CN103881032A - Preparation method for scratch-resistant smooth high-gloss resin - Google Patents
Preparation method for scratch-resistant smooth high-gloss resin Download PDFInfo
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Abstract
The invention discloses a preparation method for a scratch-resistant smooth high-gloss resin. The preparation method for the resin comprises the following steps: S1, providing a reaction solvent, adding a part of the reaction solvent into a reaction kettle, and heating; S2, providing a molecular weight regulator and an initiator, and adding the molecular weight regulator, a part of the initiator, the remainder reaction solvent and a plurality of monomers into the reaction kettle; S3, dropwise adding double-bond type silicone oil in the reaction solvent; S4, after dropwise adding the double-bond type silicone oil, insulating at a reaction temperature, then gradually adding the remainder initiator, and rising the temperature to obtain hydroxy acrylic resin. According to the preparation method for the scratch-resistant smooth high-gloss resin disclosed by the invention, the reaction solvent with high environmental friendliness is used, moreover, the steps are simple and the conditions are moderate. Moreover, the prepared scratch-resistant smooth high-gloss resin is good in printing effect, high in smoothness, good in gloss, high in safety, excellent in scratch resistance, smoothness and glossiness, and wide in application fields.
Description
Technical field
The present invention relates to the field of chemical synthesis, particularly relate to the preparation method of the smooth high gloss resin of a kind of scratch resistance.
Background technology
Owing to containing the strong carcinogenic shortcoming of the high pollutions such as a large amount of benzene,toluene,xylenes in traditional solvent type acrylic resin, be unfavorable for people's health, so do not select benzene kind solvent to become must needing of environmental protection and market as the primary solvent of solvent-type acrylic ester resin.The comprehensive comparison of cloudy surface resistance to marring, slipping and the high-luster of traditional cloudy surface BOPP film is poor, and need, by applying one deck functional coating at cloudy surface, increases its scratch resistance and smooth high gloss performance simultaneously.Simultaneously, the surface tension of BOPP film of not passing through corona is very low, be difficult at its surface printing ink, thereby cause the application surface of this kind of BOPP film to reduce, the BOPP film applying by functional layer, not only has the smooth high gloss performance of good damage resistant, simultaneously, can carry out ultraviolet ink printing on its surface, thereby widen its Application Areas.
But, due to the limitation of technology, the damage resistant coating of current BOPP sprayed film is generally oil paint, and solvent for use contains the aromatic organic solvents such as benzene,toluene,xylene, this kind solvent not only has strong carinogenicity, and more serious to the damage ratio of environment.Therefore the smooth high gloss resin of damage resistant of, developing a kind of environment-friendly type just seems particularly important.
At present, the smooth high gloss resin of various damage resistants is developed, but the performance of the smooth high gloss of damage resistant is excellent not enough, and preparation technology also exists some defects, and some does not meet environmental requirement.
For example, CN103030792A patent discloses a kind of scratch resistance light alkyd resin.It mainly, by lipid acid, polyvalent alcohol, dibasic alcohol, diprotic acid etc. are reacted under existing at solvent xylene, N-BUTYL ACETATE under the existence of catalyzer, obtains a kind of scratch resistance high-performance light alkyd resin.But the shortcoming of this product is, owing to needing in process of production to use benzene kind solvent, environmental pollution and carinogenicity are stronger; Secondly, because the temperature of reaction of Synolac is higher, need to react 180-230 DEG C of left and right, therefore, this technique belongs to highly energy-consuming technique.
CN102898937A patent discloses a kind of high rigidity scratch resistance double-component waterborne polyurethane woodenware lacquer resin.This resin is mainly made up of hydroxyl polyacrylate dispersion resin, dispersion agent, nanometer grade silica glass powder, scratch resistance wax assistant, organo-bismuth/zinc composite catalyst, water etc., and it adopts allophanate-modified HDI tripolymer as solidifying agent.It is high that the resin combining has surface hardness, surface drying with do solid work the advantages such as time shorten, activator prolongation.Add a large amount of auxiliary agents as the scratch resistance effect that nanometer grade silica glass powder, scratch resistance wax etc. obtain but this product needed is extra, not only increased production cost, and the various auxiliary agents that add affect greatly to the stability of coating.Secondly, the surface gloss of this product is at more than 70 degree, and gloss is generally on the low side, does not reach high-level high glossiness requirement.
