CN107722882A - A kind of acrylate emulsion and preparation method thereof - Google Patents
A kind of acrylate emulsion and preparation method thereof Download PDFInfo
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- CN107722882A CN107722882A CN201710993144.5A CN201710993144A CN107722882A CN 107722882 A CN107722882 A CN 107722882A CN 201710993144 A CN201710993144 A CN 201710993144A CN 107722882 A CN107722882 A CN 107722882A
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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
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- 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
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
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- 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
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- 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
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- Polymers & Plastics (AREA)
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Abstract
The invention provides a kind of acrylate emulsion and preparation method thereof, pressure sensitive adhesive including following components by being made：100 parts of monomer, monomer include mass ratio 40~80:10~50:5~15 soft monomer, hard monomer and function monomer, 180~220K of soft monomer glass transition temperature；300~400K of hard monomer glass transition temperature；Function monomer includes GMA；1~4 part of emulsifying agent；0.07~0.93 part of thermal initiator；0.03~0.07 part of reducing agent；0~3 part of silane coupler；140~160 parts of water；0.5~3 part of pH value regulator；2~4 parts of cation light initiator.Pressure sensitive adhesive mutual compatibility under the component of above-mentioned content, there is excellent water resistance, alkali resistance and pressure-sensitive；180 ° of 0.38~1.03N/25mm of peel strength；Water-fast rear non-whitening slightly turns white；Phenolphthalein, which reddens, needs 4~12min.
Description
Technical field
The present invention relates to pressure sensitive adhesive technical field, more particularly to a kind of acrylate emulsion and preparation method thereof.
Background technology
Development of Acrylate Emulsion Pressure-Sensitive Adhesive is a kind of adhesive most commonly used in Aqueous Adhesives, and its feature is：
1. decentralized medium is water rather than organic solvent, VOC free discharge；2. light resistance and weatherability are preferable, and do not allow oxidizable；③
Adhesive strength is high, has excellent 180 ° of peel strengths, initial bonding strength and holding power；4. monomer variation, energy used in preparing
Various product is designed according to different demands, it is widely used.Due to the characteristics of its is environmentally friendly and there is excellent performance, emulsion-type third
Olefin(e) acid ester pressure-sensitive is the emphasis nowadays developed.
UV-curing technology is to resolve into the principle of free radical or cation under ultraviolet light using light trigger,
The unsaturated double-bond in system or epoxide group is further set to chemically react, so as to reach quick-setting purpose.In addition,
The cross-linked network formed in Light Curing causes adhesive to have the preferably performance such as water-fast, heat-resisting and corrosion-resistant.
Therefore, application of the photocuring technology in pressure sensitive adhesive field is increasingly universal.
Traditional development of Acrylate Emulsion Pressure-Sensitive Adhesive is poor due to the compactness of glued membrane so that vapor is easily invaded and caused
Pressure sensitive adhesive characteristic declines.In addition, there is a large amount of ester groups on the strand of polymer, easily occur hydrolysis in the basic conditions and
Molecule chain break is caused, the continuity of pressure-sensitive plastic structure is destroyed.Therefore, develop a kind of alkali resistance and have excellent water-resistance
Acrylate emulsion, there is important application value.
The content of the invention
In view of this, it is an object of the invention to provide a kind of acrylate emulsion and preparation method thereof, this third
Olefin(e) acid ester emulsion pressure-sensitive has excellent alkali resistance and water resistance.
The invention provides a kind of acrylate emulsion, is made by the raw material including following parts by weight of component：
100 parts of monomer, it is 40~80 that the monomer, which includes mass ratio,:10~50:5~15 soft monomer, hard monomer and work(
Energy monomer, the glass transition temperature of the soft monomer is 180~220K；The glass transition temperature of the hard monomer is 300
~400K；The function monomer is GMA；
1~4 part of emulsifying agent；
0.07~0.93 part of thermal initiator；
0.03~0.07 part of reducing agent；
0~3 part of silane coupler；
140~160 parts of water；
0.5~3 part of pH value regulator；
2~4 parts of cation light initiator.
Preferably, the soft monomer is selected from butyl acrylate and/or Isooctyl acrylate monomer；
The one kind of the hard monomer in methyl methacrylate, vinylacetate, tertiary ethylene carbonate and styrene
It is or a variety of.
Preferably, the thermal initiator is selected from potassium peroxydisulfate and/or ammonium persulfate；
The reducing agent is selected from sodium hydrogensulfite.
