CN108102036A - Aqueous acrylic modified polyurethane resin and preparation method thereof and aqueous heat-seal adhesive - Google Patents
Aqueous acrylic modified polyurethane resin and preparation method thereof and aqueous heat-seal adhesive Download PDFInfo
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- CN108102036A CN108102036A CN201711366291.6A CN201711366291A CN108102036A CN 108102036 A CN108102036 A CN 108102036A CN 201711366291 A CN201711366291 A CN 201711366291A CN 108102036 A CN108102036 A CN 108102036A
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- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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Abstract
The invention discloses a kind of aqueous acrylic modified polyurethane resins and preparation method thereof and aqueous heat-seal adhesive, aqueous acrylic modified polyurethane resin, and by the way that the reaction of its polymerizable raw material is prepared, the raw materials by weight portion meter includes：300~470 parts of 75~100 parts of aqueous polyurethane, 15~30 parts of acrylate, 1~6 part of initiator, 1~6 part of the first neutralizer and water.The aqueous acrylic modified polyurethane resin of nucleocapsid is obtained by the reaction using core-shell emulsion polymerization for the aqueous acrylic modified polyurethane resin of the present invention, environmental protection, free from extraneous odour, it is high to be used to prepare the heat seal strength of the aqueous heat-seal adhesive of drug bubble-cap, is not in after-tack phenomenon.
Description
Technical field
The present invention relates to heat-seal adhesive technical field, in particular to a kind of aqueous acrylic modified polyurethane resin and
Its preparation method and aqueous heat-seal adhesive.
Background technology
Blister package is most risen earlier than the 1930s from Europe, and China about starts imported technology, equipment in the eighties
And raw material, at first it is single color printing, progressively develops to polychrome and color series printing later.Blister package application is very wide
It is general, it is the main packaging shape in other fields such as flexible packing material with fastest developing speed in recent years and food, health products, drug
Formula.In Key works Drug packing, it is the pit (being referred to as bubble-cap or blister) that drug is placed in the plastic hard plate through plastics sucking moulding
It is interior, then by intaglio printing and scribbled the aluminium foil heat sealing Nian Jie with the plastic hard plate of protective agent and adhesive with one and formed,
So that drug obtains safeguard protection.
At present, the material overwhelming majority used in blister package into bubble base material is polyvinyl chloride (PVC) sheet material；And blister pack
The covering material of dress is essentially all aluminium foil, commonly referred to as PTP aluminium foils.
The standard that China does not determine blister package with aluminium foil coating, but according to country of National Drug Administration
Requirements of medicament packaging container (material) the standard YBB00152002 on Aluminium Foils Packaging for Medicine, we have concluded that aluminum-plastic blister bag
Dress some main requirement of aluminium foil coating：1. with PVC or PVDC heat seals, Heat seal conditions are：155 DEG C ± 5 DEG C of temperature, pressure
Power 0.2MPa, time 1s, tensile testing machine carry out 180 ° of angular direction and remove, and peel strength must not be less than 7.0N/15mm (PVC)；
2. taking four, 100mm × 100mm samples, sample adhesive layer and protective layer are overlapped, are placed on the suitable tablet of a block size, according to
The secondary tablet that 20mm × 20mm is placed on sample and 1.0kg counterweights in 40 DEG C of baking ovens, after keeping the temperature 2h, take out, observation,
Coat side must not be bonded with protection level；3. Painting effect is good；4. readily oxidizable substance content is low.
Medicinal PTP packaging foils VC adhesives currently used in the market are solvent based product, are answered in PTP aluminium foils with plastics
It closes the medical aluminum foil PTP VC adhesives that use in package production and generally belongs to vinyl resins series, when use need to use dilution
Agent is diluted adhesive, but diluent contains substantial amounts of ethyl acetate, butyl acetate, acetone and other organic solvent more, to ring
Border and human body harm are very big, and production equipment need to be cleaned with solvent, form harm to environment and human body again, increase cost.
In addition, organic solvent price is unprecedentedly soaring in recent years, this kind of heat-seal adhesive production cost is caused to steeply rise, further limits it
Application range.
Therefore, PTP, which is packed for the Water-borne modification of heat-seal adhesive, has become the inexorable trend of market development.
The aqueous VC adhesives that occur on the market are all at present aqueous anionic polyurethane resin or with aqueous third
Olefin(e) acid resin compounding use.But it has the following disadvantages：
1. heat seal strength is inadequate；
2. it is after-tacked after winding；
3. readily oxidizable substance is exceeded；
4. import resin is substantially, it is of high cost.
