CN107312488A - Aqueous heat-seal adhesive composition for medicine bubble-cap hydrolysis and preparation method thereof - Google Patents
Aqueous heat-seal adhesive composition for medicine bubble-cap hydrolysis and preparation method thereof Download PDFInfo
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- CN107312488A CN107312488A CN201710618802.2A CN201710618802A CN107312488A CN 107312488 A CN107312488 A CN 107312488A CN 201710618802 A CN201710618802 A CN 201710618802A CN 107312488 A CN107312488 A CN 107312488A
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- Prior art keywords
- hydrolysis
- cap
- adhesive composition
- epoxy resin
- aqueous
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention provides a kind of for aqueous heat-seal adhesive composition of medicine bubble-cap hydrolysis and preparation method thereof, it includes following component：Polyester emulsion, epoxy resin latex, vistanex, hydrolysis stabilizer, tackifier, polyalcohol, diluent alcohol, diluent water, auxiliary agent.The preparation method comprises the following steps：After polyester emulsion, modified epoxy resin emulsion, vistanex are well mixed, polyalcohol, diluent alcohol, diluent water are added；Hydrolysis stabilizer, auxiliary agent and tackifier are added, are cured after stirring；The solid content of product is detected, and the solid content is adjusted to after 25%, stirring discharging.Compared with prior art, the present invention has following beneficial effect：1st, under hot and humid environment, hydrolytic resistance is significantly increased, finished product can transport by sea without having an impact to end properties；2nd, on high speed medicine-packaging machine, under high temperature heat seal is closed, glue is produced without any smell.
Description
Technical field
The present invention relates to a kind of for aqueous heat-seal adhesive composition of medicine bubble-cap hydrolysis and preparation method thereof, belong to water
Property technical field of coatings.
Background technology
The aluminium-plastic bubble plate packing of medicine is divided into PTP In Aluminium Foil Packings and tropical aluminium blister package, is between aluminium foil and PVC
Bonding.PTP packagings are that first plastic tab is put on electric heater to be allowed to soften, then thin slice is placed in grinding tool, then from upper mould
It is filled with compressed air in tool to thin slice or is vacuumized in lower mould, makes thin slice formation bubble-cap or hole, cooled down after shaping, by medicine
Product are placed in bubble-cap, and medicinal aluminum foil scribbles the one side of adhesive under certain temperature, pressure time conditions, with having been loaded with medicine
Plastic tab heat-sealing, form blister package PTP packaging materials, including medicinal aluminum foil, plastic hard plate etc..And tropical aluminium blister pack
Dress is a kind of barrier property for aiming at enhancing aluminium-plastic bubble plate packing and the packaged form that grows up, is particularly suitable for use in barrier
The packaging of the products such as higher food, medicine, health products can be required, its sealing is excellent, exquisite appearance, at present by the country
Wrapping enterprise and the extensive concern of consumer, and used by increasing wrapping enterprise.
At present in the medical packaging aluminium foil industry glue abbreviation VC glue, oiliness formula be mainly vinyl chloride-vinyl acetate resin and polyester or
Polyurethane resin, water prescription is mainly based on PAUR.Wherein, oiliness vinyl chloride-vinyl acetate resin holds due to containing free acid
Easily there are various production problems, replaced gradually by aqueous at present.But because aqueous VC is hydrophilic due to containing in resin backbone
Group, its aluminum foil finished product made hydrolytic stability under hot and humid environment is poor, so as to cause properties of product to go wrong.
It particularly may be divided into：
1st, under hot and humid environment, polyester group is hydrolyzed in resin backbone, causes intensity decreases.Finished product is transported in ocean
When defeated, its intensity declines notable；
2nd, part producer introduces carboxyl in resins synthesis on the market, and with the popularization of Modern High-Speed medicine-packaging machine, high temperature
Lower the type glue easily produces pungent tart flavour, has a strong impact on the progress of production；
3rd, storage stability is poor, general 6 months shelf-lifves
4th, levelling is poor, and formula needs to add more alcohols and leveling auxiliary agent, and cost is higher
5th, overfoaming is serious, and hopper foam is more, needs relatively low machine fast-growing production, influences efficiency
6th, freeze-thaw stability is poor, and cold district uses freeze thawing, and need to reheat thawing can use
7th, there is oiliness glue, heat seal strength declines same problem over time.
The content of the invention
For defect of the prior art, it is an object of the invention to provide a kind of water fever for medicine bubble-cap hydrolysis
Sealing composition and preparation method thereof.