CN1659202A patent discloses a kind of water-borne coatings of mar-resistance, this water-borne coatings mainly by waterborne polyurethane resin as matrix resin, water miscible alkylated melamine resin, as linking agent, combines.After this coating film, there is good glossiness and excellent mar-resistance.But this coating need to can reach final degree of crosslinking and mar-resistance in 10 minutes 82 DEG C of bakings, and is not suitable for the quick coating process of BOPP film.
Therefore,, for the problems referred to above, be necessary the preparation method of the smooth high gloss resin of scratch resistance that a kind of improvement is provided.
Summary of the invention
In view of this, the invention provides a kind of anti-zoned smooth high gloss and hinder the preparation method of resin.
To achieve these goals, the preparation method of the smooth high gloss resin of a kind of scratch resistance of the present invention, following pair of of bonding silicone molecule weight range is 3000～80000.Because the molecular weight of this pair of of bonding silicone oil is larger, the scratch resistance resin synthesizing, it has superior surperficial smoothness and resistance to marring to compare the scratch resistance resin prepared by small molecules silicone oil.
Described preparation method comprises the steps:
S1., reaction solvent is provided, and partial reaction solvent is joined in reactor, be heated to 40～140 DEG C, described reaction solvent is selected from one or more in alkane solvents, esters solvent, alcoholic solvent, alcohol ether solvent, alcoholic solvent;
S2., molecular weight regulator and initiator are provided, to the initiator, remaining reaction solvent and the some monomers that add molecular weight regulator, part in reactor,
Described some monomers comprise: being selected from vinylbenzene or α-vinylbenzene or skeleton symbol is H
2cCH
3cOOR
1compound in one or more hard monomer, being selected from skeleton symbol is H
2cCHCOOR
2compound in one or more soft monomer, and to be selected from Viscoat 295 or Phthalic acid, diallyl ester or skeleton symbol be H
2cCH
3cOOR
3, or skeleton symbol be CH
2cR
4cOR
5compound in one or more function monomer;
S3. in 0.5～1h, in reactor, drip two of bonding silicone oil, described pair of of bonding silicone molecule weight range is selected from 3000～80000, and the described pair of of bonding silicone oil is selected from one or more in hydroxyl vinyl silicone oil or unsaturated polyether organic silicone oil or unsaturated polyester organic silicone oil or vinyl silicone oil compounds;
S4. drip two of bonding silicone oil, under temperature of reaction, after insulation, in 0.5～1h, add gradually remaining initiator, and the temperature that raises is to carrying out after secondary insulation higher than 8～12 DEG C of temperature of reaction, obtains the scratch resistant Hydroxylated acrylic resin of solvent-borne type.
As a further improvement on the present invention, described alkane solvents comprises: normal hexane, normal heptane, octane, long chain alkane or their mixture; Described esters solvent comprises: vinyl acetic monomer, N-BUTYL ACETATE; Described alcoholic solvent comprises: Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol; Described alcohol ether solvent comprises: butyl glycol ether, propandiol butyl ether, propylene glycol monomethyl ether; Described solvent of ether ester type comprises: 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate, ethylene glycol ether acetate.
As a further improvement on the present invention, described initiator is selected from one or more in following material: benzoyl peroxide, peroxidation 2 ethyl hexanoic acid tert-pentyl ester, the peroxidation 2 ethyl hexanoic acid tert-butyl ester, 1, two (tert-pentyl peroxide) the cyclic group alkane of 1-, 1, two (the tert-pentyl peroxides)-3 of 1-, 3, 5-trimethyl-cyclohexane, peroxidation acetic acid tert-pentyl ester, peroxide acid tert-amyl acetate, peroxidation 3, 3, the 5 tri-methyl hexanoic acid tert-butyl esters, peroxidized t-butyl perbenzoate, 3, two (t-butyl peroxy) ethyl hexanoates of 3-, dicumyl peroxide, di-t-butyl peroxide, peroxidation two tert-pentyls, tertbutyl peroxide, t-amyl peroxy hydrogen, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile).
