CN1195015C - Components, preparing process and usage of hot-fusible adhesive - Google Patents
Components, preparing process and usage of hot-fusible adhesive Download PDFInfo
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Abstract
The present invention belongs to the technical field of adhesive, which relates to composition, a manufacture method and a purpose of hot-melt adhesive. The hot-melt adhesive is manufactured by using polyethylene polymer, peroxide initiator, polarity unsaturated monomer and organic solvents by reactive extrusion technology; by adding resin acceptor and using synthetic hybrid technology and low molecular object elimination technology, manufactured hot-melt adhesive has the advantages of good adhesive joint performance and use technology, low volatile matter contents and small smell. The hot-melt adhesive can be used for plastic / plastic, the hot melt adhesive joint of plastic / metal, and can be especially suitable for outer layer polyethylene (crosslinked polyethylene) of an aluminium-plastic composite pressure pipe and aluminium, the coextrusion hot melt adhesive joint of inner layer polyethylene (crosslinked polyethylene) and the aluminium, toughener of nylon and polypropylene, compatilizer of filled plastics, such as the polypropylene, ABS, etc., carrier resin, such as color master batches, antibiosis master batches, flame resistant master batches, nanometer master batches, etc.
Description
The present invention relates to adhesive field, particularly hotmelt further relates to the composition and the manufacture method thereof of hotmelt.
The kind of hotmelt is a lot, mainly contain ethene-vinyl acetate copolymer, polyester, nylon, low molecular weight polyethylene etc., the consumption maximum of therein ethylene-vinyl acetate copolymer, but because its temperature tolerance relatively poor (Vicat softening point only is 69 ℃), range of application is very restricted; The low molecular weight polyethylene hotmelt is mobile better, but because nonpolarity group in the molecular structure, it is only applicable to the less demanding occasion of adhesiveproperties with relatively poor by the adhesive property of bonding matrix, as the clothes lining etc.The polyethylene graft copolymer hotmelt can be realized the bonding of plastics such as similar polyethylene, polypropylene, nylon and plastics or plastics and metal than low molecular weight polyethylene hotmelt good combination property.The preparation method of polyethylene hotmelt mainly contains two kinds, ie in solution method and reaction extrusion molding.Solution method is used a large amount of organic solvents, long reaction time, and production efficiency is low, the product cost height, environmental pollution is serious.The reaction extrusion molding does not use or only uses a small amount of solvent, can realize continuous production, the production efficiency height, and constant product quality, cost are low, enjoy common people's concern.
It is the co-extruding adhesive of main component that Chinese patent 96108999 discloses with the graft polyolefin, the mixture (A) that contains at least a high density polyethylene(HDPE) (A1) and at least a ethylene copolymer (A2), by monomer cografting (A1) such as unsaturated carboxylic acid or carboxylic acid anhydride or their derivative and mixture (A2), the tackiness agent that this invention relates to is mainly used in the gasoline fuel tank.Do not introduce the technical scheme that how to guarantee each component mixing uniformity of tackiness agent and how to reduce low-molecular material content.
Chinese patent 93111514 discloses a kind of manufacture method of aluminium-plastics hot-fusible binder.The hotmelt of this invention adopts acetone or esters solvent, adds vinylchlorid-vinyl acetate between to for plastic-toxilic acid terpolymer resin, adds the copolyesters of ethylene glycol-dimethyltrimethylene glycol-terephthalate-last of the ten Heavenly stems diester, mixes to form.This aluminium-plastics hot-fusible binder adopts the solution method manufacturing; Be coated to earlier by the surface of bonding matrix during use, treat the solvent evaporates film forming after, 150 ℃ of down heat-sealings, can not be directly at high temperature hot melt apply.
U.S. Pat 5382615 discloses a kind of modified poly ethylene hotmelt that is used to pack.The hotmelt of this invention consist of 5～20 parts of ethene-alkyl acrylate copolymers, 40～70 parts of polyethylene graft copolymers, 15～35 parts of tackifying resins, 5～20 parts in low viscosity wax.Contain low viscosity wax in the hotmelt that this invention relates to, the thermotolerance of hotmelt is relatively poor, is mainly used in packing, at room temperature uses.