Preferably, the emulsifying agent is selected from model DNS-86 reactive emulsifiers, model FS-40 anionics emulsify
It is one or more in agent and model DP-100 nonionic emulsifier.
Preferably, the cation light initiator is selected from the cation light initiator and/or salt compounded of iodine class of sulfosalt class
Cation light initiator.
Preferably, the silane coupler is selected from model KH550 silane couplers and/or model KH560 silane is even
Join agent.
Preferably, the pH value regulator is selected from ammoniacal liquor, N, one kind in N- dimethylisopro panolamines and triethanolamine or
It is a variety of.
The invention provides a kind of preparation method of acrylate emulsion described in above-mentioned technical proposal, including it is following
Step：
A) after mixing partial emulsifier and water, monomer is added, stirs, obtains pre-emulsion；
B) after remainder emulsifying agent and water being mixed, then pre-emulsion described with part mixing, part thermal initiation is added dropwise
Agent and partial reduction agent, reaction, obtain seed emulsion；
C) remainder thermal initiator, remainder reducing agent, remainder pre-emulsion are added dropwise to the seed breast
In liquid, then insulation curing, after adjusting pH value using pH value regulator, silane coupler is added, cation is added after stirring
Light trigger, it is dispersed with stirring, obtains acrylic acid ester emulsion.
Preferably, the temperature of reaction is 45~55 DEG C in the step b)；The time of reaction is 25~35min.
Preferably, the temperature of insulation curing is 85~90 DEG C in the step c), be incubated time of curing for 1.5~
2.5h；
The time of the dropwise addition is 3~4h.
The invention provides a kind of acrylate emulsion, is made by the raw material including following parts by weight of component：It is single
100 parts of body, it is 40~80 that the monomer, which includes mass ratio,:10~50:5~15 soft monomer, hard monomer and function monomer, it is described
The glass transition temperature of soft monomer is 180~220K；The glass transition temperature of the hard monomer is 300~400K；It is described
Function monomer includes GMA；1~4 part of emulsifying agent；0.07~0.93 part of thermal initiator；Reducing agent 0.03
~0.07 part；0~3 part of silane coupler；140~160 parts of water；0.5~3 part of pH value regulator；Cation light initiator 2~4
Part.The acrylate emulsion uses function monomer GMA as copolymer, with other components
Mutual compatibility, by cation photocuring, make the reaction between emulsion particle and emulsion particle by epoxide group in emulsion pressure-sensitive
Crosslinking is produced, strengthens the compactness of glued membrane, and then improve the water resistance and alkali resistance of pressure sensitive adhesive.Also there is excellent pressure-sensitive；
Emulsion pressure-sensitive particle diameter distribution is narrow, and storge quality is stable, and its preparation technology is simple, is easy to apply.Test result indicates that：Propylene
Acid esters emulsion pressure-sensitive outward appearance is milky blueing light, standing stability time ＞ 3 months；180 ° of peel strengths are 0.38~
1.03N/25mm；25 DEG C, non-whitening after 24h；90 DEG C, non-whitening or slightly turn white after 10min；Redden time of needs of phenolphthalein is
4~12min.
Brief description of the drawings
Fig. 1 is the DLS spectrograms of acrylate emulsion prepared by the embodiment of the present invention 1.
Embodiment
The invention provides a kind of acrylate emulsion, is made by the raw material including following parts by weight of component：
100 parts of monomer, it is 40~80 that the monomer, which includes mass ratio,:10~50:5~15 soft monomer, hard monomer and work(
Energy monomer, the glass transition temperature of the soft monomer is 180~220K；The glass transition temperature of the hard monomer is 300
~400K；The function monomer includes GMA；
1~4 part of emulsifying agent；
0.07~0.93 part of thermal initiator；
0.03~0.07 part of reducing agent；
0~3 part of silane coupler；
140~160 parts of water；
0.5~3 part of pH value regulator；
2~4 parts of cation light initiator.
The preparing raw material of acrylate emulsion provided by the invention includes 100 parts of monomer.In the present invention, it is described
It is 40~80 that monomer, which includes mass ratio,:10~50:5~15 soft monomer, hard monomer and function monomer.The glass of the soft monomer
Change transition temperature is 180~220K；The soft monomer be preferably selected from butyl acrylate, Isooctyl acrylate monomer, ethyl acrylate and
One or more in EHMA, it is more preferably selected from butyl acrylate and/or Isooctyl acrylate monomer.
The glass transition temperature of the hard monomer is 300~400K；The hard monomer is preferably selected from methyl methacrylate
One or more in ester, vinylacetate, tertiary ethylene carbonate and styrene.
