CN109609065A - A kind of aluminizer compound adhesive and preparation method thereof - Google Patents
A kind of aluminizer compound adhesive and preparation method thereof Download PDFInfo
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- CN109609065A CN109609065A CN201811344364.6A CN201811344364A CN109609065A CN 109609065 A CN109609065 A CN 109609065A CN 201811344364 A CN201811344364 A CN 201811344364A CN 109609065 A CN109609065 A CN 109609065A
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- parts
- compound adhesive
- water
- itaconic acid
- aluminizer
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- 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
- C09J135/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention belongs to adhesive field fields, and in particular to a kind of aluminizer compound adhesive and preparation method are prepared by following component ratio: itaconic acid, and 35 parts；Butyl acrylate, 15 parts；Ethyl acrylate, 20 parts；Hydroxy propyl methacrylate, 10 parts；Azodiisobutyronitrile, 10 parts；Tert-dodecyl mercaptan, 3 parts；Diethyl ethylene diamine, 5 parts；Water-base epoxy phosphate, 7 parts；The preparation method of above-mentioned aluminizer compound adhesive is to sequentially add itaconic acid, butyl acrylate, ethyl acrylate, hydroxy propyl methacrylate and diethyl ethylene diamine, is stirred 30 minutes under 600~800r/min revolving speed；Azodiisobutyronitrile and tert-dodecyl mercaptan is added, is stirred 10 minutes under 800~1000r/min revolving speed；Water-base epoxy phosphate is added, under 500~600r/min revolving speed, stirs 10 minutes.Compound adhesive caking property of the present invention is good, and water resistance and heat-resisting quantity are good.
Description
Technical field
The invention belongs to adhesive fields, and in particular to a kind of aluminizer compound adhesive and preparation method thereof.
Background technique
Aluminizer is to be plated one layer of very thin metallic aluminium using special process on plastic film (PET base material) surface and formed
A kind of composite soft packaging material, the processing method of most common of them is exactly to lead under high vacuum state when the vacuum aluminum-coated methods of number
It crosses high temperature and metallic aluminium is melted into evaporation, be stacked into the steam precipitation of aluminium on PET base material surface, so that PET base material surface be made to have
There is metallic luster.Since it had not only had a characteristic of plastic film, but also the characteristic with metal, be it is a kind of it is cheap it is beautiful, performance is excellent
Good, practical packaging material is widely used in the packaging of all kinds of dry goods (tealeaves, candy etc), while can also answer
It is packed for jam, pickles, flavouring, high-temperature sterilization food, agriculture chemicals etc..In process of production, when PET base material is not aluminized
Before, the precoating treatment for needing to carry out water soluble acrylic acid primer, makes aluminium layer and PET base material obtains certain binding force, so as to
Processing.
Existing aluminizer glue is mostly water-and acrylate polymerized emulsion, since it is desired that having to PET material stronger viscous
Relay.From the point of view of the range that the use of aluminizer is related to, aluminizer can touch all kinds of poor environments, such as high temperature, each class I liquid I,
And existing aluminizer is using aluminizer can be because of aluminizer glue non-refractory at a high temperature of long-time after such aluminizer glue
The case where reason cracks；Again because the reason of aluminizer glue poor water resistance takes off under the washing away or contact of aqueous
It falls, to influence the scope of application of the aluminizer.
Summary of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, to provide a kind of aluminizer with compound
Glue and preparation method thereof.
The technical solution adopted by the present invention to solve the technical problems is: a kind of aluminizer compound adhesive, it is characterised in that:
Raw material includes itaconic acid, butyl acrylate, ethyl acrylate, hydroxy propyl methacrylate (HPMA), azodiisobutyronitrile
(AIBN), tert-dodecyl mercaptan, diethyl ethylene diamine and water-base epoxy phosphate, by following component example preparation in mass ratio
At: itaconic acid, 25-35 parts；Butyl acrylate, 10-15 parts；Ethyl acrylate, 15-20 parts；Hydroxy propyl methacrylate, 5-10
Part；Azodiisobutyronitrile, 10-15 parts；Tert-dodecyl mercaptan, 3-5 parts；Diethyl ethylene diamine, 5-10 parts；Water-base epoxy phosphate,
5-7 parts.
Preferably, with compound adhesive, its raw material is specifically formulated by following component example in mass ratio aluminizer；Itaconic acid, 35
Part；Butyl acrylate, 15 parts；Ethyl acrylate, 20 parts；Hydroxy propyl methacrylate, 10 parts；Azodiisobutyronitrile, 10 parts；Uncle
Lauryl mercaptan, 3 parts；Diethyl ethylene diamine, 5 parts；Water-base epoxy phosphate, 7 parts.
