CN102504733A - Water-blush-resistant fluoride and siloxane modified waterborne pressure-sensitive adhesive and polyethylene protective film - Google Patents

Water-blush-resistant fluoride and siloxane modified waterborne pressure-sensitive adhesive and polyethylene protective film Download PDF

Info

Publication number
CN102504733A
CN102504733A CN2011103892755A CN201110389275A CN102504733A CN 102504733 A CN102504733 A CN 102504733A CN 2011103892755 A CN2011103892755 A CN 2011103892755A CN 201110389275 A CN201110389275 A CN 201110389275A CN 102504733 A CN102504733 A CN 102504733A
Authority
CN
China
Prior art keywords
water
weight
protective film
sensitive adhesive
pressure sensitive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2011103892755A
Other languages
Chinese (zh)
Other versions
CN102504733B (en
Inventor
柯跃虎
王洪
王见红
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuxi Delta new material Co., Ltd.
Original Assignee
GUANGDONG TAMAY NEW MATERIALS CO Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by GUANGDONG TAMAY NEW MATERIALS CO Ltd filed Critical GUANGDONG TAMAY NEW MATERIALS CO Ltd
Priority to CN201110389275.5A priority Critical patent/CN102504733B/en
Publication of CN102504733A publication Critical patent/CN102504733A/en
Application granted granted Critical
Publication of CN102504733B publication Critical patent/CN102504733B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention discloses a preparation method of a water-blush-resistant fluoride and siloxane modified waterborne pressure-sensitive adhesive for a polyethylene protective film, and the method is used for synthesizing a cross-linking type water-blush-resistant fluoride and siloxane modified waterborne pressure sensitive adhesive with less emulsifier dosage and excellent performance by introducing an organic siloxane monomer and a fluoride-containing vinyl monomer to perform copolymerization modification in a polymerizing process, compounding by utilizing an emulsifier, and adopting a seed emulsion polymerization method. The invention also provides a preparation method of the polyethylene protective film, and the prepared protective film is excellent in water blush resistance, and guarantees that the surface of a protected material does not have residual adhesive of the torn film and is not polluted after the protective film is used outdoors for a long time according to the requirement.