The polyolefin graft copolymer hotmelt generally adopts the chemical reaction method manufacturing, the height of its performance, the homogeneity of quality and stability etc. depend on the physical mixed homogeneity of hotmelt each component before reaction to a great extent, reaction process and reaction residual low-molecular material content etc. in the after product.Prior art US4612155 has introduced in the each component adding forcing machine and has carried out two sections mixing, before adding forcing machine, each component is finished pre-mixing in high-speed mixer, a large amount of maleic anhydride, organo-peroxides etc. of using, long mixing time, the Preblend temperature raises, and reaches more than 80 ℃ when the highest, superoxide meeting premature decomposition, inhomogeneous reaction can take place in each component; Short mixing time, premature decomposition can not take place in superoxide, but the mixed effect of each component is difficult to reach requirement.Prior art has been emphasized the importance of the quality uniformity of monomer and polyolefine grafts, but seldom proposes comprehensive terms of settlement.The polyolefine graft reaction is an incomplete reaction, certainly exist a certain amount of unreacted monomer in the product, and also can there be a certain amount of oligopolymer in the reaction product, be referred to as low-molecular material, the existence of these low-molecular materials can make polyolefine grafts hotmelt with by the bubble of generation at the interface of bonding matrix, reduction is to the adhesiveproperties of matrix, and prior art does not relate to and removes low-molecular material residual in the final product how effectively, how to improve the smell of hotmelt etc.These problems do not solve, and their effects in many application can be not best, as the higher hotmelt of performance requriements, as the plastic-aluminum composite pressure pipe hotmelt, whether satisfies the life-time service requirement, is difficult to reach a conclusion.
At above-mentioned deficiency, the purpose of this invention is to provide a kind ofly mix, the composition and the manufacture method thereof of the poor hotmelt of low-molecular material, the purposes of at least a this hotmelt also is provided.
The hotmelt that the present invention relates to contains main components such as polyethylene based polymers, peroxide initiator, unsaturated polar monomer, organic solvent, also can add other supplementary additives, further improve its over-all properties or give hotmelt some specific performance properties, each component through pre-mixing, extrude mixing, reaction, exhaust etc. and make.
The essentially consist of the hotmelt raw material that the present invention relates to contains at least:
Polyethylene based polymers 100 weight parts
Peroxide initiator 0.005～0.1 weight part
Unsaturated polar monomer 0.15～1.0 weight part
Organic solvent 0.2～1.0 weight part
The polyethylene based polymers that the hotmelt that the present invention relates to uses be selected from homopolymerization or with new LDPE (film grade), medium-density polyethylene or the high density polyethylene(HDPE) of other second, third monomer copolymerization or their composition, ethene and contain one or more and have 3～12 carbon atoms preferably, the multipolymer of the alpha-olefin of 4～8 carbon atoms particularly, in addition, also can contain a spot of unsaturated double-bond in the sub polyethylene subchain.
The peroxide initiator decomposes at a certain temperature, causing the polyethylene molecule produces free radical and excites unsaturated monomer, thereby on the polyethylene molecule, finish the graft copolymerization of unsaturated monomer, obtain containing in the molecular structure hotmelt of polar group, with produced bigger Intermolecular Forces by bonding matrix surface, improved the bonding strength between hotmelt and matrix.Usually the peroxide initiator comprises dialkyl peroxide, diacyl peroxide, peroxocarbonate, alkyl peroxide class; preferred benzoyl peroxide (BPO), peroxidized t-butyl perbenzoate (TPB), dicumyl peroxide (DCP), its consumption is 0.005～0.1 weight part.
Unsaturated polar monomer in the constituent is finished graft reaction with polyethylene under the effect of peroxide initiator, the polar carbonyl group is introduced in the sub polyethylene subchain, strengthen the polyethylene graft copolymer hotmelt with by the adhesiveproperties of bonding matrix, preferred at least a unsaturated carboxylic acid or their derivative (comprising carboxylic acid anhydride or carboxylicesters etc.) or their composition that contains carbonyl, vinylformic acid for example, methacrylic acid, (methyl) Isooctyl acrylate monomer, (methyl) Propylene glycol monoacrylate, methyl propenoic acid glycidyl fat, maleic anhydride, toxilic acid, fumaric acid, methylene-succinic acid, dibutyl maleinates etc., its consumption are 0.15～1.0 weight part.