The content of the invention
In view of this, a kind of aqueous acrylic modified polyurethane resin provided by the invention and preparation method thereof and water fever
Sealing preferably overcomes the above-mentioned problems of the prior art and defect, aqueous acrylic modified polyurethane tree of the invention
The aqueous acrylic modified polyurethane resin of nucleocapsid structure is obtained by the reaction using nuclear-shell emulsion polymerization for fat, and environmental protection, free from extraneous odour are used
It is high in the heat seal strength for the aqueous heat-seal adhesive for preparing drug bubble-cap, be not in after-tack phenomenon.
A kind of aqueous acrylic modified polyurethane resin, by the way that the reaction of its polymerizable raw material is prepared, the raw material is pressed
Parts by weight meter includes：75~100 parts of aqueous polyurethane, 15~30 parts of acrylate, 1~6 part of initiator, the first neutralizer 1
~6 parts and 300~470 parts of water.
Further, the initiator is azodiisobutyronitrile.10~15 parts of methyl methacrylate, butyl acrylate 1
~5 parts, 1~5 part of hydroxy-ethyl acrylate, 1~5 part of acrylic acid
Further, first neutralizer is 2-amino-2-methyl-1-propanol.
Further, the acrylate is methyl methacrylate, butyl acrylate, hydroxy-ethyl acrylate and acrylic acid
In at least three kinds.
Further, the aqueous polyurethane by 100~130 parts of polyalcohols, 80~100 parts of isocyanate compounds,
0.04~0.08 part of metal-based catalysts, 23~26 parts of organic solvents, 7~9 parts of hydroxy-ethyl acrylates, 7~10 part of second neutralization
Agent and 630~770 parts of water are prepared.
Further, the polyalcohol for polytetramethylene ether diol, butanediol and dihydromethyl propionic acid in mass ratio
16.67:1:1.83 mixture；The isocyanate compound is isophorone diisocyanate and hexa-methylene diisocyanate
Ester in mass ratio 2:1 mixture；The organic solvent is N-Methyl pyrrolidone；Second neutralizer is triethylamine；Institute
Metal-based catalysts are stated as dibutyl tin laurate, organo-bismuth or organo-bismuth zinc.
The present invention also provides a kind of preparation method of aqueous acrylic modified polyurethane resin, the water soluble acrylic acid changes
Property polyurethane resin be above-mentioned aqueous acrylic modified polyurethane resin；The preparation method includes：
Aqueous polyurethane and acrylate are reacted into 1~1.5h at 80~90 DEG C；Then initiator is added in, 80~85
1~1.5h is reacted at DEG C, 90~95 DEG C of 1~1.5h of reaction is continuously heating to, is cooled to 50~60 DEG C, adding in neutralizer makes pH
It is worth for 8.0~8.5, is filtered after being finally cooled to room temperature.
Further, the filtering is filtered using 300~500 mesh nets.
The present invention also provides a kind of aqueous heat-seal adhesive, by the gross mass of the aqueous heat-seal adhesive for 100% based on, including with
The raw material of lower mass percent：80~90% aqueous acrylic modified polyurethane resins, 0.3~0.5% antifoaming agent, 0.1~
0.5% levelling agent, 0.1~0.5% wetting agent, the water of 1~3% coalescents and surplus；The aqueous acrylic modified poly- ammonia
Ester resin is above-mentioned aqueous acrylic modified polyurethane resin.
Further, the coalescents are alcohol ester 12.
Compared with prior art, a kind of aqueous acrylic modified polyurethane resin of the invention and preparation method thereof and aqueous
The advantageous effect of heat-seal adhesive is：
Nucleocapsid structure is obtained by the reaction using nuclear-shell emulsion polymerization in the aqueous acrylic modified polyurethane resin of the present invention
Aqueous acrylic modified polyurethane resin, environmental protection, free from extraneous odour are used to prepare the heat seal strength of the aqueous heat-seal adhesive of drug bubble-cap
Height is not in after-tack phenomenon.
For the above objects, features and advantages of the present invention is enable to be clearer and more comprehensible, preferred embodiment cited below particularly is made detailed
It is described as follows.
Specific embodiment
It is of the invention for the ease of understanding, it elaborates with reference to the mode of embodiment to technical scheme,
Many details are elaborated in the following description in order to fully understand the present invention.
But the invention can be embodied in many other ways as described herein, those skilled in the art can be with
Similar improvement is done without violating the connotation of the present invention, therefore the present invention is not limited to the specific embodiments disclosed below.
Unless otherwise defined, all technologies used herein and scientific terminology have and the common skill of fields of the present invention
The normally understood identical meaning of art personnel.When there is a conflict, the definition in this specification shall prevail.
Term as used herein：
Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that covering
Non-exclusionism includes.It is wanted for example, composition, step, method, product or device comprising listed elements are not necessarily limited to those
Element, but can include not expressly listed other elements or such composition, step, method, product or device it is intrinsic
Element.
