CN107189723A - Waterborne dry-type laminated adhesive and preparation method thereof - Google Patents
Waterborne dry-type laminated adhesive and preparation method thereof Download PDFInfo
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- CN107189723A CN107189723A CN201710423659.1A CN201710423659A CN107189723A CN 107189723 A CN107189723 A CN 107189723A CN 201710423659 A CN201710423659 A CN 201710423659A CN 107189723 A CN107189723 A CN 107189723A
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- laminated adhesive
- emulsifying agent
- initiator
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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
- 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
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- 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
-
- 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
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of waterborne dry-type laminated adhesive and preparation method thereof, the laminated adhesive includes following raw material by weight：20 35 parts of butyl acrylate, 10 20 parts of styrene, 0.5 5 parts of acrylic acid, 0.5 5 parts of functional monomer, 0.2 1 parts of emulsifying agent, 0.08 0.3 parts of initiator, 0.1 0.7 parts of buffer, 45 55 parts of water, 0.5 3.0 parts of functional aid, 0.15 part of oxidant.Laminated adhesive solid content >=48% that the present invention is provided, higher active ingredient just there is excellent lid powder ability, it is this product safety, aqueous, environmental protective, with low cost also with excellent flow leveling, it is easy to industrialized production；Transparency is high, and lid powder ability is strong, and rate of drying is fast, and heat resistance is good with frost resistance, and initial bonding strength is all good with holding power；Mechanical adaptability is good, and cutting can be carried out after 12 hours to mounting, the operation of concavo-convex and deep embossing.
Description
Technical field
The invention belongs to adhesive area, and in particular to waterborne dry-type laminated adhesive and preparation method thereof, in particular deep embossing
The not aqueous laminating adhesive of skinning.
Background technology
There is a kind of laminating adhesive paper to have packaging material both bright attractive in appearance in the market, and wear-resisting waterproof, thus be widely adopted.It is this
Material is polypropylene（BOPP）, terylene（PET）Or polyvinyl chloride（PVC）It is used Deng with being made in adhesive bonding to paper
Adhesive be Laminating adhesive.The Laminating adhesive of Chinese market can be divided into following three type；Heat class, organic solvent class and aqueous multiple
Film glue.Class Laminating adhesive is heated using pre-coating film by the way of, in-convenience in use, cohesive force is low, should not following process, thus less adopt
With.Organic solvent class Laminating adhesive, due to a large amount of using organic solvents such as toluene, gasoline, ethyl acetates, thus Material Cost it is high,
Working condition is poor, production and application and storage are dangerous, injure healthy and severe contamination environment；Another is hot melt
Laminated adhesive, such technology and production equipment are mainly controlled by European and American developed countries, and the product price eighteenth of the twenty is expensive.Existing aqueous laminating
Glue mainly has two types：One kind is cold rubberizing.Compounded or using outer normal emulsion polymerization production by base-material of VAE emulsions mostly
Form, although reached safe and environment-friendly requirement to a certain extent, but be only applicable packing timber low-grade or that ink layer is thin
On material, however it remains accommodation is narrow, low production efficiency, the not enough shortcoming of lid powder ability, holding power.Although the country also has big
Produce water-based dry-type complex film adhesive producer in batches, but in terms of current exquisite packaging needs deep embossing technique, but can not be from basic solution
Certainly and adapt to.
The content of the invention
It is an object of the invention to provide a kind of waterborne dry-type laminated adhesive and preparation method thereof, the waterborne dry-type laminated adhesive is safe and environment-friendly,
Lid powder ability is strong, and transparency is high, and heat resistance is good with frost resistance, and initial bonding strength has good with holding power, with low cost.
In order to solve the above technical problems, the technical solution adopted in the present invention is：A kind of waterborne dry-type laminated adhesive, including by
The following raw material of parts by weight meter：
20-35 parts of butyl acrylate, 10-20 parts of styrene, 0.5-5 parts of acrylic acid, 0.5-5 parts of functional monomer, emulsifying agent
0.2-1 parts, 0.08-0.3 parts of initiator, 0.1-0.7 parts of buffer, 45-55 parts of water, 0.5-3.0 parts of functional aid, oxidant
0.15 part.