Description

Fluorinated silicone modified water-borne pressure sensitive adhesive of a kind of water-fast albefaction and polyethylene protective film
Technical field
The present invention relates to a kind of preparation method of polyethylene protective film use pressure sensitive adhesive, be specifically related to the preparation method of a kind of polyethylene protective film with the fluorinated silicone modified water-borne pressure sensitive adhesive of water-fast albefaction.
Background technology
Protective membrane is a kind of surface protection, wrapping material that are used to protect the commodity surface; It is attached to the surface of commodity such as each metalloid, aluminium-plastic panel, plastic plate, coated steel, stainless steel plate, aluminium section bar, stone material, glass, instrument, furniture; Make it in manufacturing, transportation, secondary processing, storage and use, protect the surface, avoid commodity to receive pollution, scratch and slow down the oxidation on commodity surface.The application of protective membrane, not only can improve product visual appearance, make things convenient for materials processed, also can improve simultaneously the utilization ratio of material, reduce production costs.
Protective membrane is made up of substrate layer and pressure-sensitive adhesive layer, generally carries out suitability for industrialized production with coating method, and promptly on the membranaceous base material that has made, the pressure-sensitive adhesive of coating emulsion attitude or solution state adds heat extraction solvent or dispersion agent then, batches and the film that is protected.The GPF (General Protection False film generally with Vilaterm (PE) film as base material, therefore anti-the making of coating solvent type polyacrylate(s) pressure sensitive adhesive has a large amount of volatile organic compounds (VOC) to discharge in process of production.These volatile organic compoundss not only can cause the comparison serious environmental to pollute, and also can cause bigger harm to the healthy of user.For this reason, reducing volatile organic compounds is the significant problem that China's surface protection product industry is faced.
The enhancing of environmental consciousness; Make the water-borne pressure sensitive adhesive stick obtain faster development, but general acrylic ester aquosity pressure sensitive adhesive has been owing to adopted a large amount of hydrophilic emulsifiers or protective colloid, the protective membrane of processing is when wet environment or open air are drenched with rain; Can very fast suction turn white; Obviously descending appears in the protective membrane performance, even causes material to be scrapped owing to degumming problem occurring, causes tremendous loss.In order to remedy this defective on vinylformic acid (ester) resin property, generally need it is carried out modification to improve its performance.
One of innovative approach is to adopt an organosilane monomer that water-borne pressure sensitive adhesive is carried out modification; Because the bond energy of Si-O key is greater than the bond energy of C-C key in the common organic polymer; Therefore silicone resin has good thermotolerance, anti-ozone, resistance to UV aging; And because surface tension is little, water and other pollutent are difficult for adhering to, so silicone resin has good moistureproofness, water resisting property and anti-steam property etc.
Two of innovative approach is to introduce the functional fluoropolymer monomer to carry out modification; It is one of hot research in recent years; Fluoropolymer has characteristics such as excellent two thin property and automatically cleaning, and reason is that the perfluor side chain stretches in the polymkeric substance in air, occupied the interface of polymkeric substance and air; Greatly reduce the surface energy of polymkeric substance, it is difficult to by organic liquid and water infiltration.And C-F key bond energy is big, stable, and the structure that side chain coats main chain forms well " shielding protection " to the polymkeric substance interior molecules, makes its thermostability with height and outstanding water tolerance.
Adopt thermoplastic acrylic ester aquosity pressure sensitive adhesive separately, all there are certain problem in its water tolerance, solvent resistance, thermotolerance etc.And when letex polymerization, introducing can realize crosslinked functional group, makes it when dry solidification, produces crosslinkedly, forms tridimensional network, thereby further improves water resistance.
Patent relevant for the relevant water-borne pressure sensitive adhesive of surface protection film; Like " peelable release emulsion pressure-sensitive adhesive and pressure sensitive adhesion sheet " (patent publication No. CN1517422A) a kind of composition and preparation method of peelable emulsion pressure-sensitive described; It comprises acrylic emulsion polymkeric substance and the additional crosslink agent that contains the water dispersible POLYMETHYLENE POLYPHENYLISOCYANATE; But the reaction of water has reduced cross-linking efficiency in water dispersible POLYMETHYLENE POLYPHENYLISOCYANATE and the emulsion; Thereby reduced water resistance, also can cause obviously shorten the working life of glue." the heat and moisture-proof protective membrane is with the preparation method of emulsion pressure-sensitive and surface protection film " (number of patent application CN200710018641.X) describes the hot protective membrane of a kind of moisture-proof and uses emulsion pressure-sensitive; But still adopted more non-reactive emulsifier in its preparation process; And do not adopt the dual modified method of fluorine silicon, can go up still at resistance to water-whitening and be weak.
Summary of the invention
The objective of the invention is to the above technical problem that will solve, provide a kind of polyethylene protective film with the fluorinated silicone modified water-borne pressure sensitive adhesive of water-fast albefaction and contain the polyethylene protective film of this pressure sensitive adhesive.
The fluorinated silicone modified water-borne pressure sensitive adhesive preparation method of water-fast albefaction of the present invention has adopted semicontinuous hungry attitude charging technology, pre-emulsification technology and seeded emulsion polymerization technology, and its preparation process may further comprise the steps:
1) will be the deionized water of 60 weight parts, the emulsifier mix of 0.5~2.0 weight part; Adopt 600~1200 rev/mins stirring velocity to stir; Be that 4~10 alkyl methacrylate, 90~174 weight part alkyl carbon atoms numbers are 4~18 alkyl acrylate, the vinyl fluorochemical monomer of 5~20 weight parts, the vinyl organosilicon monomer of 3~15 weight parts, the functional monomer of 7~15 weight parts slowly then with the alkyl carbon atoms number of 0~25 weight part; The chain-transfer agent of the cross-linking monomer of 02~2.0 weight part, 0.1~1.0 weight part splashes into; Stirred 10~30 minutes, and obtained pre-emulsion;
2) deionized water of 160 weight parts, the pH regulator agent and 25~80 weight part step 1) gained pre-emulsions of 0.2~1.2 weight part are mixed, be warming up to 78~90 ℃, logical nitrogen; Deoxygenation; To add the initiator of 0.2~0.4 weight part then, initiator system begins polymerization, reacts 20~50 minutes; Initiator with remaining step 1) gained pre-emulsion and 0.4~1.0 weight part under 70~85 ℃ temperature of reaction splashes into respectively, drips off in 3~5 hours;
3) drip after, be warmed up to 85~95 ℃ of reactions 30~60 minutes, cool to 40~70 ℃ again, add 0.2~0.5 weight part initiator after, continue reaction 1~3 hour, cooling then, the pH value of regulating product is 7~9, is cooled to room temperature, the filtration discharging.
Alkyl methacrylate of the present invention be in TEB 3K, Jia Jibingxisuanyizhi, NSC 20956, Octyl methacrylate, the Isooctyl methacrylate any one or multiple.
Alkyl acrylate of the present invention be in methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, Isooctyl acrylate monomer, lauryl acrylate and the octadecyl acrylate any one or multiple.
Vinyl fluorochemical monomer of the present invention be in trifluoroethyl methacrylate, methylacrylic acid hexafluoro butyl ester, methylacrylic acid 19 fluorine esters, vinylformic acid trifluoro ethyl ester, vinylformic acid hexafluoro butyl ester, the vinylformic acid 19 fluorine esters any one or multiple.
Vinyl organosilicon monomer of the present invention be in gamma-methyl allyl acyloxypropyl three isopropoxy silane, γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three different third oxosilanes any one or multiple.
Functional monomer of the present invention be in vinylformic acid, methylacrylic acid, Hydroxyethyl acrylate, Rocryl 400, Propylene glycol monoacrylate, NMA, acrylic amide, diacetone-acryloamide(DAA) and the SY-Monomer G any one or multiple.
Cross-linking monomer of the present invention be in trimethylolpropane trimethacrylate, Dipentaerythritol five propenoate and the TGM 1 any one or multiple.
Chain-transfer agent of the present invention be in n-dodecyl mercaptan, uncle's lauryl mercaptan and the mercaptoethanol any one or multiple.
Emulsifying agent of the present invention be in the reactions type emulsifying agent any one or multiple: sodium vinyl sulfonate (SVS); Allyl ethers hydroxypropyl azochlorosulfonate acid sodium (COPS-1); 2-acrylamido-2-methyl propane sulfonic acid sodium (AMPS-NA); Allyl polyether vitriol (V-10S); Alkylphenol allyl polyether vitriol (V-20S); 2-allyl ethers-3-hydroxy propane-1-sodium sulfonate (UCAN-1); Acrylamido sodium isopropyl xanthate (A-2405); Allyloxy polyoxyethylene nonylphenol sulfate of ammoniac (KL-100); Allyloxy polyoxyethylene nonylphenol ammonium sulfate (SE-10); Allyloxy AESA (SR-10); Alkylamide vinyl sulfonic acid sodium (DNS-86).
Adopt reactive emulsifier; Be to utilize they self two keys to participate in reaction; Be grafted on the polymer molecular chain, thereby obtain the water-borne pressure sensitive adhesive of high-solid lower-viscosity, and effectively alleviate conventional emulsifier at the migration problem of filming; Reduce the possibility that its suction is turned white, further improve the performances such as water tolerance of filming.
Initiator of the present invention has adopted thermal initiation system and redox initiation system, in Potassium Persulphate, ammonium persulphate, sodium sulfite anhy 96, tertbutyl peroxide, the sodium formaldehyde sulphoxylate any one or multiple.The initiator of redox system can obviously reduce the system residual monomer content at a lower temperature, thereby further improves the water resistance of water-borne pressure sensitive adhesive.
The present invention also provides a kind of polyethylene protective film that contains the fluorinated silicone modified water-borne pressure sensitive adhesive of said water-fast albefaction.
Described polyethylene protective film; Prepare according to following steps: get the fluorinated silicone modified water-borne pressure sensitive adhesive of each said water-fast albefaction of claim 1-10 of 100 weight parts, add the polyfunctionality aziridine crosslinker of 0.1~2.0 weight part while stirring, added the back dispersed with stirring 20 minutes; Evenly coat the gained glue on the polyvinylidene film again; After the oven dry, 50 ℃ solidified 24 hours, and made finished product.
The present invention is through introducing organo-siloxane monomer and fluorine-containing vinyl monomer at polyethylene protective film in the fluorinated silicone modified water-borne pressure sensitive adhesive polymerization process with water-fast albefaction; Carry out modification by copolymerization; Utilize reactive emulsifier; Adopt seed emulsion polymerization, synthesize have that solid content is higher, the emulsifying agent consumption is less, the polyethylene protective film of excellent performance is with the fluorinated silicone modified water-borne pressure sensitive adhesive of the water-fast albefaction of cross-linking type.Emulsion is when film forming; Except performances such as an organosilane monomer that utilize to introduce, water tolerance that fluorochemical monomer improves emulsion, weathering resistance, thermotolerance; Can also through crosslinkable functional group crosslinking reaction take place, thereby further improve the over-all properties of protective membrane in the pressure sensitive adhesive solidification process.
Compared with prior art; The water-borne pressure sensitive adhesive of the present invention's preparation has adopted reactive emulsifier to carry out polymerization, and it is dual modified to utilize an organosilane monomer and fluorochemical monomer to carry out again, and the resistance to water-whitening that has improved pressure sensitive adhesive greatly can; The polyethylene protective film of processing is out of doors in the life-time service process; Water-tolerant can not occur that the protective membrane difficulty is torn and the risk of coming unstuck, and synthesis route is simple and direct, produce and be easy to control.
Embodiment
In order to explain that better the present invention, spy enumerate following embodiment, but the present invention is not limited in following embodiment.