Conjunction " by ... form " exclude any element do not pointed out, step or component.If be used in claim,
This phrase will make claim be closed, it is made not include the material in addition to the material of those descriptions, but relative
Except customary impurities.When phrase " by ... form " be rather than immediately following theme in the clause that appears in claim main body after
When, only it is limited to the element described in the clause；Other elements be not excluded the claim as a whole it
Outside.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value limits, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether the scope separately discloses.For example, when open
During scope " 1~5 ", described scope should be interpreted as including scope " 1~4 ", " 1~3 ", " 1~2 ", " 1~2 and 4~
5 ", " 1~3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise scope intention includes its end
Value and all integers and fraction in the range.
"and/or" is used to represent that one of illustrated situation or both may to occur, for example, A and/or B includes (A
And B) and (A or B).
A kind of aqueous acrylic modified polyurethane resin, by the way that the reaction of its polymerizable raw material is prepared, the raw material is pressed
Parts by weight meter includes：
Such as 75 parts, 80 parts, 85 parts, 90 parts, 95 parts or 100 parts of 75~100 parts of aqueous polyurethane；
Such as 15 parts, 18 parts, 20 parts, 23 parts, 25 parts or 30 parts of 15~30 parts of acrylate；
Such as 1 part, 2 parts, 3 parts, 4 parts, 5 parts or 6 parts of 1~6 part of initiator；
First such as 1 part of 1~6 part of neutralizer, 2 parts, 3 parts, 4 parts, 5 parts or 6 parts；
Such as 300 parts, 330 parts, 350 parts, 380 parts, 400 parts, 420 parts, 450 parts or 470 parts of 300~470 parts of water.
Preferably, the initiator is azodiisobutyronitrile.10~15 parts of methyl methacrylate, butyl acrylate 1~5
Part, 1~5 part of hydroxy-ethyl acrylate, 1~5 part of acrylic acid
Preferably, first neutralizer is 2-amino-2-methyl-1-propanol (AMP-95).Certainly, described first neutralize
Agent can also be ammonium hydroxide, sodium hydroxide or dimethylethanolamine (DMEA) etc..
Further, the acrylate is methyl methacrylate (MMA), butyl acrylate (BA), acrylic acid hydroxyl second
At least three kinds in ester (HEA) and acrylic acid (AA).Preferably.The acrylate is methyl methacrylate (MMA), propylene
Acid butyl ester (BA), hydroxy-ethyl acrylate (HEA) and acrylic acid (AA)
Preferably, the aqueous polyurethane is by 100~130 parts of polyalcohols, 80~100 parts of isocyanate compounds, 0.04
~0.08 part of metal-based catalysts, 23~26 parts of organic solvents, 7~9 parts of hydroxy-ethyl acrylates, 7~10 part of second neutralizer and
630~770 parts of water are prepared.
Specifically, the parts by weight of above-mentioned polyalcohol can be enumerated as 100 parts, 105 parts, 110 parts, 115 parts, 120 parts, 125
Part or 130 parts etc.；The parts by weight of the isocyanate compound can be enumerated as 80 parts, 85 parts, 90 parts, 95 parts or 100 parts etc.；
The parts by weight of the metal-based catalysts can be enumerated as 0.04 part, 0.05 part, 0.06 part, 0.07 part or 0.08 part etc.；It is described
The parts by weight of organic solvent can be enumerated as 23 parts, 24 parts, 25 parts or 26 parts etc.；The parts by weight of the hydroxy-ethyl acrylate can
It is enumerated as 7 parts, 7.5 parts, 8 parts, 8.5 parts or 9 parts etc.；The parts by weight of second neutralizer can be enumerated as 7 parts, 7.5 parts, 8
Part, 8.5 parts, 9 parts, 9.5 parts or 10 parts etc.；The parts by weight of the water can be enumerated as 630 parts, 650 parts, 680 parts, 700 parts,
730 parts, 750 parts or 770 parts etc..
Preferably, the polyalcohol is polytetramethylene ether diol (PTMEG), butanediol (BDO) and dihydromethyl propionic acid
(DMPA) in mass ratio 16.67:1:1.83 mixture；The molecular weight of the polytetramethylene ether diol (PTMEG) is preferably
1000~3000.
The isocyanate compound is isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HDI)
In mass ratio 2:1 mixture.
The organic solvent is N-Methyl pyrrolidone (NMP).
Second neutralizer is triethylamine；It should be noted that second neutralizer can also be ammonium hydroxide, sodium hydroxide
Or dimethylethanolamine (DMEA) etc..
The metal-based catalysts are dibutyl tin laurate, organo-bismuth or organo-bismuth zinc.
The composition principle of above-mentioned aqueous polyurethane is：- OH+NCO-=NHCO-.