The function monomer is GMA；The function monomer preferably also includes cross-linking monomer；Institute
It is preferably hydroxyethyl methacrylate to state cross-linking monomer.
The preparing raw material of acrylate emulsion provided by the invention includes 1~4 part of emulsifying agent, preferably 1.5~
3.7 part.The emulsifying agent be preferably selected from model DNS-86 reactive emulsifiers, model FS-40 anionic emulsifier and
It is one or more in model DP-100 nonionic emulsifier.
The preparing raw material of acrylate emulsion provided by the invention includes 0.07~0.93 part of thermal initiator and gone back
Former 0.03~0.07 part of agent.The thermal initiator and reducing agent form oxidation-reduction system, and oxidation-reduction system can reduce
The temperature of emulsion polymerization process, avoid epoxide group and occur in the course of the polymerization process because temperature is too high inside latex particle
Ring-opening reaction, epoxide group is retained, reacted again in cation UV curing process, between enhancing emulsion particle
Crosslinking degree, improve the compactness of glued membrane.
The preparing raw material of acrylate emulsion provided by the invention includes 0~3 part of silane coupler, is preferably
0.2~2.6 part.In the present invention, the silane coupler is preferably selected from model KH550 silane couplers and/or model
KH560 silane couplers.
The preparing raw material of acrylate emulsion provided by the invention includes 140~160 parts of water, preferably 150~
155 parts.The water is preferably selected from deionized water.
The preparing raw material of acrylate emulsion provided by the invention includes 0.5~3 part of pH value regulator；Preferably
0.7~2.8 part.In the present invention, the pH value regulator is preferably selected from ammoniacal liquor, N, N- dimethylisopro panolamines and triethanolamine
In one or more.
The preparing raw material of acrylate emulsion provided by the invention includes 2~4 parts of cation light initiator, preferably
For 2.3~3.6 parts.In the present invention, the cation light initiator be preferably selected from sulfosalt class cation light initiator and/
Or the cation light initiator of salt compounded of iodine class；It is more preferably selected from the model Gencure 842 of Hypon profit Chemical Co., Ltd.
Cation light initiator and/or the cation light initiators of model Gencure 831.
The invention provides a kind of preparation method of acrylate emulsion described in above-mentioned technical proposal, including it is following
Step：
A) after mixing partial emulsifier and water, monomer is added, stirs, obtains pre-emulsion；
B) after remainder emulsifying agent and water being mixed, then pre-emulsion described with part mixing, part thermal initiation is added dropwise
Agent and partial reduction agent, reaction, obtain seed emulsion；
C) remainder thermal initiator, remainder reducing agent, remainder pre-emulsion are added dropwise to the seed breast
In liquid, insulation curing after adjusting pH value using pH value regulator, adds silane coupler, and cationic photopolymerization is added after stirring and is drawn
Agent is sent out, is dispersed with stirring, obtains acrylate emulsion.
After the present invention mixes partial emulsifier and water, monomer is added, stirs, obtains pre-emulsion.The emulsifying agent,
The species of water and monomer is consistent with the species of emulsifying agent, monomer and water described in above-mentioned technical proposal, will not be repeated here.The portion
The dosage for dividing emulsifying agent is preferably the 50% of emulsifying agent entirety dosage.
Partial emulsifier and water are preferably blended in beaker by the present invention；It is preferred that mixed under conditions of stirring；It is described to stir
The speed mixed is preferably 480~520rpm, more preferably 500rpm.Add the speed that stirs after monomer be preferably 950~
1050rpm, more preferably 1000rpm；It is preferably 25~35min to add after monomer the time stirred, more preferably 30min.
After obtaining pre-emulsion, after the present invention mixes remainder emulsifying agent and water, then with the part pre-emulsion
Mixing, the part thermal initiator aqueous solution and the partial reduction agent aqueous solution is added dropwise, reaction, obtains seed emulsion.
The present invention preferably mixes remainder emulsifying agent and water in reactor well known to those skilled in the art.It is remaining
Partial emulsifier and water preferably mix under conditions of stirring；The speed of the stirring is preferably 330~360rpm, more preferably
350rpm.The present invention mixes remainder emulsifying agent and water under conditions of heating；Be preferably heated to after 45~55 DEG C again and
The part pre-emulsion mixing.The quality of the part pre-emulsion accounts for the 5% of the quality of all pre-emulsions.
