CN104277188B - Self-crosslinking acrylate emulsion as well as preparation method and application thereof - Google Patents
Self-crosslinking acrylate emulsion as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a self-crosslinking acrylate emulsion as well as a preparation method and an application thereof. The self-crosslinking acrylate emulsion contains a macromonomer having the following structure shown in the specification. According to the self-crosslinking acrylate emulsion, by introducing the macromonomer having a long-side-chain structure and phenol-terminated isocyanate groups into the acrylate emulsion, the self-curing at a high temperature of the emulsion is achieved and the adhesive force between a polyester film and a functional coating is effectively improved. After the emulsion prepared by the preparation method disclosed by the invention and a coating liquid prepared from a matting agent and water are coated on the surface of the polyester coating and are subjected to thermocuring to form a film, the surface performance of film-formed latex can be significantly improved and the polyester film surface coating, the whole of which cannot fall off when the coating is boiled in water for 30 minutes, is prepared.
Description
Technical field
The present invention relates to macromolecule emulsion preparing technical field, particularly a kind of mylar primary coat self-crosslinking acrylic
Ester emulsion and preparation method thereof.
Background technology
Biaxial stretching polyester (BOPET) thin film is a kind of thin-film material of excellent performance, is widely used in electrical equipment, packaging
With production fields such as sensitive materials.Being continually changing with the market demand, is modified to mylar having become as one kind and
Gesture, coats one layer of chemical substance (as ink, adhesive) in polyester film surface, can give thin film special performance, can expand
The use field of thin film.But the surface tension of mylar is relatively low, ink easily occurs, phenomenon that adhesive comes off it is impossible to
Meet use requirement it is therefore necessary to its modifying surface, to improve its surface property, improve it and functional coating between
Adhesive force.
In prior art, such as acrylic acid ester emulsion for improving mylar adhesive force of Zhou Shoufa and preparation method thereof
Chinese patent application, be reaction monomers from hard monomer, soft monomer and function monomer, synthesized a kind of third using polymerisation in solution
Olefin(e) acid ester emulsion, and it is coated on BOPET film surface, to improve the surface property of BOPET film, improve thin film attachment
Power.Yin Wu select acrylic acid, butyl acrylate, methyl methacrylate, emulsifying agent alkylphenol polyoxyethylene (OP-10), ten
Dialkyl sulfonates (SDS), surface active monomer 2- acrylamide -2- methyI-oropvD sodium sulfonate (AMPS) close for reaction raw materials
Become Soap-Free Acrylate Emulsion, be prepared for the acrylic acid ester emulsion that adhesive force grade is 1 grade.
Although the acrylic emulsion that above-mentioned technology provides can improve the surface property of mylar, in practical application
In, aforesaid propylene acid esters emulsion needs additional firming agent, just enables to be fully cured, and easily causes and joins that liquid program is loaded down with trivial details and external reinforcement
Agent reactivity is higher, leads to coating fluid to need the disadvantage now with the current, effect duration is short.
Content of the invention
The technical problem to be solved is the defect and deficiency for prior art, provides a kind of selfing bipropenyl
Acid esters emulsion, after this acrylic acid ester emulsion is coated on polyester film surface, can improve after longitudinally, laterally stretching and high-temperature shaping
Adhesive force between mylar and functional coating, is prepared for 30 minutes 100% adeciduate mylar coatings of decocting in water.
The invention solves the problems that another technical problem be the preparation method that above-mentioned self-crosslinking acrylic emulsion is provided.
The present invention the 3rd technical problem also to be solved is the polyester providing surface to be coated with aforesaid propylene yogurt liquid
Film.
For solving above-mentioned technical problem, the present invention adopts following technical proposals：
A kind of self-crosslinking acrylic ester emulsion, contains the macromole of following structure in described self-crosslinking acrylic ester strand
Monomer：
Wherein：R isN is 15～35.