The present invention also provides a kind of preparation method of aqueous acrylic modified polyurethane resin, the water soluble acrylic acid changes
Property polyurethane resin be above-mentioned aqueous acrylic modified polyurethane resin；The preparation method includes：
By aqueous polyurethane and acrylate at 80~90 DEG C such as 80 DEG C, 82 DEG C, 85 DEG C, 88 DEG C or 90 DEG C reaction 1~
1.5h；Then initiator is added in, 1~1.5h is reacted at 80~85 DEG C such as 80 DEG C, 81 DEG C, 82 DEG C, 83 DEG C, 84 DEG C or 85 DEG C,
90~95 DEG C of such as 90 DEG C, 91 DEG C, 92 DEG C, 93 DEG C, 94 DEG C or 95 DEG C 1~1.5h of reaction are continuously heating to, are cooled to 50~60
DEG C such as 50 DEG C, 53 DEG C, 55 DEG C, 58 DEG C or 60 DEG C, adding in the first neutralizer makes pH value for 8.0~8.5, after being finally cooled to room temperature
Filtering.
Preferably, the filtering is carried out using the net of 300~500 mesh such as 300 mesh, 350 mesh, 400 mesh, 450 mesh or 500 mesh
Filtering.
The present invention also provides a kind of aqueous heat-seal adhesive, by the gross mass of the aqueous heat-seal adhesive for 100% based on, including with
The raw material of lower mass percent：80~90% aqueous acrylic modified polyurethane resins, 0.3~0.5% antifoaming agent, 0.1~
0.5% levelling agent, 0.1~0.5% wetting agent, the water of 1~3% coalescents and surplus；The aqueous acrylic modified poly- ammonia
Ester resin is above-mentioned aqueous acrylic modified polyurethane resin.
Specifically, the content of above-mentioned aqueous acrylic modified polyurethane resin can be enumerated as 80%, 82%, 85%, 88%
Or 90% etc.；The content of the antifoaming agent can be enumerated as 0.3%, 0.35%, 0.4%, 0.45% or 0.5% etc.；The levelling
The content of agent can be enumerated as 0.1%, 0.2%, 0.3%, 0.4% or 0.5% etc.；The content of the wetting agent can be enumerated as
0.1%th, 0.2%, 0.3%, 0.4% or 0.5% etc.；The content of the coalescents can be enumerated as 1%, 1.5%, 2%,
2.5% or 3% etc..
Preferably, the coalescents are alcohol ester 12.Above-mentioned antifoaming agent can be polyether modified siloxane antifoaming agent；It is described
Levelling agent can be modified poly ester levelling agent；The wetting agent can be polyether modified siloxane wetting agent.
Above-mentioned water is preferably deionized water, naturally it is also possible to for pure water or ultra-pure water etc..
For the ease of understanding the present invention, the technical solution further illustrated the present invention with reference to embodiment.Applicant
Statement, the present invention are illustrated by the following examples detailed process equipment and the technological process of the present invention, but not office of the invention
It is limited to following detailed process equipments and technological process, that is, does not mean that the present invention should rely on above-mentioned detailed process equipment and technique stream
Cheng Caineng is implemented.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to each original of product of the present invention
The equivalence replacement of material and the addition of auxiliary element, the selection of concrete mode etc. all fall within protection scope of the present invention and open model
Within enclosing.
Embodiment 1
(1) aqueous polyurethane is prepared：To with agitating device, thermometer, N2Four mouthfuls of glass flasks of entrance and condenser pipe
The middle polytetramethylene ether diol for adding in 90 parts of molecular weight as 1000,5.4 parts of butanediols, the vacuum dehydration 1h at 110 DEG C,
80 DEG C are cooled to, then adds in 9.9 parts of dihydromethyl propionic acids and 23 parts of N-Methyl pyrrolidones, stirring makes dihydromethyl propionic acid complete
After portion is molten, the mixed liquor of 54 parts of isophorone diisocyanate and 27 parts of hexamethylene diisocyanates, about 1h are added dropwise thereto
It drips off, then adds in 0.04 part of organic bismuth catalyst thereto, be persistently stirred to react 4h, be cooled to 60 DEG C, add in 0.03 part to benzene
7 parts of hydroxy-ethyl acrylates are added dropwise after diphenol, 20min is dripped off, insulation reaction 4h；Add in 7 parts of triethylamines in and 0.5h, add 630 parts
Deionized water, Strong dispersion 0.5h, distills out butanone, obtains translucent aqueous polyurethane.
