CN106381103B - Water polyacrylic acid adhesive and preparation method thereof - Google Patents
Water polyacrylic acid adhesive and preparation method thereof Download PDFInfo
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- CN106381103B CN106381103B CN201610914791.8A CN201610914791A CN106381103B CN 106381103 B CN106381103 B CN 106381103B CN 201610914791 A CN201610914791 A CN 201610914791A CN 106381103 B CN106381103 B CN 106381103B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
The invention discloses a kind of water-based plastic packaging composite adhesive and preparation method thereof, the aqueous, environmental protective polyacrylate adhesives composition, by weight, comprising：A kind of 80 95 parts of surface tension is less than 25Dyn/cm and the polyacrylate dispersion containing carboxylic group and hydroxyl group；A kind of 3 19.5 parts of silane containing at least three hydrolyzable alkoxies；A kind of bleeding agent of 0.5 2 parts of nonionic alkyl polyoxyethylene polyoxypropylene ether block copolymers.The polyacrylate composite adhesive of the present invention can carry out gluing compound winding under the compounding machine speed more than 180 ms/min, and be capable of providing bright apparent and more than 1.0N/15mm the intensity having no time；Package compound application applied to high speed can provide relatively good adhesive force, apparent and resistance to hot pressing trickling property.
Description
Technical field
The present invention relates to a kind of polyacrylate adhesives and preparation method thereof more particularly to one kind to be used to pack compound use
Aqueous, environmental protective polyacrylate adhesives and preparation method thereof.The polyacrylate adhesives are transported at a high speed especially suitable for needing
Turn compound flexible package application, with relatively good apparent, adhesion strength and heat resistanceheat resistant pressure trickling property.
Background technology
For Flexible-Packaging Industry, with the convenient purification of more and more product requirements, rapid and inexpensive；Plastics package
What is developed is very rapid, in particular for food and pharmaceutical packing.This is because plastics package can high speed print,
Compound, winding, cutting, are easily produced on a large scale；In addition the side that plastics package is of low cost, is readily transported and applies
Just property all gradually substitutes traditional packaging in many industries.
During prepared by plastics package, formed by the Film laminated of multilayered structure, needed for reaching
The apparent and impact of performance.Such as the various structures such as BOPP/CPP, CPP/ aluminium/BOPP, BOPP/PET.In these structures
In, it is required for using and adhesive is used to the very crucial chemical composition of entire multilayered structure-compound.Select suitable adhesive not
But can play and the film of multilayer is bonded together, and can also play increase tearing strength, resistance to boiling, it is ageing-resistant, resistance oxygen,
Block water and other effects.So it is inseparable to prepare high performance composite packaging with the composite adhesive used.
Packing compound mainly has solvent type, no-solvent type and aqueous with adhesive.Solvent type is compound have been existed with adhesive
Many years are applied in plastic flexible package, most of performance requirements of flexible package application can be reached substantially, there is rate of drying
Soon, the advantages that operating of machine speed is fast, the high and apparent effect of intensity is good.But a large amount of solvent is needed in use, to environment
It causes greatly to pollute, while between will also result in more serious health hazards in the operating personnel producing that construct.Although pass through
The harm that solvent volatilizees to environment and people can be reduced by installing solvent recovery unit additional, but solvent is unable to reach recycling completely, also
It is to have a certain amount of solvent and volatilize away in operation to damage；And the solvent used is all low-flash organises
Close object, not only these solvents belong to hazardous chemical, need to carry out in certain working environment, and if misoperation also
Fire or explosion can be caused.As environmental protection standard and relevant law are more and more stringenter, can be caused using solvent type adhesive
The significantly promotion of cost, the more serious risk eliminated and stop production that may be faced.And market have to flexible package it is powerful
Demand, therefore there is an urgent need to use that the product of solvent type adhesive can be substituted, so as to which no-solvent type and aqueous adhesive should
It transports and gives birth to.Relative to the composite adhesive of no-solvent type, aqueous type composite adhesive is more environmentally-friendly and easy to operate, usually aqueous
Composite adhesive is all one-component, does not need to carry out live allotment as the bicomponent system of no-solvent type, does not match weighing and miss
Difference and influence of the mixing evenness to performance；After Aqueous Adhesives are compound at the scene can following machine can reach preferable intensity,
It does not need to need to cure for a long time as no-solvent type system just obtain required intensity, therefore life can be greatly improved
It produces efficiency and reduces energy consumption.Also, aqueous composite adhesive unharmful substance, almost without VOC, and in no-solvent type system
The curing agent component containing isocyanates would generally be used, due to the requirement to reactivity and cost, often using containing
The curing agent of TDI, TDI belong to toxic articles, and micro residual will result in great harm, very high especially for requiring
Food packaging；Another is important be it is compound after it is apparent, using aqueous compound adhesive in wrapup procedure is operated
Judge apparent, and the composite membrane of no-solvent type system needs to judge after curing, therefore, eating aqueous compound adhesive can
Greatly to reduce the risk of finished product visual defects.