A kind of method preparing above-mentioned self-crosslinking acrylic ester emulsion, it comprises the steps：
(1) add 50～100 mass parts N-Methyl pyrrolidone, 10～50 mass parts isophorones two different in the reactor
Cyanate, Deca 5～20 mass parts phenol under room temperature, it is warming up to 40～70 DEG C of reaction 2～4h, add 50～450 mass parts
Polyether polyol is simultaneously warming up to 75～85 DEG C, and insulation reaction 1～2h adds the hydroquinone of 0.05～0.25 mass parts, and
It is warming up to 85～100 DEG C, add the allyl glycidyl ether of 0.2～0.25 mass parts p-methyl benzenesulfonic acid and 5～25 mass parts,
Insulation reaction 2～4h, obtains macromonomer after cooling.
(2) 150～250 mass parts deionized waters and 0.5～2.5 mass parts reactive emulsifier is taken to add another reactor
In, it is uniformly mixed, obtain mixture A, standby；
(3) by above-mentioned for 2～10 mass parts macromonomer, the ethylene glycol dimethacrylate of 2～5 mass parts, 10～
The functional monomer mixing of the hard monomer of 35 mass parts, the soft monomer of 10～35 mass parts and 5～15 mass parts, obtains mix monomer
B, standby；
(4) weigh the mixture A of 1/5～1/2 mass, and add 0.5～1.5 mass parts initiator, obtain initiator solution,
Standby；
(5) 0.4～1.2 mass parts pH buffer and 1/10～1/4 matter are added in the reactor containing remaining mixture A
Mix monomer B, the pre-emulsification 20～40min of amount, is warming up to 75～85 DEG C, Deca initiator solution, and in question response device, liquid becomes
Lan Hou, is simultaneously added dropwise initiator solution and remaining mix monomer B, is incubated 1.5～4h, is cooled to 40～60 DEG C, plus alkali after adding
It is 7～8 that liquid adjusts pH value, obtains self-crosslinking acrylic ester emulsion.
Said method, described polyether polyol includes the polypropylene glycol that molecular weight is 1000～2000.
Said method, described reactive emulsifier is sodium p styrene sulfonate, in polyoxyalkylene nonyl 2, 2-Oxydiphenol acrylate
One kind or combination in any.
Said method, described hard monomer is one of styrene, vinylacetate, acrylic acid methyl ester. or combination in any.
Said method, described soft monomer is n-butyl acrylate, Isobutyl 2-propenoate, ethyl acrylate, butyl acrylate
One of or combination in any.
Said method, described functional monomer is acrylic acid, methacrylic acid, THFMA, methyl
One of isobornyl acrylate, 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate or combination in any.
Said method, described initiator is one of potassium peroxydisulfate, Ammonium persulfate. or combination in any；Described pH buffering
Agent is one of sodium bicarbonate, disodium hydrogen phosphate or combination in any.
Said method, described alkali liquor is ammonia, N, one of N- dimethylethanolamine or combination in any.
A kind of mylar, the bottom that aforesaid propylene acid esters emulsion is made is contained at least one surface.
Compared with prior art, the invention has the advantages that：
1. the acrylic acid ester emulsion that the present invention provides, introduces a kind of macromonomer, this monomer has long side in strand
Chain structure, by introducing long side-chain structure in the structure, can be effectively improved the adhesive force between mylar and functional coating.
2. the acrylic acid ester emulsion that the present invention provides need not add firming agent, simplify and join liquid program, the coating fluid preparing
Can standing time long, it is to avoid firming agent class coating fluid need to be added to need now with the current problem, and the introducing of isocyanate groups,
The adhesive force between mylar and functional coating can be improved further.
3. the mylar that the present invention provides, adhesive force is excellent, and after coating function layer, after decocting in water, functional layer is difficult for drop-off.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, but embodiments of the present invention are not
It is limited to this.
Embodiment 1
1. the preparation of self-crosslinking acrylic ester emulsion
(1) 80gN- methyl pyrrolidone, 30g isophorone diisocyanate, Deca under room temperature are added in the reactor
12g phenol, is warming up to 50 DEG C of reaction 3h, adds the polypropylene glycol (M of 200gw=1500) and be warming up to 80 DEG C, insulation reaction
1.5h, adds the hydroquinone of 0.2g, and is warming up to 90 DEG C；Add the allyl glycidyl of 0.2g p-methyl benzenesulfonic acid and 16g
Glycerin ether, carries out insulation reaction 2.5h, obtains macromonomer after cooling.