After organic solvent is dissolved as homogeneous solution with solid-state unsaturated polar monomer and peroxide initiator, guarantee uniform mixing with other component, these organic solvents can be a kind of in ketone, the ester class or their mixture, preferred rudimentary ketone, ester class, wherein acetone, butanone, pimelinketone, ethyl acetate can be distinguished use separately or mix and use.Its consumption is 0.2～1.0 weight part.
The hotmelt that the present invention relates to can also contain other additive, mainly comprises two classes.One class is a cross-linked inhibitor, and another kind of is coupling agent on the ordinary meaning.The main effect of cross-linked inhibitor is in the process of polycthylene grafted reaction, suppress the polyethylene crosslinking by product formation, one or more the combination in lactan, laurolactam, the tert.-butyl phenol of selecting oneself of these cross-linked inhibitors, consumption is generally 0～2 weight part.Coupling agent class additive is used for residual unsaturated monomer or other the low molecule of product reactionless, reduces the low-molecular material content in the hotmelt effectively, improves the smell of hotmelt, and consumption is generally 0～3 weight part.These additives can be selected from the one or more combination in silane coupling agent, titanic acid ester or the aluminic acid ester, preferred KH-550, KH-560, KH-570, NDZ-101, NDZ-102.
The manufacturing processed of hotmelt may further comprise the steps successively:
(1) dissolving: adopt organic solvent that the solid constituent beyond the polyethylene in the hotmelt constituent is dissolved, be beneficial to each component and realize good mixing at short notice.
(2) pre-mixing: refer to the mixing of each component in mixing machine.Preferred high-speed mixer, mixing time is generally 0.5min～5min, preferred 1min～3min.In each component mixing process, because the material friction produces a large amount of heats, temperature of charge raises, and can cause the superoxide premature decomposition.For the control peroxide initiator decomposes in early days, temperature of charge should be no more than 60 ℃ in the mixing process, preferably is no more than 40 ℃.This had both realized the full and uniform mixing of each component, and too early inhomogeneous reaction takes place the peroxide initiator premature decomposition of having avoided again causing owing to temperature is too high in the mixing process.
(3) reaction is extruded: comprise that further mixing, reaction, the fugitive constituent of hotmelt each component in forcing machine removes.
Mixing in the forcing machine: pre-mixed material adds in the forcing machine, in forcing machine after the fusion through mixing section, under molten state, each component is further mixed and homogenizing.In forcing machine especially twin screw extruder, the fused material is mediated piece it is produced powerful the shearing through the kneading piece time, and the dispersion mixing of each component is good.The fused material is set up a pressure zone in the kneading district, and material forms anti-stream, the distribution good mixing effect of each component.The once dispersion fully and the mixing that distributes of experience in forcing machine again of pre-so mixed material, each component is able to sufficient homogenizing, and the interface between the each component material fully contacts, for the homogeneous reaction of each component is had laid a good foundation.It is too high to it should be noted that feeding section and mixing section temperature are difficult for, avoid too much organo-peroxide premature decomposition, the temperature of these sections with below the matrix resin fusing point 30 ℃ and more than the fusing point between 80 ℃ for well, 10 ℃～50 ℃ is best more than the matrix resin fusing point.
Reaction: the reactor of hotmelt is single screw extrusion machine or twin screw extruder, be preferably single screw extrusion machine or engagement co-rotating twin screw extruder, the more preferably mixed milling type of section metering or the response type co-rotating twin screw extruder of band mixing section.Forcing machine has a plurality of feeding sections, can carry out different temperature as required and set, and is generally 80 ℃～260 ℃, is preferably 100 ℃～250 ℃; The forcing machine rotating speed is 20r/min～280r/min, is preferably 50r/min～240r/min.
The material of good mixing enters conversion zone and finishes reaction, conversion zone length be L～4L for well (L is cylindrical shell length of forcing machine, and D is a screw diameter, L=4D), conversion zone length be 2L～4L for well, be best with 2L～3L; Temperature of reaction be 140 ℃～260 ℃ for well, be best with 160 ℃～250 ℃.
Deviating from of fugitive constituent: each component is after the forcing machine conversion zone is finished reaction, and material enters exhaust section, carry out vacuum exhaust, as much as possiblely removes low-molecular material residual in the product.Water ring or vane-type vacuum pump are adopted in vacuum exhaust, and vacuum tightness be-0.05MPa～-0.1MPa, preferably-0.07MPa～-0.1MPa.