As a further improvement on the present invention, described step S2 also comprises: in reactor, add reductive agent, described reductive agent is selected from one or more in following material: sodium bisulfite, rongalite, ferrous sulfate.
As a further improvement on the present invention, described molecular weight regulator is: Dodecyl Mercaptan, 2 mercapto ethanol or the mixing of the two.
As a further improvement on the present invention, in described step S1, the reaction solvent joining in reactor is 0.1～10wt% of reaction solvent total amount.
As a further improvement on the present invention, described skeleton symbol is H
2cCH
3cOOR
1compound comprise: methyl methacrylate, isobornyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA.
As a further improvement on the present invention, described skeleton symbol is H
2cCHCOOR
2compound comprise: butyl acrylate, Isooctyl acrylate monomer, ethyl propenoate.
As a further improvement on the present invention, described skeleton symbol is H
2cCH
3cOOR
3compound comprise: methacrylic acid, hydroxyethyl methylacrylate, Rocryl 410, glycidyl methacrylate.
As a further improvement on the present invention, described skeleton symbol is CH
2cR
4cOR
5compound comprise: vinylformic acid, acrylamide, Methacrylamide, N hydroxymethyl acrylamide.
As a further improvement on the present invention, the ratio of described hard monomer, soft monomer and function monomer obtains by FOX equation, and described FOX equation is:
As a further improvement on the present invention, described molecular weight regulator and some monomers adopt the mode dripping to join in reactor, and the time for adding of described molecular weight regulator and some monomers is 3～5h.
For achieving the above object, the preparation method of the smooth high gloss resin of another kind of scratch resistance of the present invention, it comprises the steps:
S1., reaction solvent is provided, and partial reaction solvent is joined in reactor, be heated to 40～140 DEG C, described reaction solvent is selected from one or more in alkane solvents, esters solvent, alcoholic solvent, alcohol ether solvent, alcoholic solvent;
S2., molecular weight regulator and initiator are provided, to the initiator, remaining reaction solvent and the some monomers that add molecular weight regulator, part in reactor,
Described some monomers comprise: being selected from vinylbenzene or α-vinylbenzene or skeleton symbol is H
2cCH
3cOOR
1compound in one or more hard monomer, being selected from skeleton symbol is H
2cCHCOOR
2compound in one or more soft monomer, and to be selected from Viscoat 295 or Phthalic acid, diallyl ester or skeleton symbol be H
2cCH
3cOOR
3, or skeleton symbol be CH
2cR
4cOR
5compound in one or more function monomer;
S3. in 0.5～1h, in reactor, drip two of bonding silicone oil, the described pair of of bonding silicone oil is selected from one or more in hydroxyl vinyl silicone oil or unsaturated polyether organic silicone oil or unsaturated polyester organic silicone oil or vinyl silicone oil compounds, drips in two of bonding silicone oil processes and adds part initiator;
S4. drip two of bonding silicone oil, under temperature of reaction, after insulation, in 0.5～1h, add gradually remaining initiator, and the temperature that raises is to carrying out after secondary insulation higher than 8～12 DEG C of temperature of reaction, obtains solvent type hydroxyl organosilicon acrylic resin;
S5. in described Hydroxylated acrylic resin, add neutralizing agent, in and the time be 15-60min, neutral temperature is 50-100 DEG C, adds deionized water high speed dispersion, the time is 1-3h, thereby obtain water based acrylic resin.
Compared with prior art, the invention has the beneficial effects as follows: the preparation method of scratch resistance resin of the present invention adopts the reaction solvent that the feature of environmental protection is high, and its step is simple, mild condition.And the scratch resistance resin printing effect of preparing is good, slipping is high, transparency is high, glossiness is good, safe, has excellent scratch resistance and wide application field.
Brief description of the drawings
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, the accompanying drawing the following describes is only some embodiment that record in the present invention, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the method flow schematic diagram of preparation method's one embodiment of the preparation method of scratch resistance resin of the present invention;
Fig. 2 is the method flow schematic diagram of preparation method's one embodiment of the preparation method of another scratch resistance resin of the present invention.
Embodiment
As shown in Figure 1, the present invention discloses the preparation method of the smooth high gloss resin of a kind of scratch resistance, and it comprises the steps:
S1., reaction solvent is provided, and partial reaction solvent is joined in reactor, be heated to 40～140 DEG C, described reaction solvent is selected from one or more in alkane solvents, esters solvent, alcoholic solvent, alcohol ether solvent, alcoholic solvent.