According to the advantages of above-mentioned aqueous composite adhesive, many businesses and institutions carry out a large amount of research and product is opened
Hair.ROHM AND HAAS introduces water-based emulsion composite membrane adhesive, can reach the requirement of the packaging of general food, but exist
The shortcomings that combined strength bination is relatively low, wetability is inadequate, apparent difference, especially when high machine speed operates, spread is uneven, causes to be permitted
More white points and adhesion strength are inhomogenous.Simultaneously because drying time is shorter, do not reach complete during machine under compound winding
It is dry, cause adhesion strength inadequate, be typically only capable to reach 0.3-0.6N/15mm, it is also necessary to further heat aging 24 hours with
On can be only achieved required intensity.The waste of the energy can be caused in this way, but also contains the moisture evaporation solvent in maturing process
The defects of causing white point.
Patent CN104263292 discloses a kind of aqueous laminated adhesive and sticks agent and preparation method thereof, using the side of emulsion polymerization
Method prepares the system of the self-crosslinking containing Diacetone Acrylamide and ADH, admittedly being contained in 48-50%, viscosity is in 100-500mPa.s.
But disclosed technology can not be met the requirements under the dry type compound condition to run at high speed, due to prepared in drying course
The Diacetone Acrylamide component of adhesive can be crosslinked with ADH components, lead to compoiste adhering strength reduction；And in 100-
Upper glue roller can occur to glue that the uniformity is bad under the viscosity of 500mPa.s, and that causes after overlay film apparent strip occur and be unable to reach
The smooth requirement in surface.Patent CN103059784 disclose a kind of food and medicine flexible package aqueous modeling-modeling composite adhesive and
Preparation method, using pre-emulsification seeded emulsion polymerization technique, prepared emulsion-type adhesive combined strength bination can reach big
In 1.2N/15mm.But sodium vinyl sulfonate or 2- acrylamide -2- methyl are used for multiple times in the disclosed embodiments and description
Propane sulfonic acid sodium salt is as emulsifier；It is known that both substances can not make hydrophobic acrylic ester monomer and phenylethylene list
Body forms pre-emulsion, because stable polymer emulsion can not be prepared into.United States Patent (USP) US6190767 discloses a kind of lotion
The preparation method of type adhesive, which use the long-chain aliphatic acrylate more than 50%, using polymerizable emulsifier, system
The good lotion of water-fast moisture-proof is obtained, there is good adhesiveness to non-polar substrate.Although aqueous composite adhesive achieves very big
Progress, but compared with solvent type composite adhesive, operability, wetability, adhesion strength under the conditions of high machine speed
Apparent with product all also has a certain distance.Therefore, it is possible to overcome the product of the above defect and technology be there is an urgent need for it is non-
It is often significant.
Invention content
In view of the drawbacks described above of the prior art, the technical problems to be solved by the invention are to provide one kind in high machine speed condition
There is down preferable wetability, adhesion strength and the apparent aqueous, environmental protective composite adhesive of good product.
To achieve the above object, the present invention provides a kind of polyacrylate composite adhesive of aqueous, environmental protective and its preparations
Methods and applications.The polyacrylate composite adhesive under the compounding machine speed more than 180 ms/min can glue-answer
Conjunction-winding, and it is capable of providing bright apparent and more than 1.0N/15mm the intensity having no time.