Further, the functional monomer be DAAM, acrylic acid -2- hydroxyl second fat, Isooctyl acrylate monomer,
Methymethacrylate and diallyl phthalate.Other functional monomer also includes acrylamide, and its addition is accounted for
The 0.05% of total raw material weight.
Further, the emulsifying agent is anion and nonionic compound emulsifier；Initiator is ammonium persulfate；Buffer is Asia
Niter cake and sodium acid carbonate, functional aid are oxalyl dihydrazide, defoamer, wetting agent and ammoniacal liquor.
Further, described emulsifying agent by 0.06-0.5 parts alkyl phenol polyethenoxy ether sodium sulfate, 0.08-0.3 parts
Epoxy ethane-epoxy propane-epoxy butane copolymer and 0.06 ~ 0.2 part of 1- propenyloxy group -2- hydroxypropanesulfonic acid sodium group
Into.
Further, the functional aid is 0.5-2 parts of ammoniacal liquor, 0.15 ~ 0.4 part of oxalyl dihydrazide, 0.1 ~ 0.3 part of profits
Humectant and defoamer.
Further, the ammoniacal liquor is 20wt% ammoniacal liquor, for adjusting pH value and viscosity.
Further, described oxidant is 30wt% hydrogen peroxide.
The invention further relates to prepare the method for the laminated adhesive, it is characterised in that comprise the following steps：
1）Butyl acrylate, styrene, acrylic acid and functional monomer and partial emulsifier are emulsified, pre-emulsification is obtained
Liquid；
2）Buffer, part initiator and remaining emulsifying agent are subjected to heating stirring and dissolving, 2 ~ 5wt% pre- breast is then added
Change liquid and do seed, further emulsification；
3）To step 2）Remaining pre-emulsion and remaining initiator are added dropwise in the liquid of gained, was dripped in 3-4 hours,
Then oxidant is added, 1-2 hours are incubated at 80-85 DEG C；40-45 DEG C is finally cooled to, functional aid is added dropwise, PH is adjusted
It is worth for 6.5-7.5, filters, discharge to obtain waterborne dry-type laminated adhesive.
Further, in operating process every time emulsification or be added dropwise mixing when, all in accordance with need add water.
The waterborne dry-type laminated adhesive that my present invention is provided its have the advantages that：
1）Butyl acrylate is used for soft monomer, makes aqueous laminating adhesive transparency high, with excellent toughness and water resistance.
2）Styrene is added, with excellent reactivity, while the phenyl ring of hydrophobic structure is remarkably improved the resistance to of emulsion
Aqueous and alkali resistance.
3）Adding acrylic acid then can both improve particle diameter and the distribution of latex, increase the viscosity and stability of emulsion, and not
Cause water-fast, the alkaline resistance properties of reduction emulsion.
4）Reacted by adding in DAAM, glue system by oxalyl dihydrazide as solidify afterwards agent, can
To significantly improve peel strength and resistance to deep embossing performance.Pass through butyl acrylate, styrene, methyl methacrylate and double third
The reasonable volume of ketone acrylamide, determines the rational glass transition temperature of polymer, it is ensured that the perfection of initial bonding strength and holding power
It is unified.Diallyl phthalate is as plasticiser, the cohesive force between regulation glass transition temperature and enhancing and film.Adopt
On the one hand it can promote epigranular as stabilizer, protecting colloid with acrylamide；On the other hand make as thickener
With compared to only pH is adjusted by ammoniacal liquor before controlling that in viscosity, the present invention use of ammoniacal liquor can be reduced, optimize production environment.
Using anionic and non-ionic composite emulsifying system, make the greasy particle diameter detailed catalogue of emulsion, modest viscosity, stability, water resistance,
Alkali resistance is good, and glued membrane intensity is high.