For the each component uniform mixing, reaction is hotmelt fully, through behind the exhaust section, low-molecular material removes in a large number, if need further to reduce volatile content, can behind exhaust section, add additive, make itself and remaining a small amount of low-molecular material reaction, reduce the content of the low-molecular material in the product, improve the smell of hotmelt product greatly.
The each component of the hotmelt that the present invention relates to can not mix in mixing machine and in the direct segmentation adding extruder, rely on the shearing elements in the forcing machine that each component is carried out fully effective mixing.Polyethylene based polymers adopts twin screw to be metered into by first charging opening, the solid unsaturated monomer through heating in water bath to more than the fusing point 20 ℃, be metered into second charging opening through volume pump, mix through first mixing section with polyethylene based polymers, the length of first mixing section is L
1=4D, the peroxide initiator enters second mixing section then through the adding of the 3rd charging opening, mixes with other component, and the length of second mixing section is L
2=4D～8D, through two sections strong shear-mixed, the dispersion of each component and the mixing that distributes can reach requirement, and the advantage of this process is airtight continuous charging, pollutes less to surrounding environment.
The hotmelt that the present invention relates to is used for the hot melt adhesion of paper/plastics, plastic/plastic, plastic/metal, be specially adapted to the hot melt adhesion inside and outside coating of polyethylene (crosslinked polyethylene)/aluminium/polyethylene (crosslinked polyethylene) composite pressure pipe (abbreviation plastic-aluminum composite pressure pipe), use good manufacturability, polyethylene, aluminium had fabulous adhesiveproperties, coat-thickness is even, surfacing.
The hotmelt that the present invention relates to also can be used for other various multi-layer co-extruded hot melt adhesions, as multi-layer co-extruded composite oil tank, laminated film, composited aluminum and plastic decking; Nylon, polyacrylic toughner; The compatilizer of filled plastics such as polypropylene, ABS; The vector resin of colour batch, antibacterial plastic concentrate, flame-retardant master batch, nano composite material usefulness nanometer masterbatch etc., the properties-correcting agent of polyethylene printing material etc.
The Vicat softening point of the hotmelt that the present invention relates to is greater than 100 ℃, and volatile content is 0.07%～0.19%.
The hotmelt quality that the present invention relates to is even, stable, has better comprehensive performance, volatile content is extremely low in the hotmelt, it is with big by the interface contact area of bonding matrix, in conjunction with more firm, can be owing to not producing a large amount of bubbles at the interface, cause local stress concentration and the interface is destroyed; Because the abundant eliminating of low-molecular material in the hotmelt, the smell of hotmelt is little, is beneficial to use.
The hotmelt manufacturing process that the present invention relates to is simple, but continuous automatic production, the production efficiency height, pollution-free substantially, be suitable for large, medium and small batch process.
Embodiment
Embodiment 1
0.5g benzoyl peroxide (BPO) and 30g maleic anhydride (MAH) are dissolved in the butanone of 40g; With homogeneous solution and 10kg melt flow rate (MFR) is that the pre-mixing time is 60s, obtains Preblend in the linear polyethylene adding high-speed mixer of 2g/10min; It is Φ 45 that Preblend is added screw diameter, and screw slenderness ratio is 27: 1 a mixed milling type engagement co-rotating twin screw extruder, extrudes rotating speed 180r/min～240r/min, 250 ℃ of forcing machine conversion zone temperature, and vacuum tightness-0.08MPa～-0.1MPa; Add 6gKH-570 behind the exhaust section, continue to extrude, make hotmelt, salient features sees Table 1.
This hotmelt is used for polyethylene (crosslinked polyethylene)/aluminium/polyethylene (crosslinked polyethylene) composite pressure pipe (abbreviation plastic-aluminum composite pressure pipe) outer layer polyethylene (crosslinked polyethylene) and aluminium, the hot melt adhesion coating of inner layer polyethylene and aluminium, smell is little, manufacturability, adhesiveproperties are good, the multiple-unit tube surfacing.