Wherein, the comparatively environmental protection of reaction solvent that the present invention adopts, particularly, described alkane solvents comprises: normal hexane, normal heptane, octane, long chain alkane or their mixture; Described esters solvent comprises: vinyl acetic monomer, N-BUTYL ACETATE; Described alcoholic solvent comprises: Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol; Described alcohol ether solvent comprises: butyl glycol ether, propandiol butyl ether, propylene glycol monomethyl ether; Described solvent of ether ester type comprises: 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate, ethylene glycol ether acetate.
In addition the partial reaction solvent joining, in reactor is 0.1～10wt% of reaction solvent total amount.Reactor can adopt the polymerization reaction kettle that disposes agitator, temperature controller, prolong, nitrogen conduit.
S2. provide molecular weight regulator and initiator, to the initiator, remaining reaction solvent and the some monomers that add molecular weight regulator, part in reactor.
Described some monomers comprise: being selected from vinylbenzene or α-vinylbenzene or skeleton symbol is H
2cCH
3cOOR
1compound in one or more hard monomer, being selected from skeleton symbol is H
2cCHCOOR
2compound in one or more soft monomer, and to be selected from Viscoat 295 or Phthalic acid, diallyl ester or skeleton symbol be H
2cCH
3cOOR
3, or skeleton symbol be CH
2cR
4cOR
5compound in one or more function monomer.
Wherein, R
1, R
2, R
3, R
4, R
5represent substituting group, according to substituent difference, described skeleton symbol is H
2cCH
3cOOR
1compound can comprise: methyl methacrylate, isobornyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA.Described skeleton symbol is H
2cCHCOOR
2compound can comprise: butyl acrylate, Isooctyl acrylate monomer, ethyl propenoate.Described skeleton symbol is H
2cCH
3cOOR
3compound can comprise: methacrylic acid, hydroxyethyl methylacrylate, Rocryl 410, glycidyl methacrylate.Described skeleton symbol is CH
2cR
4cOR
5compound can comprise: vinylformic acid, acrylamide, Methacrylamide, N hydroxymethyl acrylamide.
In addition, the ratio of described hard monomer, soft monomer and function monomer can obtain by FOX equation, and described FOX equation is:
In this FOX equation, W
1, W
2... W
n, be respectively the massfraction of each monomer in multipolymer; Tg
1, Tg
2, Tg
3... Tg
nbe respectively the corresponding thermodynamic temperature of each monomer.
Further, described molecular weight regulator and some monomers adopt the mode dripping to join in reactor, and the time for adding of described molecular weight regulator and some monomers is 3～5h.
Described molecular weight regulator can be: Dodecyl Mercaptan, 2 mercapto ethanol or the mixing of the two.Utilize after molecular weight regulator adjusts, the molecular weight of the multipolymer that institute's polymerization obtains can be controlled in 4000～400000 scope.
One or more in the optional certainly following material of described initiator: benzoyl peroxide, peroxidation 2 ethyl hexanoic acid tert-pentyl ester, the peroxidation 2 ethyl hexanoic acid tert-butyl ester, 1, two (tert-pentyl peroxide) the cyclic group alkane of 1-, 1, two (the tert-pentyl peroxides)-3 of 1-, 3, 5-trimethyl-cyclohexane, peroxidation acetic acid tert-pentyl ester, peroxide acid tert-amyl acetate, peroxidation 3, 3, the 5 tri-methyl hexanoic acid tert-butyl esters, peroxidized t-butyl perbenzoate, 3, two (t-butyl peroxy) ethyl hexanoates of 3-, dicumyl peroxide, di-t-butyl peroxide, peroxidation two tert-pentyls, tertbutyl peroxide, t-amyl peroxy hydrogen, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile).
Described step S2 also comprises: in reactor, add reductive agent, one or more in the optional certainly following material of described reductive agent: sodium bisulfite, rongalite, ferrous sulfate.
S3. in 0.5～1h to dripping two of bonding silicone oil in reactor, the described pair of of bonding silicone oil is selected from one or more in hydroxyl vinyl silicone oil or unsaturated polyether organic silicone oil or unsaturated polyester organic silicone oil or vinyl silicone oil compounds.