(2) aqueous acrylic modified polyurethane resin is prepared：75 parts of above-mentioned aqueous polyurethanes are taken, are added in stirring dress
It puts, in four mouthfuls of glass flasks of thermometer, condenser pipe and constant pressure funnel；Then by 10 parts of methyl methacrylates, 5 part third
Reaction bulb is added in after olefin(e) acid butyl ester, 5 parts of hydroxy-ethyl acrylates and 1 part of acrylic acid mixing, is warming up to 85 DEG C；It is stirred for bottoming polymerization
2 parts of initiator monomer solutions are added dropwise from dropping funel in 1h；After being added dropwise, 1h is first reacted at 85 DEG C, is then heated up 90 DEG C,
After the reaction was continued 1h, 50 DEG C are cooled to, it is 8.0~8.5 to add in neutralizer AMP-95 adjustment pH value；Room temperature is finally cooled to,
Using 400 mesh net filtrations to get water type acrylic acid modified polyurethane resin.
(3) aqueous heat-seal adhesive is prepared：80 parts of above-mentioned aqueous acrylic modified polyurethane resins is taken to pour into reaction cylinder, then
It will be added in reaction cylinder, used after 0.3 part of antifoaming agent, 0.1 part of levelling agent, 0.1 part of wetting dilution agent with 1 part of alcohol ester 12
The rotating speed stirring 30min of 500r/min；18.5 deionized waters are added in above-mentioned reaction cylinder again, continue stir 15min to get
Aqueous heat-seal adhesive.
Embodiment 2
(1) aqueous polyurethane is prepared：To with agitating device, thermometer, N2Four mouthfuls of glass flasks of entrance and condenser pipe
The middle polytetramethylene ether diol for adding in 95 parts of molecular weight as 1000,5.7 parts of butanediols, the vacuum dehydration 1h at 110 DEG C,
80 DEG C are cooled to, then adds in 10.5 parts of dihydromethyl propionic acids and 243 parts of N-Methyl pyrrolidones, stirring makes dihydromethyl propionic acid
After whole is molten, the mixed liquor of 58 parts of isophorone diisocyanate and 29 parts of hexamethylene diisocyanates is added dropwise thereto, about
1h is dripped off, then adds in 0.05 part of organic bismuth catalyst thereto, is persistently stirred to react 4h, is cooled to 60 DEG C, 0.03 part of addition is right
7.5 parts of hydroxy-ethyl acrylates are added dropwise after benzenediol, 20min is dripped off, insulation reaction 4h；Add in 7.5 parts of triethylamines in and 0.5h, add
650 parts of deionized waters, Strong dispersion 0.5h distill out butanone, obtain translucent aqueous polyurethane.
(2) aqueous acrylic modified polyurethane resin is prepared：80 parts of above-mentioned aqueous polyurethanes are taken, are added in stirring dress
It puts, in four mouthfuls of glass flasks of thermometer, condenser pipe and constant pressure funnel；Then by 12 parts of methyl methacrylates, 4 part third
Reaction bulb is added in after olefin(e) acid butyl ester, 4 parts of hydroxy-ethyl acrylates and 2 parts of acrylic acid mixing, is warming up to 85 DEG C；It is stirred for bottoming polymerization
2 parts of initiator monomer solutions are added dropwise from dropping funel in 1.5h；After being added dropwise, 1.5h is first reacted at 85 DEG C, then heats up 95
DEG C, after the reaction was continued 1.5h, 60 DEG C are cooled to, it is 8.0~8.5 to add in neutralizer AMP-95 adjustment pH value；Finally it is cooled to
Room temperature, using 300 mesh net filtrations to get water type acrylic acid modified polyurethane resin.
(3) aqueous heat-seal adhesive is prepared：85 parts of above-mentioned aqueous acrylic modified polyurethane resins is taken to pour into reaction cylinder, then
It will be added in reaction cylinder, used after 0.4 part of antifoaming agent, 0.2 part of levelling agent, 0.5 part of wetting dilution agent with 2 parts of alcohol esters 12
The rotating speed stirring 30min of 500r/min；11.9 parts of water are added in above-mentioned reaction cylinder again, continue to stir 15min to get aqueous
Heat-seal adhesive.
Embodiment 3
(1) aqueous polyurethane is prepared：To with agitating device, thermometer, N2Four mouthfuls of glass flasks of entrance and condenser pipe
The middle polytetramethylene ether diol for adding in 100 parts of molecular weight as 1000,6 parts of butanediols, the vacuum dehydration 1h at 110 DEG C,
80 DEG C are cooled to, then adds in 11 parts of dihydromethyl propionic acids and 25 parts of N-Methyl pyrrolidones, stirring makes dihydromethyl propionic acid complete
After portion is molten, 60 parts of isophorone diisocyanate and the mixed liquor with 30 parts of hexamethylene diisocyanates are added dropwise thereto, about
1h is dripped off, then adds in 0.06 part of organic bismuth catalyst thereto, is persistently stirred to react 4h, is cooled to 60 DEG C, 0.03 part of addition is right
8 parts of hydroxy-ethyl acrylates are added dropwise after benzenediol, 20min is dripped off, insulation reaction 4h；Add in 8.5 parts of triethylamines in and 0.5h, add
700 parts of deionized waters, Strong dispersion 0.5h distill out butanone, obtain translucent aqueous polyurethane.
