CN1566249A - Hot-melt adhesive compositions and the use thereof - Google Patents
Hot-melt adhesive compositions and the use thereof Download PDFInfo
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- CN1566249A CN1566249A CN 03141307 CN03141307A CN1566249A CN 1566249 A CN1566249 A CN 1566249A CN 03141307 CN03141307 CN 03141307 CN 03141307 A CN03141307 A CN 03141307A CN 1566249 A CN1566249 A CN 1566249A
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- polyvinylpyrrolidone
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Abstract
The invention relates to a hot melt glue composition and its use in manufacturing antifalsification paper, the hot-melt adhesive composition comprises, (a) mixture of 25-45 wt% of solvent type polyurethane and water-based adhesive, (b) 5-10 wt% of auxiliary agent, and (c) 50-70 wt% of solvent.
Description
Invention field
The present invention relates to a kind of hot-melt adhesive composition, this hot-melt adhesive composition can effectively improve safety line in the anti-forge paper, especially the fastness that combines of fenestration safety line and paper.The invention still further relates to and use this hot melt adhesive to make the method for described anti-forge paper.
Background of invention
Safety line is widely used in the anti-forge paper as a kind of effective false proof measure, comprises the paper of special purposes such as banknote, Valued Securities, vellum paper, by many countries employing in the world.This anti-forge paper requires the combination of paper yarn that good fastness will be arranged, and can normally use and circulate under hot and humid circulation environment to keep paper (especially bank note), the isolating phenomenon of paper yarn can not occur.
The dispensing of safety line is an important step of this paper manufacturing processed, and safety line is embedded in the paper, and hot melt adhesive is crucial in conjunction with tie, and the effect by hot melt adhesive can realize combining of safety line and paper fiber.In the present way in this area, no matter the solvent borne polyurethane hot melt adhesive is all adopted in the fully buried safety line or the setting of fenestration safety line.But facts have proved that for the fenestration safety line because the paper yarn bonded area is little many, identical operations causes paper yarn to descend in conjunction with fastness, in circulation, can influence use because temperature, humidity and people for effect such as rubbing, the paper yarn separation occurs.For addressing this problem, during the bank note of country such as English, U.S., Singapore is made, adopt the safety line of composite structure, be coated with water-base cement at the outermost of composite structure, to guarantee crumpling resistance energy preferably.This technology has increased processing step, and the coating quality of this water-base cement is vulnerable to the influence of coating apparatus in process of production, for some coating apparatus, for example common printed machine, because problems such as baking oven performance easily cause drying not thorough, the performance of the bank note of influence, thus very high to the requirement of equipment.
Anti-counterfeiting technology is improving day by day, specific coding for example is set in safety line can improves security, therefore the cheque paper that has added safety line is had an optimistic view of in the industry and is generally used, seek suitable hot melt adhesive, under the condition that needn't change paper technology and equipment on a large scale, effectively improve the fastness that combines of safety line and paper, become the problem of concern in the industry.
Summary of the invention
Main contents of the present invention provide a kind of new hot-melt adhesive composition, it combines the effect of the hot melt adhesive and the water-base cement of present use, the manufacturing that the hot melt adhesive of preparing is used for anti-forge paper can improve the fastness that combines of safety line and paper, is particularly useful for the setting of fenestration safety line.
Comprise (the weight percent sum of each component is 100%) in the hot-melt adhesive composition of the present invention:
(a) mixture of the solvent borne polyurethane of 25-45wt.% and water-base cement;
(b) auxiliary agent of 5-10wt.%;
(c) solvent of 50-70wt.%;
Wherein, the blending ratio of solvent borne polyurethane and water-base cement is 6 in the component (a): 4-9: 1, be preferably about 2: 1-5: and 1, more preferably about about 3: 1.
In the hot-melt adhesive composition of the present invention, urethane is thermoplastic polyester type polyurethane or polyether(poly)urethane, is preferably linear structure, and molecular weight is at 20000-40000, and softening temperature is at 100-130 ℃, and normal temperature is solid-state.
Described water-base cement is meant any hydroaropic substance that can be compatible with above-mentioned urethane, comprises polyvinylpyrrolidone, polyvinylpyrrolidone//vinyl acetate copolymers, polyoxyethylene (PEO) or polyoxyethylene glycol etc.
