CN101864025A - Preparation method and application of polyacrylate microgel emulsion - Google Patents
Preparation method and application of polyacrylate microgel emulsion Download PDFInfo
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- CN101864025A CN101864025A CN 201010204461 CN201010204461A CN101864025A CN 101864025 A CN101864025 A CN 101864025A CN 201010204461 CN201010204461 CN 201010204461 CN 201010204461 A CN201010204461 A CN 201010204461A CN 101864025 A CN101864025 A CN 101864025A
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Abstract
The invention provides a polyacrylate microgel emulsion synthesized by a soap-free emulsion polymerization mode, which comprises the following process flows: (1) pre-emulsification: mixing a plurality of monomers for emulsification to prepare a pre-emulsion, (2) seed polymerization: a small amount of pre-emulsion is subjected to polymerization reaction under the activation of an initiator to prepare seed liquid, (3) polymerization reaction: continuously dropwise adding the pre-emulsion into the seed liquid to prepare the microgel, (4) ammoniating: the aqueous microgel polyacrylate emulsion is prepared by dropwise adding an ammonia water solution to adjust the pH, has simple process, easily controlled conditions and easy large-scale production, can be used as a main component of an aqueous binder for flexible package plastic-plastic compounding, and has strong binding power to a base material, water resistance, heat resistance, environmental protection and high drying speed.
Description
Technical field
The present invention relates to technical field of macromolecules, relate to a kind of preparation method of polyacrylate microgel emulsion especially and be applied to package compound and use with sizing agent.
Background technology
Along with the enhancing of people's environmental consciousness with to the attention of food product pack safety, package compound with tackiness agent more and more higher standard and requirement is proposed also.In the binding agent of China's food composite soft packaging bag usefulness, the solvent borne polyurethane tackiness agent occupies more than 90%, and solvent-free and water-based compound binding agent accounts for less than 10%.There is dissolvent residual harm in Solvent Adhesive, the no-solvent type compound binding agent can not satisfy the requirement of poach crane high temperature steaming, and need special equipment and aqueous binders can directly apply to dry complex equipment, and can reach all performance requriementss of no-solvent type binding agent, so aqueous binder replaces the direction that Solvent Adhesive will be the compound sizing agent development of following food product pack.
Emulsifier-free emulsion polymerization claims emulsifier-free emulsion polymerization again, and it refers to not add fully or only add the emulsion polymerization process of micro-emulsifying agent (its concentration is less than etherealness micellar concentration CMC) in polymerization process.Emulsifier-free emulsion polymerization is removed the aftertreatment of removing emulsifying agent from, and the polymer emulsion surface cleaning, and the particle diameter monodispersity of micelle is good, and particle is big.The emulsion latex particle gets and is stablely determined by the surfactivity oligopolymer, improves polymkeric substance and gets polarity, makes particle surface and aqueous phase interface interact, and the reduction interface gets the Cibbs free energy, can improve the stability of particle.
Microgel is a kind of polymer particle with intramolecular crosslinking structure, but stable dispersion is in organic solvent or water.The particle diameter of microgel is 1nm～1 μ m, and swelling to a certain degree can take place in liquid phase.In polymerization process, micro-gel surface or inner residual a large amount of active groups (as two keys, carboxyl, epoxy group(ing) etc.), these groups under proper condition with other monomers or polymkeric substance generation crosslinking reaction, produce network polymer.This type of microgel is referred to as reactive micro-gel.
Reactive emulsifier generally all contains two keys, can participate in polyreaction, and after polymerization process or polyreaction, surfactant molecule can be strongly bound on the latex particle.Polymerisable emulsifying agent is divided into anionic polymerisable emulsifier, cationic polymerizable emulsifying agent, non-ionic type polymerisable emulsifier and both sexes polymerisable emulsifier by the type of its hydrophilic group.
Number of patent application: 200610118725 disclose a kind of preparation method and application of reactive polyacrylate microgel.This method comprises that (1) is synthetic: compound emulsifying agent adds monomer, stirs, and pre-emulsification adds initiator, makes translucent micro polymer latex; (2) ammonification: stir dropping ammonia solution down, regulate p H value 7～8, make the emulsion of transparent clear.Its application is above-mentioned microgel emulsion to be added make the compound fabric pigment printing binding agent in the binding agent for pigment printing and other raw material is made into printing paste together.Coagulate the aqueous assembly glue that compound usefulness is moulded in inapplicable soft packaging but this reactive polyacrylate is little.