Embodiment 1:
Prepare the fluorinated silicone modified water-borne pressure sensitive adhesive of water-fast albefaction according to following concrete steps:
(1) deionized water of 60 weight parts, the alkylamide vinyl sulfonic acid sodium (DNS-86) of 0.5 weight part, the sodium vinyl sulfonate (SVS) of 0.5 weight part are joined in the there-necked flask; Adopt 800 rev/mins stirring velocity to stir; Slow then TEB 3K, the different monooctyl ester of 93 parts by weight of acrylic, 75 parts by weight of acrylic butyl esters, 10 parts by weight of acrylic hexafluoro butyl esters, gamma-methyl allyl acyloxypropyl three (isopropoxy) silane of 10 weight parts, 3 parts by weight of acrylic hydroxyl ethyl esters, 4 parts by weight of acrylic with 5 weight parts; 0.5 the n-dodecyl mercaptan of the TGM 1 of weight part, 0.1 weight part splashes into, and stirs that to obtain pre-emulsion in 30 minutes subsequent use;
(2) deionized water of 160 weight parts, the sodium hydrogencarbonate and 40 weight part step (1) the gained pre-emulsions of 0.8 weight part are joined in the four-hole boiling flask that has TM and reflux condensing tube; Begin to be warming up to 80 ℃; Logical nitrogen in system, deoxygenation, the ammonium persulphate with 0.2 weight part joins in the system then; Initiator system begins polymerization, reacts 40 minutes.Ammonium persulphate (dissolving with appropriate amount of deionized water in advance) with remaining step (1) gained pre-emulsion and 0.6 weight part under 80 ℃ temperature of reaction splashes into respectively, drips off in 3.5 hours;
(3) drip after, be warmed up to 85 ℃ the reaction 40 minutes, cool to 70 ℃; After adding the sodium formaldehyde sulphoxylate (rongalite) of tertbutyl peroxide, 0.1 weight part of 0.1 weight part; Continue reaction 1.5 hours, cooling then, the pH value of regulating product is 7~9; Be cooled to room temperature, filter discharging.
Prepare polyethylene protective film according to following concrete steps:
In the above-mentioned emulsion pressure-sensitive that makes of 100 weight parts; Add 1 of 1.0 weight parts while stirring; 1-azelaoyl nonanedioyl two [2-methylaziridine] added the back dispersed with stirring 20 minutes, the gained glue was evenly coated on the polyvinylidene film that thickness is 50 μ m again; This polyvinylidene film coated face is through corona treatment, its surface tension >=38 dyne.After the oven dry,, make polyethylene protective film 50 ℃ of curing ovens 24 hours.
Each item performance technologies index according to following testing method test pressure sensitive adhesive:
1.180 ° stripping strength:, use the desktop tension testing machine to measure according to GB/T 2792-1998.Test result is seen table 1.
2. resistance to water-whitening can be tested: the polyethylene protective film of processing is cut into wide rectangular of 25mm, is soaked in respectively in boiling water and the tap water, observe the situation of turning white.Test result is seen table 1.
3. protective membrane pasting board weather resistance test: whether polyethylene protective film is attached on the mirror steel plate, is positioned in the outdoor environment, placed 6 months, tear this protective membrane from the mirror steel plate, observing plate surface has cull.Test result is seen table 1.
Embodiment 2:
Prepare the fluorinated silicone modified water-borne pressure sensitive adhesive of water-fast albefaction according to following concrete steps:
(1) deionized water of 60 weight parts, the allyloxy AESA (SR-10) of 0.5 weight part are joined in the there-necked flask; Adopt 800 rev/mins stirring velocity to stir; The methylacrylic acid 19 fluorine esters of the slow then TEB 3K with 10 weight parts, the different monooctyl ester of 88 parts by weight of acrylic, 85 parts by weight of acrylic butyl esters, 5 weight parts, the vinyltrimethoxy silane of 3 weight parts, 3 parts by weight of acrylic hydroxypropyl acrylates, 4 parts by weight of acrylic, the SY-Monomer G of 2 weight parts, the trimethylolpropane trimethacrylate of 0.2 weight part, the mercaptoethanol of 0.3 weight part splash into; Stirred 30 minutes; Obtain pre-emulsion, subsequent use;
(2) deionized water of 160 weight parts, the sodium hydrogencarbonate of 1.2 weight parts and step (1) the gained pre-emulsion of 54 weight parts are joined in the four-hole boiling flask that has TM and reflux condensing tube; Begin to be warming up to 84 ℃; Logical nitrogen in system, deoxygenation, the Potassium Persulphate with 0.2 weight part joins in the system then; Initiator system begins polymerization, reacts 30 minutes.Potassium Persulphate (using the deionized water dissolving of 4 weight parts in advance) with remaining step (1) gained pre-emulsion and 0.4 weight part under 85 ℃ temperature of reaction splashes into respectively, drips off in 3 hours;
(3) drip after, be warmed up to 90 ℃ the reaction 30 minutes, cool to 65 ℃; After adding the rongalite of tertbutyl peroxide, 0.2 weight part of 0.2 weight part, continue reaction 1 hour, then cooling; The pH value of regulating product is 7~9, is cooled to room temperature, filters discharging.
Prepare polyethylene protective film according to following concrete steps:
In the above-mentioned emulsion pressure-sensitive that makes of 100 weight parts; Add 1 of 0.4 weight part while stirring, 1-(1, the 3-phenylene dicarbonyl) two [2-methylaziridines]; Added the back dispersed with stirring 20 minutes; Again glue evenly being coated thickness is on the 50 μ m polyvinylidene films, and this polyvinylidene film coated face is through corona treatment, its surface tension >=38 dyne.After waiting to dry,, make protective membrane 50 ℃ of curing ovens 24 hours.
Each item performance technologies index according to following testing method test pressure sensitive adhesive:
1.180 ° stripping strength:, use the desktop tension testing machine to measure according to GB/T 2792-1998.Test result is seen table 1.
2. resistance to water-whitening can be tested: the protective membrane of processing is cut into wide rectangular of 25mm, is soaked in respectively in boiling water and the tap water, observe the situation of turning white.Test result is seen table 1.
3. protective membrane pasting board weather resistance test: whether protective membrane is attached on the mirror steel plate, is positioned in the outdoor environment, placed 6 months, tear protective membrane from the mirror steel plate, observing plate surface has cull.Test result is seen table 1.
Embodiment 3:
Prepare the fluorinated silicone modified water-borne pressure sensitive adhesive of water-fast albefaction according to following concrete steps:
(1) deionized water of 60 weight parts, the alkylamide vinyl sulfonic acid sodium (DNS-86) of 0.7 weight part, the allyloxy polyoxyethylene nonylphenol ammonium sulfate (SE-10) of 0.8 weight part are joined in the there-necked flask; Adopt 600 rev/mins stirring velocity to stir; The Rocryl 400 of the slow then γ-methacryloxypropyl trimethoxy silane with 20 parts by weight of acrylic methyl esters, 50 parts by weight of acrylic ethyl esters, the different monooctyl ester of 104 parts by weight of acrylic, 6 parts by weight of acrylic hexafluoro butyl esters, 8 weight parts, 4 weight parts, 5 parts by weight of acrylic, the NMA of 3 weight parts, the TGM 1 of 0.8 weight part, the n-dodecyl mercaptan of 0.1 weight part splash into; Stirred 30 minutes; Obtain pre-emulsion, subsequent use;
(2) deionized water of 160 weight parts, the sodium hydrogencarbonate and 80 weight part step (1) the gained pre-emulsions of 0.8 weight part are joined in the four-hole boiling flask that has TM and reflux condensing tube; Begin to be warming up to 78 ℃; Logical nitrogen in system, deoxygenation, the ammonium persulphate with 0.25 weight part joins in the system then; Initiator system begins polymerization, reacts 50 minutes.Ammonium persulphate (using the deionized water dissolving of 5 weight parts in advance) with remaining step (1) gained pre-emulsion and 0.5 weight part under 78 ℃ temperature of reaction splashes into respectively, drips off in 4 hours;
(3) drip after, be warmed up to 88 ℃ of reactions 60 minutes, cool to 55 ℃, add the sodium sulfite anhy 96 of ammonium persulphate, 0.1 weight part of 0.2 weight part after, continue reaction 2 hours, cooling then, the pH value of regulating product is 7~9, is cooled to room temperature, the filtration discharging.
Prepare polyethylene protective film according to following concrete steps:
In the above-mentioned emulsion pressure-sensitive that makes of 100 weight parts; Add 2,2 of 1.5 weight parts while stirring, 4-trimethylammonium hexanedioyl two [2-ethyl Soluol XC 100]; Added the back dispersed with stirring 20 minutes; Again glue evenly being coated thickness is on the 50 μ m polyvinylidene films, and this polyvinylidene film coated face is through corona treatment, its surface tension >=38 dyne.After waiting to dry,, make polyethylene protective film 50 ℃ of curing ovens 24 hours.
Each item performance technologies index according to following testing method test pressure sensitive adhesive:
1.180 ° stripping strength:, use the desktop tension testing machine to measure according to GB/T 2792-1998.Test result is seen table 1.
2. resistance to water-whitening can be tested: the polyethylene protective film of processing is cut into wide rectangular of 25mm, is soaked in respectively in boiling water and the tap water, observe the situation of turning white.Test result is seen table 1.
3. protective membrane pasting board weather resistance test: whether polyethylene protective film is attached on the aluminium section bar, is positioned in the outdoor environment, placed 6 months, tear protective membrane from the mirror steel plate, observing plate surface has cull.Test result is seen table 1.
Embodiment 4:
Prepare the fluorinated silicone modified water-borne pressure sensitive adhesive of water-fast albefaction according to following concrete steps:
(1) deionized water of 60 weight parts, the allyl ethers hydroxypropyl azochlorosulfonate acid sodium of 1.0 weight parts, the allyl polyether vitriol of 1.0 weight parts are joined in the there-necked flask; Adopt 1200 rev/mins stirring velocity to stir; The methylacrylic acid hexafluoro butyl ester of the Isooctyl methacrylate of the slow then Octyl methacrylate with 12 weight parts, 13 weight parts, 90 parts by weight of acrylic octadecyl esters, 20 weight parts, the vinyltriethoxysilane of 15 weight parts, 4 parts by weight of acrylic, the methylacrylic acid of 2 weight parts, the acrylic amide of 6 weight parts, the diacetone-acryloamide(DAA) of 3 weight parts, the trimethylolpropane trimethacrylate of 1.0 weight parts, Dipentaerythritol five propenoate of 1.0 weight parts, the n-dodecyl mercaptan of 0.5 weight part, uncle's lauryl mercaptan of 0.5 weight part splash into; Stirred 10 minutes; Obtain pre-emulsion, subsequent use;
(2) deionized water of 160 weight parts, the sodium hydrogencarbonate and 25 weight part step (1) the gained pre-emulsions of 02 weight part are joined in the four-hole boiling flask that has TM and reflux condensing tube; Begin to be warming up to 90 ℃; Logical nitrogen in system, deoxygenation, the Potassium Persulphate with 0.4 weight part joins in the system then; Initiator system begins polymerization, reacts 20 minutes.Ammonium persulphate (using the deionized water dissolving of 5 weight parts in advance) with remaining step (1) gained pre-emulsion and 1.0 weight parts under 70 ℃ temperature of reaction splashes into respectively, drips off in 5 hours;
(3) drip after, be warmed up to 95 ℃ the reaction 40 minutes, cool to 40 ℃; After adding the sodium formaldehyde sulphoxylate of tertbutyl peroxide, 0.2 weight part of 0.3 weight part, continue reaction 3 hours, then cooling; The pH value of regulating product is 7~9, is cooled to room temperature, filters discharging.
Prepare polyethylene protective film according to following concrete steps:
In the above-mentioned emulsion pressure-sensitive that makes of 100 weight parts; Add 2,2 of 1.5 weight parts while stirring, 4-trimethylammonium hexanedioyl two [2-ethyl Soluol XC 100]; Added the back dispersed with stirring 20 minutes; Again glue evenly being coated thickness is on the 50 μ m polyvinylidene films, and this polyvinylidene film coated face is through corona treatment, its surface tension >=38 dyne.After waiting to dry,, make polyethylene protective film 50 ℃ of baking oven after fixing 24 hours.
Each item performance technologies index according to following testing method test pressure sensitive adhesive:
1.180 ° stripping strength:, use the desktop tension testing machine to measure according to GB/T 2792-1998.Test result is seen table 1.
2. resistance to water-whitening can be tested: the polyethylene protective film of processing is cut into wide rectangular of 25mm, is soaked in respectively in boiling water and the tap water, observe the situation of turning white.Test result is seen table 1.
3. protective membrane pasting board weather resistance test: whether polyethylene protective film is attached on the aluminium section bar, is positioned in the outdoor environment, placed 6 months, tear protective membrane from the mirror steel plate, observing plate surface has cull.Test result is seen table 1.
Each item performance technologies index test result of table 1 pressure sensitive adhesive of the present invention