Preferably, the K value of employed polyvinylpyrrolidone is preferably in 30-60 at 15-90.(according to Europe and American Pharmacopeia, the molecular-weight average of polymkeric substance can be used the K value representation, and promptly the K value is to get by the relative viscosity of 1% aqueous solution is calculated, so K macromolecule more is big more); The polymerization ratio of polyvinylpyrrolidone//vinyl acetate copolymers (VP/Va) is 30/70-70/30, is preferably 40/60-60/40, and the K value is greatly about 32-45 (K value implication is the same).
According to composition of the present invention, the water-base cement material is preferably polyvinylpyrrolidone or polyvinylpyrrolidone//vinyl acetate copolymers.
In this hot-melt adhesive composition, auxiliary agent is the material of the suitable property of any processing that improves hot melt adhesive, can comprise a kind of in flow agent, micro mist wax, the adhesion promoter or several as required.Preferably, flow agent can be solvent type polysiloxane-polyether copolymer (for example TEGO GLIDE 440 of TEGO CHEMIE SERVICEGMBH production), and add-on can be at about 1%-2%; Micro mist wax can use polytetrafluoroethylmodified modified class material (as LAWTER INTERNATIONAL, the SLIP MOST3 type of INC), and add-on is 3%-5%; Adhesion promoter can use oiliness compound (as LAWTERINTERNATIONAL, the SOY GRIP of INC), and add-on is at 1%-2%.Described solvent can be alcohol or ketones solvent, should be able to make the fine dissolving of polyurethane adhesive and water-base cement, and the indefiniteness example has: acetone, butanone, pimelinketone, ethanol, Virahol etc.
Hot-melt adhesive composition of the present invention has utilized the hot melt of urethane and water-base cement (for example polyvinylpyrrolidone) hydrophilic character and has had hydrophilic and dual characteristics hot melt.Adjust the ratio of hydroaropic substance and urethane, can regulate the water-soluble of composition, make the hot melt adhesive that obtains adapt to corresponding paper technology.With the polyvinylpyrrolidone is example, polyvinylpyrrolidone and linear polyester form the coating of half interpenetrating network structure jointly in the production, become the initial stage with the paper fiber in conjunction with (glue hot melt or water-soluble back molecule and paper fibre-effects) paper in paper-making process is leaf, under the effect of water, peptization expands and is penetrated in the paper fiber structure, and moisture reduces in the drying process of paper; Drying temperature surpasses 100 ℃, then gum softening fusion, and further infiltration drives sticking of safety line in the paper fiber, thereby realizes the mortise of line and paper.
Utilize hot-melt adhesive composition of the present invention to prepare and be applicable to the hot melt adhesive that safety line is provided with in the cheque paper manufacturing, especially the setting of fenestration safety line, the preparation method of this hot melt adhesive is very simple, only need add solvent, auxiliary agent, water-base cement and solvent borne polyurethane successively, can use the mixing tank that is provided with high-speed stirring, heat or do not heat, when heated and stirred, temperature can be about 50 ℃, difference according to agitation condition, generally can stir 2-4 hour, and be stirred to sizing material and be uniformly dispersed, thorough mixing.
According to a further aspect in the invention, this hot melt adhesive especially be can be used for having the manufacturing of the anti-forge paper of safety line, in dispensing safety line operation, use thermosol coating safety line substrate surface of the present invention, do not change present production technique, the firmness of safety line setting in the paper is significantly improved, the particular requirement that can not increase manufacturing facilities simultaneously.
When using thermosol manufacturing of the present invention to be provided with the anti-forge paper of safety line, because this thermosol (for example has very wide paper technology adaptability, the ratio of the hot melt adhesive urethane and the water-sol such as polyvinylpyrrolidone can be adjusted according to the paper technology situation, satisfy under the different technology conditions finally in conjunction with fastness), so paper technology is not had particular requirement and improves needs, and it is basic identical that promptly working method and prior art are used the process of polyurethane adhesive.Hot melt adhesive of the present invention can use separately aborning, promptly uses this hot melt adhesive directly to be coated with.But well stick performance for hot melt adhesive is had, promote the combination of paper yarn better, preferably adopt multi-layer coated mode,, be coated with hot melt adhesive of the present invention then at safety line substrate surface elder generation's coated polyester and/or polyurethane adhesive.The requirement of polyurethane adhesive as hereinbefore, and described vibrin is the linear saturated polyester resin of molecular weight at 10000-18000,40-60 ℃ of its second-order transition temperature, softening temperature 110-150 ℃.