(2) take 200g deionized water, 1.2g sodium p styrene sulfonate to add in another reactor, be uniformly mixed, obtain
Mixture A, standby；
(3) by above-mentioned for 7g macromonomer, the ethylene glycol dimethacrylate of 3g, 25g styrene, 15g acrylic acid just
Butyl ester, the mixing of 6g methacrylic acid, obtain mix monomer B, standby；
(4) weigh the mixture A of 50.3g, and add 0.8g potassium peroxydisulfate, obtain initiator solution, standby；
(5) the mix monomer B of 0.6g sodium bicarbonate and 9.4g, pre- breast are added in the reactor containing remaining mixture A
After changing 30min, it is warming up to 80 DEG C, after Deca initiator solution to emulsion becomes basket, be simultaneously added dropwise initiator solution and remaining mixing
Monomer B, is incubated 2.5h after adding, is cooled to 60 DEG C, and it is 7 that ammonification water adjusts pH value, obtains self-crosslinking acrylic ester emulsion.
2. the preparation of mylar：
The above-mentioned self-crosslinking acrylic ester emulsion of 20g, 0.4g wetting agent, 0.3g silica dispersion emulsion and 80g is taken to go
Ionized water, is uniformly dispersed through high-shear emulsion machine, obtains the precoating underlying liquid that mylar is coated with.
Polyester slice is melt extruded the casting sheet being cooled into No yield point, carry out longitudinal stretching, in its surface-coated
After precoating underlying liquid, then carry out cross directional stretch, winding obtains the optical polyester film with bottom.
Embodiment 2
1. the preparation of self-crosslinking acrylic ester emulsion
(1) 50gN- methyl pyrrolidone, 20g isophorone diisocyanate, Deca 8g under room temperature are added in the reactor
Phenol, is warming up to 60 DEG C of reaction 2.5h, adds the polypropylene glycol (M of 90gw=1000) and be warming up to 75 DEG C, insulation reaction 1.5h,
Add the hydroquinone of 0.15g, and be warming up to 88 DEG C；Add the allyl glycidol of 0.21g p-methyl benzenesulfonic acid and 10g
Ether, carries out insulation reaction 2h, obtains macromonomer after cooling.
(2) 180g deionized water, 1.5g polyoxyalkylene nonyl 2, 2-Oxydiphenol acrylate is taken to add in another reactor, stirring mixing
Uniformly, obtain mixture A, standby；
(3) by above-mentioned for 4g macromonomer, the ethylene glycol dimethacrylate of 2g, 5g vinylacetate, 6g acrylic acid
Methyl ester, 6g Isobutyl 2-propenoate, 8g ethyl acrylate, the mixing of 6g THFMA, obtain mix monomer B, standby；
(4) weigh the mixture A of 36.3g, and add 0.6g Ammonium persulfate., obtain initiator solution, standby；
(5) add the mix monomer B of 0.6g disodium hydrogen phosphate and 4.1g in the reactor containing remaining mixture A, in advance
After emulsifying 25min, it is warming up to 78 DEG C, after Deca initiator solution to emulsion becomes basket, be simultaneously added dropwise initiator solution and residue is mixed
Close monomer B, after adding, be incubated 3h, be cooled to 55 DEG C, plus N, it is 8 that N- dimethylethanolamine adjusts pH value, obtains self-crosslinking acrylic
Ester emulsion.
2. the preparation of mylar：
Using above-mentioned self-crosslinking acrylic ester emulsion, the preparation method according to mylar in embodiment 1 is prepared.
Embodiment 3
1. the preparation of self-crosslinking acrylic ester emulsion
(1) 80gN- methyl pyrrolidone, 40g isophorone diisocyanate, Deca under room temperature are added in the reactor
16g phenol, is warming up to 45 DEG C of reaction 2.5h, adds the polypropylene glycol (M of 360gw=2000) and be warming up to 76 DEG C, insulation reaction
1.5h, adds the hydroquinone of 0.15g, and is warming up to 95 DEG C；Add the pi-allyl contracting of 0.22g p-methyl benzenesulfonic acid and 20g
Water glycerin ether, carries out insulation reaction 2h, obtains macromonomer after cooling.