Claims (12)

1. a polyethylene protective film is characterized in that processing according to following steps with the fluorinated silicone modified water-borne pressure sensitive adhesive of water-fast albefaction:
1) will be the deionized water of 60 weight parts, the emulsifier mix of 0.5~2.0 weight part; Adopt 600~1200 rev/mins stirring velocity to stir; Be that 4~10 alkyl methacrylate, 90~174 weight part alkyl carbon atoms numbers are 4~18 alkyl acrylate, the vinyl fluorochemical monomer of 5~20 weight parts, the vinyl organosilicon monomer of 3~15 weight parts, the functional monomer of 7~15 weight parts slowly then with the alkyl carbon atoms number of 0~25 weight part; The chain-transfer agent of the cross-linking monomer of 02~2.0 weight part, 0.1~1.0 weight part splashes into; Stirred 10~30 minutes, and obtained pre-emulsion;
2) deionized water of 160 weight parts, the pH regulator agent and 25~80 weight part step 1) gained pre-emulsions of 0.2~1.2 weight part are mixed, be warming up to 78~90 ℃, logical nitrogen; Deoxygenation; To add the initiator of 0.2~0.4 weight part then, initiator system begins polymerization, reacts 20~50 minutes; Initiator with remaining step 1) gained pre-emulsion and 0.4~1.0 weight part under 70~85 ℃ temperature of reaction splashes into respectively, drips off in 3~5 hours;
3) drip after, be warmed up to 85~95 ℃ of reactions 30~60 minutes, cool to 40~70 ℃ again, add 0.2~0.5 weight part initiator after, continue reaction 1~3 hour, cooling then, the pH value of regulating product is 7~9, is cooled to room temperature, the filtration discharging.
2. polyethylene protective film according to claim 1 is characterized in that with the fluorinated silicone modified water-borne pressure sensitive adhesive of water-fast albefaction: said alkyl methacrylate be in TEB 3K, Jia Jibingxisuanyizhi, NSC 20956, Octyl methacrylate, the Isooctyl methacrylate any one or multiple.
3. polyethylene protective film according to claim 1 is characterized in that with the fluorinated silicone modified water-borne pressure sensitive adhesive of water-fast albefaction: described alkyl acrylate be in methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, Isooctyl acrylate monomer, lauryl acrylate and the octadecyl acrylate any one or multiple.
4. polyethylene protective film according to claim 1 is characterized in that with the fluorinated silicone modified water-borne pressure sensitive adhesive of water-fast albefaction: described vinyl fluorochemical monomer be in trifluoroethyl methacrylate, methylacrylic acid hexafluoro butyl ester, methylacrylic acid 19 fluorine esters, vinylformic acid trifluoro ethyl ester, vinylformic acid hexafluoro butyl ester, the vinylformic acid 19 fluorine esters any one or multiple.
5. polyethylene protective film according to claim 1 is characterized in that with the fluorinated silicone modified water-borne pressure sensitive adhesive of water-fast albefaction: described vinyl organosilicon monomer be in gamma-methyl allyl acyloxypropyl three isopropoxy silane, γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three different third oxosilanes any one or multiple.
6. polyethylene protective film according to claim 1 is characterized in that with the fluorinated silicone modified water-borne pressure sensitive adhesive of water-fast albefaction: described functional monomer be in vinylformic acid, methylacrylic acid, Hydroxyethyl acrylate, Rocryl 400, Propylene glycol monoacrylate, NMA, acrylic amide, diacetone-acryloamide(DAA) and the SY-Monomer G any one or multiple.
7. polyethylene protective film according to claim 1 is characterized in that with the fluorinated silicone modified water-borne pressure sensitive adhesive of water-fast albefaction: described cross-linking monomer be in trimethylolpropane trimethacrylate, Dipentaerythritol five propenoate and the TGM 1 any one or multiple.
8. polyethylene protective film according to claim 1 is characterized in that with the fluorinated silicone modified water-borne pressure sensitive adhesive of water-fast albefaction: described chain-transfer agent be in n-dodecyl mercaptan, uncle's lauryl mercaptan and the mercaptoethanol any one or multiple.
9. polyethylene protective film according to claim 1 is characterized in that with the fluorinated silicone modified water-borne pressure sensitive adhesive of water-fast albefaction: said emulsifying agent be in the reactions type emulsifying agent any one or multiple: sodium vinyl sulfonate, allyl ethers hydroxypropyl azochlorosulfonate acid sodium, 2-acrylamido-2-methyl propane sulfonic acid sodium, allyl polyether vitriol, alkylphenol allyl polyether vitriol, 2-allyl ethers-3-hydroxy propane-1-sodium sulfonate, acrylamido sodium isopropyl xanthate, allyloxy polyoxyethylene nonylphenol sulfate of ammoniac, allyloxy polyoxyethylene nonylphenol ammonium sulfate, allyloxy AESA, alkylamide vinyl sulfonic acid sodium.
10. polyethylene protective film according to claim 1 is characterized in that with the fluorinated silicone modified water-borne pressure sensitive adhesive of water-fast albefaction: said step 2) and the initiator in the step 3) be in Potassium Persulphate, ammonium persulphate, sodium sulfite anhy 96, tertbutyl peroxide, the sodium formaldehyde sulphoxylate any one or multiple.
11. a polyethylene protective film is characterized in that containing the fluorinated silicone modified water-borne pressure sensitive adhesive of each said water-fast albefaction of claim 1 to 10.
12. polyethylene protective film according to claim 11; It is characterized in that preparing: get the fluorinated silicone modified water-borne pressure sensitive adhesive of each said water-fast albefaction of claim 1-10 of 100 weight parts, add the polyfunctionality aziridine crosslinker of 0.1~2.0 weight part while stirring, added the back dispersed with stirring 20 minutes according to following steps; Evenly coat the gained glue on the polyvinylidene film again; After the oven dry, 50 ℃ solidified 24 hours, and made finished product.
CN201110389275.5A 2011-11-29 2011-11-29 Water-blush-resistant fluoride and siloxane modified waterborne pressure-sensitive adhesive and polyethylene protective film Active CN102504733B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201110389275.5A CN102504733B (en) 2011-11-29 2011-11-29 Water-blush-resistant fluoride and siloxane modified waterborne pressure-sensitive adhesive and polyethylene protective film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201110389275.5A CN102504733B (en) 2011-11-29 2011-11-29 Water-blush-resistant fluoride and siloxane modified waterborne pressure-sensitive adhesive and polyethylene protective film