Described pair of of bonding silicone molecule weight range is 3000～80000.Thereby because the molecular weight of this pair of of bonding silicone oil is larger, the snappiness of the scratch resistance resin synthesizing, smooth and high gloss performance is comparatively outstanding, it has superior surperficial smoothness and resistance to marring to compare the scratch resistance resin prepared by small molecules silicone oil.
S4. drip two of bonding silicone oil, after being incubated under temperature of reaction, in 0.5～1h, add gradually remaining initiator, and the temperature that raises is to carrying out after secondary insulation higher than 8～12 DEG C of temperature of reaction, obtains the solvent-borne type Hydroxylated acrylic resin of the smooth high gloss of scratch resistance.
Wherein, drip two of bonding silicone oil, under temperature of reaction, be preferably incubated 1h.Meanwhile, add gradually remaining initiator in 0.5～1h, and the temperature that preferably raises is to carrying out secondary insulation higher than 10 DEG C of temperature of reaction, the time of secondary insulation is 2h.
The preparation method of the smooth high gloss resin of solvent-borne type scratch resistance providing based on the invention described above, the invention still further relates to the application of the smooth high gloss resin of this solvent-borne type scratch resistance as the functional coating of BOPP film.
Below in conjunction with concrete comparative example and embodiment, the performance of the smooth high gloss resin of scratch resistance to the preparation method by the smooth high gloss resin of scratch resistance of the present invention and preparation is carried out comparative illustration.
Comparative example 1
In a polymerization reaction kettle that disposes agitator, temperature controller, prolong, nitrogen conduit, add, by mass percentage, 54 parts of Virahols, are heated to 75 DEG C.Then the mixture of 48 parts of vinylbenzene, 28 parts of hydroxyethyl methylacrylates, 16 parts of butyl acrylates, 2 parts of vinylformic acid, 1 portion of Phthalic acid, diallyl ester, 5 parts of vinyl three (beta-methoxy-oxyethyl group) silane monomer, 0.5 part of lauryl mercaptan, 2.5 parts of 2,2'-Azobis(2,4-dimethylvaleronitrile), 13 parts of Virahols was added gradually in polymerization reaction kettle in 4 hours, after dropwising, 75 degree insulation 1 hour, again add 0.5 part of 2,2'-Azobis(2,4-dimethylvaleronitrile), then temperature to the 80 degree insulation 2 hours that raises.Finally, be cooled to room temperature, discharging.Both can obtain the solvent-borne type Hydroxylated acrylic resin of solid content 60%.
Comparative example 2
In a polymerization reaction kettle that disposes agitator, temperature controller, prolong, nitrogen conduit, add, by mass percentage, 54 parts of Virahols, are heated to 75 DEG C.Then the mixture of 48 parts of vinylbenzene, 28 parts of hydroxyethyl methylacrylates, 16 parts of butyl acrylates, 2 parts of vinylformic acid, 1 portion of Phthalic acid, diallyl ester, 5 parts of vinyltriisopropenyloxysilane monomers, 0.5 part of lauryl mercaptan, 2.5 parts of 2,2'-Azobis(2,4-dimethylvaleronitrile), 13 parts of Virahols was added gradually in polymerization reaction kettle in 4 hours, after dropwising, 75 degree insulation 1 hour, again add 0.5 part of 2,2'-Azobis(2,4-dimethylvaleronitrile), then temperature to the 80 degree insulation 2 hours that raises.Finally, be cooled to room temperature, discharging.Both can obtain the solvent-borne type Hydroxylated acrylic resin of solid content 60%.
Embodiment 1
In a polymerization reaction kettle that disposes agitator, temperature controller, prolong, nitrogen conduit, add 54 parts of Virahols, be heated to 75 DEG C.The mixture of the vinyl hydroxy silicone oil that is then 18000 by 48 parts of vinylbenzene, 28 parts of hydroxyethyl methylacrylates, 16 parts of butyl acrylates, 2 parts of vinylformic acid, 1 portion of Phthalic acid, diallyl ester, 5 parts of molecular weight, 0.5 part of lauryl mercaptan, 2.5 parts of 2,2'-Azobis(2,4-dimethylvaleronitrile), 13 parts of Virahols added gradually in polymerization reaction kettle in 4 hours, after dropwising, 75 degree insulation 1 hour, again add 0.5 part of 2,2'-Azobis(2,4-dimethylvaleronitrile), then temperature to the 80 degree insulation 2 hours that raises.Finally, be cooled to room temperature, discharging.Both can obtain the solvent-borne type Hydroxylated acrylic resin of solid content 60%.
