CN1285382A - Composition of composite crosslinking type aqueous compound film adhesive and preparation process thereof - Google Patents
Composition of composite crosslinking type aqueous compound film adhesive and preparation process thereof Download PDFInfo
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- CN1285382A CN1285382A CN 99117830 CN99117830A CN1285382A CN 1285382 A CN1285382 A CN 1285382A CN 99117830 CN99117830 CN 99117830 CN 99117830 A CN99117830 A CN 99117830A CN 1285382 A CN1285382 A CN 1285382A
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Abstract
The preparation method of compound crosslinked water double-film adhesive is characterized by its compositions of (wt%) 13%-30% of butyl acrylate, 6%-15% of ethyl acrylate, 0.5%-5% of acrylic acid, 0.5%-5% of functional conomer, 0.2%-1% of emulsifier, 0.05%-0.2% of initiating agent, 0.1%-0.8% of buffer, 55%-75% of water and 0.1%-1.0% of ammonia water. The emulsion polymerization method is used to obtain the invented product. It uses the functional monomers containing carboxy, hydroxyl and amino to participate in the copolymerization so as to obtain polymer chain containing multifunctional group which can produce several crosslinking reaction and make the adhesive possess stronger cohesive force and cohesional strength, and raise its water-proofing and solvent-resisting properties.
Description
The present invention relates to the composition and the preparation method of tackiness agent, relate in particular to a kind of composition and preparation method of composite crosslinking type aqueous compound film adhesive.
Paper is compound can to make printed matter surface light, level and smooth more, and color and luster is more bright-coloured and be rich in stereoscopic sensation, also plays protection against the tide, false proof, folding, effect such as wear-resisting simultaneously.In recent years, paper compound or mould compounding technology in printing, packaging industry is widely used and develop rapidly, the compound demand that sticks with glue agent also increases severely thereupon.The subject matter of paper-plastic composite adhesive existence at present is still to use toluene in a large number, noxious solvent and thinners such as dimethylbenzene, not only the healthy of operator caused serious harm, and it is inflammable, explosive, very inconvenience of transportation and storage, because such tackiness agent main component is that ethylene-vinyl acetate resin (is permitted to grind Li Guoxiong, tackiness agent, 4,15,1989); styrene-butadiene rubber(SBR) (Zhang Jianying, Chinese tackiness agent; 4 (5); 10,1995) etc., weathering resistance; solvent resistance is relatively poor; the not ideal enough and poor stability of bonding fastness, multiple film product occurs wrinkling easily; bubble; phenomenons such as delamination.
Therefore, develop a kind of nontoxic, pollution-free, convenient, safety, paper-plastic composite adhesive has great importance cheaply, the emulsion-type water accack is considered to the most rising, comprehensively virgin rubber kind (H.J.Fricke, the L.Maempel of replace solvents type paper-plastic lamination tackiness agent, bonding, 18 (2), 25,1997).
The composition and the preparation method that the purpose of this invention is to provide a kind of composite crosslinking type aqueous compound film adhesive.
In order to achieve the above object, the present invention takes following measures:
The proportioning of the composition of composite crosslinking type aqueous compound film adhesive is:
A butyl acrylate 13～30wt%
B ethyl propenoate 6～15wt%
C vinylformic acid 0.5～5wt%
D functional monomer 0.5～5wt%
E emulsifying agent 0.2～1wt%
F initiator 0.05～0.2wt%
G buffer reagent 0.1～0.8wt%
H water 55～75wt%
I ammoniacal liquor 0.1～1.0wt%
The preparation method of composite crosslinking type aqueous compound film adhesive is that its proportioning is:
A butyl acrylate 13～30wt%
B ethyl propenoate 6～15wt%
C vinylformic acid 0.5～5wt%
D functional monomer 0.5～5wt%
E emulsifying agent 0.2～1wt%
F initiator 0.05～0.2wt%
G buffer reagent 0.1～0.8wt%
H water 55～75wt%
I ammoniacal liquor 0.1～1.0wt%
Its preparation method is: water, buffer reagent, emulsifying agent are added in the reactor, and stirring and dissolving 10～20 minutes adds 1/6～1/4 mix monomer, after the emulsification 30～40 minutes, add 1/5～1/2 initiator, be warming up to 70～85 ℃, react after 30～40 minutes, begin to drip residual monomers and initiator, drip in 2～4 hours, insulation began cooling, to 40～45 ℃ after 1～2 hour under 80～85 ℃, dropping ammonia, regulating the pH value is that 5～7,120 order filter clothes filter discharging.