Publications (2)

Publication Number Publication Date
CN102504733A true CN102504733A (en) 2012-06-20
CN102504733B CN102504733B (en) 2014-07-09

Family

ID=46216870

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110389275.5A Active CN102504733B (en) 2011-11-29 2011-11-29 Water-blush-resistant fluoride and siloxane modified waterborne pressure-sensitive adhesive and polyethylene protective film

Country Status (1)

Country Link
CN (1) CN102504733B (en)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103660653A (en) * 2012-09-06 2014-03-26 上海纳尔数码喷印材料股份有限公司 Digital inkjet material made from water-borne pressure sensitive adhesive
CN103951783A (en) * 2014-05-09 2014-07-30 苏州飞翔新材料研究院有限公司 Method for preparing polymer emulsion
CN103952105A (en) * 2014-03-28 2014-07-30 广东达美新材料有限公司 Fluorosilicone modified aqueous pressure-sensitive adhesive used for polyethylene protection film, and preparation method thereof
CN104193659A (en) * 2014-08-20 2014-12-10 上海东升新材料有限公司 Benzoyl sulfydryl ester compound as well as preparation method and application thereof
CN105860884A (en) * 2016-06-25 2016-08-17 江阴市江泰高分子新材料有限公司 Polyacrylate emulsion pressure-sensitive adhesive and PE protection film thereof
CN105885745A (en) * 2015-04-15 2016-08-24 广州都邦材料科技有限公司 Silicon-fluorine modified polyacrylate pressure-sensitive adhesive emulsion for PVC high-temperature-resistant adhesive tape, preparation method and application
CN106010386A (en) * 2016-06-25 2016-10-12 江阴市江泰高分子新材料有限公司 Emulsion pressure-sensitive adhesive and PE protection film prepared from same
JP2018028055A (en) * 2016-05-24 2018-02-22 ザ・ボーイング・カンパニーThe Boeing Company Novel thermoresponsive adhesive material, method of making the material, and methods of use
CN107746691A (en) * 2017-11-17 2018-03-02 佛山霄绫包装材料有限公司 PE film adhesives, preparation method and the PE films of a kind of scratch resistance
CN109837045A (en) * 2019-02-28 2019-06-04 广东星宇耐力新材料股份有限公司 A kind of tracery fitting water-fast white emulsion adhesive and preparation method thereof
CN110540819A (en) * 2019-08-09 2019-12-06 王秀云 Preparation method of high-temperature-resistant and high-strength acrylate pressure-sensitive adhesive
CN110591610A (en) * 2019-10-14 2019-12-20 上海固柯胶带科技有限公司 Pressure-sensitive adhesive
CN110746903A (en) * 2019-10-25 2020-02-04 江苏国胶新材料有限公司 Water-based acrylate pressure-sensitive adhesive for automobile protective film and preparation method thereof
CN111019549A (en) * 2019-11-07 2020-04-17 南京清尚新材料科技有限公司 Acid and alkali resistant cold-seal adhesive, preparation method thereof and adhesive tape prepared from same
CN111171745A (en) * 2019-12-27 2020-05-19 无锡达美新材料有限公司 Durable high-surface-energy polyethylene protective film and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101649165A (en) * 2009-08-31 2010-02-17 广东达美胶粘制品有限公司 Ultraviolet curing pressure sensitive adhersive for polyethylene protective film and preparation method thereof
CN102020956A (en) * 2010-11-24 2011-04-20 广东达美胶粘制品有限公司 Polyacrylate hot-melt pressure sensitive adhesive for polyethylene protective film and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101649165A (en) * 2009-08-31 2010-02-17 广东达美胶粘制品有限公司 Ultraviolet curing pressure sensitive adhersive for polyethylene protective film and preparation method thereof
CN102020956A (en) * 2010-11-24 2011-04-20 广东达美胶粘制品有限公司 Polyacrylate hot-melt pressure sensitive adhesive for polyethylene protective film and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
李新跃: "液体可剥离胶的研究", 《四川理工学院学报》 *
武鹏等: "保护膜用压敏胶剥离强度增幅研究", 《中国胶粘剂》 *
王雪荣等: "聚烯烃用的丙烯酸酯类乳液胶粘剂的研究进展", 《粘接》 *

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103660653A (en) * 2012-09-06 2014-03-26 上海纳尔数码喷印材料股份有限公司 Digital inkjet material made from water-borne pressure sensitive adhesive
CN103952105A (en) * 2014-03-28 2014-07-30 广东达美新材料有限公司 Fluorosilicone modified aqueous pressure-sensitive adhesive used for polyethylene protection film, and preparation method thereof
CN103951783A (en) * 2014-05-09 2014-07-30 苏州飞翔新材料研究院有限公司 Method for preparing polymer emulsion
CN103951783B (en) * 2014-05-09 2016-06-29 苏州飞翔新材料研究院有限公司 A kind of preparation method of polymer emulsion
CN104193659A (en) * 2014-08-20 2014-12-10 上海东升新材料有限公司 Benzoyl sulfydryl ester compound as well as preparation method and application thereof
CN104193659B (en) * 2014-08-20 2016-01-27 上海东升新材料有限公司 Benzoyl group thiol esters compounds, its preparation method and its application
CN105885745A (en) * 2015-04-15 2016-08-24 广州都邦材料科技有限公司 Silicon-fluorine modified polyacrylate pressure-sensitive adhesive emulsion for PVC high-temperature-resistant adhesive tape, preparation method and application
CN105885745B (en) * 2015-04-15 2018-08-07 广州都邦材料科技有限公司 The polyacrylate pressure-sensitive lotion and preparation method and application that PVC High temperature-resistanadhesive adhesive tapes fluosilicic is modified
JP7038749B2 (en) 2016-05-24 2022-03-18 ザ・ボーイング・カンパニー New heat-responsive adhesive, how to make its material and how to use it
JP2018028055A (en) * 2016-05-24 2018-02-22 ザ・ボーイング・カンパニーThe Boeing Company Novel thermoresponsive adhesive material, method of making the material, and methods of use
JP2020143282A (en) * 2016-05-24 2020-09-10 ザ・ボーイング・カンパニーThe Boeing Company Novel thermoresponsive adhesive material, method for making the material and method for utilizing the same
CN105860884A (en) * 2016-06-25 2016-08-17 江阴市江泰高分子新材料有限公司 Polyacrylate emulsion pressure-sensitive adhesive and PE protection film thereof
CN106010386A (en) * 2016-06-25 2016-10-12 江阴市江泰高分子新材料有限公司 Emulsion pressure-sensitive adhesive and PE protection film prepared from same
CN107746691A (en) * 2017-11-17 2018-03-02 佛山霄绫包装材料有限公司 PE film adhesives, preparation method and the PE films of a kind of scratch resistance
CN109837045A (en) * 2019-02-28 2019-06-04 广东星宇耐力新材料股份有限公司 A kind of tracery fitting water-fast white emulsion adhesive and preparation method thereof
CN110540819A (en) * 2019-08-09 2019-12-06 王秀云 Preparation method of high-temperature-resistant and high-strength acrylate pressure-sensitive adhesive
CN110591610A (en) * 2019-10-14 2019-12-20 上海固柯胶带科技有限公司 Pressure-sensitive adhesive
CN110591610B (en) * 2019-10-14 2021-08-17 上海固柯胶带科技有限公司 Pressure-sensitive adhesive
CN110746903B (en) * 2019-10-25 2021-08-06 江苏国胶新材料有限公司 Water-based acrylate pressure-sensitive adhesive for automobile protective film and preparation method thereof
CN110746903A (en) * 2019-10-25 2020-02-04 江苏国胶新材料有限公司 Water-based acrylate pressure-sensitive adhesive for automobile protective film and preparation method thereof
CN111019549A (en) * 2019-11-07 2020-04-17 南京清尚新材料科技有限公司 Acid and alkali resistant cold-seal adhesive, preparation method thereof and adhesive tape prepared from same
CN111171745A (en) * 2019-12-27 2020-05-19 无锡达美新材料有限公司 Durable high-surface-energy polyethylene protective film and preparation method thereof