(2) 240g deionized water, 1g Sodium styrene sulfonate, 1g polyoxyalkylene nonyl 2, 2-Oxydiphenol acrylate is taken to add another reaction
In device, it is uniformly mixed, obtain mixture A, standby；
(3) by above-mentioned for 8g macromonomer, the ethylene glycol dimethacrylate of 4g, 25g vinylacetate, 20g propylene
Acid butyl ester, 5g acrylic acid, the mixing of 2g isobornyl methacrylate, obtain mix monomer B, standby；
(4) weigh the mixture A of 80.7g, and add 0.4g Ammonium persulfate. and 0.8g potassium peroxydisulfate, obtain initiator solution,
Standby；
(5) the mix monomer B of 0.8g sodium bicarbonate and 10.7g, pre- breast are added in the reactor containing remaining mixture A
After changing 20min, it is warming up to 82 DEG C, after Deca initiator solution to emulsion becomes basket, be simultaneously added dropwise initiator solution and remaining mixing
Monomer B, is incubated 2h after adding, and is cooled to 50 DEG C, plus N, and it is 8 that N- dimethylethanolamine adjusts pH value, obtains self-crosslinking acrylic ester
Emulsion.
2. the preparation of mylar：
Using above-mentioned self-crosslinking acrylic ester emulsion, the preparation method according to mylar in embodiment 1 is prepared.
Embodiment 4
1. the preparation of self-crosslinking acrylic ester emulsion
(1) 100gN- methyl pyrrolidone, 50g isophorone diisocyanate, Deca under room temperature are added in the reactor
20g phenol, is warming up to 60 DEG C of reaction 2.5h, adds the polypropylene glycol (M of 90gw=1000), the polypropylene glycol (M of 200gw=
1500) and be warming up to 78 DEG C, insulation reaction 2h, adds the hydroquinone of 0.12g, and is warming up to 88 DEG C；Add 0.2g pair
Toluenesulfonic acid and the allyl glycidyl ether of 25g, carry out insulation reaction 3h, obtain macromonomer after cooling.
(2) 150g deionized water, 0.6g reactive emulsifier Sodium styrene sulfonate, 0.2g polyoxyalkylene nonyl 2, 2-Oxydiphenol propylene are taken
Acid esters adds in another reactor, is uniformly mixed, obtains mixture A, standby；
(3) by above-mentioned for 2g macromonomer, the ethylene glycol dimethacrylate of 2g, 8g styrene, 2g acrylic acid methyl ester.,
4g n-butyl acrylate, 8g Isobutyl 2-propenoate, 4g THFMA, 2g 2-(Acryloyloxy)ethanol, 4g methyl-prop
Olefin(e) acid hydroxyl ethyl ester mixes, and obtains mix monomer B, standby；
(4) weigh the mixture A of 37.7g, and add 0.6g Ammonium persulfate., obtain initiator solution, standby；
(5) add the mix monomer B of 0.6g disodium hydrogen phosphate and 7.2g in the reactor containing remaining mixture A, in advance
After emulsifying 30min, it is warming up to 85 DEG C, and Deca initiator solution becomes after basket to emulsion, is simultaneously added dropwise initiator solution and residue
Mix monomer B, is incubated 4h after adding, is cooled to 55 DEG C, and it is 7 that ammonification water adjusts pH value, obtains self-crosslinking acrylic ester emulsion.
2. the preparation of mylar：
Using above-mentioned self-crosslinking acrylic ester emulsion, the preparation method according to mylar in embodiment 1 is prepared.
