthetic latex; Cosan waits and suppresses fruit russeting; though it has improved gas permeability; but can not prevent that sealing enters in the diaphragm from the occupied pore of these inorganic matters; thereby can not play the fruit rust inhibition effectively; it is oil-in-water type oxidic polyethylene or the paraffin of 1000-5000 and the water permeability that is improved diaphragm by the polyvinyl acetate of emulsion polymerization preparation that Japan Patent J47-34620 adopts mean molecule quantity; but poor adhesion; when dilution is used, be difficult to stick on the fruit surface equably.Japan Patent J48-503 adopts the suspension of white carbon black and polyvinylchloride latex as the fruit anti-rust agent for treatment, but its formed film ductility is good inadequately, and preparation is complicated, and cost is also high.General emulsified wax can not form continuous protecting film, thereby can not use as fruit antirust agent.

The objective of the invention is to propose that a kind of adhesiveness is strong, film forming continuously, evenly, the ductility of film is good, and have and to appear the steam that respiration of fruits evaporates, and can not penetrate extraneous aqueous water, easy to use, with low cost, preparation simply has the fruit antirust agent and the preparation thereof of extensive raw material sources.

The composition of the fruit antirust agent that the present invention proposes is: (percentage by weight, down together)

Pertroleum wax 7.0～40.0%

Dispersant 1.0～7.0%

Modified resin 5.0～35.0%

Gelating agent 0.05～1.6%

Compound emulsifying agent 3.0～10.0%

Water surplus

Fruit antirust agent preferably is made up of following:

8.0～35.0%, fusing point is that 54～58 ℃ refining paraffin wax white or the dropping point with microstructure are 75～80 ℃ ceresin(e) or the mixture of the two;

1.0～5.0% white oil, machinery oil or the mixture of the two;

6.0～30.0% modified resin.Being prepared as follows of modified resin: with 3.5-4.5 part rosin, hydrogenated rosin or their mixture and 2-8 part mean molecule quantity is that the polyisobutene of 500-2000 is at 125-190 ℃ with by 0.001-0.5 part C ₁₀～C ₃₀There is down stirring reaction 3-8.5 hour in modifier saturated or unsaturated fat acid sodium-salt or their mixture composition.

0.1～1.2% aliphatic amine, acid amides or the mixture of the two;

3.5～8.5% compound emulsifying agent of forming by anion surfactant and non-ionic surface active agent.Wherein anionic surface agent alive is preferentially recommended with C ₁₀-C ₃₀Saturated or unsaturated fatty acid or their mixture are formed; Non-ionic surface active agent is preferentially recommended with C ₁₀-C ₃₀The mixture of fatty alcohol-polyoxyethylene ether or derivatives thereof form.

Surplus is a water, recommends to use soft water, but optional.

The preparation method of fruit antirust agent of the present invention carries out under heating condition.In order with the 8.0-3.5% pertroleum wax, the 1.0-5.0% dispersant, the modified resin for preparing in advance of 6.0-30.0%, the gelating agent of 0.1-1.2%, 3.5～8.5% compound emulsifying agent adds in stainless steel or the enamel mixing reactor, temperature preferably is controlled between 60-140 ℃, slowly mix about 1.5～4.0 hours of reaction, again 50-100 ℃ excess water is added and mix, with mechanical agitation or colloid mill or homogenizer or ultrasonic emulsification 1.0-4.0 hour, be cooled to room temperature then, aging 10-30 hour again, can obtain fruit antirust agent of the present invention.

Fruit antirust agent of the present invention has adopted the pertroleum wax of wide material sources to make main raw material, thereby with low cost, has adopted dispersant thereby protecting film evenly continuous; Thereby adopted the modified resin that natural resin is carried out modification to make the hydrophobicity of protecting film strong, good permeability has the characteristic that can see through vaporous water and can not see through aqueous water, and can grow up and extend automatically with fruit, do not break, adopted gelating agent thereby adhesiveness strong.Dilution can stick on the fruit surface when using effectively, forms uniform protecting film; Adopted compound emulsifying agent, possessed extremely strong resistance to hard water, all can dilute, can breakdown of emulsion not take place and influence use with various natural waters; Adopted emulsifying technology thereby can spray with various Spray painting tools easily.

Be described more specifically the present invention with embodiment below.

Embodiment 1

1, the preparation of modified resin

With 1.5 parts of (weight, rosin down together), be equipped with in the reactor of 0.005 part of hexadecanoic acid sodium salt and 0.03 part of gaidic acid sodium 0.6 part hydrogenated rosin and 2.5 parts of mean molecule quantities are about 1000 polyisobutene adding, stirring reaction is about 5 hours under about 170 ℃ of temperature, promptly gets modified resin.

2, the preparation of fruit antirust agent (following all be weight percentage)

10% dropping point is 75 ℃ the ceresin(e) with microstructure;

12.0% dropping point is 80 ℃ the ceresin(e) with microstructure;

5.0% fusing point is 56 ℃ a refining paraffin wax white;

1.8% machinery oil;

6.5% modified resin;

The two diethanol amine of 0.15% NIL-12(lauroyl);

0.3% hexadecyldimethyl benzyl ammonium tertiary amine;

1.2% cocinic acid;

1.0% octadecanoid acid;

2.5% OS-15(fatty alcohol and ethylene oxide condensate)

By tab sequential it is added in about 90 ℃ of stainless steels or enamel reaction mixer that have an agitator, slowly stirring reaction is about 3.5 hours, after more about 85 ℃ of water being added mixing, with the emulsification of mechanical agitation emulsifier about 4 hours, be cooled to room temperature then, promptly made a kind of fruit antirust agent of the present invention again in aging about 20 hours.