Manufacturing method according to the invention, the glue spread of hot melt adhesive can be decided according to operational condition and technology, and generally speaking, if coated heat melten gel only, glue spread should be 5 gram/m at least
2Perhaps be coated with urethane earlier, glue spread is 3-4 gram/m
2, coated heat melten gel 4-5 gram/m then
2Perhaps, first coated polyester, glue spread is 1-1.5 gram/m
2, being coated with urethane then, glue spread is 2-3 gram/m
2, and then coated heat melten gel 4-4.5 gram/m
2In actual production, can use special edition roller, to guarantee the thickness of coating.So-called special edition roller, be meant the version roller that is specifically designed to coating that electronic engraving, laser sculpture, corrosion or cotton ginning are made that passes through that can reach the regulation glue spread, for specialty plate-making factory,, can produce the version roller that satisfies glue spread fully usually as long as propose the requirement of glue spread.Except that the version roller, in the coating operation other equipment there are not special requirement, just require printing press or coating machine to have enough drying poweies to satisfy the drying under the big situation of spread, preferably use coating machine.
Because what safety line was used is PET (polyethylene terephthalate) film, has the polar carboxylic group in its structure, also there are carboxyl, hydroxyl, carbonyl isopolarity group through after the corona treatment, amino in the hot melt adhesive of the present invention, ester group and ehter bond can form hydrogen bond with it or chemical reaction takes place, thereby form firm bonding.Two kinds of thermosols of urethane and polyester structurally have similarity, all contain group-COO-, help combining of hot melt adhesive and base material.Method of the present invention is utilized this group and film surface molecule to form hydrogen bond exactly or chemical reaction is taken place, and be penetrated in the anti-counterfeiting information layer, make anti-counterfeiting information layer and PET base material form firm one-piece construction, guaranteed that anti-counterfeiting information is not damaged under the life-time service state.
The preferred manufacture method according to the present invention, at safety line substrate surface (may be coated with the anti-counterfeiting information layer) coating urethane, utilize urethane and base material and hot melt adhesive of the present invention all to have the characteristic of good affinity exactly, played good ligation.Another kind of method of the present invention is that the mechanism of action is similar at substrate surface elder generation coated polyester layer, and structurally many one decks can be protected anti-counterfeiting information better, make it have better weather resistance and anti-materialization etc.
Anti-forge paper of the present invention is preferably the product that is provided with the fenestration safety line, comprises bank-note paper, bond paper, various vellum paper, for example passport paper, driving license paper etc.
Fully buried safety line of the present invention is meant that safety line is intactly placed the anti-forge paper that forms in the paper, and the fenestration safety line is meant and partly places safety line in the paper, the anti-forge paper that the what is called " in the window " that other has part to be revealed in some regulations zone (or random areas) forms is used for the manufacturing of bank note at present more.
Identical with common process, the hot melt adhesive glue spread that the present invention put down in writing all refers to dry-coated amount.
The manufacturing process of relevant anti-forge paper, the concrete manufacturing process that especially is provided with the anti-forge paper of safety line (comprising fully buried safety line or fenestration safety line) is the known technology of this area, does not belong to the claimed category of the present invention.Improvements over the prior art of the present invention are to discharge in the safety line operation the special hot melt adhesive of use and have replaced employed polyurethane adhesive in this class paper is made at present, comprise that direct coating or layering repeatedly are coated with, so, the concrete steps of relevant paper-making process, as not relating in the present specification, all should be considered as to implement according to known technology.
In sum, the improvement of the present invention by hot melt adhesive is formed, be used for being provided with production, the especially setting of fenestration safety line of the anti-forge paper of safety line, can effectively improve the fastness that combines of line and paper, simultaneous test shows, safety line is difficult for separating with paper, that is, the crumpling resistance of paper improves, not only help the raising of security, the cycle that also can prolong circulation and use.Exempted the technology that is coated with water-base cement in the prior art at the outside surface of safety line, also reduced investment at the special-purpose coating machine of this step.