Advantage of the present invention is: prepared tackiness agent does not contain any organic solvent, and is nontoxic, helps the healthy of environment protection and operator, and is easy to transportation and storage.
Owing to adopt acrylic ester monomer as bonding composition, tackiness agent of the present invention has the bonding strength height, luminance brightness is good, weathering resistance, poor solvent resistance that the rubber-like solvent adhesive produces have been overcome, not ideal enough and the poor stability of bonding fastness, phenomenons such as the easy appearance of multiple film product is wrinkling, foaming, delamination.
Another distinguishing feature of the present invention is to add to contain carboxyl, hydroxyl and amino function monomer participation copolyreaction respectively, formation contains the polymer chain of multiple functional groups such as carboxyl, hydroxyl and amino, multiple crosslinking reaction can take place in these polymer chains that contain functional group each other and with functional groups such as the carboxyl on plastics film surface, hydroxyls, thereby give stronger bonding force of this tackiness agent and bonding strength, improve the force of cohesion and water-fast, the solvent resistance of tackiness agent.
The present invention selects for use negatively charged ion and nonionic emulsifying agent as compound emulsifying agent, can improve the polymerization stability and the package stability of tackiness agent, helps the wettability of tackiness agent on film surfaces such as polyethylene, polypropylene simultaneously.
Because the present invention adopts water as dispersion medium, has not only eliminated the discharging of poisonous organic solvent in the multiple membrane process, helps the healthy of environment protection and workman, and can reduce the cost of adhesive products greatly.
Elaborate below in conjunction with embodiment:
The proportioning of the composition of composite crosslinking type aqueous compound film adhesive is:
A butyl acrylate 15～28wt%
B ethyl propenoate 7～13wt%
C vinylformic acid 1～4wt%
D functional monomer 1.5～4wt%
E emulsifying agent 0.4～0.8wt%
F initiator 0.1～0.2wt%
G buffer reagent 0.3～0.5wt%
H water 60～70wt%
I ammoniacal liquor 0.4～0.8wt%
The preparation method of composite crosslinking type aqueous compound film adhesive is that its proportioning is:
A butyl acrylate 15～28wt%
B ethyl propenoate 7～13wt%
C vinylformic acid 1～4wt%
D functional monomer 1.5～4wt%
E emulsifying agent 0.4～0.8wt%
F initiator 0.1～0.2wt%
G buffer reagent 0.3～0.5wt%
H water 60～70wt%
I ammoniacal liquor 0.4～0.8wt%
Its preparation method is: water, buffer reagent, emulsifying agent are added in the reactor, and stirring and dissolving 10～20 minutes adds 1/6～1/4 mix monomer, after the emulsification 30～40 minutes, add 1/5～1/2 initiator, be warming up to 70～85 ℃, react after 30～40 minutes, begin to drip residual monomers and initiator, drip in 2～4 hours, insulation began cooling, to 40～45 ℃ after 1～2 hour under 80～85 ℃, dropping ammonia, regulating the pH value is that 5～7,120 order filter clothes filter discharging.
Above-mentioned D material is selected the vinyl monomer that contains amino, hydroxyl, carboxyl or epoxy group(ing) functional group for use.The E material is selected negatively charged ion and nonionic compound emulsifier for use; The G material is selected sodium bisulfite, sodium bicarbonate, yellow soda ash for use.
Contain amino vinyl monomer and select acrylamide, N hydroxymethyl acrylamide for use; The vinyl monomer of hydroxyl is selected hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Rocryl 410, Rocryl 410, Propylene glycol monoacrylate for use; The vinyl monomer that contains epoxy group(ing) is selected glycidyl methacrylate for use.
Anionic emulsifier is selected Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium laurylsulfonate for use; Nonionic emulsifying agent is selected paregal O, OS-10, OP-10, OP-7, OP-20 for use.
