CN1164711C - Aqueous solution of new-type antistatic agent and its prepn - Google Patents

Aqueous solution of new-type antistatic agent and its prepn Download PDF

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Publication number
CN1164711C
CN1164711C CNB011307498A CN01130749A CN1164711C CN 1164711 C CN1164711 C CN 1164711C CN B011307498 A CNB011307498 A CN B011307498A CN 01130749 A CN01130749 A CN 01130749A CN 1164711 C CN1164711 C CN 1164711C
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China
Prior art keywords
antistatic agent
lithium
macromolecular compound
aqueous solution
reaction
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CNB011307498A
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CN1403528A (en
Inventor
杰 魏
魏杰
秦长喜
刘瀛
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Beijing University of Chemical Technology
China Lucky Film Group Corp
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Beijing University of Chemical Technology
China Lucky Film Group Corp
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Priority to CNB011307498A priority Critical patent/CN1164711C/en
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Abstract

The present invention relates to a novel aqueous solution for antistatic agents and a preparation method for the solution. The novel aqueous solution for antistatic agents comprises a high molecular compound (I), lithium salt and water, is used for antistatic coating layers of photosensitive supports, and can enable the supports to have high transparence and low surface resistance without influencing the photographic performance of photosensitive films. The formula is H (OCH2CH2) n-OOC-R1-CONH-R2-NHCO-R1-COO (CH2CH2O) nH, wherein R1 is-CH=CH-,-CH2-CH2,-C6H4-or-CH2-; R2 is C2-C4 alkylidene; n=9-45.