Thermal initiator and reducing agent are preferably dissolved in water by the present invention, obtain the thermal initiator aqueous solution and reducing agent
The aqueous solution.In actual practice it is preferred to the fast drop part thermal initiator aqueous solution and the partial reduction agent aqueous solution are to reactor
In.The temperature of the reaction is preferably 45~55 DEG C；The time of the reaction is 25~35min, more preferably 30min.
After obtaining seed emulsion, the present invention is by the remainder thermal initiator aqueous solution, remainder reducing agent aqueous solution, surplus
Remaining part divides pre-emulsion to be added dropwise in the seed emulsion, insulation curing, after adjusting pH value using pH value regulator, adds silicon
Alkane coupling agent, cation light initiator is added after stirring, is dispersed with stirring, obtains acrylate emulsion.
After seed emulsion system is preferably warming up to 50~60 DEG C by the present invention, the first constant pressure funnel, the second perseverance is respectively adopted
Press funnel and the 3rd constant pressure funnel that the remainder thermal initiator aqueous solution, remainder reducing agent aqueous solution, remainder is pre-
Emulsion droplet is added in the seed emulsion；The remainder thermal initiator aqueous solution, remainder reducing agent aqueous solution
Time for adding is both preferably 3~4h, more preferably 3.5h；The time that remainder pre-emulsion is added dropwise is preferably 2.8~3.2h,
More preferably 3h.In the present invention, the temperature of the insulation curing is preferably 85~90 DEG C, more preferably 88 DEG C；The insulation
The time of curing is preferably 1.5~2.5h, more preferably 2h.Air cooling after the insulation curing.
Present invention preferably employs pH value regulator to adjust pH value to 7~8, more preferably 7.The pH value regulator, silane
The species and dosage of coupling agent and cation light initiator and pH value regulator, silane coupler and sun described in above-mentioned technical proposal
The species of ionic photoinitiator is consistent with dosage, will not be repeated here.
The present invention is preferably by preparation described in acrylate emulsion described in above-mentioned technical proposal or above-mentioned technical proposal
Method prepare acrylate emulsion it is coated successively, drying and ultraviolet lighting solidification be made pressure sensitive adhesive tape.
In the present invention, photocuring (UV-curing) process of pressure sensitive adhesive is：After emulsion pressure-sensitive drying, through LT-
The ultraviolet crawler type photo solidification machine of UV102 types carries out ultraviolet light solidification.
The present invention carries out correlated performance test to above-mentioned emulsion：
(1) emulsion pattern and stability：The state and color of emulsion are observed, and emulsion is loaded on transparent 10ml centrifuge tubes
In, observe the stability under its static condition.
(2) 180 ° of peel strength tests：Tested according to GB/T 2792-2014, use 180 ° of electronic stripping tester (BLJ-C
Type, Jinan San Quan Zhong Shi laboratory apparatus Co., Ltd), emulsion is coated in thickness as 25 μm through electricity with 100 μm of bar spreader
On dizzy polyester film, 90 DEG C of baking 20min are used as test in an oven；
(3) water-whitening resistance can be tested：With reference to GB/T 1733-1993, the bar by the emulsion prepared with 100 μ m thicks
Spreader is coated on slide, and 90 DEG C of baking 20min, respectively scribble slide the part of glued membrane in 25 DEG C of conditions in an oven
Under be immersed in water 10min in water be immersed under the conditions of 24h and 90 DEG C, observe the degree of turning white of glued membrane, its degree of turning white can table
Non-whitening is shown as, slightly turns white, turn white, seriously turn white, turn white and ftractures；
(4) alkaline resistance properties is tested：The emulsion prepared is coated on 10cm*10cm with the bar spreader of 100 μ m thicks
The shiny surface of release liners, in an oven 90 DEG C baking 20min, release liners are converted into it is small box-like, wherein scribbling the shiny surface court of glued membrane
Outside, a small amount of phenolphthalein powder is placed on carton, carton is soaked in 2.5% sodium hydrate aqueous solution, observation phenolphthalein becomes red
Time used is to characterize the alkali corrosion resistance performance of glued membrane.
(5) emulsion particle diameter is tested：Using the Zeta potential and Particle Size Analyzer of Brookhaven companies, the flat of emulsion is characterized
Equal particle diameter and polydispersity coefficient.