(2) aqueous acrylic modified polyurethane resin is prepared：90 parts of above-mentioned aqueous polyurethanes are taken, are added in stirring dress
It puts, in four mouthfuls of glass flasks of thermometer, condenser pipe and constant pressure funnel；Then by 12 parts of methyl methacrylates, 3 part third
Reaction bulb is added in after olefin(e) acid butyl ester, 3 parts of hydroxy-ethyl acrylates and 3 parts of acrylic acid mixing, is warming up to 82 DEG C；It is stirred for bottoming polymerization
2 parts of initiator monomer solutions are added dropwise from dropping funel in 1h；After being added dropwise, 1h is first reacted at 85 DEG C, is then heated up 90 DEG C,
After the reaction was continued 1h, 50 DEG C are cooled to, it is 8.0~8.5 to add in 3 parts of neutralizer AMP-95 adjustment pH value；Finally it is cooled to room
Temperature, using 400 mesh net filtrations to get water type acrylic acid modified polyurethane resin.
(3) aqueous heat-seal adhesive is prepared：88 parts of above-mentioned aqueous acrylic modified polyurethane resins is taken to pour into reaction cylinder, then
It will be added in reaction cylinder, used after 0.5 part of antifoaming agent, 0.4 part of levelling agent, 0.3 part of wetting dilution agent with 3 parts of alcohol esters 12
The rotating speed stirring 30min of 500r/min；8.8 parts of water are added in above-mentioned reaction cylinder again, continue to stir 15min to get aqueous
Heat-seal adhesive.
Embodiment 4
(1) aqueous polyurethane is prepared：To with agitating device, thermometer, N2Four mouthfuls of glass flasks of entrance and condenser pipe
It is middle to add in the polytetramethylene ether diol, 6.3 parts of butanediols that 105 parts of molecular weight are 1000, the vacuum dehydration at 110 DEG C
1h is cooled to 80 DEG C, then adds in 11.6 parts of dihydromethyl propionic acids and 26 parts of N-Methyl pyrrolidones, and stirring makes dihydroxymethyl third
After sour whole is molten, 66 parts of isophorone diisocyanate and the mixing with 33 parts of hexamethylene diisocyanates are added dropwise thereto
Liquid, about 1h drip off, then add in 0.08 part of organic bismuth catalyst thereto, are persistently stirred to react 4h, are cooled to 60 DEG C, add in 0.03
8.5 parts of hydroxy-ethyl acrylates are added dropwise after part hydroquinone, 20min is dripped off, insulation reaction 4h；Add in 7 parts of triethylamines in and 0.5h,
Add 750 parts of water, Strong dispersion 0.5h distills out butanone, obtains translucent aqueous polyurethane.
(2) aqueous acrylic modified polyurethane resin is prepared：1.5 parts of above-mentioned aqueous polyurethanes are taken, are added in stirring dress
It puts, in four mouthfuls of glass flasks of thermometer, condenser pipe and constant pressure funnel；Then by 13 parts of methyl methacrylates, 3 part third
Reaction bulb is added in after olefin(e) acid butyl ester, 3 parts of hydroxy-ethyl acrylates and 4 parts of acrylic acid mixing, is warming up to 82 DEG C；It is stirred for bottoming polymerization
2 parts of initiator monomer solutions are added dropwise from dropping funel in 1h；After being added dropwise, 1h is first reacted at 82 DEG C, is then heated up 90 DEG C,
After the reaction was continued 1h, 50 DEG C are cooled to, it is 8.0~8.5 to add in 4 parts of neutralizer AMP-95 adjustment pH value；Finally it is cooled to room
Temperature, using 400 mesh net filtrations to get water type acrylic acid modified polyurethane resin.
(3) aqueous heat-seal adhesive is prepared：90 parts of above-mentioned aqueous acrylic modified polyurethane resins is taken to pour into reaction cylinder, then
It will be added in reaction cylinder, used after 0.4 part of antifoaming agent, 0.5 part of levelling agent, 0.4 part of wetting dilution agent with 3 parts of alcohol esters 12
The rotating speed stirring 30min of 500r/min；5.7 parts of deionized waters are added in above-mentioned reaction cylinder again, continue to stir 15min, i.e.,
Obtain aqueous heat-seal adhesive.