Embodiment 2
In a polymerization reaction kettle that disposes agitator, temperature controller, prolong, nitrogen conduit, add 40 parts of N-BUTYL ACETATEs and 40 parts of 1-Methoxy-2-propyl acetates, be heated to 95 DEG C.The mixture of the bi-vinyl polyether silicone oil that is then 3000 by 46 vinylbenzene, 28 parts of hydroxyethyl methylacrylates, 17 parts of butyl acrylates, 2.5 parts of methacrylic acids, 0.5 part of tri methylol triacrylate, 6 parts of molecular weight, 2.6 parts of peroxidation 2 ethyl hexanoic acid tert-butyl esters, 10 parts of N-BUTYL ACETATEs, 10 parts of 1-Methoxy-2-propyl acetates added gradually in polymerization reaction kettle in 4 hours, after dropwising, 95 DEG C of insulations 1 hour, again add 0.3 part of peroxidation 2 ethyl hexanoic acid tert-butyl ester, then temperature to the 105 DEG C insulation 2 hours that raises.Finally, be cooled to room temperature, discharging.Both can obtain the solvent-borne type Hydroxylated acrylic resin of solid content 50%.
Embodiment 3
In a polymerization reaction kettle that disposes agitator, temperature controller, prolong, nitrogen conduit, add 45 parts of propylene glycol monomethyl ethers and 45 parts of 2-Butoxyethyl acetates, be heated to 125 DEG C.The mixture of the vinyl hydroxy silicone oil that is then 25000 by 53 parts of vinylbenzene, 28 parts of hydroxyethyl methylacrylates, 10 parts of butyl acrylates, 2 parts of vinylformic acid, 5 parts of molecular weight, 2 portions of Phthalic acid, diallyl esters, 3 parts of peroxidation acetic acid tert-pentyl esters, 5 parts of propylene glycol monomethyl ethers, 5 parts of 2-Butoxyethyl acetates added gradually in polymerization reaction kettle in 4 hours, after dropwising, 125 DEG C of insulations 1 hour, again add 0.5 part of peroxidation acetic acid tert-pentyl ester, then temperature to the 135 DEG C insulation 2 hours that raises.Finally, be cooled to room temperature, discharging.Both can obtain the solvent-borne type Hydroxylated acrylic resin of solid content 50%.
Embodiment 4
In a polymerization reaction kettle that disposes agitator, temperature controller, prolong, nitrogen conduit, add 40 parts of propandiol butyl ethers and 40 parts of 2-Butoxyethyl acetates, be heated to 125 DEG C.The mixture of the trivinyl silicone oil that is then 50000 by 55 parts of vinylbenzene, 30 parts of Rocryl 410s, 10 parts of butyl acrylates, 2 parts of methacrylic acids, 1 portion of Phthalic acid, diallyl ester, 2 parts of molecular weight, 0.5 part of lauryl mercaptan, 3 parts of di-t-butyl peroxides, 10 parts of propandiol butyl ethers, 10 parts of 2-Butoxyethyl acetates added gradually in polymerization reaction kettle in 4 hours, after dropwising, 125 DEG C of insulations 1 hour, again add 0.5 part of di-t-butyl peroxide, then temperature to the 135 DEG C insulation 2 hours that raises.Finally, be cooled to room temperature, discharging.Both can obtain the solvent-borne type Hydroxylated acrylic resin of solid content 50%.
Properties for above-described embodiment and comparative example preparing product is tested, and test result is as shown in table 1 below:
Table 1
Wherein, before the solvent-borne type Hydroxylated acrylic resin of preparing through above-mentioned each comparative example and embodiment is tested, first it is processed.Particularly, itself and Bayer isocyanate curing agent N3390 are carried out to mixture.When mixture, according to different Bayer cyanate NCO group, the ratio of the contained OH group molar ratio of hydroxy acrylate 1:1～1:0.9 is uniformly mixed, uniform coating is on BOPP film.Then dry at 45～65 DEG C, then carry out the thermofixation processing in later stage.Then test accordingly.