The invention provides a kind of acrylate emulsion, is made by the raw material including following parts by weight of component：It is single
100 parts of body, it is 40~80 that the monomer, which includes mass ratio,:10~50:5~15 soft monomer, hard monomer and function monomer, it is described
The glass transition temperature of soft monomer is 180~220K；The glass transition temperature of the hard monomer is 300~400K；It is described
Function monomer includes GMA；1~4 part of emulsifying agent；0.07~0.93 part of thermal initiator；Reducing agent 0.03
~0.07 part；0~3 part of silane coupler；140~160 parts of water；0.5~3 part of pH value regulator；Cation light initiator 2~4
Part.The acrylate emulsion uses function monomer GMA as copolymer, with other components
Mutual compatibility, by cation photocuring, make the reaction between emulsion particle and emulsion particle by epoxide group in emulsion pressure-sensitive
Crosslinking is produced, strengthens the compactness of glued membrane, and then improve the water resistance and alkali resistance of pressure sensitive adhesive.Also there is excellent pressure-sensitive；
Emulsion pressure-sensitive particle diameter distribution is narrow, and storge quality is stable, and its preparation technology is simple, is easy to apply.Test result indicates that：Propylene
Acid esters emulsion pressure-sensitive outward appearance is milky blueing light, standing stability time ＞ 3 months；180 ° of peel strengths are 0.38~
1.03N/25mm；25 DEG C, non-whitening after 24h；90 DEG C, non-whitening or slightly turn white after 10min；Redden time of needs of phenolphthalein is
4~12min.
In order to further illustrate the present invention, with reference to embodiment to a kind of acrylate pressure-sensitive adhesive provided by the invention and
Its preparation method is described in detail, but they can not be interpreted as into limiting the scope of the present invention.
Embodiment 1
(1) pre-emulsification of monomer：By going for 1.03 mass parts DNS-86 and 0.12 mass parts DP-100 and 34.8 mass parts
Ionized water is mixed in beaker, and heating water bath is to using glass bar stirring and dissolving under the conditions of 50 DEG C, then is placed in electric blender stirring
Under, mixer rotating speed is 500rpm, sequentially adds 4 mass parts acrylic acid, 20 mass parts butyl acrylates, 53.5 mass parts propylene
The different monooctyl ester of acid, 18 mass parts methyl methacrylates, 1.5 mass parts hydroxyethyl methacrylates, the contracting of 3 mass parts methacrylic acids
Water glyceride, mixing speed is slowly increased to 1000rpm after monomer addition, then pre-emulsification is made in constant speed stirring half an hour
Liquid；
(2) prepared by seed emulsion：0.248 mass parts potassium peroxydisulfate and 0.052 mass parts sodium hydrogensulfite are dissolved in 1 respectively
In the deionized water of mass parts.1.03 mass parts DNS-86 and 0.12 mass parts DP-100 and the deionization of 103.2 mass parts
Water mixes, and is sufficiently stirred and dissolves by heating, be placed in reactor, constant speed stirs and is warming up to 45~55 DEG C, and mixing speed is
350rpm, the pre-emulsion of 6.8 mass parts is added, after question response temperature in the kettle is constant, it is water-soluble quickly to instill potassium peroxydisulfate successively
There is blue light in liquid and aqueous solution of sodium bisulfite, insulation reaction half an hour, system, and seed emulsion is made；
(3) prepared by emulsion：Reactor is warming up to 50~60 DEG C, and 0.248 mass parts potassium peroxydisulfate and 0.052 mass parts is sub-
Niter cake is dissolved in the deionized water of 5 mass parts respectively, is at the uniform velocity dripped it respectively with the first constant pressure funnel and the second constant pressure funnel
It is added in reactor, time for adding is 3.5 hours；Separately remaining pre-emulsion is added dropwise in reactor with the 3rd constant pressure funnel, dripped
It is 3 hours between added-time；After thermal initiator and reducing agent are added dropwise, 88 DEG C are warming up to, insulation curing two hours, air cooling, is dripped
Ammonification water regulation system pH value adds the silane coupler KH-KH560 of 3 mass parts, after stirring 10min, adds 4 matter to 7.5
The Gencure 842 of part is measured, is discharged after being dispersed with stirring 10min, obtains acrylate emulsion.
The present invention carries out dynamic light scattering (DLS) test to acrylate emulsion prepared by embodiment 1, as a result sees
Fig. 1, Fig. 1 are the DLS spectrograms of acrylate emulsion prepared by the embodiment of the present invention 1.Fig. 1 finds out：Prepared by embodiment 1
The average grain diameter of acrylate emulsion is 107.6nm, coefficient of dispersion PI=0.060.