The present invention prepares the polyacrylic acid composite adhesive of aqueous, environmental protective using the mode of emulsion polymerization, compound
Enough intensity is provided in wrapup procedure, not needing to curing can directly use.The aqueous polyacrylamide acid compound adhesive of the present invention
Glutinous agent remains relatively good mobility during gluing, the scratch that will not be caused the film forming adherency of upper glue roller and occur
Floating phenomenon；Meanwhile with very excellent wetting and osmosis, it is ensured that the compatibility of different ink systems, no
The exudation of ink residue and nonwetting phenomenon can be caused.
The water polyacrylic acid adhesive of the present invention, by weight, comprising：1) a kind of 80-95 parts of surface tension is low
In 25Dyn/cm and polyacrylate dispersion containing carboxylic group and hydroxyl group；2) 3-19.5 parts one kind contains at least three
The silane of a hydrolyzable alkoxy；3) 0.5-2 parts of a kind of nonionic alkyl polyoxyethylene polyoxypropylene ether block copolymers
Bleeding agent.
In the specific embodiment of the present invention, the polyacrylic acid of the present invention containing carboxylic group and hydroxyl group
Ester lotion includes hard monomer, soft monomer, the monomer containing carboxylic group and the monomer containing hydroxyl group, emulsifier.
Preferably, by weight, the content of hard monomer is 10-28wt%；The content of soft monomer is 70-90wt%；Contain
The total content of the monomer of carboxyl and hydroxyl group is 2-15wt%；The content of emulsifier is 0.4-1wt%.It is highly preferred that by weight
Gauge, the content of monomer containing carboxylic group contains hydroxyl group in 1-5wt% in polyacrylate dispersion of the present invention
Content of monomer in 1-10wt%.
Preferably, the hard monomer includes styrene and methyl methacrylate；Soft monomer is preferably ethyl acrylate, third
One or several kinds in olefin(e) acid butyl ester, Isooctyl acrylate monomer, Isobutyl methacrylate；Monomer containing carboxylic group is preferred
For one or more of acrylic acid, methacrylic acid, itaconic acid, maleic acid；Monomer containing hydroxyl group is preferably hydroxyl second
It is a kind of or several in base acrylate, hydroxypropyl acrylate, hydroxyethyl meth acrylate, hydroxypropyl methacrylate
Kind；Emulsifier is succinic acid salt emulsifier, preferably alkyl succinate emulsifier.
In a preferred embodiment of the invention, at least three hydrolyzable alkoxy silanes that contain are selected from tetramethyl
Oxysilane, tetraethoxysilane, tetraisopropoxysilan, trimethoxymethylsila,e, triethoxy methyl silicane, trimethoxy
Base phenyl silane, triethoxyphenylsilan, trimethoxy vinyl silane, Triethoxyvinylsilane, 3- glycidol ethers three
One or more of methoxy silane.
To obtain preferable apparent effect and bond effect, wetting action and osmosis of the adhesive to base material and ink
It is most important, it is even more important in the recombination process of the packaging film of multiplex priting.In another better embodiment of the present invention,
It is employed herein a kind of containing the non-of at least block copolymer of the polyoxyethylene poly-oxygen propylene aether of the alkylol of 8-18 carbon
Ion alkyl polyoxyethylene polyoxypropylene ether block copolymers be bleeding agent, the block copolymer of the polyoxyethylene poly-oxygen propylene aether
Molecular structure be：
Wherein x, m, n be integer, x=4-16；M=6-12；N=2-6.
In a specific embodiment of the present invention, most excellent effect can be obtained when the HLB value of bleeding agent is in 7-12.When
When x is more than 8, the first adhesion strength of adhesive can be effectively improved.It is highly preferred that bleeding agent A1 used in the present invention is x
=11, m=10, n=3.
The present invention also provides a kind of methods for preparing the aqueous, environmental protective polyacrylate adhesives composition, are divided into
Four key steps；Polyacrylate dispersion is prepared by emulsion polymerization first；Then in acid condition with containing hydrolyzable group
The silane of group is reacted, and adjusts pH later to alkalinity；Bleeding agent is added to be uniformly mixed.It is as follows：
The first step：Parts by weight are taken as 0.4-1 parts of alkyl succinate emulsifier, 10-20 parts of deionized waters, 10-28 parts
Hard monomer, 70-90 parts of soft monomers stir into uniform monomer emulsion；Weigh again 1-5 parts carboxylic monomer and 1-10 parts
Hydroxyl monomer, then add in 5-10 parts of water and be prepared into hydrophilic monomer aqueous solution.
