CN100475866C - Method for preparing acrylic ester pressure sensitive glue emulsion without using butal acrylate and use - Google Patents

Method for preparing acrylic ester pressure sensitive glue emulsion without using butal acrylate and use Download PDF

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CN100475866C
CN100475866C CNB2005100344005A CN200510034400A CN100475866C CN 100475866 C CN100475866 C CN 100475866C CN B2005100344005 A CNB2005100344005 A CN B2005100344005A CN 200510034400 A CN200510034400 A CN 200510034400A CN 100475866 C CN100475866 C CN 100475866C
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quality percentage
sodium
percentage composition
butyl acrylate
pressure sensitive
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CN1858075A (en
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李建宗
吴伟卿
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Guangdong Hongchang New Material Technology Co., Ltd
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HONGCHANG ADHESIVE TAPES FACTORY GUANGZHOU CITY
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Abstract

The present invention relates to recipe, production process and application of novel acrylate pressure sensitive glue emulsion. The new acrylate pressure sensitive glue emulsion product has performance similar to that of conventional butyl acrylate pressure sensitive glue emulsion, but cheaper and facile material and environment friendship.

Description

Produce the method for making and the application of acrylate pressure-sensitive adhesive emulsion without butyl acrylate
Technical field:
The present invention relates to not use fully butyl acrylate (BA), and the synthetic performance of homologue, derivative and other monomer of using acrylate is the similar pressure-sensitive adhesive emulsion of the synthetic performance of principal monomer to using with BA.
Background technology:
Pressure-sensitive adhesive tape is a kind of very useful material, plays a significant role in national economy, and making the main former material of pressure sensitive adhesive has two big class, i.e. rubber and esters of acrylic acid materials.The early stage main rubber that uses prepares pressure-sensitive adhesive, but this type of tackiness agent adds that the development of acrylic ester monomer production technology is very fast, price is suitable owing to come with some shortcomings on the performance.Therefore formed rubber-type ratio decline in the pressure sensitive adhesive, the situation of the very fast rising of esters of acrylic acid, arrived the eighties, esters of acrylic acid has entered Rapid development stage, and its consumption is increasing, the research of this respect is also more and more, arrived late nineteen eighties, it is main raw material that the early 1990s has basically formed with the butyl acrylate, and it accounts for more than 80% of monomer total amount.Better with BA production pressure sensitive adhesive product performance; production technique is also ripe; and it is simpler; but run into the appearance of the oil crisis second half year in 2004; this butyl acrylate output from oil also descends greatly; the market supply shortage of following and coming; big bulge in price; by oil, not only produced BA, in fact be series product; wherein some homologue or derivative are then good and cheap; but unsalable, utilize petroleum resources and overcome oil crisis and bring difficulty for more reasonable, the surrogate of seeking BA is highly significant.According to pressure sensitive adhesive manufacturing principle, infer in theory as also producing performance classes without BA like the pressure-sensitive glue of producing with BA, reach abroad also beyond example though this China is industrial.But,, prepared successfully no BA pressure-sensitive glue finally, and performance and basic identical with BA production glue through repetition test according to producing the pressure sensitive adhesive principle.
Summary of the invention:
The object of the present invention is to provide a kind of synthetic performance of homologue, derivative and other monomer of BA of using without BA fully to synthesize the preparation method and the application of the similar pressure sensitive adhesive of performance as principal monomer to using BA.
The invention provides and a kind ofly synthesize performance and use the similar pressure-sensitive adhesive of BA without BA, its composition characteristic is:
1, monomers such as (methyl) vinylformic acid and ester class thereof, be selected from (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) glycidyl acrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) 2-EHA, acrylamide, vinylbenzene, vinyl cyanide, vinyl acetate, dibutyl maleate, among the dioctyl maleate etc. 5~8 kinds, preferred (methyl) vinylformic acid, ethyl propenoate, (methyl) Hydroxyethyl acrylate, methyl methacrylate, 2-EHA, vinyl cyanide, vinyl acetate, dioctyl maleate, the quality percentage composition is 35-65%, and wherein each content is 0.25-60%;