5）Solid content >=46% of the present invention, higher active ingredient is with excellent lid powder ability, also with excellent
Flow leveling.
6）By the sensitive control of temperature in the formula of raw material and making and technique, reaction system can be preferably controlled
Temperature, uses this product safety, aqueous, environmental protective, with low cost, it is easy to industrialized production；Transparency is high, and lid powder ability is strong, dries
Speed is fast, and heat resistance is good with frost resistance, and initial bonding strength is all good with holding power；Mechanical adaptability is good, and cutting can be carried out pair after 12 hours
Mount, the operation of concavo-convex and deep embossing.
7）The present invention, which adds the polymer chain containing carboxyl, hydroxyl and amino, can occur a variety of cross-linking reactions, assign adhesive
Stronger bonding force and adhesive strength after final solidification, it is ensured that the deep performance for embossing not skinning.
Embodiment
The present invention is further illustrated with reference to embodiment, but the scope of protection of present invention is not limited to implement
The scope of example statement.
Embodiment 1：
By weight, 34 parts of butyl acrylate, 14 parts of styrene, 0.7 part of acrylic acid, 0.7 part of DAAM, propylene
1.2 parts of acid -2- hydroxyl second fat, 0.15 part of Isooctyl acrylate monomer and 0.2 part of methyl methacrylate, diallyl phthalate
0.6 part, 0.05 part of acrylamide, 0.3 part of emulsifying agent, 0.08 part of initiator ammonium persulfate, 0.1 part of buffer, 47 parts of water, ammoniacal liquor
0.5 part, 0.15 part of oxalyl dihydrazide, wetting agent and defoamer totally 0.1 part and 0.15 part of oxidant.In emulsifying agent anion and it is non-from
Sub- emulsifying agent respectively accounts for half.
When preparing the laminated adhesive, comprise the following steps：
1）By butyl acrylate, styrene, acrylic acid, DAAM, acrylic acid -2- hydroxyl second fat, Isooctyl acrylate monomer,
Methyl methacrylate, diallyl phthalate, acrylamide and 0.1 part of emulsifying agent, 18 parts of water are mixed and emulsified,
Obtain pre-emulsion；
2）Buffer, 0.05 part of initiator, remaining emulsifying agent and 20 parts of water are subjected to heating stirring and dissolvings, step 1 is then taken）
The 2wt% of pre-emulsion add wherein as seed, further emulsification；
3）To step 2）Remaining pre-emulsion, remaining initiator and 7 parts of water are added dropwise in the liquid of gained, in 3-4 hours
Drip, then add oxidant, 1 hour is incubated at 80-85 DEG C；Finally be cooled to 40-45 DEG C, be added dropwise functional aid and
Remaining water, regulation pH value is 6.5-7.5, is filtered, discharge to obtain waterborne dry-type laminated adhesive.
In obtained waterborne dry-type laminated adhesive, solid content is that 48.2%, pH is 7.5.
Embodiment 2：
By weight, 20 parts of butyl acrylate, 10 parts of styrene, 0.5 part of acrylic acid, 0.5 part of DAAM, propylene
0.2 part of acid -2- hydroxyl second fat, 0.1 part of Isooctyl acrylate monomer and 0.2 part of methyl methacrylate, diallyl phthalate 0.5
Part, 0.3 part of emulsifying agent, 0.08 part of initiator ammonium persulfate, 0.1 part of buffer, 50 parts of water, 0.5 part of ammoniacal liquor, oxalyl dihydrazide 0.15
Part, wetting agent and defoamer totally 0.1 part and 0.15 part of oxidant.