According to the literature, domestic existing Donghua University, South China Science ﹠ Engineering University are coated with big duckweed study group, Cao of University Of Tianjin with research units such as beautiful study group all in the work of carrying out this respect.They mainly concentrate on the preparation method and the sign of reactive micro-gel, and the preparation method who has reported comprises conventional emulsion polymerization, core-shell emulsion polymerization, and micro-emulsion polymerization rarely has the report of emulsifier-free emulsion polymerization mode.The applied research of reactive micro-gel emulsion seldom, the scope of application only limit to paint field and the weaving rubber cement, yet there are no at package printing industry use adhesive area and use.
In soft packaging industry, the compound traditional tackiness agent that uses of composite membrane dry method is solvent-based adhesive, must be by the dry Ex-all of drying tunnel solvent wherein, so that follow-up applying processing, produce quality products, therefore in recombination process, have a large amount of solvents to get rid of, form the huge source of pollution that pollute operation workshop and surrounding enviroment, totally unfavorable to workers'health and environmental protection work; The use of solvent, the hidden danger of aspects such as burning in addition, blast and so on, becomes a big defective of its application, also becomes industry extensive concern and one of difficulty of making great efforts to capture.The Application and Development of aqueous binder for solving the compound existing for a long time safety of dry method, environmental issue, provides an excellent approach.
At present aqueous binder at aspect of performance (as bonding force, thermotolerance, water-fast, solvent resistance and printing adaptability) to different substrate materials also far away less than Solvent Adhesive, especially boiling resistance can and rate of drying aspect.To this, the direction of research mainly is to set about from the polymerization technique aspect of emulsion both at home and abroad.
Summary of the invention
The present invention adopts the emulsifier-free emulsion polymerization mode to synthesize polyacrylate microgel emulsion, utilizes the bonding force of its active group raising to various base materials; Utilize mechanical propertys such as the hardness of high crosslink density and no soap characteristic raising glued membrane and tensile strength, improve thermotolerance, water tolerance and the solvent resistance of glued membrane; Utilize the characteristic of its high-solid lower-viscosity to improve rate of drying, thereby it is slow to solve water-and acrylate emulsion adhesive inherent rate of drying, the stripping strength of composite prod is low, and defective such as heat-resisting, resistance to medium difference reaches the technological difficulties of the performance of solvent borne polyurethane tackiness agent.
The present invention solves the problems of the technologies described above the technical scheme that is adopted to be:
A kind of preparation method of polyacrylate microgel emulsion, it may further comprise the steps:
1, pre-emulsification: take by weighing 200～250 parts of deionized waters, with the deionized water total amount 1/3～2/3,100 parts of (flexible monomers of long-chain: butyl acrylate of mix monomer; Functional monomer: the monomer of Hydroxyethyl acrylate, vinylformic acid, epoxy group(ing); Polyfunctionality monomer: Triethylene glycol dimethacrylate or Vinylstyrene), reactive emulsifier adds in the emulsification still, high-speed stirring is carried out pre-emulsification 10～30min, pre-emulsion.
2, seeding polymerization: in reactor, add the residue deionized water 20%～40%, nonionic emulsifying agent, stirring heating, temperature reaches 60 ℃, add initiator a, when temperature reaches 75 ℃, drip the described pre-emulsion of 20%～40% step 1 fast, and at 75～85 ℃ of insulation reaction 30min.
3, polyreaction: after seeding polymerization was finished, beginning dripped described pre-emulsion of remaining step 1 and initiator b simultaneously, and temperature of reaction is controlled at 80～90 ℃, insulation reaction 30～60min, and discharging is filtered in cooling, makes translucent micro polymer latex.
4, ammonification: be cooled to 60～70 ℃, dropping ammonia solution under the violent stirring, regulating pH value is 7～8, makes polyacrylate microgel emulsion.