Second step：A certain amount of water is added in into reaction bulb, is heated to 80-95 DEG C.Then start that the first step is added dropwise simultaneously
The monomer emulsion and hydrophilic monomer aqueous solution of preparation and by total weight of monomer calculate 0.2-1.0 parts initiator it is water-soluble
Liquid；Time control is added at 2-5 hours.
Third walks：The pH value of lotion is controlled in 3-6, adds in alkoxy silane, 30-50 DEG C is stirred 30-60 minutes, Ran Houjia
Enter ammonium hydroxide to neutralize to pH value to 7.0-9.0.
4th step：The bleeding agent of nonionic alkyl polyoxyethylene polyoxypropylene ether block copolymers is added in, is uniformly mixed i.e.
Obtain the aqueous, environmental protective polyacrylate adhesives.
Preferably, hydrophilic monomer aqueous solution shifts to an earlier date 30 than the aqueous solution of monomer emulsion and radical initiator in second step
Minute adds, and 1-3 hours are kept the temperature after adding.
It is found in the specific implementation process of the present invention, when carboxyl and hydroxyl water-soluble monomer will be contained in emulsion polymerization process
In individually carry out being added dropwise prepared lotion wetting and surface tension significantly than it is common by the two type monomers with
Other monomers are prepared into monomer emulsion mixture will get well be added dropwise.And adhesion strength also has different degrees of raising, especially
It is the completion of dropwise addition before earlier than monomer emulsion.
In the present invention, the surface tension used is less than 25Dyn/cm and the polypropylene containing carboxylic group and hydroxyl group
The glass transition temperature of acid esters lotion is -40~5 DEG C；It is preferred that -40~-10 DEG C；More preferably -30~10 DEG C.Glass transition temperature is profit
It is calculated with Fox formula (T.G.Fox, Bull.Am.Physics Soc., volume 1, the 3rd phase, page 123 (1956)), that is, right
For the Tg values of copolymer of monomer M1 and M2 are calculated：
1/Tg (calculated value)=w (M1)/Tg (M1)+w (M2)/Tg (M2)
Wherein, Tg (calculated value) is the glass transition temperature of the copolymer calculated；W (M1) is monomer M1 in copolymer
Weight fraction；W (M2) is the weight fraction of monomer M2 in copolymer；Tg (M1) is the glass transition temperature of M1 homopolymers；Tg
(M2) it is the glass transition temperature of M2 homopolymers；All temperature are in terms of ° K.The glass transition temperature of homopolymer can be
For example, " Polymer Handbook "《Polymer handbook》(J.Brandrup and E.H.Immergut are edited, Interscience
Publish) in find.
The polymerization process of the present invention is emulsion polymerization, and used initiator is water soluble starter, such as Ammonium Persulfate 98.5, mistake
One or several kinds in sodium sulphate, potassium peroxydisulfate, tert-butyl hydroperoxide；More electedly, using Ammonium Persulfate 98.5 and persulfuric acid
Sodium is as initiator system.
In a specific embodiment of the present invention, initiation system can be thermal initiation either redox initiation system, such as
Radical initiator, reaction temperature is at 80-95 DEG C；The dosage of initiator is preferably the 0.2-1.0wt% (lists based on polymer
The total weight of body).
When preparing aqueous, environmental protective polyacrylate adhesives composition, add in alkoxy silane when reaction temperature and pH
It is extremely important, it is preferable that pH value to be kept to be added in 3-6,30-50 DEG C is stirred 30-60 minutes.If pH value is too low, reaction interval
Degree can acutely cause system unstable；PH value is excessively high, and reaction is insufficient, and required effect is not achieved.Preferably, temperature control exists
30-50 DEG C, mixing time was controlled at 30-60 minutes, can adequately be acted in this way, and mixing time will not be caused long
Waste production capacity.
On the other hand, the present invention also provides a kind of answering in packaging by the aqueous, environmental protective polyacrylate adhesives
With the especially application in the plastics package of food and daily necessities.
The plastics package that the aqueous, environmental protective polyacrylate adhesives prepared are used as food and daily necessities is done by the present invention
In compound, under conditions of operation machine speed reaches 180-280m/min, gelatin viscosity is almost unchanged, and upper glue roller is without coagulated state；
By 15 meters of 70-80 DEG C of drying tunnels, then carry out compound, lower machine winding combined strength bination can reach more than 1.0N/15mm.It is apparent
Mingguang City is bright, no floating and the reticulate pattern marking.The wetting effect that the system of ink was printed especially for large area more preferably, does not need to
Packing instructions can be reached by carrying out curing.