Embodiment 1:
A butyl acrylate 190kg
B ethyl propenoate 90kg
C vinylformic acid 23kg
D functional monomer 23.6kg is wherein: hydroxyethyl methylacrylate 14kg
N hydroxymethyl acrylamide 9.6kg
E emulsifying agent 5.2kg
Wherein: OP-10 2kg
Sodium dodecylbenzene sulfonate 3.2kg
F ammonium persulphate 1.48kg
G sodium bicarbonate 4.00kg
H water 680kg
I ammoniacal liquor 5.9kg
Its preparation method is: water, buffer reagent, emulsifying agent are added in the reactor, and stirring and dissolving 10～20 minutes adds 1/6～1/4 mix monomer, after the emulsification 30～40 minutes, add 1/5～1/2 initiator, be warming up to 70～85 ℃, react after 30～40 minutes, begin to drip residual monomers and initiator, drip in 2～4 hours, insulation began cooling, to 40～45 ℃ after 1～2 hour under 80～85 ℃, dropping ammonia, regulating the pH value is that 5～7,120 order filter clothes filter discharging.
More than the performance index of the composite crosslinking type aqueous compound film adhesive for preparing as stated above of prescription are as follows:
Outward appearance: white emulsion
PH value: 6～7
Solid content/%:32 ± 1
Stability/year:＞1
Solvent resistance: wrinkle resistant, non-foaming
Stripping strength/N (2.5cm)
-1:＞3.2
Embodiment 2:
A butyl acrylate 260kg
B ethyl propenoate 83kg
C vinylformic acid 30kg
D functional monomer 29.8kg
Wherein: hydroxyethyl methylacrylate 16.6kg
N hydroxymethyl acrylamide 13.2kg
E emulsifying agent 6.5kg
Wherein: OP-10 3.3kg
Sodium dodecylbenzene sulfonate 3.2kg
F ammonium persulphate 1.8kg
G sodium bicarbonate 3.00kg
H water 620kg
I ammoniacal liquor 5.0kg preparation method is with embodiment 1.
More than the performance index of the composite crosslinking type aqueous compound film adhesive for preparing as stated above of prescription are as follows:
Outward appearance: white emulsion
PH value: 6～7
Solid content/%:39 ± 1
Stability/year:＞1
Solvent resistance: wrinkle resistant, non-foaming
Stripping strength/N (2.5cm)
-1:＞3.5
Embodiment 3:
A butyl acrylate 239kg
B ethyl propenoate 76kg
C vinylformic acid 20kg
D functional monomer 20.3kg
Wherein: hydroxyethyl methylacrylate 12.3kg
N hydroxymethyl acrylamide 8kg
E emulsifying agent 8.3kg
Wherein: OP-10 5.6kg
Sodium dodecylbenzene sulfonate 2.7kg
F ammonium persulphate 1.6kg
G sodium bicarbonate 2.00kg
H water 650kg
I ammoniacal liquor 2.0kg preparation method is with embodiment 1.
More than the performance index of the composite crosslinking type aqueous compound film adhesive for preparing as stated above of prescription are as follows:
Outward appearance: white emulsion
PH value: 6～7
Solid content/%:35 ± 1
Stability/year:＞1
Solvent resistance: wrinkle resistant, non-foaming
Stripping strength/N (2.5cm)
-1:＞3.3
Above-mentioned compound film adhesive can directly use when being used for multiple film or an amount of dilute with water after use, the basic technology parameter is as follows: drying tunnel temperature, 65 ℃; Roller temperature, 70 ℃, roller pressure, 15～18Kg/cm
2Chart drive speed 〉=800m/h.Product cutting at that time behind the multiple film after the shutdown, need not directly get final product with the clear water cleaning with organic solvent cleaning equipments such as toluene.
The compound product that obtains of compound film adhesive that makes with the present invention has flat appearance, the luminance brightness height, and solvent resistance is good, is ideal " green " compound film adhesive.