The microgel emulsion that makes according to the preparation method of above-mentioned polyacrylate microgel emulsion is polymerized by following parts by weight of raw materials component:
100 parts of mix monomers
1～1.2 part of emulsifying agent
0.2～0.4 part of radical initiator
200～250 parts of deionized waters
0～0.04 part of PH conditioning agent
Described mix monomer comprises: the flexible monomer of long-chain, functional monomer, polyfunctionality monomer, and its parts by weight of raw materials component is:
A, the flexible monomer of long-chain
75 parts of butyl acrylates
B, functional monomer
7.2～17 parts of Hydroxyethyl acrylates
1.2～2.4 parts in vinylformic acid
0.3～0.8 part of epoxy-based functional monomer
C polyfunctionality monomer
Vinylstyrene
Or 0.1～0.4 part of Triethylene glycol dimethacrylate
Described emulsifying agent comprises:
0.1～0.2 part of reactive emulsifier,
0.1 part of nonionic emulsifier;
Described radical initiator comprises: initiator a, initiator b, and its material component is:
Initiator a
K
2S
2O
80.12 part,
H
26 parts of O
Initiator b
0.15 part of tertbutyl peroxide
H
25 parts of O
When initiator amount was 0.2～0.4, the acrylic acid esters co-polymer emulsion of preparation was blue phase, the emulsion granularity is little, and the good stability of emulsion.The adding method of initiator: when initiator added the people to pre-emulsion, monomer reaction was more complete, so the transformation efficiency height; Add initiator on this basis again one time, unreacted residual monomer is reacted, transformation efficiency further improves.APS thermolysis in water produces small amount of H SO
4 -, this ion further is ionized into H
+And SO
4 2-Ion, thereby along with the carrying out of polyreaction, system pH reduces, the change of pH value can have influence on the emulsifying effectiveness of emulsifying agent and the efficiency of initiation of initiator again, thereby micelle size and distribution are exerted an influence.Therefore adopt and add PH conditioning agent ammoniacal liquor.
Described PH conditioning agent is an ammoniacal liquor for 0～0.04 part.
A kind of application of polyacrylate microgel emulsion is to be main component with above-mentioned microgel emulsion, prepares soft packaging and moulds compound use tackiness agent.
The beneficial effect of the invention:
1, adopt the reactive surfactant emulsifying agent to reduce electrolytical content in the emulsion, reduce that foamy forms and product in impurity, improved the performance of emulsion simultaneously at aspect such as water-fast.
2, adopt the synthetic polyacrylate microgel emulsion of no soap emulsifier-free emulsion polymerization mode to be, the preparation emulsion, earlier synthetic seed emulsion continues to add the method for emulsion again, improves turnover ratio, can make high-solid lower-viscosity and get microgel emulsion.
3, the reactive micro-gel polypropylene ester emulsion of the present invention preparation is added to soft packaging and moulds in the aqueous binders of compound usefulness, can improve the rate of drying of aqueous binders, the adhesiveproperties and the boiling resistance of base material.
4, microgel emulsion of the present invention as the technical performance index that the water-based sizing agent of main component preparation reaches is: outward appearance: milky white liquid; PH value: 7.5～8.5; Solid content: 41.0～43.0%; Viscosity: 12.5～13.5 seconds (being coated with 4 glasss 25 ℃); Quality guaranteed period:＞6 months; Freeze-thaw stability: by 5 times; Stripping strength:＞1.2N/15mm (VMPET or VMCPP/BOPP or PET);＞1.8N/15mm (CPP/BOPP or PET);＞10N/15mm (heat-sealing).
Below in conjunction with embodiment, the present invention is further described.
Specific embodiment
Embodiment 1
Present embodiment provides a kind of preparation method of polyacrylate microgel emulsion, and it may further comprise the steps:
1, pre-emulsification: take by weighing 200～250 parts of deionized waters, with the deionized water total amount 1/3～2/3,100 parts of mix monomers (the flexible monomers of long-chain: 75 parts of butyl acrylates, functional monomer: 0.3 part of the monomer of 7.2 parts of Hydroxyethyl acrylates, 1.2 parts in vinylformic acid, epoxy group(ing), 0.1 part of Vinylstyrene), 0.1 part of reactive emulsifier adds in the emulsification still polyfunctionality monomer:, high-speed stirring, carry out pre-emulsification 10～30min, get emulsion.
2, seeding polymerization: in reactor, add the residue deionized water 20%～40%, 0.1 part of nonionic emulsifying agent, stirring heating, temperature reach 60 ℃, add initiator a (component: K
2S
2O
80.12 part, H
2O6 part) reach 75 ℃ when temperature, drip the described pre-emulsion of 20%～40% step 1 fast, and at 75～85 ℃ of insulation reaction 30min.