If without specified otherwise, as described in the present invention, each preferred solution and other preferred solution party
Case be combined with each other, so as to form new technical solution.Since length is limited, combination technique is not described in detail,
However, it is all by the technical solution that be combined with each other all it is believed that the clearly statement carried out in the present invention.
The technique effect of the design of the present invention, concrete structure and generation is made furtherly below with reference to specific embodiment
It is bright, it is fully understood from the purpose of the present invention, feature and effect to help those skilled in the art.But the present invention is not limited to these
Example.
Specific embodiment
The raw material used in each embodiment in the present invention is all commercial goods, specific as follows：
Embodiment 1：
Under nitrogen protection, 360 grams of deionized water is added in into 2 liters of reaction bulbs, is begun to warm up to 85 DEG C.By 180 grams go from
Sub- water, 10 grams of dioctyl succinate acid esters sodium sulfonates (20% solution), 486 grams of BA, 100 grams of ST, 102 grams of MMA are mixed
Uniformly obtain stable white monomer emulsion.7.1 grams of AA and 7.1 gram of HEMA are weighed to a vial, then add in 20 grams
Deionized water obtains aqueous solution.When the temperature of reaction bulb reaches 85 DEG C, following raw materials according is gradually added in：Contain 1.2 grams of sodium carbonate
The solution of 10 grams of deionized waters, the monomer emulsion of 18 grams of above-mentioned preparations and 3 grams of AA and HEMA aqueous solution and 2.0 grams
Ammonium Persulfate 98.5 is dissolved in the solution in 15 grams of deionized waters.There is heat release, treat that temperature is not increasing, then maintain the temperature of reaction bulb
Spend be 85 DEG C under conditions of, remaining monomer emulsion is added within 3 hours, drips the water-soluble of AA and HEMA within 2.5 hours
Liquid drips the solution that 2.0 grams of ammonium persulfates are dissolved in 80 grams of deionized waters in 3 hours.2 hours are kept the temperature after adding, then
80 DEG C are cooled to, adds in 5.0 gram 0.1% of ferrous sulfate aqueous solution, 0.8 gram 70% of t-BHP is then added in and is dissolved in 30 grams
The solution of deionized water and 0.5 gram of SBS are dissolved in the solution in 30 grams of deionized waters, continue heat preservation 1 hour.40 DEG C are cooled to,
It is 3.2 to test pH value, adds in 221.5 grams of tetramethoxy silica alkane, this temperature is kept to stir 30 minutes, then adds in ammonium hydroxide
(28%) 6.8 gram adjusts pH value to alkalinity.34 grams of bleeding agent A1 are added, are stirred evenly, are cooled to room temperature, 300 mesh screen mistakes
Filter obtains aqueous composite adhesive.Gained adhesive pH value 7.5, viscosity 100cps.