Description

A kind of antistatic agent aqueous solution and preparation thereof
Technical field
The present invention relates to the antistatic agent aqueous solution and preparation thereof in the sensitive film sheet base coating.
Background technology
The electrostatic problem of sensitive materials relates to a plurality of kinds such as colour positive, film, x-ray film, lithographic film, is a major issue in sensitive materials production and the use all the time.Especially in recent years, enforcement along with technology such as the raising of sensitive materials light sensitivity and high temperature rapid processing, serious electrostatic problem causes sensitive film to produce static spot, Newton's rings phenomenon, make that photographic fog increases, light sensitivity reduces, sharpness descends, even cause film to use and scrap, therefore, the electrostatic problem that solves sensitive film is more urgent, particularly prevents that generation of static electricity from being one of the problem that will note in the sensitive film production when coating.
Solve the electrostatic problem of sensitive film, the most frequently used method is that coating one antistatic backing is realized on the sheet base, by means of antistatic backing, sensitive materials has had enough good electroconductibility, make static charge be delivered to the coating apparatus guide shaft and discharge, in order to avoid certain point reaches too high electric density, thereby the danger of electric charge accumulation is reduced to minimum.Common employed static inhibitor mainly contains: (1) water absorbability inorganic salts; (2) water absorbability tensio-active agent and polymkeric substance carboxylic acid or Sulfonates; (3) ultra micro particulate metal oxide.
Up to now, reported the patent documentation of the synthetic and application facet that is used for antistatic agents used in photographic films in a large number both at home and abroad, each film manufacturer has also used different types of chemical substance to make antistatic agent to solve the electrostatic problem of sensitive materials, as day opening 95,239,531 medium and small western six companies disclose the photographic material of the anti-static coating that contains metal oxide particle, USP5,484,694, USP5, Kodak has also reported correlation technique in 356,468; 95,244, the 355 Konica companies that open disclosed and had R day A(CH 2CH 2O) nThe compound of H structure is as anti-static coating; European patent 693,709 discloses the antistatic material of fluoropolymer; USP5, Kodak has also reported the polymer-type antistatic technique in 366,855.At present, using more antistatic agent both at home and abroad is above-mentioned (2) type polymer type surface promoting agent, such as poly styrene sulfonate etc.All these all belong to above-mentioned three types antistatic agent, use these materials that sensitive materials is all had certain anti-static effect, but often also have some defectives.Anti-static effect is poor after a little while in add-on for (3) the kind method of use, and add-on influences the transparency of sensitive materials for a long time.Preceding two kinds of methods have certain antistatic property, especially method (2) is the main at present research of sensitive materials and a large amount of method of using, but because method (1) and (2) all are the purposes that reaches conduction by means of water sorption, thereby antistatic effect is poor under low-humidity environment, and moisture absorption seriously can cause between film inter-adhesive again under high humidity environment.
Purpose of the present invention
A kind of novel high polymer ionogen antistatic agent and preparation method thereof is provided.
The technical solution adopted in the present invention
A kind of antistatic agent aqueous solution that is used for sensitive materials polyester film base coating is made up of macromolecular compound, lithium salts and the water of following structure (I), and the each component weight percent is:
Macromolecular compound (I) content 8～30%,
Lithium salts 2～5%,
Water 65～90%.
(I)：H(OCH 2CH 2)nOCOR 1CONHR 2NHCOR 1COO(CH 2CH 2O)nH
R wherein 1For-CH=CH-,-CH 2-CH 2-,-C 6H 4-,-CH 2-,
R 2Be C 2-C 4Alkylidene group;
N is the positive integer of 9-45.
Preferred version is: macromolecular compound content is 15～20%; Lithium salt content 3～4%.
Described lithium salts is lithium chloride, lithium perchlorate, lithium thiocyanate, trifluoromethyl sulfonic acid lithium, can be that one or more lithium salts mix.
The preparation method of macromolecular compound provided by the invention (I), the half ester of diacid or dianhydride and polyoxyethylene glycol is combined to, temperature of reaction 50--140 ℃; Esterification products carries out crosslinking reaction with diamines again, temperature of reaction 50--120 ℃, makes high molecular polymer.
The half ester product that obtains diacid or dianhydride by above-mentioned reaction can be measured conversion rate of esterification by KOH saponification, the method that detects excessive KOH with the HCl reference liquid then.
Above-mentioned product and lithium salts blend, form polymer electrolyte, preparation obtains the antistatic agent aqueous solution, directly joins in the prime-coating liquid of sensitive materials polyester film base or the backing layer coating fluid to use, and its consumption in sensitive materials support anti-static coating is 2-10%.
Macromolecular compound relies on its temporary transient polarity compatible with lithium salts fully, and promotes dissociating of lithium salts by the interaction between polymer and metal ion, thereby still has high ionic conductivity under the lower situation of humidity.This will fundamentally be implemented under low wet environment and even the vacuum condition still has good electrical conductivity, and becomes permanent antistatic agent, thoroughly solves the antistatic problem of sensitive materials.
The present invention compares as antistatic agent with other similar polyelectrolyte type material, its advantage is that mainly diacid, dicarboxylic anhydride class material and the polyoxyethylene glycol selecting to suit synthesize esterification products, and it is crosslinked with amine substance, it mixes as the antistatic agent film-forming properties strong than independent use polyoxyethylene glycol with inorganic salt, be easy to mix with sensitive film polyester film base coating liquid, the transparency is good, and water absorbability is poor, at different humidity lower surface resistance stabilization.
Above-mentioned antistatic agent is joined in the sensitive materials support prime-coating liquid, coat on the support, be drying to obtain the sensitive materials support that can be coated with photographic emulsion.Antistatic agent of the present invention is applied to sensitive film polyester film base prime-coating, and the sheet primary surface resistance after the coating can reach 10 7～10 8Ω (RH=30%).
Embodiment
Below by embodiment the present invention is described further.