Also Published As

Publication number Publication date
CN102504733B (en) 2014-07-09

Similar Documents

Publication Publication Date Title
CN102504733B (en) Water-blush-resistant fluoride and siloxane modified waterborne pressure-sensitive adhesive and polyethylene protective film
CN102492379B (en) Fog-resistant aqueous pressure-sensitive adhesive and polyethylene protection film containing same
CN101974299B (en) High temperature-resistant polyacrylate pressure-sensitive adhesive emulsion and preparation method and application thereof
CN103214628B (en) A kind of acrylic resin modified and preparation method thereof for weatherability coating
CN100551985C (en) The acrylic pressure sensitive adhesive composition that is used for polarizing coating
CN103074011B (en) Single-component water-borne pressure sensitive adhesive for sun-proof and heat-insulating film
CN109868026B (en) Organic silicon modified acrylate resin, preparation method thereof and hydrophobic weather-resistant slow-release modified acrylic resin coating
CN103923334A (en) Fluorosilicone release film and preparation method thereof
CN101798776B (en) Water-based paper polishing oil and preparation method thereof
CN104342073A (en) Organic silicon modified phenyl emulsion pressure-sensitive adhesive with high release force and low residue as well as preparation method thereof and application
CN105237675A (en) Polyacrylic woodware emulsion with core-shell bi-crosslinking structure and preparation method thereof
CN102382236B (en) Cationic organosilicon-acrylate aqueous dispersion and preparation method thereof
CN103059211B (en) Vinyl acetate-acrylate copolymer emulsion, its synthesis method and application
CN1331901C (en) High-silicon content shell-core structured silicon/acrylic emulsion and method for preparing same
CN105237676A (en) Water-soluble organosilicon-modified acrylic resin and preparation method thereof
CN104592462A (en) Silica sol modified acrylic emulsion and preparation and application thereof
CN105713540A (en) Preparation method of ultralight strippable self-exhausting acrylate pressure-sensitive coating material
CN103772617A (en) Silicone-acrylate copolymer emulsion and preparation method thereof
CN108359047A (en) A kind of waterborne acrylic paint and preparation method thereof that graphene is modified
CN109054570B (en) Environment-friendly high-strength elastic coating and preparation method thereof
CN105622831A (en) Preparation method of acrylic acid organic silicon soap-free copolymerization emulsion
CN105367697A (en) Silicone acrylic emulsion having core-shell structure and preparation method thereof
CN107163761A (en) A kind of colorful base paint emulsion of excellent performance and preparation method thereof
CN104592848A (en) BOPET release film and preparation method thereof
CN107118650B (en) Silica sol/polyacrylate emulsion containing hydroxyl-amino resin baking varnish and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
GR01 Patent grant
C14 Grant of patent or utility model
TR01 Transfer of patent right

Effective date of registration: 20160222

Address after: Qingfeng town, Gangbei District, Guigang City in the Guangxi Zhuang Autonomous Region Tan Village 537100 Tallowtree Tun No. 144-1

Patentee after: Huang Dongjiu

Address before: 528325 Guangdong Province, Foshan city Shunde District Xingtan town Qi Road No. 266

Patentee before: Guangdong Tamay New Materials Co., Ltd.

C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20170329

Address after: 519000 Guangdong city of Zhuhai province Hengqin Baohua Road No. 6, room 105 -1866

Patentee after: Zhuhai Hongyuan Management Consulting Co. Ltd.

Address before: Qingfeng town of Guangxi Province in 537100 Gangbei District, Guigang City, Qin Tun Village Tallowtree No. 144-1

Patentee before: Huang Dongjiu

TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20170621

Address after: 214181 Jiangsu Province, Wuxi Huishan industrial agglomeration area north road transformation

Patentee after: Wuxi Delta new material Co., Ltd.

Address before: 519000 Guangdong city of Zhuhai province Hengqin Baohua Road No. 6, room 105 -1866

Patentee before: Zhuhai Hongyuan Management Consulting Co. Ltd.

TR01 Transfer of patent right