Embodiment 2
3g dicumyl peroxide (DCP) is dissolved in the 20g acetone; With homogeneous solution and 10kg melt flow rate (MFR) is that high density polyethylene(HDPE) (trade mark is 7006A), the 15g Isooctyl acrylate monomer of 7g/10min adds in the high-speed mixer, and pre-mixing 90s obtains Preblend; It is Φ 30 that Preblend is added screw diameter, screw slenderness ratio is 37: 1 a response type engagement co-rotating twin screw extruder, at forcing machine rotating speed 80r/min～100r/min, 188 ℃～198 ℃ of extrusion reaction section temperature, vacuum tightness-0.07MPa～-O.09MPa making hotmelt down, salient features sees Table 1.
These hotmelt 8 weight parts add in the polypropylene (trade mark is PP1300) of 92 weight parts, 10% lime carbonate (granularity 400 orders) filling, and notched Izod impact strength is greater than 7kJ/m
2
Embodiment 3
1.2g benzoyl peroxide (BPO) is dissolved in the ethyl acetate of 30g; With homogeneous solution and 10kg melt flow rate (MFR) is that new LDPE (film grade) (trade mark is 1C7A), the 15g Isooctyl acrylate monomer of 7g/10min adds in the high-speed mixer, and the pre-mixing time is 120s; Obtain Preblend; It is Φ 30 that Preblend is added screw diameter, screw slenderness ratio is the single screw extrusion machine of 30: 1 band mixing section, at forcing machine rotating speed 170r/min～200r/min, 220 ℃～240 ℃ of extrusion reaction section temperature, vacuum tightness-0.08MPa～-making hotmelt under the 0.1MPa, salient features sees Table 1.
This hotmelt is used for plastic-aluminum composite pressure pipe, adhesiveproperties excellence, multiple-unit tube surfacing.
Embodiment 4
10g peroxidized t-butyl perbenzoate (TPB) is dissolved in the butanone of 80g; With homogeneous solution and 10kg melt flow rate (MFR) is that high density polyethylene(HDPE), the 100g vinylformic acid of 20g/10min adds in the high-speed mixer, and the pre-mixing time is 60s, obtains Preblend; It is Φ 30 that Preblend is added screw diameter, screw slenderness ratio is 37: 1 a response type co-rotating twin screw extruder, forcing machine rotating speed 180r/min～240r/min, 250 ℃ of extrusion reaction section temperature, vacuum tightness-0.08MPa～-making hotmelt under the 0.1MPa, salient features sees Table 1.
This hotmelt temperature tolerance is better, is used for the hot water plastic-aluminum composite pressure pipe, bonding firm, even, multiple-unit tube surfacing.
Embodiment 5
The hexanolactam of 15g dicumyl peroxide (DCP), 38g maleic anhydride and 6g is dissolved in the acetone of 100g; With homogeneous solution and 10kg melt flow rate (MFR) is that the pre-mixing time is 90s, obtains Preblend in the high density polyethylene(HDPE) adding high-speed mixer of 15g/10min; It is Φ 30 that Preblend is added screw diameter, and screw slenderness ratio is 37: 1 a response type engagement co-rotating twin screw extruder, forcing machine rotating speed 80r/min～100r/min, and 188 ℃～198 ℃ of extrusion reaction section temperature, vacuum tightness-0.07MPa～-0.09MPa; Exhaust section adds NDZ-101, continues to extrude, and makes hotmelt, and salient features sees Table 1.
This hotmelt is used to improve the toughness of Reinforced Nylon 66 (content of glass fiber 30%), and consumption is 12% o'clock, and the notched Izod impact strength of Reinforced Nylon 66 is by 7kJ/m
2Bring up to 12.8kJ/m
2
Embodiment 6
Appointed condition: response type engagement co-rotating twin screw extruder, screw diameter Φ 30, length-to-diameter ratio 48: 1.
Processing condition: section metering is reinforced, add polyethylene earlier and carry out fusion, add unsaturated monomer at second charging opening, mix through mixing section, the ethyl acetate solution that adds dicumyl peroxide again at the 3rd charging opening again through two mixing sections, is finished mixing of superoxide and other component, entering conversion zone then and finish reaction, is exhaust section behind the conversion zone; Forcing machine rotating speed 120r/min～150r/min; The forcing machine feeding section is to 140 ℃～190 ℃ of the temperature of conversion zone, 195 ℃～205 ℃ of temperature of reaction; Vacuum tightness-0.07MPa～-0.09MPa.
Prescription: medium-density polyethylene (melt flow rate (MFR) 9.0g/10min) 100
Dicumyl peroxide (DCP) 0.08
Maleic anhydride (MAH) 0.8
Ethyl acetate 0.5
This hotmelt is used for the compound coating of polyethylene/nylon, and adhesiveproperties is good.