Embodiment 5
1. the preparation of self-crosslinking acrylic ester emulsion
(1) 60gN- methyl pyrrolidone, 25g isophorone diisocyanate, Deca under room temperature are added in the reactor
10g phenol, is warming up to 65 DEG C of reaction 3.5h, adds the polypropylene glycol (M of 68gw=1000), the polypropylene glycol (M of 90gw=2000)
And it is warming up to 78 DEG C, and insulation reaction 1.5h, add the hydroquinone of 0.18g, and be warming up to 85 DEG C；Add 0.24g to first
Benzenesulfonic acid and the allyl glycidyl ether of 13g, carry out insulation reaction 2.5h, obtain macromonomer after cooling.
(2) 200g deionized water, 1.2g reactive emulsifier Sodium styrene sulfonate, 0.4g polyoxyalkylene nonyl 2, 2-Oxydiphenol propylene are taken
Acid esters adds in another reactor, is uniformly mixed, obtains mixture A, standby；
(3) by above-mentioned for 5g macromonomer, the ethylene glycol dimethacrylate of 2.5g, 2g styrene, 4g vinyl acetate
Ester, 6g acrylic acid methyl ester., 4g n-butyl acrylate, 5g Isobutyl 2-propenoate, 2g ethyl acrylate, 4g methacrylic acid isoborneol
Ester, the mixing of 2g 2-(Acryloyloxy)ethanol, obtain mix monomer B, standby；
(4) weigh the mixture A of 50.4g, and add 0.5g Ammonium persulfate., 0.6g potassium peroxydisulfate, obtain initiator solution, standby
With；
(5) the mix monomer B of 0.8g sodium bicarbonate and 6.5g, pre- breast are added in the reactor containing remaining mixture A
After changing 35min, it is warming up to 82 DEG C, and Deca initiator solution becomes after basket to emulsion, be simultaneously added dropwise initiator solution and residue is mixed
Close monomer B, after adding, be incubated 3h, be cooled to 50 DEG C, plus N, it is 8 that N- dimethylethanolamine adjusts pH value, obtains self-crosslinking acrylic
Ester emulsion.
2. the preparation of mylar：
Using above-mentioned self-crosslinking acrylic ester emulsion, the preparation method according to mylar in embodiment 1 is prepared.
Adhesion performance is tested：Solidify blast liquid, UV hardening with radiation in surface-coated UV of above-mentioned mylar tape bottom
After obtain brightness enhancement film, on the surface of brightness enhancement film, hundred lattice are drawn using the method that GB/T9286 specifies, are then placed in entering in 100 DEG C of boiling water
Row decocting in water 30min, surveys the adhesive force between mylar and brightness enhancement film, the frame counter adhesive force being retained with paint film, 100% expression
Lattice are not had to come off, adhesive force is best.Test result is shown in Table 1.
Table 1 adhesive force test result
Claims (10)
1. a kind of self-crosslinking acrylic ester emulsion is it is characterised in that contain following in described self-crosslinking acrylic ester emulsion raw material
The macromonomer of structure：
Wherein：R isN is 15～35.
2. a kind of method preparing self-crosslinking acrylic ester emulsion as claimed in claim 1 is it is characterised in that preparation is walked as following
Suddenly carry out：
(1) 50～100 mass parts N-Methyl pyrrolidone, 10～50 mass parts isophorone diisocyanate are added in the reactor
Ester, Deca 5～20 mass parts phenol under room temperature, it is warming up to 40～70 DEG C of reaction 2～4h, add the polyethers of 50～450 mass parts
Polyhydric alcohol is simultaneously warming up to 75～85 DEG C, and insulation reaction 1～2h adds the hydroquinone of 0.05～0.25 mass parts, and heats up
To 85～100 DEG C, add the allyl glycidyl ether of 0.2～0.25 mass parts p-methyl benzenesulfonic acid and 5～25 mass parts, insulation
Reaction 2～4h, obtains macromonomer after cooling；
(2) 150～250 mass parts deionized waters and 0.5～2.5 mass parts reactive emulsifier is taken to add in another reactor,
It is uniformly mixed, obtain mixture A, standby；
(3) by above-mentioned for 2～10 mass parts macromonomer, the ethylene glycol dimethacrylate of 2～5 mass parts, 10～35 matter
The functional monomer mixing of the hard monomer, the soft monomer of 10～35 mass parts and 5～15 mass parts of amount part, obtains mix monomer B, standby
With；
(4) weigh the mixture A of 1/5～1/2 mass, and add 0.5～1.5 mass parts initiator, obtain initiator solution, standby
With；
(5) 0.4～1.2 mass parts pH buffer and 1/10～1/4 mass are added in the reactor containing remaining mixture A
Mix monomer B, pre-emulsification 20～40min, are warming up to 75～85 DEG C, Deca initiator solution, after in question response device, liquid becomes basket,
It is simultaneously added dropwise initiator solution and remaining mix monomer B, is incubated 1.5～4h after adding, is cooled to 40～60 DEG C, plus alkali liquor is adjusted
PH value is 7～8, obtains self-crosslinking acrylic ester emulsion.