The present invention is achieved by the following technical solutions：
In a first aspect, the invention provides a kind of aqueous heat-seal adhesive composition for medicine bubble-cap hydrolysis, it includes
The following component of percentage：
For above-mentioned raw materials used parameter area, selection gist is as follows：
Polyester emulsion：If higher than this scope, anti-hydrolytic performance is improved, but cost is higher, if less than this scope, glue-line is strong
Degree is relatively low；
Epoxy resin latex：Higher than this range effects intensity, decline less than this scope hydrolytic resistance；
Vistanex；Higher than this scope storage stability intensity, reduction, less than this range intensity reduction hydrolytic resistance drop
It is low；
Hydrolysis stabilizer；Higher than the reduction of this range intensity, less than the reduction of this scope hydrolytic stability；
Tackifier；Higher than this scope, viscosity is too high, and the disadvantages such as the wire drawings such as sagging occurs in levelling；Less than this scope, glue glues
Degree is too small, excessive glue problem occurs；
Polyalcohol：More influence intensity is remained higher than this scope, during drying, during less than this scope, anti-freeze thawing is poor；
Diluent alcohol；Higher than the increase of this scope cost, less than the extension of this scope drying time, production cost is improved；
Diluent water；It is poor higher than this scope levelling, do not reach Theoretical Design less than this scope and contain admittedly；
Auxiliary agent：Intensity is reduced higher than this scope, less than this scope, the obvious levelling of overfoaming is deteriorated, and is unfavorable for production.
Preferably, the polyester emulsion include makrolon base water polyurethane, it is polyether-modified polyurethane, organic
One or more in silicon-modified polyester resin.
Preferably, the preparation method of the makrolon base water polyurethane is：
By oligomer polyol and toluene di-isocyanate(TDI) after 85 DEG C are reacted, bishydroxymethyl propionic acid and two is added
Dibutyl tin laurate, is reacted at 85 DEG C, adds BDO and trimethylolpropane, is contained in 60 DEG C of reactions to-NCO
Amount no longer changes, and obtains performed polymer；
After the pH value of the performed polymer is neutralized into 7.5, adds water and emulsified, obtain the aqueous poly- ammonia of the makrolon base
Ester.Carbonate polyurethane prepared by the method is used for aqueous heat-seal adhesive, with excellent hydrolytic resistance.
Preferably, the epoxy resin includes modified aqueous epoxy resin emulsion, modifying epoxy resin by organosilicon
At least one of emulsion, polyurethane modified epoxy resin emulsion, olefin-modified epoxy resin.
Preferably, the preparation method of the modified aqueous epoxy resin is：
By epoxy resin and modified function monomer after 115 DEG C or so are reacted, salt is neutralized into, regulation pH value is 7~
8, deionized water is added, is reacted at 50 DEG C, obtains the modified aqueous epoxy resin emulsion.Aqueous ring prepared by the method
Oxygen tree fat, can improve the intensity and hydrolytic stability of glue-line.
Preferably, the vistanex includes EVA emulsions, polyvinyl alcohol, Carboxy, aqueous vinyl chloride-vinyl acetate resin
In one or more.
Preferably, the hydrolysis stabilizer be carbodiimides, tert-butyl catechol, hexa,
One or more in azodicarbonamide.
Preferably, the tackifier are Rhelolate295 emulsions and/or H416A emulsions；The auxiliary agent is
One or more in AP7010, DF1181, GS-4013, FS444, FLOW300, N- ethyl pyrrolidone；The polyalcohol is
One or more in ethylene glycol, glycerine, propane diols, trimethylolpropane；The diluent alcohol is ethanol, isopropanol, just
One or more in propyl alcohol.
Second aspect, present invention also offers a kind of aqueous heat-seal adhesive combination for being as previously described for medicine bubble-cap hydrolysis
The preparation method of thing, it comprises the following steps：
By polyester emulsion, modified epoxy resin emulsion, vistanex it is well mixed after, add polyalcohol, diluent alcohol,
Diluent water；
Hydrolysis stabilizer, auxiliary agent and tackifier are added, are cured after stirring；
The solid content of product is detected, and the solid content is adjusted to after 25%, stirring discharging.