The salient features of table 1 hotmelt
| Sequence number | Melt flow rate (MFR) g/10min | T stripping strength kN/m | Volatile content % |
| Embodiment 1 | 1.2 | 3.4 | 0.19 |
| Embodiment 2 | 0.6 | 3.3 | 0.07 |
| Embodiment 3 | 1.6 | 2.9 | 0.08 |
| Embodiment 4 | 2.9 | 2.85 | 0.18 |
| Embodiment 5 | 3.9 | 3.1 | 0.12 |
| Embodiment 6 | 3.5 | 3.1 | 0.14 |
Claims (7)
1 one kinds of hotmelts, Vicat softening point are greater than 100 ℃, and volatile content is 0.07%～0.19%, and raw materials used constituent contains at least:
Polyethylene based polymers 100 weight parts
Peroxide initiator 0.005～0.1 weight part
Unsaturated polar monomer 0.15～1.0 weight part
Organic solvent 0.2～1.0 weight part.
The described hotmelt of 2 claims 1, described polyethylene based polymers be homopolymerization or with the new LDPE (film grade) of second, third monomer copolymerizable, medium-density polyethylene, high density polyethylene(HDPE), linear polyethylene in a kind of or combination that they are several.
The described hotmelt of 3 claims 1, the melt flow rate (MFR) of described polyethylene based polymers are 1g/10min～20g/10min.
The described hotmelt of 4 claims 1, described peroxide initiator are selected from a kind of in dicumyl peroxide, benzoyl peroxide, the peroxidized t-butyl perbenzoate or combination that they are several.
The described hotmelt of 5 claims 1, described unsaturated polar monomer are a kind of in dibutyl maleinate, MALEIC ANHYDRIDE, vinylformic acid, the Isooctyl acrylate monomer or combination that they are several.
The described hotmelt of 6 claims 1, described organic solvent are selected from a kind of in butanone, acetone, the ethyl acetate or combination that they are several.
The described hotmelt of 7 claims 1 adopts the reaction extrusion process preparation, it is characterized in that various auxiliary agents add with the form of solution, carry out removing of low-molecular material in the reaction extrusion.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB011149116A CN1195015C (en) | 2001-04-30 | 2001-04-30 | Components, preparing process and usage of hot-fusible adhesive |
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| CNB011149116A CN1195015C (en) | 2001-04-30 | 2001-04-30 | Components, preparing process and usage of hot-fusible adhesive |
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| CN1195015C true CN1195015C (en) | 2005-03-30 |
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| CN101580680B (en) * | 2009-03-27 | 2012-02-15 | 广州鹿山新材料股份有限公司 | Crosslinkable polyethylene hot-melt adhesive composition and preparation method and application thereof |
| EP2656000B1 (en) * | 2010-12-21 | 2015-08-12 | E. I. du Pont de Nemours and Company | Trauma reducing pack |
| CN102286258B (en) * | 2011-06-16 | 2013-01-09 | 上海邦中高分子材料有限公司 | Adhesive resin special for aluminum plastic pipes and preparation method for adhesive resin |
| CN102399519A (en) * | 2011-12-24 | 2012-04-04 | 山东东宏管业有限公司 | Hot melt adhesive for steel plastic composite pipeline and production method of hot melt adhesive |
| CN102816282B (en) * | 2012-09-21 | 2014-04-30 | 南京棠城塑胶有限公司 | Method for restraining cross-linking side reaction in process of melt-grafting reaction |
| CN103436193B (en) * | 2013-08-22 | 2015-04-08 | 刘信东 | Grafted LLDPE (Linear Low-Density Polyethylene) based metal bonding film |
| CN107603516A (en) * | 2017-09-25 | 2018-01-19 | 广州爱奇实业有限公司 | A kind of preparation method of adhesive and its application in artificial turf back line with rubber field |
| CN109024090A (en) * | 2018-09-27 | 2018-12-18 | 杭州大唐印刷有限公司 | A kind of DIY can mark the production technology of label paper |
| CN115216243A (en) * | 2022-07-14 | 2022-10-21 | 广东汇齐新材料有限公司 | Environment-friendly high-viscosity hot melt adhesive film and preparation method thereof |
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