3, polyreaction: after seeding polymerization was finished, beginning dripped the described pre-emulsion of remaining step 1 and initiator b (0.15 part of tertbutyl peroxide, H simultaneously
25 parts of O), temperature of reaction is controlled at 80～90 ℃, insulation reaction 30～60min, and discharging is filtered in cooling, makes translucent micro polymer latex.
4, ammonification: be cooled to 60～70 ℃, dropping ammonia solution is 0.01 part under the violent stirring, regulates pH value to 7～8, makes polyacrylate microgel emulsion.
The microgel of above-mentioned preparation is added soft packaging to be moulded in the compound binding agent dispersed with stirring and makes the aqueous binders that compound usefulness is moulded in soft packaging.
The reactive micro-gel polypropylene ester emulsion high-solid lower-viscosity that present embodiment makes, good stability, it is joined soft packaging mould adhesive property and the boiling resistance that improves assembly glue in the aqueous binders of compound usefulness, also improved rate of drying, the technical indicator that product of the present invention reaches is as follows:
Embodiment 2
Present embodiment provides the preparation method of polyacrylate microgel emulsion, and its manufacturing step is substantially the same manner as Example 1, and its difference is: the raw material of the polyacrylate microgel emulsion that present embodiment makes consists of:
75 parts of butyl acrylates
10 parts of Hydroxyethyl acrylates
1.5 parts in vinylformic acid
0.6 part of epoxy-based functional monomer
2 parts of Vinylstyrenes
0.15 part of reactive emulsifier
0.1 part of nonionic emulsifier
220 parts of deionized waters
0.02 part of PH conditioning agent
Described radical initiator comprises that the material component of initiator a, initiator b is:
K
2S
2O
80.15 part,
H
27.5 parts of O
Initiator b
0.15 part of tertbutyl peroxide
H
25 parts of O
The present embodiment effect is identical with embodiment 1.
Embodiment 3
Present embodiment provides the preparation method of polyacrylate microgel emulsion, and its manufacturing step is substantially the same manner as Example 1, and its difference is: the raw material of the polyacrylate microgel emulsion that present embodiment makes consists of:
75 parts of butyl acrylates
15 parts of Hydroxyethyl acrylates
2.4 parts in vinylformic acid
0.6 part of epoxy-based functional monomer
0.7 part of Vinylstyrene
0.15 part of reactive emulsifier
0.1 part of nonionic emulsifier
250 parts of deionized waters
0.02 part of PH conditioning agent
Described radical initiator comprises that the material component of initiator a, initiator b is:
K
2S
2O
80.15 part,
H
27.5 parts of O
Initiator b
0.15 part of tertbutyl peroxide
H
25 parts of O
The present embodiment effect is identical with embodiment 1.
Embodiment 4
Present embodiment provides the preparation method of polyacrylate microgel emulsion, and its manufacturing step is substantially the same manner as Example 1, and its difference is: the raw material of the polyacrylate microgel emulsion that present embodiment makes consists of:
75 parts of butyl acrylates
15 parts of Hydroxyethyl acrylates
1.5 parts in vinylformic acid
0.6 part of epoxy-based functional monomer
0.2 part of Vinylstyrene
0.15 part of reactive emulsifier
0.1 part of nonionic emulsifier
230 parts of deionized waters
0.02 part of PH conditioning agent
Described radical initiator comprises that the material component of initiator a, initiator b is:
K
2S
2O
80.15 part
H
27.5 parts of O
Initiator b
0.15 part of tertbutyl peroxide
H
25 parts of O
The present embodiment effect is identical with embodiment 1.
Embodiment 5
Present embodiment provides the preparation method of polyacrylate microgel emulsion, and its manufacturing step is substantially the same manner as Example 1, and its difference is: the raw material of the polyacrylate microgel emulsion that present embodiment makes consists of:
75 parts of butyl acrylates
15 parts of Hydroxyethyl acrylates
2 parts in vinylformic acid
0.3 part of epoxy-based functional monomer
0.3 part of Vinylstyrene
0.15 part of reactive emulsifier
0.1 part of nonionic emulsifier
250 parts of deionized waters
0.01 part of PH conditioning agent
Described radical initiator comprises that the material component of initiator a, initiator b is:
K
2S
2O
80.15 part,
H
27.5 parts of O
Initiator b
0.15 part of tertbutyl peroxide
H
25 parts of O
The present embodiment effect is identical with embodiment 1.