A kind of preparation method of above-mentioned aluminizer compound adhesive, which comprises the steps of:
(1) itaconic acid, butyl acrylate, ethyl acrylate, hydroxy propyl methacrylate and diethyl ethylene diamine are successively added
Enter into stirred tank, under 600~800r/min speed conditions, stirs 30min；
(2) azodiisobutyronitrile is added and tert-dodecyl mercaptan continues to stir under 800~1000r/min speed conditions
10min；
(3) water-base epoxy phosphate is added, in the case where 500~600r/min speed conditions, stirs 10min, is aluminized
Film compound adhesive.
Compared to the prior art the present invention, has the following advantages that and effect:
(1) itaconic acid is utilized to replace material based on acrylic acid, itaconic acid is containing there are two each other while playing close cohesive force
γ carboxyls can form stronger hydrogen bond mutually, can there is preferable water resistance after film forming, improve the adhesive force to substrate,
The time for saving hybrid reaction reduces preparation cost simultaneously；
(2) acrylic acid that the acrylic resin synthesized using itaconic acid as carboxylic monomer is synthesized with using acrylic acid as carboxylic monomer
Resin is compared, and glass transition temperature is lower, can be reduced the dosage of soft monomer, reduces the production cost of the compound adhesive, reduces film forming
Auxiliary dosage can directly wind after making PET film coating baking, the row of organic matter is reduced while improving the efficiency of coating line
It puts；
(3) water-base epoxy phosphate is added in hybrid reaction, is made by water-base epoxy phosphoric acid device self structure mixed multiple
Closing glue has good heat resistance, while can also improve compound adhesive to the adhesive force of metal base.
Specific embodiment
It is understandable in order to enable the above objects, features and advantages of the present invention to become apparent, below to of the invention specific
Embodiment is described in detail.
, aluminizer compound adhesive raw material Selecting research
Existing aluminizer glue is generally water-and acrylate polymerized emulsion, and in order to improve the use of such aluminizer glue operation
Property, it can also add the auxiliary agents such as levelling agent, defoaming agent.Acrylic ester polymerization lotion, that is, acrylic acid, the butyl acrylate, propylene of routine
The mixed emulsion of sour methyl esters, now in order to promote the water resistance of the aluminizer glue, by the experiment screening of multiple and different proportions, by third
Olefin(e) acid replaces with itaconic acid.Itaconic acid compares acrylic acid, has similar cohesive force, while itaconic acid is containing there are two γ each other
Carboxyl can form stronger hydrogen bond mutually, can there is preferable water resistance after film forming.Two γ carboxyls each other, can be improved pair
The adhesive force of substrate, moreover it is possible to form chelate with metal ion, therefore the acrylic acid primer synthesized can be using tap water as it
Diluent can be time saving while reducing cost without with deionized water.
On the other hand, under the conditions of identical acid value, the acrylic resin that is synthesized using itaconic acid as carboxylic monomer with third
Olefin(e) acid is compared as the acrylic resin that carboxylic monomer synthesizes, the former glass transition temperature is lower, therefore is replaced using itaconic acid
Acrylic acid can be reduced the dosage of soft monomer, reduce the production cost of the compound adhesive.And suitably reduce the glass of acrylic resin
Change temperature, reduce coalescing agent dosage, can directly be wound after making PET film coating baking.Coating line can be improved in this way
Efficiency reduces the discharge of organic matter.
Further, select hydroxy propyl methacrylate as additive and main bridging property in all kinds of polymerized monomers
Monomer can be improved the efficiency of mixing.In addition, in order to make raw material preferably carry out hybrid reaction in process,
Azodiisobutyronitrile and tert-dodecyl mercaptan are added as initiator, reduces the time of the copolymerization mixed process.And 12 sulphur of uncle
Pure and mild acrylic emulsion system is not sufficiently stable in hybrid reaction, selects diethyl ethylene diamine that mixing is added with certain proportion,
It can play in the polymerization and adjust stable effect.
Further, in order to improve the heat resistance of the compound adhesive, choose multiclass have the resin of certain heat resistance into
Row addition proportioning test screening, finally selects to add water-base epoxy phosphate in polymerized emulsion monomer.Pass through water-base epoxy phosphorus
Sour device self structure makes mixed compound adhesive have good heat resistance, while also can be further improved compound adhesive to metal
The adhesive force of substrate.
Based on above-mentioned, the raw material of aluminizer compound adhesive includes itaconic acid, butyl acrylate, ethyl acrylate, methyl-prop
Olefin(e) acid hydroxypropyl acrylate (HPMA), azodiisobutyronitrile (AIBN), tert-dodecyl mercaptan, diethyl ethylene diamine and water-base epoxy phosphoric acid
Ester is formulated by following component example in mass ratio: itaconic acid, and 25-35 parts；Butyl acrylate, 10-15 parts；Ethyl acrylate,
15-20 parts；Hydroxy propyl methacrylate, 5-10 parts；Azodiisobutyronitrile, 10-15 parts；Tert-dodecyl mercaptan, 3-5 parts；Diethyl
Ethanol amine, 5-10 parts；Water-base epoxy phosphate, 5-7 parts.