Embodiment 5
(1) aqueous polyurethane is prepared：To with agitating device, thermometer, N2Four mouthfuls of glass flasks of entrance and condenser pipe
It is middle to add in the polytetramethylene ether diol, 6.6 parts of butanediols that 110 parts of molecular weight are 1000, the vacuum dehydration at 110 DEG C
1h is cooled to 80 DEG C, then adds in 12.1 parts of dihydromethyl propionic acids and 26 parts of N-Methyl pyrrolidones, and stirring makes dihydroxymethyl third
After sour whole is molten, 66 parts of isophorone diisocyanate and the mixing with 33 parts of hexamethylene diisocyanates are added dropwise thereto
Liquid, about 1h drip off, then add in 0.08 part of organic bismuth catalyst thereto, are persistently stirred to react 4h, are cooled to 60 DEG C, add in 0.03
7 parts of hydroxy-ethyl acrylates are added dropwise after part hydroquinone, 20min is dripped off, insulation reaction 4h；Add in 9.5 parts of triethylamines in and 0.5h,
Add 770 parts of deionized waters, Strong dispersion 0.5h distills out butanone, obtains translucent aqueous polyurethane.
(2) aqueous acrylic modified polyurethane resin is prepared：100 parts of above-mentioned aqueous polyurethanes are taken, are added in stirring dress
It puts, in four mouthfuls of glass flasks of thermometer, condenser pipe and constant pressure funnel；Then by 15 parts of methyl methacrylates, 1 part third
Reaction bulb is added in after olefin(e) acid butyl ester, 1 part of hydroxy-ethyl acrylate and 3 parts of acrylic acid mixing, is warming up to 85 DEG C；It is stirred for bottoming polymerization
3.5 parts of initiator monomer solutions are added dropwise from dropping funel in 1h；After being added dropwise, 1h is first reacted at 85 DEG C, then heats up 90
DEG C, after the reaction was continued 1h, 50 DEG C are cooled to, it is 8.0~8.5 to add in 4 parts of neutralizer AMP-95 adjustment pH value；Finally it is cooled to
Room temperature, using 500 mesh net filtrations to get water type acrylic acid modified polyurethane resin.
(3) aqueous heat-seal adhesive is prepared：90 parts of above-mentioned aqueous acrylic modified polyurethane resins is taken to pour into reaction cylinder, then
It will be added in reaction cylinder, used after 0.5 part of antifoaming agent, 0.5 part of levelling agent, 0.5 part of wetting dilution agent with 3 parts of alcohol esters 12
The rotating speed stirring 30min of 500r/min；5.5 parts of deionized waters are added in above-mentioned reaction cylinder again, continue to stir 15min, i.e.,
Obtain aqueous heat-seal adhesive.
Comparative example 1
(1) aqueous polyurethane is prepared：To with agitating device, thermometer, N2Four mouthfuls of glass flasks of entrance and condenser pipe
The middle polytetramethylene ether diol for adding in 100 parts of molecular weight as 1000,6 parts of butanediols, the vacuum dehydration 1h at 110 DEG C,
80 DEG C are cooled to, then adds in 11 parts of dihydromethyl propionic acids and 25 parts of N-Methyl pyrrolidones, stirring makes dihydromethyl propionic acid complete
After portion is molten, 60 parts of isophorone diisocyanate and the mixed liquor with 30 parts of hexamethylene diisocyanates are added dropwise thereto, about
1h is dripped off, then adds in 0.06 part of organic bismuth catalyst thereto, is persistently stirred to react 4h, is cooled to 60 DEG C, 0.03 part of addition is right
8 parts of hydroxy-ethyl acrylates are added dropwise after benzenediol, 20min is dripped off, insulation reaction 4h；Add in 8.5 parts of triethylamines in and 0.5h, add
700 parts of deionized waters, Strong dispersion 0.5h distill out butanone, obtain translucent aqueous polyurethane.
(2) aqueous heat-seal adhesive is prepared：88 parts of above-mentioned aqueous polyurethanes is taken to pour into reaction cylinder, then with 3 parts of alcohol esters 12
It will be added to after 0.5 part of antifoaming agent, 0.4 part of levelling agent, 0.3 part of wetting dilution agent in reaction cylinder, using the rotating speed of 500r/min
Stir 30min；8.8 parts of deionized waters are added in above-mentioned reaction cylinder again, continue to stir 15min to get aqueous heat-seal adhesive.
Aqueous heat-seal adhesive and commercially available aqueous VC adhesives prepared by Examples 1 to 5 and comparative example 1 is coated on aluminium foil
On, then 9s is toasted in the case where temperature is 170 DEG C, it winds, then hot pressing is bonded 1s at 240 DEG C with PVC；And it smell during to hot pressing, returns
Sticky to be detected with peel strength, testing result is as shown in table 1 below.