2, used emulsifying agent is selected polyoxyethylene octylphenol ether for use, polyoxyethylene nonylphenol ether, polyoxyethylene ether sulfate, CO-436, CO-458, CO-558, XN-45S, JS-2, sulfo-succinic acid salt A102, A103, A-501, A-18, alkyl diphenyl ether disulfonate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, AB-2350, A-45, A-18, COPS-1, B-CEA etc., preferred 2~3 kinds of quality percentage compositions are 0.2-3%, and optional is 0.2-1.5%.
3, initiator system is selected water-soluble persulphate, hydrogen peroxide, tertbutyl peroxide, hydrogen phosphide cumene for use, sodium formaldehyde sulphoxylate, and the quality percentage amounts is 0.1-1.0%, preferred 0.2-1.0%.
4, other composition, the PH conditioning agent is selected from SODIUM PHOSPHATE, MONOBASIC, primary ammonium phosphate, sodium bicarbonate, bicarbonate of ammonia, optional sodium bicarbonate or bicarbonate of ammonia, the quality percentage composition is 0.1-1.0%, is preferably 0.1-0.8%.
Chain-transfer agent is lauryl mercaptan, quality percentage composition 0.005-0.03%.Deionized water, quality percentage composition are 30-50%.Ammoniacal liquor quality percentage composition is 0.45-0.8%.
Preparation method without the modified pressure-sensitive acrylate emulsion of butyl acrylate preparation is characterized in that following step:
1, the pre-emulsification of monomer
Partial emulsifier is dissolved in after deionized water stirs, progressively adds and select monomer for use, as homologue, derivative and other monomer etc. of (methyl) vinylformic acid, (methyl) Hydroxyethyl acrylate, butyl acrylate.
2, polyreaction
In deionized water, add partial emulsifier, initiator, PH conditioning agent, be warming up to certain temperature after stirring evenly, drip prepared monomer pre-emulsion and initiator solution in 1 after ten minutes, be controlled in 3~5h and drip off, be incubated 1h then.
3, aftertreatment
After the insulation, temperature is reduced to 70 ℃, adds the aftertreatment material, closes the bisulphite sodium water solution as the tertbutyl peroxide aqueous solution, methyl, reacts half an hour, is cooled to 50 ℃, transfers about PH to 6 with the PH conditioning agent.
Produce modified aqueous acrylic acid ester emulsion-type pressure-sensitive without butyl acrylate, the product performance test is as follows: common performance is by the universal method test, the pressure sensitive adhesive mechanic property test method, tack is pressed the GB-4852-84 standard, 180 ° of stripping strengths are pressed the GB-2792-81 test, hold to glue and test by GB-4851-84.
The modified acroleic acid ester pressure-sensitive of the no butyl acrylate that this law is prepared, package stability can reach more than 1 year, was applicable to that BOPP is that the Pressuresensitive Tape of base material also can be used for the PE film or films such as PVC, PET are the adhesive tape of base material.
Embodiment:
The following examples can make those skilled in the art understand the present invention, but do not limit the present invention in any way.
Embodiment 1
1, prescription (by mass percentage)
Figure C20051003440000051
2, preparation method
A. the pre-emulsification of monomer
With partial emulsifier be dissolved in stir in the deionized water after, progressively add various monomers, as homologue, derivative and other monomer etc. of (methyl) vinylformic acid, (methyl) Hydroxyethyl acrylate, butyl acrylate.
B, polyreaction
In deionized water, add partial emulsifier, initiator, PH conditioning agent, be warming up to certain temperature after stirring evenly, drip prepared monomer pre-emulsion and initiator solution in 1 after ten minutes, be controlled in 3~5h and drip off, be incubated 1h then.
C, aftertreatment
After the insulation, temperature is reduced to 70 ℃ and adds the aftertreatment material, closes the bisulphite sodium water solution as the tertbutyl peroxide aqueous solution, methyl, and reaction is cooled to 50 ℃ after half an hour, transfers about PH to 6 with the PH conditioning agent.
Produce modified aqueous acrylic acid ester emulsion-type pressure-sensitive without butyl acrylate, the product performance test is as follows: general property, adopt universal method, and the pressure sensitive adhesive mechanic property test method, tack is pressed the GB-4852-84 standard, 180 ° of stripping strengths are pressed the GB-2792-81 test, hold to glue and test by GB-4851-84.
The modified acroleic acid ester pressure-sensitive of the no butyl acrylate that this law is prepared, package stability can reach more than 1 year, was applicable to that BOPP is that the Pressuresensitive Tape of base material also can be used for the PE film or films such as PVC, PET are the adhesive tape of base material.
3, the performance of emulsion
Figure C20051003440000061
(gluing thickness is 20 ± 1um in the performance test of B, pressure sensitive adhesive.)
Embodiment 2
1, prescription (with example 1)
Replace dioctyl maleate with dibutyl maleate, all the other are with embodiment 1.
2, preparation method's (with example one).
3, emulsion property (with example one).