, aluminizer compound adhesive quality proportioning preferred research
Embodiment 1-8.
The optimization formula ingredient and its mass fraction of the present embodiment, as shown in table 1 below:
Test method
The raw material proportioning of 1-8 obtains compound adhesive through this embodiment, is detected using following methods:
1, caking property, by compound adhesive coated in PET base material, metallic film in covering is rolled twice by 2KG idler wheel, is taken out
After do glue peel strength test.
2, compound adhesive is coated in PET base material, metal foil in covering by water resistance with the testing standard of K6857-1973
Film is placed in normal-temperature water after its film forming and impregnates (simulated time 72H), and using current scour, (simulated time is
48H), it is observed after taking-up.
Compound adhesive performance parameter made from embodiment 1-8 is as shown in table 2 below:
Matching obtained compound adhesive by embodiment 6 known to the test of embodiment 1-8 has better caking property and good
Water resistance.
Embodiment 9-14.
Water-base epoxy phosphate, the conduct pair of simultaneous selection embodiment 8 is added in the optimization formula embodiment 6 that above-mentioned experiment obtains
As usual, specific mass fraction is as indicated at 3:
Test method
The raw material proportioning of 9-14 obtains adhesive through this embodiment, is detected using following methods:
1, caking property, by compound adhesive coated in PET base material, metal in covering is rolled twice by 2KG idler wheel, is done after taking-up
Glue peel strength test.
2, water boiling resistance detects, and by compound adhesive coated in PET base material, metallic film in covering is put into after its film forming
In 100 DEG C of water, after spending 30 minutes, takes out, observed.The test can detect water resistance and heat-resisting quantity simultaneously.
Compound adhesive performance parameter made from embodiment 9-14 is as shown in table 4 below:
By the way that embodiment 11 matches obtained compound adhesive water resistance known to the test of embodiment 9-14 and heat-resisting ability is good, have
Very strong caking property is best.
Test based on the above embodiment, this aluminizer with compound adhesive raw material preferably by following component in mass ratio example prepare and
At: itaconic acid, 35 parts；Butyl acrylate, 15 parts；Ethyl acrylate, 20 parts；Hydroxy propyl methacrylate, 10 parts；Azo two is different
Butyronitrile, 10 parts；Tert-dodecyl mercaptan, 3 parts；Diethyl ethylene diamine, 5 parts；Water-base epoxy phosphate, 7 parts.
, aluminizer compound adhesive production technology research
The preparation method of above-mentioned aluminizer compound adhesive, includes the following steps:
(1) itaconic acid, butyl acrylate, ethyl acrylate, hydroxy propyl methacrylate and diethyl ethylene diamine are successively added
Enter into stirred tank, under 600~800r/min speed conditions, stirs 30min；
(2) azodiisobutyronitrile is added and tert-dodecyl mercaptan continues to stir under 800~1000r/min speed conditions
10min；
(3) water-base epoxy phosphate is added, in the case where 500~600r/min speed conditions, stirs 10min, is aluminized
Film compound adhesive.
First mixed emulsion forms stabilising system in preparation process, adds water-base epoxy phosphate, can be improved mixing effect
Rate, while making entire emulsion system more evenly.
The key technical indexes for the aluminizer compound adhesive that the present invention is described: 1, appearance: milky thick liquid (mesh
It surveys)；2, solid content (%): 50 ± 1 (ISO 3251)；3, viscosity (cPs/25 DEG C): 200-300(ISO 976).
The aluminizer that is described of the present invention replaces material based on acrylic acid with compound adhesive with itaconic acid, plays close bonding
γ carboxyls can form stronger hydrogen bond mutually to itaconic acid each other containing there are two while power, can have after film forming preferable resistance to
It is aqueous；Two γ carboxyls each other, can be improved the adhesive force to substrate, moreover it is possible to be formed and be chelated with metal ion in itaconic acid
Object, therefore the acrylic acid primer synthesized can be using tap water as its diluent, without with deionized water, it can be time saving
Cost is reduced simultaneously.What the acrylic resin synthesized using itaconic acid as carboxylic monomer was synthesized with using acrylic acid as carboxylic monomer
Acrylic resin is compared, the former glass transition temperature is lower, is replaced acrylic acid using itaconic acid, be can be reduced the dosage of soft monomer,
Reduce the production cost of the compound adhesive.And suitably reduce the glass transition temperature of acrylic resin, moreover it is possible to reduce coalescing agent use
Amount can directly wind after making PET film coating baking, the discharge of organic matter is reduced while improving the efficiency of coating line.This
Outside, water-base epoxy phosphate is added in hybrid reaction, and mixed compound adhesive is made by water-base epoxy phosphoric acid device self structure
There is good heat resistance, while also can be further improved compound adhesive to the adhesive force of metal base.