Show according to the test result of comparative example and embodiment, Hydroxylated acrylic resin scratch resistant performance excellence prepared by the preparation method of the smooth high gloss resin of solvent-borne type scratch resistance of the present invention, can resistance to finger scratch, and all can't see film surface damage from various angles.Meanwhile, embodiment 1～3 shows, UV printing treatment can be carried out in resin coating surface.
As shown in Figure 2, under same inventive concept, the present invention also provides the preparation method of another kind of water-based scratch resistance resin: the step of preparing front four steps of this resin and solvent type resin is consistent, and increase on this basis step S5, in hydroxyl organosilicon acrylic resin, add neutralizing agent, in and the time be 15～60min, neutral temperature is 50～100 DEG C, again the hydroxyl organosilicon acrylic resin after neutralization is mixed with deionized water, hydroxyl organosilicon acrylic resin is disperseed in deionized water high speed, jitter time is 1～3h, thereby obtains water based acrylic resin.
Below in conjunction with concrete comparative example and embodiment, the performance of the smooth high gloss resin of water-based scratch resistance to the preparation method by the smooth high gloss resin of another kind of water-based scratch resistance of the present invention and preparation is carried out comparative illustration.
Comparative example 1
By 60 parts of deionized waters, 1.0 parts of 1-allyloxy-3-(4-nonylphenol)-2-propyl alcohol polyoxyethylene (10) ether ammonium sulfates, 0.4 part, 1-allyloxy-3-(4-nonylphenol)-2-propyl alcohol polyoxyethylene (10) ether, 0.5 part of sodium bicarbonate joins in polymerization reaction kettle, heated and stirred, it is fully dissolved, slow down for subsequent use.
To in deionized water, add in reactor, the temperature to 40 DEG C of rising reactor, under high-speed stirring, add 1.6 parts of 1-allyloxy-3-(4-nonylphenol)-2-propyl alcohol polyoxyethylene (10) ether ammonium sulfates, 0.8 part, 1-allyloxy-3-(4-nonylphenol)-2-propyl alcohol polyoxyethylene (10) ether, carry out pre-emulsification 30 minutes, emulsifying agent is well-dispersed in water.After being uniformly dispersed, under high-speed stirring, slowly add monomer: 46 parts of vinylbenzene, 32 parts of butyl acrylates, 20 parts of hydroxyethyl methylacrylates, 2.0 parts, vinylformic acid, vigorous stirring obtains pre-emulsion for 30 minutes.
8% pre-emulsion in pre-emulsification still is added in polymerization reaction kettle, stir, the temperature to 75 DEG C that then raises, adds the initial initiator aqueous solution, continues to be warming up to 80～85 DEG C, occurs being incubated 0.5h at 80～85 DEG C after blue light.After insulation finishes, in polymerization reaction kettle, drip residue pre-emulsion and initiator, wherein pre-emulsion 3～3.5h drips off simultaneously, and initiator 3.5～4h drips off, and reaction temperature control is at 80～85 DEG C.After initiator adds, be warming up to 85～90 DEG C, insulation 0.5h.After insulation finishes, be down to below 40 DEG C, can obtain the aqueous acrylic emulsion of appearance milky white.
Comparative example 2
In a polymerization reaction kettle that disposes agitator, temperature controller, prolong, nitrogen ingress pipe, add 30 parts of Virahols, be heated to 80 DEG C.Then the mixture of 45 parts of vinylbenzene, 20 parts of hydroxyethyl methylacrylates, 30 parts of butyl acrylates, 5 parts of vinylformic acid, 1.5 parts of lauryl mercaptans, 2.0 parts of 2,2'-Azobis(2,4-dimethylvaleronitrile), 10 parts of Virahols was added gradually in polymerization reaction kettle in 3.5 hours.After dropwising, 80 DEG C of insulations 1 hour, again add 0.5 part of 2,2'-Azobis(2,4-dimethylvaleronitrile), the temperature to 90 that raises gradually DEG C insulation 2 hours.Then, reduce temperature to 55 DEG C, add 6.5 parts of N, N-dimethylethanolamine neutralizes, in and the time be 30 minutes, after neutralization, under the high speed shear of 2000 revs/min, add 130 parts of deionized water water inlets to disperse, jitter time is 1 hour, after dispersion, can obtain the water-based hydroxyl acrylic acid dispersion resin of appearance milky white.