The outward appearance and standing stability for the acrylate emulsion that the present invention is prepared to embodiment 1 are observed, and are tied
Fruit is shown in Table 1, and table 1 is the outward appearance and standing stability result of acrylate emulsion prepared by the embodiment of the present invention 1~4：
The outward appearance and standing stability result of acrylate emulsion prepared by the embodiment of the present invention 1~4 of table 1
Peel strength, water-whitening resistance and the alkali resistance for the acrylate emulsion that the present invention is prepared to embodiment 1 are entered
Row test, test result are shown in Table 2, table 2 be acrylate emulsion prepared by the embodiment of the present invention 1~4 peel strength,
Water-whitening resistance and alkali resistance test result：
The peel strength of acrylate emulsion prepared by the embodiment of the present invention 1~4 of table 2, water-whitening resistance and alkaline-resisting
Property test result
Embodiment 2
(1) pre-emulsification of monomer：By going for 1.03 mass parts DNS-86 and 0.12 mass parts DP-100 and 34.8 mass parts
Ionized water is mixed in beaker, and heating water bath is to using glass bar stirring and dissolving under the conditions of 50 DEG C, then is placed in electric blender stirring
Under, mixer rotating speed is 500rpm, sequentially adds 4 mass parts acrylic acid, 60 mass parts butyl acrylates, 10 mass parts acrylic acid
Different monooctyl ester, 13 mass parts tertiary ethylene carbonates, 3 mass parts hydroxyethyl methacrylates, 10 mass parts Glycidyl methacrylates are sweet
Grease, mixing speed is slowly increased to 1000rpm after monomer addition, then pre-emulsion is made in constant speed stirring half an hour；
(2) prepared by seed emulsion：0.248 mass parts potassium peroxydisulfate and 0.052 mass parts sodium hydrogensulfite are dissolved in 1 respectively
In the deionized water of mass parts.1.03 mass parts DNS-86 and 0.12 mass parts DP-100 and the deionization of 103.2 mass parts
Water mixes, and is sufficiently stirred and dissolves by heating, be placed in reactor, constant speed stirs and is warming up to 45~55 DEG C, and mixing speed is
350rpm, the pre-emulsion of 6.8 mass parts is added, after question response temperature in the kettle is constant, it is water-soluble quickly to instill potassium peroxydisulfate successively
There is blue light in liquid and aqueous solution of sodium bisulfite, insulation reaction half an hour, system, and seed emulsion is made；
(3) prepared by emulsion：Reactor is warming up to 50~60 DEG C, and 0.248 mass parts potassium peroxydisulfate and 0.052 mass parts is sub-
Niter cake is dissolved in the deionized water of 5 mass parts respectively, is at the uniform velocity dripped it respectively with the first constant pressure funnel and the second constant pressure funnel
It is added in reactor, time for adding is 3.5 hours；Separately remaining pre-emulsion is added dropwise in reactor with the 3rd constant pressure funnel, dripped
It is 3 hours between added-time；After thermal initiator and reducing agent are added dropwise, 88 DEG C are warming up to, insulation curing two hours, air cooling, is dripped
Ammonification water regulation system pH value adds the Gencure 842 of 4 mass parts, is discharged after being dispersed with stirring 10min, obtain propylene to 7.5
Acid esters emulsion pressure-sensitive.
The outward appearance and standing stability for the acrylate emulsion that the present invention is prepared to embodiment 2 are observed, and are tied
Fruit is shown in Table 1.Peel strength, water-whitening resistance and the alkali resistance for the acrylate emulsion that the present invention is prepared to embodiment 2 are entered
Row test, test result are shown in Table 2.