Embodiment 2

1, the preparation of modified resin

With 20 parts of (weight, down with) rosin, 0.8 part of hydrogenated rosin and 3.5 parts of mean molecule quantities are that 1500 polyisobutene adding is equipped with in the reactor of 0.015 part of oleic acid sodium, and stirring reaction is about 8 hours under about 150 ℃ of temperature, promptly gets modified resin.

2, the preparation of fruit antirust agent (following all be weight percentage)

80 ℃ of ceresin(e)s of 5.0% dropping point with microstructure;

The refining paraffin wax white that 11.0% fusing point is 58 ℃;

The refining paraffin wax white that 3.0% fusing point is 54 ℃;

2.5% white oil;

1.0% machinery oil;

7.3% modified resin;

0.25% diethanol amine;

The two diethanol amine of 0.10% coconut acyl;

0.5% gaidic acid;

1.5% octadecanoid acid;

The condensation product of 2.8% EL-40(castor oil and oxirane);

The full thing that contracts of 0.5% 0-20(laruyl alcohol and oxirane);

Excess water

Press embodiment 1 described method preparation, different is that emulsion process was formed by homogenizer emulsification in 2 hours.

Embodiment 3.

1, the preparation of modified resin

With 1.2 parts of (weight, rosin down together), be equipped with in the reactor of 0.008 part of cocinic acid sodium and 0.005 part of gaidic acid sodium 1.0 part hydrogenated rosin and 2 parts of mean molecule quantities are about 800 polyisobutene adding, stirring reaction is about 7 hours under about 130 ℃ of temperature, gets final product.

2, the preparation of fruit antirust agent (following all be weight percentage)

8.0% dropping point is 75 ℃ of ceresin(e)s with microstructure;

15.0% fusing point is 58 ℃ a refining paraffin wax white;

7.0% fusing point is 56 ℃ a refining paraffin wax white;

2.2% white oil

1.5% machinery oil;

8.5% modified resin;

0.32% LOM-11(coconut acyl list diethanol amine);

0.10% triethanolamine;

2.8% oleic acid;

1.5% gaidic acid;

1.7% π-10(alkyl phenol and ethylene oxide condensate);

Excess water

Press embodiment 1 described method preparation, different is that emulsion process was formed by colloid mill emulsification in 3 hours.

Following result of the test is used for illustrating the applicable cases of embodiment.

The prepared fruit antirust agent application result of embodiment 1 is as follows: (to the short green apple of gold)

Annotate: 1,10 times of fingers with 10 times of fruit antirust agent dilute with waters after, spray in 10 days is once behind the apple fallen flowers; 10 times * 2 refer to spray for the second time in 18 days behind the fallen flowers spraying once in 10 days behind the apple fallen flowers behind 10 times of the fruit antirust agent dilute with waters, and the rest may be inferred for all the other, down with.

2, " contrast " result for not spraying fruit antirust agent.

3, the fruit russeting area is by 5 grades of system classification;

0 grade: rustless;

1 grade: rust is arranged below 1/4;

2 grades: 1/4-2/4 has rust;

3 grades: 2/4-3/4 has rust;

4 grades: rust is arranged more than 3/4.

Fruit russeting index %=(∑ (fruit russeting degree % * rank))/(highest number)

4, same under the fruit russeting Index for Calculation

The antirust agent application result following (to Gold Delicious apple) that embodiment 2 is prepared

The fruit antirust agent application result following (to the short green apple of gold) that embodiment 3 is prepared

Claims

1, a kind of be used to prevent fruit antirust agent that fruit produces rust staining by: pertroleum wax, compound emulsifying agent and water are formed, and it is characterized in that also containing dispersant, modified resin and gelating agent.Characteristic formula is as follows: (percentage by weight)

Pertroleum wax 7.0～40.0%

Dispersant 1.0～7.0%

Modified resin 5.0～35.0%

Gelating agent 0.05～1.6%

Compound emulsifying agent 3.0～10.0%

Water surplus

2, it is characterized in that according to the described fruit antirust agent of claim 1 described pertroleum wax is: paraffin, ceresine or the mixture of the two.

3, it is characterized in that according to the described fruit antirust agent of claim 1 described dispersant is: white oil, machinery oil or the mixture of the two.

4, it is characterized in that according to the described fruit antirust agent of claim 1 described gelating agent is: aliphatic amine, acid amides or the mixture of the two.

5, it is characterized in that according to the described fruit antirust agent of claim 1 described compound emulsifying agent is: form by anion surfactant and non-ionic surface active agent.

6, it is characterized in that according to the described fruit antirust agent of claim 1 described modified resin is: be that the polyisobutene of 500-2000 formed in stirring reaction 2-10 hour by 2-5 part (weight, down with) rosin, hydrogenated rosin or their mixture and 2-8 part mean molecule quantity in the presence of 120-200 ℃ and 0.001～0.5 part of modifier.

7, it is characterized in that according to the described fruit antirust agent of claim 6 said modifier is made up of the sodium salt of saturated fatty acid, unsaturated fatty acid or the two mixture.

8, a kind of fruit antirust agent preparation method is characterized in that: under 60-140 ℃ of condition, after pertroleum wax, dispersant, resin, gelating agent, compound emulsifying agent melted in order, hybrid reaction 1.5～4.0 hours, mix with 50-100 ℃ of water again and carry out emulsification and be cooled to room temperature, aging through 10-30 hour again.

9,, can adopt mechanical agitation, homogenizer homogenizing, colloid mill or ultrasonic emulsification according to the preparation method of the described fruit antirust agent of claim 8.