Embodiment 2：
Under nitrogen protection, 360 grams of deionized water is added in into 2 liters of reaction bulbs, is begun to warm up to 85 DEG C.By 180 grams go from
Sub- water, 8.5 grams of single dodecyl succinate ester monocarboxylic acid disodium sulfonates (30% solution), 332 grams of BA, 300 grams of EA, 49.2 grams
ST, 7.0 grams of MMA are mixed evenly to obtain stable white monomer emulsion.7.1 grams of AA and 7.1 gram of HEMA are weighed
To a vial, 20 grams of deionized waters are then added in, obtain aqueous solution.When the temperature of reaction bulb reaches 85 DEG C, gradually add in
Following raw materials according：The solution of 10 grams of deionized waters containing 1.0 grams of sodium carbonate, the monomer emulsion and 5 grams of MAA of 20 grams of above-mentioned preparations
The solution being dissolved in the aqueous solution of HEMA and 3.5 grams of Ammonium Persulfate 98.5s in 15 grams of deionized waters.There is heat release, treat temperature not
It is increasing, is then maintaining the temperature of reaction bulb under conditions of 85 DEG C, to add remaining monomer emulsion within 3 hours, 2.5
Hour drips the aqueous solution of MAA and HEMA, and 1.0 grams of ammonium persulfates are dripped in 3 hours and are dissolved in 80 grams of deionized waters
Solution.2 hours are kept the temperature after adding, then cools to 80 DEG C, 5.0 gram 0.1% of ferrous sulfate aqueous solution is added in, then adds in
1.2 gram 70% of t-BHP is dissolved in the solution of 30 grams of deionized waters and 0.8 gram of SBS is dissolved in solution in 30 grams of deionized waters,
Continue heat preservation 1 hour.40 DEG C are cooled to, test pH value is 3.2, adds in 68.6 grams of trimethoxy methylsiloxane, keeps this temperature
Then degree stirring 30 minutes adds in (28%) 6.8 gram of ammonium hydroxide and adjusts pH value to alkalinity.7.63 grams of bleeding agent A1 are added, are stirred
Uniformly, room temperature is cooled to, aqueous composite adhesive is obtained by filtration in 300 mesh screens.Gained adhesive pH value 7.8, viscosity are
80cps。
Embodiment 3：
Under nitrogen protection, 360 grams of deionized water is added in into 2 liters of reaction bulbs, is begun to warm up to 85 DEG C.By 180 grams go from
Sub- water, 10 grams of dioctyl succinate acid esters sodium sulfonates (20% solution), 505 grams of BA, 100 grams of ST, 19.4 grams of MMA are mixed
Uniformly obtain stable white monomer emulsion.7.1 grams of MAA and 70.2 gram of HEMA are weighed to a vial, then add in 20
Gram deionized water, obtains aqueous solution.When the temperature of reaction bulb reaches 85 DEG C, following raw materials according is gradually added in：Contain 1.2 grams of carbonic acid
10 grams of deionized water solutions of sodium, the monomer emulsion of 18 grams of above-mentioned preparations and the aqueous solution and 2.0 of 10 grams of MAA and HEMA
Gram Ammonium Persulfate 98.5 is dissolved in the solution in 15 grams of deionized waters.There is heat release, treat that temperature is not increasing, then maintain reaction bulb
Under conditions of temperature is 85 DEG C, remaining monomer emulsion, the 2.5 hours water for dripping MAA and HEMA are added within 3 hours
Solution drips the solution that 2.0 grams of ammonium persulfates are dissolved in 80 grams of deionized waters in 3 hours.2 hours are kept the temperature after adding, so
After cool to 80 DEG C, add in 5.0 gram 0.1% of ferrous sulfate aqueous solution, then add in 0.8 gram 70% of t-BHP and be dissolved in 30
The solution and 0.5 gram of SBS of gram deionized water are dissolved in the solution in 30 grams of deionized waters, continue heat preservation 1 hour.Cool to 40
DEG C, test pH value is 3.5, adds in 136.75 grams of tetramethoxy silica alkane, this temperature is kept to stir 50 minutes, then adds in ammonium hydroxide
(28%) 4.5 gram adjusts pH value to alkalinity.24 grams of bleeding agent A1 are added, are stirred evenly, are cooled to room temperature, 300 mesh screen mistakes
Filter obtains aqueous composite adhesive.Gained adhesive pH value 7.5, viscosity 120cps.
Embodiment 4：
Under nitrogen protection, 360 grams of deionized water is added in into 2 liters of reaction bulbs, is begun to warm up to 85 DEG C.By 180 grams go from
Sub- water, 10 grams of dioctyl succinate acid esters sodium sulfonates (20% solution), 505 grams of BA, 54.4 grams of ST, 100 grams of MMA are mixed
Uniformly obtain stable white monomer emulsion.35.1 grams of MAA and 7.1 gram of HEMA are weighed to a vial, then add in 20
Gram deionized water, obtains aqueous solution.When the temperature of reaction bulb reaches 85 DEG C, following raw materials according is gradually added in：Contain 2.8 grams of carbonic acid
The aqueous solution of 5 grams of deionized water solutions of sodium, the monomer emulsion of 18 grams of above-mentioned preparations and 10 grams of MAA and HEMA and 2.0 grams
Ammonium Persulfate 98.5 is dissolved in the solution in 15 grams of deionized waters.There is heat release, treat that temperature is not increasing, then maintain the temperature of reaction bulb
Spend be 85 DEG C under conditions of, remaining monomer emulsion is added within 3 hours, drips the water-soluble of MAA and HEMA within 2.5 hours
Liquid drips the solution that 2.0 grams of ammonium persulfates are dissolved in 80 grams of deionized waters in 3 hours.2 hours are kept the temperature after adding, then
80 DEG C are cooled to, adds in 5.0 gram 0.1% of ferrous sulfate aqueous solution, 0.8 gram 70% of t-BHP is then added in and is dissolved in 30 grams
The solution of deionized water and 0.5 gram of SBS are dissolved in the solution in 30 grams of deionized waters, continue heat preservation 1 hour.40 DEG C are cooled to,
It is 2.5 to test pH value, adds in 136.75 grams of tetraethoxy silica alkane, this temperature is kept to stir 50 minutes, then adds in ammonium hydroxide
(28%) 6.5 gram adjusts pH value to alkalinity.24 grams of bleeding agent A1 are added, are stirred evenly, are cooled to room temperature, 300 mesh screen mistakes
Filter obtains aqueous composite adhesive.Gained adhesive pH value 7.0, viscosity 150cps.