The concrete structure of macromolecular compound is as follows:
1、H(OCH 2CH 2) 9OOCCH＝CHCONHC 2H 4NHCOCH＝CHCOO(CH 2CH 2) 9H
2、H(OCH 2CH 2) 13.5OOCC 6H 4CONHCH 2CH 2NHCOC 6H 4COO(CH 2CH 2) 13.5H
3、H(OCH 2CH 2) 23OOCCONHCH 2CH 2CH 2NHCOCOO(CH 2CH 2) 23H
4、H(OCH 2CH 2) 9OOCC 2H 4CONH(CH 2) 4NHCOC 2H 4COO(CH 2CH 2) 9H
5、H(OCH 2CH 2) 45OOC(CH 2) 3CONHC 2H 4NHCO(CH 2) 3COO(CH 2CH 2) 45H
Anti-static polymer electrolyte preparation of the present invention is exemplified below:
Embodiment 1:
Have in the there-necked flask of mechanical stirrer, prolong and thermometer, add polyoxyethylene glycol (molecular weight 400) 122.4 grams, MALEIC ANHYDRIDE 30.0 grams stir, heat temperature raising to 50 ℃, react 3 hours.Drip quadrol 9.1 grams and stir, temperature is controlled at 80 ℃, 4 hours reaction times, obtain the esterification and crosslinking product, and saponification method is measured half ester transformation efficiency 96%; With lithium thiocyanate on demand concentration be mixed with the aqueous solution, under agitation above-mentioned esterification and crosslinking product and lithium thiocyanate are slowly added by 7: 1 (weight ratio), fully stirring the back transfers pH value 7～8 with sodium hydroxide, the total consumption of deionized water is 16 parts (weight ratios), the polymer solid electrolyte antistatic agent solution of promptly secure satisfactory grades sub-compounds content 30%, lithium salt content 4%.
Embodiment 2:
Have in the there-necked flask of mechanical stirrer, prolong and thermometer, add polyoxyethylene glycol (molecular weight 600) 81.6 grams, Tetra hydro Phthalic anhydride 20.1 grams stir, heat temperature raising to 140 ℃, react 10 hours.Drip quadrol 4.4 grams and stir, temperature is controlled at 120 ℃, 6 hours reaction times, obtain the esterification and crosslinking product, and saponification method is measured half ester transformation efficiency 95%; With lithium thiocyanate on demand concentration be mixed with the aqueous solution, under agitation above-mentioned esterification and crosslinking product and lithium thiocyanate are slowly added by 4: 1 (weight ratio), fully stirring the back transfers pH value 7～8 with sodium hydroxide, the total consumption of deionized water is 15 parts (weight ratios), the polymer solid electrolyte antistatic agent solution of promptly secure satisfactory grades sub-compounds content 20%, lithium salt content 5%.
Embodiment 3:
Polyoxyethylene glycol (molecular weight 1000) 130.0 grams, oxalic acid 11.7 grams, propylene diamine 5.2 grams carry out esterification, crosslinking reaction with example 1 same apparatus and reaction conditions, and saponification method is measured half ester transformation efficiency 〉=95% and by 4: 1 (weight ratio) carboxylate joined LiClO then 4In the solution (concentration preparation on request), transfer pH value 7～8, the total consumption of deionized water is 40 parts (weight ratios), the polymer solid electrolyte antistatic agent solution of can secure satisfactory grades sub-compounds content 8%, lithium salt content 2%.
Embodiment 4:
Polyoxyethylene glycol (molecular weight 400) 80.0 grams, Succinic Acid 23.6 grams, butanediamine 8.9 grams carry out esterification, crosslinking reaction with example 1 same apparatus and reaction conditions, and saponification method is measured half ester transformation efficiency 〉=95%, by 6: 1 (weight ratio) carboxylate is joined LiCl 2In the solution (concentration preparation on request), transfer pH value 7～8, the total consumption of deionized water is 13 parts (weight ratios), the polymer solid electrolyte antistatic agent solution of can secure satisfactory grades sub-compounds content 30%, lithium salt content 5%.
Embodiment 5:
Polyoxyethylene glycol (molecular weight 2000) 240.0 grams, propanedioic acid 12.5 grams, quadrol 4.5 grams carry out esterification, crosslinking reaction with example 1 same apparatus and reaction conditions, and saponification method is measured half ester transformation efficiency 〉=95%, by 5: 1 carboxylate is joined LiClO 4In the solution (concentration preparation on request), transfer pH value 7～8, the total consumption of deionized water is 19 parts (weight ratios), the polymer solid electrolyte antistatic agent solution of can secure satisfactory grades sub-compounds content 20%, lithium salt content 4%.
Embodiment 6: the coating application example
The polymer solid electrolyte antistatic agent of synthetic preparation is joined (main component comprises that vinylidene chloride is terpolymer aqueous latex, ethanol, gelatin, Resorcinol and the water of main body monomer and methacrylic acid and methyl acrylate) in the sensitive film polyester film base prime-coating liquid by 6%, coat the polyester film base that corona treatment is crossed, promptly get the sheet base that can be coated with photographic emulsion after the drying.
Use sodium polystyrene sulfonate, polyoxyethylene nonylphenol ether sodium succinate, polyoxyethylene glycol-600/LiCLO respectively 4Replace polymer solid electrolyte antistatic agent of the present invention, consumption is 6%, joins in the aforesaid sensitive film polyester film base prime-coating liquid (component as hereinbefore), coats the polyester film base that corona treatment is crossed, sample in contrast after the drying is used with the quadrat method test performance.
The invention effect
Coating rear panel primary surface resistance and other performance such as table 1.
Use antistatic agent Surface resistivity Ω Adhesion area (4)
RH：50％ RH：30％
Example 1 example 2 examples 3 examples 4 examples 5 3.8×10 7 4.5×10 7 6.8×10 7 2.1×10 7 7.5×10 7 4.2×10 8 6.1×10 8 4.7×10 8 3.3×10 8 6.0×10 8 22％ 23％ 21％ 25％ 22％
Contrast 1 (1)Contrast 2 (2)Contrast 3 (3) 8.5×10 8 9.3×10 9 1.3×10 8 6.3×10 117.9×10 123.5×10 8 35％ 30％ 43％
(1) adopt sodium polystyrene sulfonate to make antistatic agent
(2) adopt the polyoxyethylene nonylphenol ether sodium succinate to make antistatic agent
(3) polyoxyethylene glycol-600/LiClO 4Antistatic agent
(4) the anti performance is measured the ZBG80002-88 standard of pressing
By table 1 as seen, the anti-static polymer electrolyte of the present invention preparation joins in the polyester film base prime-coating liquid, coats the sheet base that polyester film base obtains being coated with photographic emulsion, its surface resistivity relative humidity 50% and 30% o'clock all less than 10 10Ω/cm 2, adhesion area≤25% meets the requirement that is coated with photographic emulsion.To in the same old way 1 and 2, surface resistivity is less than 10 during relative humidity 50% 10Ω/cm 2, but during relative humidity 30% surface resistivity greater than 10 10Ω/cm 2, and adhesion area＞25%, it is unfavorable to store and be coated with emulsion for the sheet base; To in the same old way 3, though in relative humidity 50% and 30% o'clock surface resistivity all less than 10 10Ω/cm 2, but the adhesion area reaches 43%, and antistatic agent of the present invention is compared with the contrast antistatic agent, can reduce surface resistivity, does not produce adhesion again, has reached goal of the invention.