Compared with prior art, the present invention has following beneficial effect：
1st, under hot and humid environment, hydrolytic resistance is significantly increased, finished product can transport by sea without having an impact to end properties；
2nd, on high speed medicine-packaging machine, under high temperature heat seal is closed, glue is produced without any smell；
3rd, storage stability is excellent, can be stored more than 12 months under normal temperature；
4th, levelling is preferable, it is only necessary to add a small amount of alcohols and leveling auxiliary agent, cost-effective；
5th, intensity is higher, it is possible to decrease coating dry measure is to 50% or so of original glue-spread, and production cost is substantially reduced；
6th, freeze-thaw stability is excellent, and it is that can be used that the Northeast of China, which is used without heating and melting,；
7th, glue stability is good, and it is unchanged that coated film places 1 year intensity；
8th, it is applied widely, matrix resin content can be formulated by change in relative broad range and adjust heat seal strength, so that
Suitable for different Al foil substrates.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the ordinary skill of this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1
A kind of preparation method suitable for Key works Drug packing hydrolysis-resistant waterborne heat-seal adhesive that the present embodiment is related to, formula is shown in Table
1, this method is comprised the following steps that：
1st, first by whole emulsions, i.e. polyester emulsion, epoxy emulsion, polyolefin emulsion is sequentially added in reactor, and is kept
Stirring；
2nd,, slowly will be molten in the case where being kept stirring for after being pre-mixed whole solvents, i.e. water, diluent alcohol, polyalcohol
Agent is added in reactor, stirring 1h or so；
3rd, it is to be mixed it is uniform after, be slowly added to hydrolysis stabilizer, auxiliary agent, tackifier keep high-speed stirred 30min or so；
4th, after all components are well mixed, curing more than 12 hours is shut down；
5th, solids content is measured, and is adjusted to 25%；
6th, slowly stir 1 hour or so again, weighing and bagging.
Table 1
Embodiment 2
Formula is shown in Table 1, preparation method be the same as Example 1.
Embodiment 3.
Formula is shown in Table 1, preparation method be the same as Example 1.
Embodiment 4
Formula is shown in Table 1, preparation method be the same as Example 1.
HC-411, select day VC, JQ220 that embodiment 1~4 can be sold respectively at existing market are compared, corresponding every
Performance is shown in Table 2.
The sample comparative test result of table 2
From the data in table 2, it can be seen that under same test conditions, embodiment intensity is above control sample intensity 50% or so.High temperature
Under high humidity (60 DEG C, 80%RH) environment, comparative example intensity drops significantly to below 4N, declines degree 61%~78%, shows
Resin hydrolyzing is notable.And intensity only at most declines 1N in embodiment, decline 3~13%, hence it is evident that better than comparative example.Simultaneously because real
Apply example intensity itself higher, the use of thermal extremes super-humid conditions can be met.On the other hand, the freeze thawing resistance stability of embodiment is excellent
Good, cold district not freeze thawing is not required to liquefaction of before rising again, convenient operation.The properties such as another levelling, overfoaming, readily oxidizable substance are equal
Preferably, meet the needs of customers.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (9)
1. a kind of aqueous heat-seal adhesive composition for medicine bubble-cap hydrolysis, it is characterised in that including percentage
Following component：
2. it is used for the aqueous heat-seal adhesive composition of medicine bubble-cap hydrolysis as claimed in claim 1, it is characterised in that described poly-
Ester emulsion includes makrolon base water polyurethane, polyether-modified polyurethane, one kind in silicone modified polyester resin or several
Kind.
3. it is used for the aqueous heat-seal adhesive composition of medicine bubble-cap hydrolysis as claimed in claim 2, it is characterised in that described poly-
The preparation method of carbonate group aqueous polyurethane is：
By oligomer polyol and toluene di-isocyanate(TDI) after 85 DEG C are reacted, bishydroxymethyl propionic acid and two bays are added
Sour dibutyl tin, is reacted at 85 DEG C, adds BDO and trimethylolpropane, and extremely-NCO content is reacted not at 60 DEG C
Change again, obtain performed polymer；
After the pH value of the performed polymer is neutralized into 7.5, adds water and emulsified, obtain the makrolon base water polyurethane.
4. it is used for the aqueous heat-seal adhesive composition of medicine bubble-cap hydrolysis as claimed in claim 1, it is characterised in that the ring
Oxygen tree fat include modified aqueous epoxy resin emulsion, modifying epoxy resin by organosilicon emulsion, polyurethane modified epoxy resin emulsion,
At least one of olefin-modified epoxy resin.
5. the aqueous heat-seal adhesive composition as claimed in claim 1 for medicine bubble-cap hydrolysis as claimed in claim 4,
Characterized in that, the preparation method of the modified aqueous epoxy resin is：
By epoxy resin and modified function monomer after 115 DEG C or so are reacted, salt is neutralized into, regulation pH value is 7~8, plus
Enter deionized water, reacted at 50 DEG C, obtain the modified aqueous epoxy resin emulsion.
6. it is used for the aqueous heat-seal adhesive composition of medicine bubble-cap hydrolysis as claimed in claim 1, it is characterised in that described poly-
Olefin resin includes the one or more in EVA emulsions, polyvinyl alcohol, Carboxy, aqueous vinyl chloride-vinyl acetate resin.