Comparative example 1：
Under nitrogen protection, 380 grams of deionized water is added in into 2 liters of reaction bulbs, is begun to warm up to 85 DEG C.By 180 grams go from
Sub- water, 8 grams of lauryl sodium sulfate (20% solution), 505 grams of BA, 168.5 grams of MMA, 14.2 grams of MAA and 14.2 gram of HEMA are carried out
It is mixed evenly to obtain stable white monomer emulsion.When the temperature of reaction bulb reaches 85 DEG C, following original is gradually added in
Material：10 grams of deionized water solutions containing 1.2 grams of sodium carbonate, the monomer emulsion and 2.0 grams of persulfuric acid of 18 grams of above-mentioned preparations
Solution of the amine solvent in 15 grams of deionized waters.There is heat release, treat that temperature is not increasing, the temperature for then maintaining reaction bulb is 85
Under conditions of DEG C, remaining monomer emulsion is added within 3 hours, 2.0 grams of ammonium persulfates are dripped in 3 hours and are dissolved in 80
Solution in gram deionized water.2 hours are kept the temperature after adding, then cools to 80 DEG C, adds in 5.0 gram 0.1% of ferrous sulfate water
Solution, then add in 0.8 gram 70% of t-BHP be dissolved in the solution of 30 grams of deionized waters and 0.5 gram of SBS be dissolved in 30 grams go from
Solution in sub- water continues heat preservation 1 hour.40 DEG C are cooled to, test pH value is 3.5, adds in tetramethoxy silica alkane 136.75
Gram, this temperature is kept to stir 50 minutes, (28%) 5.5 gram of ammonium hydroxide is then added in and adjusts pH value to alkalinity, add in 100 grams of deionizations
Water is diluted, and is cooled to room temperature, and aqueous composite adhesive is obtained by filtration in 300 mesh screens.Gained adhesive pH value 7.5, viscosity
For 100cps.
Comparative example 2：
Identical with the monomer composition in embodiment 1, preparation process is identical, and four are replaced using 221.5 grams of deionized water is added
Methoxy radical siloxane.
Comparative example 3：
Identical with being formed in comparative example 1, preparation process is identical, to add in tetramethoxy silica alkane, is replaced with deionized water.
Apparent test：
Based on BOPP/CPP structures and PET/PE, the coating weight of 2.0-3.0 grams of dry weight is coated with, 240 meters of machine speed is per minute, and 15
75 DEG C of drying tunnel drying of rice, then compound winding.Lower machine cutting sees if there is bubble, floating and the nonwetting phenomenon of ink.
Cohesive force is tested：
T-shaped peel strength according to GB/T 2791-1995, is tested using tensilon, tensile speed 100mm/min.
Hot pressing trickling property：
Compound good composite membrane is sealed, 150 DEG C of heat-sealing temperature, 5 seconds, see if there is glue trickling and intensity drop
It is low.
Test result is as follows shown in table：
The preferred embodiment of the present invention described in detail above.It should be appreciated that the ordinary skill of this field is without wound
The property made labour, which according to the present invention can conceive, makes many modifications and variations.Therefore, all technician in the art
Pass through the available technology of logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Scheme, all should be in the protection domain being defined in the patent claims.