When preparing the laminated adhesive, comprise the following steps：
1）By butyl acrylate, styrene, acrylic acid, DAAM, acrylic acid -2- hydroxyl second fat, phthalic acid two
Allyl ester, Isooctyl acrylate monomer, methyl methacrylate and 0.1 part of emulsifying agent, 15 parts of water are mixed and emulsified, and obtain pre- breast
Change liquid；
2）Buffer, 0.05 part of initiator, remaining emulsifying agent and 25 parts of water are subjected to heating stirring and dissolvings, step 1 is then taken）
The 2wt% of pre-emulsion add wherein as seed, further emulsification；
3）To step 2）Remaining pre-emulsion, remaining initiator and 8 parts of water are added dropwise in the liquid of gained, in 3-4 hours
Drip, then add oxidant, 1 hour is incubated at 80-85 DEG C；Finally be cooled to 40-45 DEG C, be added dropwise functional aid and
Remaining water, regulation pH value is 6.5-7.5, is filtered, discharge to obtain waterborne dry-type laminated adhesive.Its solid content is that 46.5%, pH is 8.0.
Embodiment 3：
By weight, 35 parts of butyl acrylate, 20 parts of styrene, 5 parts of acrylic acid, 5 parts of functional monomer, 1 part of emulsifying agent, draw
Send out 0.3 part of agent, 0.7 part of buffer, 55 parts of water, 2.6 parts of functional aid, 0.15 part of oxidant.
Wherein, functional monomer is 2 parts of DAAM, 1.5 parts of acrylic acid -2- hydroxyl second fat, Isooctyl acrylate monomer
With totally 1 part of methymethacrylate, 0.5 part of diallyl phthalate.Emulsifying agent is by 0.5 part of APES
Sodium sulphate, 0.3 part of epoxy ethane-epoxy propane-epoxy butane copolymer and 0.2 part of 1- propenyloxy group -2- hydroxy propane sulphur
Sour sodium composition；Initiator is ammonium persulfate；Buffer is 0.4 part of 0.3 part of sodium hydrogensulfite and sodium acid carbonate, and functional aid is
2 parts of 0.4 part of oxalyl dihydrazide, 0.1 part of defoamer, 0.1 part of wetting agent and 20wt% ammoniacal liquor.Oxidant is 30wt% hydrogen peroxide.
During preparation：
1）Butyl acrylate, styrene, acrylic acid and functional monomer and partial emulsifier are emulsified, pre-emulsification is obtained
Liquid；
2）Buffer, part initiator and remaining emulsifying agent are subjected to heating stirring and dissolving, 2 ~ 5wt% pre- breast is then added
Change liquid and do seed, further emulsification；
3）To step 2）Remaining pre-emulsion and remaining initiator are added dropwise in the liquid of gained, was dripped in 3-4 hours,
Then oxidant is added, 1-2 hours are incubated at 80-85 DEG C；40-45 DEG C is finally cooled to, functional aid is added dropwise, PH is adjusted
It is worth for 6.5-7.5, filters, discharge to obtain waterborne dry-type laminated adhesive.
Further, in operating process every time emulsification or be added dropwise mixing when, all in accordance with need add water.
Claims (9)
1. a kind of waterborne dry-type laminated adhesive, it is characterised in that including following raw material by weight：
20-35 parts of butyl acrylate, 10-20 parts of styrene, 0.5-5 parts of acrylic acid, 0.5-5 parts of functional monomer, emulsifying agent
0.2-1 parts, 0.08-0.3 parts of initiator, 0.1-0.7 parts of buffer, 45-55 parts of water, 0.5-3.0 parts of functional aid, oxidant
0.15 part.
2. laminated adhesive according to claim 1, it is characterised in that：The functional monomer is DAAM, third
Olefin(e) acid -2- hydroxyl second fat, Isooctyl acrylate monomer, methymethacrylate and diallyl phthalate.
3. laminated adhesive according to claim 1, it is characterised in that：The emulsifying agent is anion and nonionic composite emulsifying
Agent；Initiator is ammonium persulfate；Buffer be sodium hydrogensulfite and sodium acid carbonate, functional aid be oxalyl dihydrazide, defoamer,
Wetting agent and ammoniacal liquor.