3. preparation method according to claim 2 is it is characterised in that described polyether polyol is molecular weight 1000～2000
Polypropylene glycol.
4. preparation method according to claim 3 is it is characterised in that described reactive emulsifier is p styrene sulfonic acid
One of sodium, polyoxyalkylene nonyl 2, 2-Oxydiphenol acrylate or combination in any.
5. preparation method according to claim 4 it is characterised in that described hard monomer be styrene, vinylacetate, third
One of e pioic acid methyl ester or combination in any.
6. preparation method according to claim 5 is it is characterised in that described soft monomer is n-butyl acrylate, acrylic acid
One of isobutyl ester, ethyl acrylate or combination in any.
7. preparation method according to claim 6 is it is characterised in that described functional monomer is acrylic acid, methyl-prop
In olefin(e) acid, THFMA, isobornyl methacrylate, 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate
One kind or combination in any.
8. preparation method according to claim 7 is it is characterised in that described initiator is potassium peroxydisulfate, Ammonium persulfate.
One of or combination in any；Described pH buffer is one of sodium bicarbonate, disodium hydrogen phosphate or combination in any.
9. preparation method according to claim 8 it is characterised in that described alkali liquor be ammonia, N, N- dimethylethanolamine
One of or combination in any.
10. a kind of mylar is it is characterised in that self-crosslinking as described in any one of claim 1-9 is contained at least one surface
The bottom that acrylic acid ester emulsion is made.
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| CN105924572A (en) * | 2016-06-21 | 2016-09-07 | 太仓市东明化工有限公司 | Preparation method for curing-cross-linking styrene-acrylate resin |
| CN106810646B (en) * | 2016-12-21 | 2019-08-02 | 广东玉兰集团股份有限公司 | A kind of self-cross linking type water-proof emulsion and preparation method thereof and waterproof basement membrane using water-proof emulsion preparation |
| CN111057187B (en) * | 2019-12-31 | 2023-01-13 | 广东华珀科技有限公司 | High-adhesion room-temperature self-crosslinking acrylic resin and preparation method and application thereof |
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|---|---|---|---|---|
| CN101481443A (en) * | 2009-01-23 | 2009-07-15 | 华南理工大学 | Polyurethane-polyacrylacid ester interpenetrating network polymer, preparation and use thereof |
| CN101861341A (en) * | 2007-09-18 | 2010-10-13 | 库克复合材料和聚合物公司 | The thermoset composition of the low VOC of the polyester acrylic resin that gel coating is used |
| CN103554349A (en) * | 2013-11-04 | 2014-02-05 | 常州天马集团有限公司（原建材二五三厂） | Self-crosslinking acrylate emulsion and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101861341A (en) * | 2007-09-18 | 2010-10-13 | 库克复合材料和聚合物公司 | The thermoset composition of the low VOC of the polyester acrylic resin that gel coating is used |
| CN101481443A (en) * | 2009-01-23 | 2009-07-15 | 华南理工大学 | Polyurethane-polyacrylacid ester interpenetrating network polymer, preparation and use thereof |
| CN103554349A (en) * | 2013-11-04 | 2014-02-05 | 常州天马集团有限公司（原建材二五三厂） | Self-crosslinking acrylate emulsion and preparation method thereof |
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