Embodiment 3
(1) pre-emulsification of monomer：By going for 1.03 mass parts DNS-86 and 0.12 mass parts DP-100 and 34.8 mass parts
Ionized water is mixed in beaker, and heating water bath is to using glass bar stirring and dissolving under the conditions of 50 DEG C, then is placed in electric blender stirring
Under, mixer rotating speed is 500rpm, sequentially adds 4 mass parts acrylic acid, 20 mass parts butyl acrylates, 32.5 mass parts propylene
The different monooctyl ester of acid, 37 mass parts methyl methacrylates, 1.5 mass parts hydroxyethyl methacrylates, the contracting of 5 mass parts methacrylic acids
Water glyceride, mixing speed is slowly increased to 1000rpm after monomer addition, then pre-emulsification is made in constant speed stirring half an hour
Liquid；
(2) prepared by seed emulsion：0.248 mass parts potassium peroxydisulfate and 0.052 mass parts sodium hydrogensulfite are dissolved in 1 respectively
In the deionized water of mass parts.1.03 mass parts DNS-86 and 0.12 mass parts DP-100 and the deionization of 103.2 mass parts
Water mixes, and is sufficiently stirred and dissolves by heating, be placed in reactor, constant speed stirs and is warming up to 45~55 DEG C, and mixing speed is
350rpm, the pre-emulsion of 6.8 mass parts is added, after question response temperature in the kettle is constant, it is water-soluble quickly to instill potassium peroxydisulfate successively
There is blue light in liquid and aqueous solution of sodium bisulfite, insulation reaction half an hour, system, and seed emulsion is made；
(3) prepared by emulsion：Reactor is warming up to 50~60 DEG C, and 0.248 mass parts potassium peroxydisulfate and 0.052 mass parts is sub-
Niter cake is dissolved in the deionized water of 5 mass parts respectively, is at the uniform velocity dripped it respectively with the first constant pressure funnel and the second constant pressure funnel
It is added in reactor, time for adding is 3.5 hours；Separately remaining pre-emulsion is added dropwise in reactor with the 3rd constant pressure funnel, dripped
It is 3 hours between added-time；After thermal initiator and reducing agent are added dropwise, 88 DEG C are warming up to, insulation curing two hours, air cooling, is dripped
Ammonification water regulation system pH value adds the Gencure 842 of 4 mass parts, is discharged after being dispersed with stirring 10min, obtain propylene to 7.5
Acid esters emulsion pressure-sensitive.
The outward appearance and standing stability for the acrylate emulsion that the present invention is prepared to embodiment 3 are observed, and are tied
Fruit is shown in Table 1.Peel strength, water-whitening resistance and the alkali resistance for the acrylate emulsion that the present invention is prepared to embodiment 3 are entered
Row test, test result are shown in Table 2.
Embodiment 4
(1) pre-emulsification of monomer：By going for 1.03 mass parts DNS-86 and 0.12 mass parts DP-100 and 34.8 mass parts
Ionized water is mixed in beaker, and heating water bath is to using glass bar stirring and dissolving under the conditions of 50 DEG C, then is placed in electric blender stirring
Under, mixer rotating speed is 500rpm, sequentially adds 4 mass parts acrylic acid, 20 mass parts butyl acrylates, 26 mass parts acrylic acid
Different monooctyl ester, 43.5 mass parts methyl methacrylates, 1.5 mass parts hydroxyethyl methacrylates, the contracting of 5 mass parts methacrylic acids
Water glyceride, mixing speed is slowly increased to 1000rpm after monomer addition, then pre-emulsification is made in constant speed stirring half an hour
Liquid；
(2) prepared by seed emulsion：0.248 mass parts potassium peroxydisulfate and 0.052 mass parts sodium hydrogensulfite are dissolved in 1 respectively
In the deionized water of mass parts.1.03 mass parts DNS-86 and 0.12 mass parts DP-100 and the deionization of 103.2 mass parts
Water mixes, and is sufficiently stirred and dissolves by heating, be placed in reactor, constant speed stirs and is warming up to 45~55 DEG C, and mixing speed is
350rpm, the pre-emulsion of 6.8 mass parts is added, after question response temperature in the kettle is constant, it is water-soluble quickly to instill potassium peroxydisulfate successively
There is blue light in liquid and aqueous solution of sodium bisulfite, insulation reaction half an hour, system, and seed emulsion is made；
(3) prepared by emulsion：Reactor is warming up to 50~60 DEG C, and 0.248 mass parts potassium peroxydisulfate and 0.052 mass parts is sub-
Niter cake is dissolved in the deionized water of 5 mass parts respectively, is at the uniform velocity dripped it respectively with the first constant pressure funnel and the second constant pressure funnel
It is added in reactor, time for adding is 3.5 hours；Separately remaining pre-emulsion is added dropwise in reactor with the 3rd constant pressure funnel, dripped
It is 3 hours between added-time；After thermal initiator and reducing agent are added dropwise, 88 DEG C are warming up to, insulation curing two hours, air cooling, is dripped
Ammonification water regulation system pH value adds the Gencure 842 of 4 mass parts, is discharged after being dispersed with stirring 10min, obtain propylene to 7.5
Acid esters emulsion pressure-sensitive.
The outward appearance and standing stability for the acrylate emulsion that the present invention is prepared to embodiment 4 are observed, and are tied
Fruit is shown in Table 1.Peel strength, water-whitening resistance and the alkali resistance for the acrylate emulsion that the present invention is prepared to embodiment 4 are entered
Row test, test result are shown in Table 2.