Specific embodiments
Describe enforcement of the present invention and the beneficial effect that is produced in detail below in conjunction with specific embodiment, but should not be construed as qualification protection domain of the present invention.
Embodiment 1
Urethane and K value are about 8: 2 mixture 40% for the polyvinylpyrrolidone of about 30-35;
TEGO?GLIDE440 1％
SLIP?MOST3 4％
SOY GRIP 2％
Butanone 53%
Acetone placed tell stirred pot, stir and add auxiliary agent, polyvinylpyrrolidone, urethane simultaneously successively, stirred 2-3 hour down, sizing material is uniformly dispersed, obtain hot melt adhesive at about 50 ℃.
Embodiment 2
Urethane and VP/Va are that 40/60 polyvinylpyrrolidone//vinyl acetate copolymers (the K value is 32-45) is about 3: 1 mixture 36%;
SLIP?MOST3 3％
SOY?GRIP 1％
Ethanol 60%
Ethanol placed tell stirred pot, stir and add auxiliary agent, multipolymer, urethane simultaneously successively, stirred 2 hours down, or normal temperature stirred 3-4 hour down, sizing material is uniformly dispersed, obtain thermosol at about 50 ℃.
Embodiment 3: the manufacturing of anti-forge paper
Utilize version roller and coating machine to the applying glue of PET substrate surface, at first be coated with layer of polyurethane, glue spread is controlled at about 3.5-4 gram/m
2, then at the thermosol of this layer of polyurethane surface coated embodiment 1 (, need carry out drying between twice coating, below identical), the about 4.5-5 gram/m of glue spread according to routine operation
2This base material drops into the fibre stuff (this slurry has been finished slurrying as requested) that is used for papermaking on request, and this slurry becomes the paper that is provided with the fenestration safety line through operations such as the manufacturing of page, dryings.
Annotate: the safety line base material can add anti-counterfeiting information earlier before applying glue.
Embodiment 4
Utilize version roller and coating machine to the applying glue of PET substrate surface, coated polyester layer at first, glue spread is controlled at about 1-1.5 gram/m
2, the vibrin that uses is the linear saturated polyester resin of molecular weight at 10000-18000,40-60 ℃ of its second-order transition temperature, softening temperature 110-150 ℃; Be coated with layer of polyurethane then, glue spread is controlled at about 2-2.5 gram/m
2, then at the thermosol of this layer of polyurethane surface coated embodiment 2, the about 4-4.5 gram/m of glue spread
2This base material drops into the fibre stuff (this slurry has been finished slurrying as requested) that is used for papermaking on request, and this slurry becomes the paper that is provided with the fenestration safety line through operations such as the manufacturing of page, dryings.
Annotate: the safety line base material can add anti-counterfeiting information earlier before applying glue.
Anti-ly rub test
Verify the crumpling resistance that is provided with fenestration safety line paper that several different methods obtain:
Sample: 1#, be coated with polyester glue
2#, be coated with polyester type of urethane rubber
3#, be coated with polyester type of urethane rubber after, outside surface has been coated with water-base cement
4#, embodiment 3 and 4 paper
Method: use the anti-instrument (IGT provides (dutch company), and model is IGT TESTINGSYSTEM NBS) of rubbing of IGT respectively above-mentioned paper to be carried out anti-measurement of rubbing number of times,, write down and rub number of times to separate with paper and available pin passes and exceeds at the safety line place of windowing.
The result: the 1# paper is 1-2 time,
The 2# paper is 6-10 time,
The 3# paper is 10-20 time,
The 4# paper all reaches 24-30 time.
Claims (16)
1, a kind of hot-melt adhesive composition, it comprises:
(a) mixture of the solvent borne polyurethane of 25-45wt.% and water-base cement;
(b) auxiliary agent of 5-10wt.%;
(c) solvent of 50-70wt.%;
Wherein, the blending ratio of solvent borne polyurethane and water-base cement is 6 in the component (a): 4-9: 1.
2, the described hot-melt adhesive composition of claim 1, wherein, described urethane is thermoplastic polyester type polyurethane or polyether(poly)urethane, softening temperature is at 100-130 ℃.