Claims (6)

1, a kind of antistatic agent aqueous solution that is used for sensitive materials polyester film base coating is made up of macromolecular compound, lithium salts and the water of following structure (I), and the each component weight percent is:
Macromolecular compound (I) 8～30%,
Lithium salts 2～5%,
Water 65～90%
(I)：H(OCH 2CH 2) nOCOR 1CONHR 2NHCOR 1COO(CH 2CH 2O) nH
R wherein 1For-CH=CH-,-CH 2-CH 2-,-C 6H 4-,-CH 2-,
R 2Be C 2-C 4Alkylidene group;
N is the positive integer of 9-45.
2, the antistatic agent aqueous solution according to claim 1 is characterized in that contained lithium salts is lithium chloride, lithium perchlorate, lithium thiocyanate or trifluoromethyl Lithium Sulphate.
According to the described antistatic agent aqueous solution of claim 2, it is characterized in that 3, macromolecular compound content is 15～20%; Lithium salt content 3～4%.
4, the synthetic method of the macromolecular compound described in the claim 1 (I), its synthesis step is: diacid or dianhydride and polyoxyethylene glycol carry out the half ester reaction, and temperature of reaction is 50～140 ℃; Esterification products carries out crosslinking reaction with diamines again, and temperature of reaction is 50～120 ℃.
5, the synthetic method of macromolecular compound according to claim 4 is characterized in that described diacid is propanedioic acid or Succinic Acid.
6, the synthetic method of macromolecular compound according to claim 4 is characterized in that described dianhydride is MALEIC ANHYDRIDE or Tetra hydro Phthalic anhydride.
CNB011307498A 2001-08-23 2001-08-23 Aqueous solution of new-type antistatic agent and its prepn Expired - Fee Related CN1164711C (en)

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CN1314634C (en) * 2004-09-17 2007-05-09 南京理工大学 Static electricity reducing processing method for single chemical compound explosive
CN101805521A (en) * 2010-03-19 2010-08-18 东莞市宏达新材料有限公司 Antistatic silica gel composition and preparation method thereof
CN102304221A (en) * 2011-08-25 2012-01-04 吴江市北厍盛源纺织品助剂厂 Antistatic agent for preparing antistatic polyurethane

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