Claims (10)
1. the composition of a composite crosslinking type aqueous compound film adhesive is characterized in that its proportioning is:
A butyl acrylate 13～30wt% B ethyl propenoate 6～15wt% C vinylformic acid 0.5～5wt% D functional monomer 0.5～5wt% E emulsifying agent 0.2～1wt% F initiator 0.05～0.2wt% G buffer reagent 0.1～0.8wt% H water 55～75wt% I ammoniacal liquor 0.1～1.0wt%
2. the composition according to claims 1 described a kind of composite crosslinking type aqueous compound film adhesive is characterized in that its proportioning is:
A butyl acrylate 15～28wt%
B ethyl propenoate 7～13wt%
C vinylformic acid 1～4wt%
D functional monomer 1.5～4wt%
E emulsifying agent 0.4～0.8wt%
F initiator 0.1～0.2wt%
G buffer reagent 0.3～0.5wt%
H water 60～70wt%
I ammoniacal liquor 0.4～0.8wt%
3. the preparation method of a composite crosslinking type aqueous compound film adhesive is characterized in that its proportioning is:
A butyl acrylate 13～30wt%
B ethyl propenoate 6～15wt%
C vinylformic acid 0.5～5wt%
D functional monomer 0.5～5wt%
E emulsifying agent 0.2～1wt%
F initiator 0.05～0.2wt%
G buffer reagent 0.1～0.8wt%
H water 55～75wt%
I ammoniacal liquor 0.1～1.0wt%
Its preparation method is: water, buffer reagent, emulsifying agent are added in the reactor, and stirring and dissolving 10～20 minutes adds 1/6～1/4 mix monomer, after the emulsification 30～40 minutes, add 1/5～1/2 initiator, be warming up to 70～85 ℃, react after 30～40 minutes, begin to drip residual monomers and initiator, drip in 2～4 hours, insulation began cooling, to 40～45 ℃ after 1～2 hour under 80～85 ℃, dropping ammonia, regulating the pH value is that 5～7,120 order filter clothes filter discharging.
4. according to the preparation method of claims 3 described a kind of composite crosslinking type aqueous compound film adhesives, it is characterized in that its proportioning is:
A butyl acrylate 15～28wt%
B ethyl propenoate 7～13wt%
C vinylformic acid 1～4wt%
D functional monomer 1.5～4wt%
E emulsifying agent 0.4～0.8wt%
F initiator 0.1～0.2wt%
G buffer reagent 0.3～0.5wt%
H water 60～70wt%
I ammoniacal liquor 0.4～0.8wt%
Its preparation method is: water, buffer reagent, emulsifying agent are added in the reactor, and stirring and dissolving 10～20 minutes adds 1/6～1/4 mix monomer, after the emulsification 30～40 minutes, add 1/5～1/2 initiator, be warming up to 70～85 ℃, react after 30～40 minutes, begin to drip residual monomers and initiator, drip in 2～4 hours, insulation began cooling, to 40～45 ℃ after 1～2 hour under 80～85 ℃, dropping ammonia, regulating the pH value is that 5～7,120 order filter clothes filter discharging.
5. according to the composition of claims 1 and 2 described a kind of composite crosslinking type aqueous compound film adhesives, it is characterized in that D expects to select for use the vinyl monomer that contains amino, hydroxyl, carboxyl or epoxy group(ing) functional group.The E material is selected negatively charged ion and nonionic compound emulsifier for use; The G material is selected sodium bisulfite, sodium bicarbonate, yellow soda ash for use.
6. according to the composition of claims 5 described a kind of composite crosslinking type aqueous compound film adhesives, it is characterized in that, contain amino vinyl monomer and select acrylamide, N hydroxymethyl acrylamide for use; The vinyl monomer of hydroxyl is selected hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Rocryl 410, Propylene glycol monoacrylate for use; The vinyl monomer that contains epoxy group(ing) is selected glycidyl methacrylate for use.
7. according to the composition of claims 5 described a kind of composite crosslinking type aqueous compound film adhesives, it is characterized in that anionic emulsifier is selected Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium laurylsulfonate for use; Nonionic emulsifying agent is selected paregal O, OS-10, OP-10, OP-7, OP-20 for use.
8. according to the preparation method of claims 3 and 4 described a kind of composite crosslinking type aqueous compound film adhesives, it is characterized in that D expects to select for use the vinyl monomer that contains amino, hydroxyl, carboxyl or epoxy group(ing) functional group.The E material is selected negatively charged ion and nonionic compound emulsifier for use; The G material is selected sodium bisulfite, sodium bicarbonate, yellow soda ash for use.
9. according to the preparation method of claims 8 described a kind of composite crosslinking type aqueous compound film adhesives, it is characterized in that, contain amino vinyl monomer and select acrylamide, N hydroxymethyl acrylamide for use; The vinyl monomer of hydroxyl is selected hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Rocryl 410, Propylene glycol monoacrylate for use; The vinyl monomer that contains epoxy group(ing) is selected glycidyl methacrylate for use.
10. according to the preparation method of claims 8 described a kind of composite crosslinking type aqueous compound film adhesives, it is characterized in that anionic emulsifier is selected Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium laurylsulfonate for use; Nonionic emulsifying agent is selected paregal O, OS-10, OP-10, OP-7, OP-20 for use.
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