3, the described hot-melt adhesive composition of claim 1, wherein, described water-base cement comprises polyvinylpyrrolidone, polyvinylpyrrolidone//vinyl acetate copolymers, polyoxyethylene or polyoxyethylene glycol.
4, the described thermosol composition of claim 3, wherein, the polymerization ratio of polyvinylpyrrolidone//vinyl acetate copolymers is 30/70-70/30.
5, the described thermosol composition of claim 3, wherein, the K value of polyvinylpyrrolidone is at 15-90.
6, the described hot-melt adhesive composition of claim 1, wherein, described auxiliary agent comprises a kind of in flow agent, micro mist wax and the adhesion promoter or several.
7, the described hot-melt adhesive composition of claim 1, wherein, described solvent is alcoholic solvent or ketones solvent.
8, a kind of hot melt adhesive adopts each described hot-melt adhesive composition of claim 1-7, under agitation adds solvent, auxiliary agent, water-base cement, solvent borne polyurethane successively, thorough mixing and obtaining.
9, the described hot melt adhesive of claim 8, wherein, water-base cement is polyvinylpyrrolidone or polyvinylpyrrolidone//vinyl acetate copolymers.
10, the application of each described hot-melt adhesive composition of claim 1-7 in making anti-forge paper.
11, the described application of claim 10, wherein, described anti-forge paper is provided with the fenestration safety line, comprises bank-note paper, bond paper, vellum paper.
12, the manufacture method that has the anti-forge paper of safety line, the safety line base material of it has comprised in the slurries of paper-making fibre dispensing surface coated claim 8 or 9 described hot melt adhesives.
13, the described manufacture method of claim 12, wherein, described safety line substrate surface has been coated with layer of polyurethane earlier, is coated with this thermosol then.
14, the described manufacture method of claim 12, wherein, described safety line substrate surface has been coated with polyester resin layer, layer of polyurethane and this hot melt adhesive successively.
15, the described manufacture method of claim 14, wherein, described vibrin is linear saturated polyester's resin, 110-150 ℃ of its softening temperature.
16, the described manufacture method of claim 12, wherein, described anti-forge paper is provided with the fenestration safety line, comprises bank-note paper, bond paper, vellum paper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03141307 CN1258576C (en) | 2003-06-10 | 2003-06-10 | Hot-melt adhesive compositions and the use thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03141307 CN1258576C (en) | 2003-06-10 | 2003-06-10 | Hot-melt adhesive compositions and the use thereof |
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| CN1566249A true CN1566249A (en) | 2005-01-19 |
| CN1258576C CN1258576C (en) | 2006-06-07 |
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| CN 03141307 Expired - Fee Related CN1258576C (en) | 2003-06-10 | 2003-06-10 | Hot-melt adhesive compositions and the use thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102533162A (en) * | 2011-12-28 | 2012-07-04 | 广州鹿山新材料股份有限公司 | Preparation method of poly ethylene (PE) hot melt glue powder for 3PE anti-corrosion pipelines |
| CN101724371B (en) * | 2009-12-18 | 2012-09-26 | 中钞特种防伪科技有限公司 | Hot melt adhesive composition and application thereof |
| CN108300405A (en) * | 2018-03-19 | 2018-07-20 | 苏州世华新材料科技有限公司 | A kind of no base material reaction fiber type conductive hot melt adhesive tape and its with glue and preparation method |
-
2003
- 2003-06-10 CN CN 03141307 patent/CN1258576C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724371B (en) * | 2009-12-18 | 2012-09-26 | 中钞特种防伪科技有限公司 | Hot melt adhesive composition and application thereof |
| CN102533162A (en) * | 2011-12-28 | 2012-07-04 | 广州鹿山新材料股份有限公司 | Preparation method of poly ethylene (PE) hot melt glue powder for 3PE anti-corrosion pipelines |
| CN102533162B (en) * | 2011-12-28 | 2013-07-03 | 广州鹿山新材料股份有限公司 | Preparation method of poly ethylene (PE) hot melt glue powder for 3PE anti-corrosion pipelines |
| CN108300405A (en) * | 2018-03-19 | 2018-07-20 | 苏州世华新材料科技有限公司 | A kind of no base material reaction fiber type conductive hot melt adhesive tape and its with glue and preparation method |
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| Publication number | Publication date |
|---|---|
| CN1258576C (en) | 2006-06-07 |
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