Claims (10)
1. a kind of water polyacrylic acid adhesive, comprising：
1) 80-95 parts of surface tension is less than 25Dyn/cm and the polyacrylate dispersion containing carboxylic group and hydroxyl group；
2) 3-19.5 parts of a kind of silane containing at least three hydrolyzable alkoxies；
3) bleeding agent of 0.5-2 parts of a kind of nonionic alkyl polyoxyethylene polyoxypropylene ether block copolymers.
2. polyacrylate adhesives as described in claim 1, by weight, wherein, it is described to contain carboxylic group and hydroxyl
The polyacrylate dispersion of group includes the list that 10-28wt% hard monomers, 70-90wt% soft monomers, 2-15wt% contain carboxyl
Body and monomer, 0.4-1wt% emulsifiers containing hydroxyl；
The hard monomer is includes styrene and methyl methacrylate；The soft monomer is selected from ethyl acrylate, acrylic acid
One or several kinds in butyl ester, Isooctyl acrylate monomer.
3. polyacrylate adhesives as claimed in claim 2, wherein, the monomer containing carboxyl is acrylic acid, methyl
One or more of acrylic acid, itaconic acid, maleic acid, content is in 1-5wt%；Monomer containing hydroxyl is hydroxyethyl
One or several kinds in ester, hydroxypropyl acrylate, hydroxyethyl meth acrylate, hydroxypropyl methacrylate, content
For 1-10wt%；The emulsifier is succinic acid salt emulsifier.
4. polyacrylate adhesives as described in claim 1, wherein, the silane is selected from tetramethoxy-silicane, tetrem
Oxysilane, tetraisopropoxysilan, trimethoxymethylsila,e, triethoxy methyl silicane, trimethoxy-benzene base silane, three
In ethoxybenzene base silane, trimethoxy vinyl silane, Triethoxyvinylsilane, 3- glycidol ether trimethoxy silanes
It is one or more of.
5. polyacrylate adhesives as described in claim 1, wherein the bleeding agent is the alkyl containing at least 8-18 carbon
The block copolymer of the polyoxyethylene poly-oxygen propylene aether of alcohol, chemical structural formula are：
Wherein x, m, n be integer, x=4-16；M=6-12；N=2-6；HLB value is 7-12.
6. the polyacrylate adhesives as described in claim 1-5 is any, wherein the vitrifying of the polyacrylate dispersion
Temperature is -40~-5 DEG C.
7. a kind of method for preparing the polyacrylate adhesives as described in claim 1-6 is any, including：
The first step：The alkyl succinate emulsifier that parts by weight are 0.4-1 parts is taken, 10-20 parts of deionized waters, 10-28 parts hard single
Body, 70-90 parts of soft monomers stir into uniform monomer emulsion；Weigh 1-5 parts carboxylic monomer and 1-10 parts containing hydroxyl
The monomer of base, 5-10 parts of water are prepared into hydrophilic monomer aqueous solution；
Second step：Monomer emulsion and hydrophilic monomer aqueous solution prepared by the first step is added dropwise in 80-95 DEG C of water, by total weight of monomer
Come the aqueous solution of the radical initiator of 0.2-1.0 parts calculated；It is 2-5 hours to add in the time；
Third walks：The pH value for controlling lotion is 3-6, adds in alkoxy silane, and 30-50 DEG C is stirred 30-60 minutes, then adds in ammonia
Water is neutralized to pH value to 7.0-9.0；
4th step：The bleeding agent of nonionic alkyl polyoxyethylene polyoxypropylene ether block copolymers is added in, is uniformly mixed and obtains
The aqueous, environmental protective polyacrylate adhesives.
8. the method as claimed in claim 7 for preparing polyacrylate adhesives, wherein, hydrophilic monomer aqueous solution in the first step
It is added within 30 minutes before the dropwise addition of the aqueous solution of monomer emulsion and radical initiator, 1-3 hours is kept the temperature after adding.
9. the method as claimed in claim 7 for preparing polyacrylate adhesives, wherein the initiator is selected from persulfuric acid
One or several kinds in ammonium, sodium peroxydisulfate, potassium peroxydisulfate, tert-butyl hydroperoxide.
10. a kind of system as described in polyacrylate adhesives or claim 7-9 as described in claim 1-6 is any are any
Application of the polyacrylate adhesives that the method for standby polyacrylate adhesives is prepared in food packaging.
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