As seen from the above embodiment, the invention provides a kind of acrylate emulsion, by including following parts by weight
The raw material of component is made：100 parts of monomer, it is 40~80 that the monomer, which includes mass ratio,:10~50:5~15 soft monomer, hard list
Body and function monomer, the glass transition temperature of the soft monomer is 180~220K；The glass transition temperature of the hard monomer
For 300~400K；The function monomer includes GMA；1~4 part of emulsifying agent；Thermal initiator 0.07~
0.93 part；0.03~0.07 part of reducing agent；0~3 part of silane coupler；140~160 parts of water；0.5~3 part of pH value regulator；Sun
2~4 parts of ionic photoinitiator.The acrylate emulsion is using function monomer GMA as altogether
Polymers, with the mutual compatibility of other components, by cation photocuring, make between emulsion particle and emulsion particle to pass through in emulsion pressure-sensitive
The reaction of epoxide group produces crosslinking, strengthens the compactness of glued membrane, and then improve the water resistance and alkali resistance of pressure sensitive adhesive.Also have
Excellent pressure-sensitive；Emulsion pressure-sensitive particle diameter distribution is narrow, and storge quality is stable, and its preparation technology is simple, is easy to apply.Experiment
As a result show：Acrylate emulsion outward appearance is milky blueing light, standing stability time ＞ 3 months；180 ° of strippings
Intensity is 0.38~1.03N/25mm；25 DEG C, non-whitening after 24h；90 DEG C, non-whitening or slightly turn white after 10min；Phenolphthalein reddens
The time needed is 4~12min.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of acrylate emulsion, it is made by the raw material including following parts by weight of component：
100 parts of monomer, it is 40~80 that the monomer, which includes mass ratio,:10~50:5~15 soft monomer, hard monomer and function list
Body, the glass transition temperature of the soft monomer is 180~220K；The glass transition temperature of the hard monomer be 300~
400K；The function monomer includes GMA；
1~4 part of emulsifying agent；
0.07~0.93 part of thermal initiator；
0.03~0.07 part of reducing agent；
0~3 part of silane coupler；
140~160 parts of water；
0.5~3 part of pH value regulator；
2~4 parts of cation light initiator.
2. acrylate emulsion according to claim 1, it is characterised in that the soft monomer is selected from acrylic acid fourth
Ester and/or Isooctyl acrylate monomer；
The one kind or more of the hard monomer in methyl methacrylate, vinylacetate, tertiary ethylene carbonate and styrene
Kind.
3. acrylate emulsion according to claim 1, it is characterised in that the thermal initiator is selected from persulfuric acid
Potassium and/or ammonium persulfate；
The reducing agent is selected from sodium hydrogensulfite.
4. acrylate emulsion according to claim 1, it is characterised in that the emulsifying agent is selected from model
One in DNS-86 reactive emulsifiers, model FS-40 anionic emulsifier and model DP-100 nonionic emulsifier
Kind is a variety of.
5. acrylate emulsion according to claim 1, it is characterised in that the cation light initiator is selected from
The cation light initiator of sulfosalt class and/or the cation light initiator of salt compounded of iodine class.
6. acrylate emulsion according to claim 1, it is characterised in that the silane coupler is selected from model
For KH550 silane couplers and/or model KH560 silane couplers.
7. acrylate emulsion according to claim 1, it is characterised in that the pH value regulator is selected from ammonia
Water, N, the one or more in N- dimethylisopro panolamines and triethanolamine.
8. the preparation method of acrylate emulsion, comprises the following steps described in a kind of claim 1~7 any one：
A) after mixing partial emulsifier and water, monomer is added, stirs, obtains pre-emulsion；
B) after remainder emulsifying agent and water being mixed, then pre-emulsion described with part mixing, be added dropwise part thermal initiator and
Partial reduction agent, reaction, obtains seed emulsion；
C) remainder thermal initiator, remainder reducing agent, remainder pre-emulsion are added dropwise in the seed emulsion,
Then insulation curing, after adjusting pH value using pH value regulator, silane coupler is added, cationic photopolymerization is added after stirring and is triggered
Agent, it is dispersed with stirring, obtains acrylate emulsion.
9. preparation method according to claim 8, it is characterised in that the temperature of reaction is 45~55 in the step b)
℃；The time of reaction is 25~35min.
10. preparation method according to claim 8, it is characterised in that the temperature of insulation curing is 85 in the step c)
~90 DEG C, the time for being incubated curing is 1.5~2.5h；
The time of the dropwise addition is 3~4h.
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| CN115678466B (en) * | 2022-10-26 | 2023-09-12 | 广东东溢新材料科技有限公司 | Acrylic adhesive and acrylic adhesive film |
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