The present invention is not limited to the foregoing description, and every all embodiments that are equal to that can realize the object of the invention are all within protection scope of the present invention.
Claims (4)
1. the preparation method of a polyacrylate microgel emulsion is characterized in that, it may further comprise the steps:
1) pre-emulsification: take by weighing 200～250 parts of deionized waters, with the deionized water total amount 1/3～2/3,100 parts of mix monomers, reactive emulsifier add in the emulsification still for 0.1～0.2 part, high-speed stirring is carried out pre-emulsification 10～30min, pre-emulsion;
2) seeding polymerization: in reactor, add the described deionized water residual content of step 1) 1/5～2/5, nonionic emulsifying agent, stirring heating, temperature reaches 60 ℃, add initiator a, when temperature reaches 75 ℃, drip the described pre-emulsion of 1/5～2/5 step 1) fast, and at 75～85 ℃ of insulation reaction 30min;
3) polyreaction: after seeding polymerization was finished, beginning dripped described pre-emulsion of remaining step 1) and initiator b simultaneously, and temperature of reaction is controlled at 80～90 ℃, insulation reaction 30～60min, and discharging is filtered in cooling, makes translucent micro polymer latex;
4) ammonification: be cooled to 60～70 ℃, dropping ammonia solution is 0～0.04 part under the violent stirring, regulates pH value to 7～8, makes polyacrylate microgel emulsion.
2. the preparation method of polyacrylate microgel emulsion according to claim 1 is characterized in that, the described mix monomer of step 1) comprises the flexible monomer of long-chain, functional monomer, polyfunctionality monomer, and its parts by weight of raw materials component is:
The flexible monomer of a long-chain
75 parts of butyl acrylates
The b functional monomer
7.2～17 parts of Hydroxyethyl acrylates
1.2～2.4 parts in vinylformic acid
0.3～0.8 part of epoxy-based functional monomer
C polyfunctionality monomer
0.1～0.4 part of Vinylstyrene.
3. the preparation method of polyacrylate microgel emulsion according to claim 1 is characterized in that step 2) the parts by weight of raw materials component of described initiator is:
Initiator a
K
2S
2O
80.12 part,
H
26 parts of O
Initiator b
0.15 part of tertbutyl peroxide
H
25 parts of O.
4. application according to the described polyacrylate microgel emulsion of claim 1 is with polyacrylate microgel emulsion, adds soft packaging and moulds dispersed with stirring in the compound binding agent, and the aqueous binders of compound usefulness is moulded in the preparation soft packaging.
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| CN2010102044612A CN101864025B (en) | 2010-06-21 | 2010-06-21 | Preparation method and application of polyacrylate microgel emulsion |
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|---|---|---|---|
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| CN103387806A (en) * | 2013-07-18 | 2013-11-13 | 东莞市芙蓉化工有限公司 | Polyacrylate emulsion pressure-sensitive adhesive having reactive microgel structure and preparation method thereof |
| CN103980412A (en) * | 2014-05-15 | 2014-08-13 | 中国建筑材料科学研究总院 | Method for preparing high-efficiency molecular sieve desiccant with nanometer core-shell structure |
| CN104774287A (en) * | 2015-03-12 | 2015-07-15 | 杭州海维特化工科技有限公司 | Polyacrylate emulsion microgel and preparation method thereof |
| CN105669914A (en) * | 2016-03-23 | 2016-06-15 | 广州天赐高新材料股份有限公司 | Freeze-thaw stable type acrylate polymer emulsion and method for preparing same |
| CN106147672A (en) * | 2015-04-07 | 2016-11-23 | 宏峰行化工(深圳)有限公司 | A kind of for moulding/mould compound aqueous polyurethane acrylate binding agent and preparation method thereof |