Wherein, peel strength is bigger, and the heat seal strength of aqueous heat-seal adhesive is higher；
After-tack performance：It is pressed against after winding with the counterweight of 7N after being put into and being toasted for 24 hours in 70 DEG C of baking oven, sees whether to return
It is viscous.
Table 1
It can be drawn by upper table 1, the heat seal strength of aqueous heat-seal adhesive prepared by the embodiment of the present invention 1~5 is significantly better than that pair
Aqueous heat-seal adhesive and the heat seal strength of commercially available aqueous VC adhesives prepared by ratio 1；And the preparation of the embodiment of the present invention 1~5
Aqueous heat-seal adhesive free from extraneous odour, is not in after-tack phenomenon；And aqueous heat-seal adhesive and commercially available aqueous VC prepared by comparative example 1 bonds
Agent, which has peculiar smell and can generate, after-tacks phenomenon.
The preferred embodiment of the present invention is above are only, is not intended to limit the invention, for those skilled in the art
For member, inventive formulation and preparation process can have various modifications and variations.Within the spirit and principles of the invention, institute
Any modification, equivalent substitution, improvement and etc. of work, should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of aqueous acrylic modified polyurethane resin, it is characterised in that：By the way that the reaction of its polymerizable raw material is prepared, institute
Stating raw materials by weight portion meter includes：75~100 parts of aqueous polyurethane, 15~30 parts of acrylate, 1~6 part of initiator, first
300~470 parts of 1~6 part of neutralizer and water.
2. aqueous acrylic modified polyurethane resin according to claim 1, it is characterised in that：The initiator is azo
Bis-isobutyronitrile.
3. aqueous acrylic modified polyurethane resin according to claim 1, it is characterised in that：First neutralizer is
2-amino-2-methyl-1-propanol.
4. aqueous acrylic modified polyurethane resin according to claim 1, it is characterised in that：The acrylate is first
At least three kinds in base methyl acrylate, butyl acrylate, hydroxy-ethyl acrylate and acrylic acid.
5. aqueous acrylic modified polyurethane resin according to claim 1, it is characterised in that：The aqueous polyurethane by
100~130 parts of polyalcohols, 80~100 parts of isocyanate compounds, 0.04~0.08 part of metal-based catalysts, 23~26 parts have
Solvent, 7~9 parts of hydroxy-ethyl acrylates, 7~10 part of second neutralizer and 630~770 parts of water are prepared.
6. aqueous acrylic modified polyurethane resin according to claim 5, it is characterised in that：The polyalcohol is poly- four
Methylene ether glycol, butanediol and dihydromethyl propionic acid in mass ratio 16.67:1:1.83 mixture；The isocyanation esterification
It is isophorone diisocyanate and hexamethylene diisocyanate in mass ratio 2 to close object:1 mixture；The organic solvent
For N-Methyl pyrrolidone；Second neutralizer is triethylamine；The metal-based catalysts are dibutyl tin laurate, have
Machine bismuth or organo-bismuth zinc.
7. a kind of preparation method of aqueous acrylic modified polyurethane resin, it is characterised in that：It is described aqueous acrylic modified poly-
Urethane resin is the aqueous acrylic modified polyurethane resin of claim 1~6 any one of them；The preparation method includes：
Aqueous polyurethane and acrylate are reacted into 1~1.5h at 80~90 DEG C；Then initiator is added in, at 80~85 DEG C
1~1.5h is reacted, 90~95 DEG C of 1~1.5h of reaction is continuously heating to, is cooled to 50~60 DEG C, adding in the first neutralizer makes pH
It is worth for 8.0~8.5, is filtered after being finally cooled to room temperature.
8. the preparation method of aqueous acrylic modified polyurethane resin according to claim 7, it is characterised in that：The mistake
Filter is filtered using 300~500 mesh nets.
9. a kind of aqueous heat-seal adhesive, it is characterised in that：It is based on 100%, including following matter by the gross mass of the aqueous heat-seal adhesive
Measure the raw material of percentage：80~90% aqueous acrylic modified polyurethane resins, 0.3~0.5% antifoaming agent, 0.1~0.5% stream
Flat agent, 0.1~0.5% wetting agent, the water of 1~3% coalescents and surplus；The aqueous acrylic modified polyurethane resin is
The aqueous acrylic modified polyurethane resin of claim 1~6 any one of them.
10. aqueous heat-seal adhesive according to claim 9, it is characterised in that：The coalescents are alcohol ester 12.
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| CN113150477A (en) * | 2021-05-25 | 2021-07-23 | 东莞市冠力胶业有限公司 | High-stability absorbent plastic and preparation method thereof |
| CN113214585A (en) * | 2021-05-25 | 2021-08-06 | 东莞市冠力胶业有限公司 | Water-based water-absorbent plastic and preparation method thereof |
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