4. laminated adhesive according to claim 1, it is characterised in that：Described emulsifying agent is gathered by 0.06-0.5 parts of alkyl phenol
Oxygen ethene ether sodium sulfate, 0.08-0.3 parts of epoxy ethane-epoxy propane-epoxy butane copolymer and 0.06 ~ 0.2 part of 1- propylene
Epoxide -2- hydroxypropanesulfonic acids sodium is constituted.
5. laminated adhesive according to claim 3, it is characterised in that：The functional aid be 0.5-2 parts of ammoniacal liquor, 0.15 ~
0.4 part of oxalyl dihydrazide, 0.1 ~ 0.3 part of wetting agent and defoamer.
6. laminated adhesive according to claim 5, it is characterised in that：The ammoniacal liquor is 20wt% ammoniacal liquor.
7. laminated adhesive according to claim 1, it is characterised in that：Described oxidant is 30wt% hydrogen peroxide.
8. prepare the method for laminated adhesive described in claim 1-7 any one, it is characterised in that comprise the following steps：
1）Butyl acrylate, styrene, acrylic acid and functional monomer and partial emulsifier are emulsified, pre-emulsification is obtained
Liquid；
2）Buffer, part initiator and remaining emulsifying agent are subjected to heating stirring and dissolving, 2-5wt% pre- breast is then added
Change liquid and do seed, further emulsification；
3）To step 2）Remaining pre-emulsion and remaining initiator are added dropwise in the liquid of gained, was dripped in 3-4 hours,
Then oxidant is added, 1-2 hours are incubated at 80-85 DEG C；40-45 DEG C is finally cooled to, functional aid is added dropwise, PH is adjusted
It is worth for 6.5-7.5, filters, discharge to obtain waterborne dry-type laminated adhesive.
9. method according to claim 8, it is characterised in that：When emulsification or dropwise addition are mixed every time in operating process,
Add water.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710423659.1A CN107189723A (en) | 2017-06-07 | 2017-06-07 | Waterborne dry-type laminated adhesive and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710423659.1A CN107189723A (en) | 2017-06-07 | 2017-06-07 | Waterborne dry-type laminated adhesive and preparation method thereof |
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| CN201710423659.1A Pending CN107189723A (en) | 2017-06-07 | 2017-06-07 | Waterborne dry-type laminated adhesive and preparation method thereof |
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Cited By (4)
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|---|---|---|---|---|
| CN109536086A (en) * | 2018-11-14 | 2019-03-29 | 南通高盟新材料有限公司 | Bi-component waterborne styrene-acrylic emulsion adhesive and preparation method thereof for boiling packaging |
| CN110655885A (en) * | 2019-11-11 | 2020-01-07 | 怀化学院 | Laminating adhesive and preparation method thereof |
| CN113372500A (en) * | 2021-07-21 | 2021-09-10 | 海南赛诺实业有限公司 | Functional acrylic emulsion and preparation method thereof, wear-resistant acrylic coating film and acrylic coating BOPP film |
| CN114214004A (en) * | 2021-12-23 | 2022-03-22 | 河南省科学院高新技术研究中心 | Composite acrylic resin hot melt adhesive and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109536086A (en) * | 2018-11-14 | 2019-03-29 | 南通高盟新材料有限公司 | Bi-component waterborne styrene-acrylic emulsion adhesive and preparation method thereof for boiling packaging |
| CN110655885A (en) * | 2019-11-11 | 2020-01-07 | 怀化学院 | Laminating adhesive and preparation method thereof |
| CN113372500A (en) * | 2021-07-21 | 2021-09-10 | 海南赛诺实业有限公司 | Functional acrylic emulsion and preparation method thereof, wear-resistant acrylic coating film and acrylic coating BOPP film |
| CN114214004A (en) * | 2021-12-23 | 2022-03-22 | 河南省科学院高新技术研究中心 | Composite acrylic resin hot melt adhesive and preparation method thereof |
| CN114214004B (en) * | 2021-12-23 | 2022-11-18 | 河南省科学院高新技术研究中心 | Composite acrylic resin hot melt adhesive and preparation method thereof |
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