| CN106147659A (en) * | 2015-04-09 | 2016-11-23 | 宏峰行化工(深圳)有限公司 | A kind of for moulding/mould compound phosphoric acrylic ester binding agent and preparation method thereof |
| CN106349423A (en) * | 2016-08-24 | 2017-01-25 | 江苏永阳新材料科技有限公司 | Water-based acrylate ceramic tile adhesive, and preparation method and application thereof |
| CN107459603A (en) * | 2017-08-30 | 2017-12-12 | 佛山市高明同德化工有限公司 | A kind of rich hydroxyl microgel emulsion and preparation method thereof |
| CN110305243A (en) * | 2019-07-02 | 2019-10-08 | 南京工业大学 | Preparation method of high-solid-content monodisperse pure acrylic colloid emulsion |
| CN113562284A (en) * | 2021-07-23 | 2021-10-29 | 上海紫丹食品包装印刷有限公司 | Food-grade packaging paper barrel |
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| CN101168650A (en) * | 2006-10-23 | 2008-04-30 | 吴达文 | Single-component self-crosslinking emulsion adhesive for dry-type composite membrane and preparation method thereof |
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| CN101168650A (en) * | 2006-10-23 | 2008-04-30 | 吴达文 | Single-component self-crosslinking emulsion adhesive for dry-type composite membrane and preparation method thereof |
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| CN103387806B (en) * | 2013-07-18 | 2015-09-09 | 东莞市芙蓉化工有限公司 | A kind of have pressure-sensitive polyacrylate emulsion glue of reactive micro-gel structure and preparation method thereof |
| CN103387806A (en) * | 2013-07-18 | 2013-11-13 | 东莞市芙蓉化工有限公司 | Polyacrylate emulsion pressure-sensitive adhesive having reactive microgel structure and preparation method thereof |
| CN103980412A (en) * | 2014-05-15 | 2014-08-13 | 中国建筑材料科学研究总院 | Method for preparing high-efficiency molecular sieve desiccant with nanometer core-shell structure |
| CN104774287B (en) * | 2015-03-12 | 2017-04-26 | 杭州海维特化工科技有限公司 | Polyacrylate emulsion microgel and preparation method thereof |
| CN104774287A (en) * | 2015-03-12 | 2015-07-15 | 杭州海维特化工科技有限公司 | Polyacrylate emulsion microgel and preparation method thereof |
| CN106147672A (en) * | 2015-04-07 | 2016-11-23 | 宏峰行化工(深圳)有限公司 | A kind of for moulding/mould compound aqueous polyurethane acrylate binding agent and preparation method thereof |
| CN106147672B (en) * | 2015-04-07 | 2018-06-19 | 宏峰行化工(深圳)有限公司 | It is a kind of to be used to moulding/moulding compound aqueous polyurethane acrylate adhesive and preparation method thereof |
| CN106147659B (en) * | 2015-04-09 | 2018-06-19 | 宏峰行化工(深圳)有限公司 | It is a kind of to be used to moulding/moulding compound phosphoric acrylic ester adhesive and preparation method thereof |
| CN106147659A (en) * | 2015-04-09 | 2016-11-23 | 宏峰行化工(深圳)有限公司 | A kind of for moulding/mould compound phosphoric acrylic ester binding agent and preparation method thereof |
| CN105669914A (en) * | 2016-03-23 | 2016-06-15 | 广州天赐高新材料股份有限公司 | Freeze-thaw stable type acrylate polymer emulsion and method for preparing same |
| CN105669914B (en) * | 2016-03-23 | 2018-12-28 | 广州天赐高新材料股份有限公司 | A kind of freeze-thaw stable type acrylate polymer emulsion and preparation method thereof |
| CN106349423A (en) * | 2016-08-24 | 2017-01-25 | 江苏永阳新材料科技有限公司 | Water-based acrylate ceramic tile adhesive, and preparation method and application thereof |
| CN106349423B (en) * | 2016-08-24 | 2018-04-10 | 江苏永阳新材料科技有限公司 | A kind of water-and acrylate ceramic tile bond and its preparation method and application |
| CN107459603A (en) * | 2017-08-30 | 2017-12-12 | 佛山市高明同德化工有限公司 | A kind of rich hydroxyl microgel emulsion and preparation method thereof |
| CN110305243A (en) * | 2019-07-02 | 2019-10-08 | 南京工业大学 | Preparation method of high-solid-content monodisperse pure acrylic colloid emulsion |
| CN113562284A (en) * | 2021-07-23 | 2021-10-29 | 上海紫丹食品包装印刷有限公司 | Food-grade packaging paper barrel |
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