Claims (4)

1. modified pressure-sensitive acrylate emulsion that does not contain butyl acrylate, its composition characteristic is:
A, be selected from 5 ~ 8 kinds in methacrylic acid, methyl methacrylate, Jia Jibingxisuanyizhi, glycidyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, methacrylic acid 2-ethylhexyl ester, acrylamide, vinylbenzene, vinyl cyanide, vinyl acetate, dibutyl maleate or the dioctyl maleate, the quality percentage composition is 35-65%, and wherein each content is 0.25-60%;
Used emulsifying agent is to select polyoxyethylene octylphenol ether for use in b, the letex polymerization, polyoxyethylene nonylphenol ether, polyoxyethylene ether sulfate, CO-436, CO-458, CO-558, XN-45S, JS-2, the sulfo-succinic acid salt, 2-3 kind among A102, A103, A-501, alkyl diphenyl ether disulfonate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, AB-2350, A-45, A-18, A55, COPS-1 or the B-CEA, quality percentage composition are 0.2-3%;
C, initiator body are selected water-soluble persulphate, hydrogen peroxide, tertbutyl peroxide, hydrogen phosphide cumene or sodium formaldehyde sulphoxylate for use, and the quality percentage amounts is 0.1-1.0%;
D, PH conditioning agent are selected from SODIUM PHOSPHATE, MONOBASIC, and primary ammonium phosphate, sodium bicarbonate or bicarbonate of ammonia, quality percentage composition are 0.1-1.0%;
E, chain-transfer agent are lauryl mercaptan, quality percentage composition 0.005-0.03%;
F, deionized water, quality percentage composition are 30-50%;
G, ammoniacal liquor quality percentage composition are 0.05-0.8%;
The said components sum is 100%.
2, the modified pressure-sensitive acrylate emulsion that does not contain butyl acrylate according to claim 1, it is characterized in that: described emulsifying agent consumption is 0.2-1.5%.
3, the modified pressure-sensitive acrylate emulsion that does not contain butyl acrylate according to claim 1 is characterized in that: described initiator quality percentage amounts is 0.2-1.0%.
4, the modified pressure-sensitive acrylate emulsion that does not contain butyl acrylate according to claim 1 is characterized in that: described PH conditioning agent quality percentage amounts is 0.1-0.8%.
CNB2005100344005A 2005-04-29 2005-04-29 Method for preparing acrylic ester pressure sensitive glue emulsion without using butal acrylate and use Active CN100475866C (en)

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CN101353283B (en) * 2008-09-08 2011-12-21 中国海洋石油总公司 Preparation of acrylic ester mixed polymer urea slow release coating agent
CN103665253B (en) * 2013-11-26 2016-07-06 青岛文创科技有限公司 A kind of high-performance water-based acrylate pressure-sensitive adhesive and manufacturing process thereof

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