Above content is only illustrations made for the present invention described in this specification.Technology belonging to the present invention
The technical staff in field can make various modifications or additions to the described embodiments or by a similar method
Substitution, content without departing from description of the invention or beyond the scope defined by this claim should belong to this
The protection scope of invention.
Claims (3)
1. a kind of aluminizer compound adhesive, it is characterised in that: raw material includes itaconic acid, butyl acrylate, ethyl acrylate, methyl
Hydroxypropyl acrylate (HPMA), azodiisobutyronitrile (AIBN), tert-dodecyl mercaptan, diethyl ethylene diamine and water-base epoxy phosphoric acid
Ester is formulated by following component example in mass ratio:
Itaconic acid, 25-35 parts；
Butyl acrylate, 10-15 parts；
Ethyl acrylate, 15-20 parts；
Hydroxy propyl methacrylate, 5-10 parts；
Azodiisobutyronitrile, 10-15 parts；
Tert-dodecyl mercaptan, 3-5 parts；
Diethyl ethylene diamine, 5-10 parts；
Water-base epoxy phosphate, 5-7 parts.
2. aluminizer compound adhesive according to claim 1, which is characterized in that specifically matched by following component example in mass ratio
It makes:
Itaconic acid, 35 parts；
Butyl acrylate, 15 parts；
Ethyl acrylate, 20 parts；
Hydroxy propyl methacrylate, 10 parts；
Azodiisobutyronitrile, 10 parts；
Tert-dodecyl mercaptan, 3 parts；
Diethyl ethylene diamine, 5 parts；
Water-base epoxy phosphate, 7 parts.
3. a kind of preparation method of above-mentioned aluminizer compound adhesive, which comprises the steps of:
(1) itaconic acid, butyl acrylate, ethyl acrylate, hydroxy propyl methacrylate and diethyl ethylene diamine are successively added
Enter into stirred tank, under 600~800r/min speed conditions, stirs 30min；
(2) azodiisobutyronitrile is added and tert-dodecyl mercaptan continues to stir under 800~1000r/min speed conditions
10min；
(3) water-base epoxy phosphate is added, in the case where 500~600r/min speed conditions, stirs 10min, is aluminized
Film compound adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811344364.6A CN109609065A (en) | 2018-11-13 | 2018-11-13 | A kind of aluminizer compound adhesive and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811344364.6A CN109609065A (en) | 2018-11-13 | 2018-11-13 | A kind of aluminizer compound adhesive and preparation method thereof |
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| CN109609065A true CN109609065A (en) | 2019-04-12 |
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| CN201811344364.6A Pending CN109609065A (en) | 2018-11-13 | 2018-11-13 | A kind of aluminizer compound adhesive and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1077455A (en) * | 1996-08-30 | 1998-03-24 | Mitsubishi Chem Basf Co Ltd | Adhesive composition for dry laminate |
| CN105602494A (en) * | 2016-02-26 | 2016-05-25 | 苏州三和开泰花线织造有限公司 | Organosilicone modified waterborne acrylate electrostatic flocking formaldehyde-free adhesive and preparation method thereof |
| CN107286797A (en) * | 2017-05-11 | 2017-10-24 | 湖北大学 | Self-emulsified aqueous epoxy phosphate anti-corrosion emulsion and preparation method thereof |
| CN108003816A (en) * | 2017-11-16 | 2018-05-08 | 广东佰合新材料科技股份有限公司 | A kind of compound special-purpose aqueous glue of aluminizer and preparation method thereof |
-
2018
- 2018-11-13 CN CN201811344364.6A patent/CN109609065A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1077455A (en) * | 1996-08-30 | 1998-03-24 | Mitsubishi Chem Basf Co Ltd | Adhesive composition for dry laminate |
| CN105602494A (en) * | 2016-02-26 | 2016-05-25 | 苏州三和开泰花线织造有限公司 | Organosilicone modified waterborne acrylate electrostatic flocking formaldehyde-free adhesive and preparation method thereof |
| CN107286797A (en) * | 2017-05-11 | 2017-10-24 | 湖北大学 | Self-emulsified aqueous epoxy phosphate anti-corrosion emulsion and preparation method thereof |
| CN108003816A (en) * | 2017-11-16 | 2018-05-08 | 广东佰合新材料科技股份有限公司 | A kind of compound special-purpose aqueous glue of aluminizer and preparation method thereof |
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Application publication date: 20190412 |