7. it is used for the aqueous heat-seal adhesive composition of medicine bubble-cap hydrolysis as claimed in claim 1, it is characterised in that the water
Solution stabilizer is the one or more in carbodiimides, tert-butyl catechol, hexa, azodicarbonamide.
8. it is used for the aqueous heat-seal adhesive composition of medicine bubble-cap hydrolysis as claimed in claim 1, it is characterised in that the increasing
Stick is Rhelolate295 emulsions and/or H416A emulsions；The auxiliary agent be AP7010, DF1181, GS-4013, FS444,
One or more in FLOW300, N- ethyl pyrrolidone；The polyalcohol is ethylene glycol, glycerine, propane diols, three hydroxyl first
One or more in base propane；The diluent alcohol is the one or more in ethanol, isopropanol, normal propyl alcohol.
9. a kind of preparation method of the aqueous heat-seal adhesive composition as claimed in claim 1 for medicine bubble-cap hydrolysis, its
It is characterised by, comprises the following steps：
After polyester emulsion, modified epoxy resin emulsion, vistanex are well mixed, polyalcohol, diluent alcohol, dilution are added
Agent water；
Hydrolysis stabilizer, auxiliary agent and tackifier are added, are cured after stirring；
The solid content of product is detected, and the solid content is adjusted to after 25%, stirring discharging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710618802.2A CN107312488A (en) | 2017-07-26 | 2017-07-26 | Aqueous heat-seal adhesive composition for medicine bubble-cap hydrolysis and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710618802.2A CN107312488A (en) | 2017-07-26 | 2017-07-26 | Aqueous heat-seal adhesive composition for medicine bubble-cap hydrolysis and preparation method thereof |
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| CN107312488A true CN107312488A (en) | 2017-11-03 |
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| CN201710618802.2A Pending CN107312488A (en) | 2017-07-26 | 2017-07-26 | Aqueous heat-seal adhesive composition for medicine bubble-cap hydrolysis and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112646531A (en) * | 2020-12-25 | 2021-04-13 | 江苏中金玛泰医药包装有限公司 | Low-easy-oxide water-based adhesive for medicine packaging and preparation method thereof |
| CN114907812A (en) * | 2022-06-21 | 2022-08-16 | 武汉弘毅共聚新材料科技有限公司 | Low-viscosity VC adhesive for drug encapsulation and preparation method and application thereof |
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| CN101117377A (en) * | 2007-09-18 | 2008-02-06 | 天津大学 | Method for preparing aqueous epoxy resin |
| CN102604336A (en) * | 2012-03-16 | 2012-07-25 | 天津市普立泰高分子科技有限公司 | Low-smoke, halogen-free and flame-retardant polyester elastomer thin-wall insulating material and preparation method thereof |
| CN104530372A (en) * | 2014-12-25 | 2015-04-22 | 张家港康得新光电材料有限公司 | Water-based polyurethane and preparation method thereof, and composite film with water-based polyurethane |
| CN106221646A (en) * | 2016-08-23 | 2016-12-14 | 上海乘鹰新材料有限公司 | Water fever sealing for medicine bubble-cap and preparation method thereof |
| CN106566400A (en) * | 2016-10-26 | 2017-04-19 | 上海维凯光电新材料有限公司 | Water varnish for protection of printable aluminum foil for drug packing and preparation method of water varnish |
-
2017
- 2017-07-26 CN CN201710618802.2A patent/CN107312488A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101117377A (en) * | 2007-09-18 | 2008-02-06 | 天津大学 | Method for preparing aqueous epoxy resin |
| CN102604336A (en) * | 2012-03-16 | 2012-07-25 | 天津市普立泰高分子科技有限公司 | Low-smoke, halogen-free and flame-retardant polyester elastomer thin-wall insulating material and preparation method thereof |
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| CN106221646A (en) * | 2016-08-23 | 2016-12-14 | 上海乘鹰新材料有限公司 | Water fever sealing for medicine bubble-cap and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112646531A (en) * | 2020-12-25 | 2021-04-13 | 江苏中金玛泰医药包装有限公司 | Low-easy-oxide water-based adhesive for medicine packaging and preparation method thereof |
| CN112646531B (en) * | 2020-12-25 | 2022-03-15 | 江苏中金玛泰医药包装有限公司 | Low-easy-oxide water-based adhesive for medicine packaging and preparation method thereof |
| CN114907812A (en) * | 2022-06-21 | 2022-08-16 | 武汉弘毅共聚新材料科技有限公司 | Low-viscosity VC adhesive for drug encapsulation and preparation method and application thereof |
| CN114907812B (en) * | 2022-06-21 | 2024-01-30 | 武汉弘毅共聚新材料科技有限公司 | Low-viscosity VC glue for medicine packaging and preparation method and application thereof |
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