Embodiment 1
In a polymerization reaction kettle that disposes agitator, temperature controller, prolong, nitrogen ingress pipe, add 30 parts of Virahols, be heated to 80 DEG C.Then the mixture of 38 parts of vinylbenzene, 27 parts of hydroxyethyl methylacrylates, 25 parts of butyl acrylates, 5 parts of vinylformic acid, 1.5 parts of lauryl mercaptans, 2.0 parts of 2,2'-Azobis(2,4-dimethylvaleronitrile), 10 parts of Virahols was added gradually in polymerization reaction kettle in 3.5 hours.After dropwising, the vinyl hydroxy silicone oil that is 20,000 by 5 parts of molecular weight and 0.3 part of 2,2'-Azobis(2,4-dimethylvaleronitrile) splashed into gradually in reactor in 0.5 hour.Then 80 DEG C of insulations 1 hour, again add 0.5 part of 2,2'-Azobis(2,4-dimethylvaleronitrile), the temperature to 90 that raises gradually DEG C insulation 2 hours.
Then, reduce temperature to 55 DEG C, add 6.5 parts of N, N-dimethylethanolamine neutralizes, in and the time be 30 minutes, after neutralization, under the high speed shear of 2000 revs/min, add 110 parts of deionized water water inlets to disperse, jitter time is 1 hour, after dispersion, can obtain the water based acrylic resin of appearance milky white.
Embodiment 2
In a polymerization reaction kettle that disposes agitator, temperature controller, prolong, nitrogen ingress pipe, add 15 parts of ethyl acetate and 15 parts of propylene glycol monomethyl ethers, be heated to 95 DEG C.Then the mixture of 42 parts of methyl methacrylates, 17 parts of hydroxyethyl methylacrylates, 30 parts of butyl acrylates, 6 parts of vinylformic acid, 1.8 parts of lauryl mercaptans, 2.2 parts of peroxidation 2 ethyl hexanoic acid tert-butyl esters was added gradually in polymerization reaction kettle in 3 hours; The mixture of the polyethers vinyl silicone oil that is then 3000 by 5 parts of molecular weight and 0.3 part of peroxidation 2 ethyl hexanoic acid tert-butyl ester added gradually in polymerization reaction kettle in 1.0 hours, 95 DEG C of insulations 1 hour.Again add 0.5 part of peroxidation 2 ethyl hexanoic acid tert-butyl ester, then temperature to the 105 DEG C insulation 2.5 hours that raises gradually.
Then, reduce temperature to 70 DEG C, add 7.4 parts of N, N-dimethylethanolamine neutralizes, in and the time be 45 minutes, after neutralization, under the high speed shear of 2000 revs/min, add 130 parts of deionized water water inlets to disperse, jitter time is 2 hours, after dispersion, can obtain the water based acrylic resin of appearance milky white.
Embodiment 3
In a polymerization reaction kettle that disposes agitator, temperature controller, prolong, nitrogen ingress pipe, add 30 parts of 2-Butoxyethyl acetates, be heated to 125 DEG C.Then 32 parts of vinylbenzene, 25 parts of hydroxyethyl methylacrylates, 20 parts of 2-EHAs, 10 parts of tertiary carbonic acid glycidyl esters, 8 parts of vinylformic acid and 2.3 parts of peroxidation acetic acid tert-pentyl esters were added gradually in reactor in 4 hours, then the mixture of the bi-vinyl silicone oil of 4 parts of molecular weight 2.5 ten thousand and 0.5 part of peroxidation acetic acid tert-pentyl ester was added gradually in polymerization reaction kettle in 1 hour, 125 DEG C of insulations 1 hour, again add 0.5 part of peroxidation acetic acid tert-pentyl ester, then temperature to the 135 DEG C insulation 2 hours that raises.
Then, reduce temperature to 80 DEG C, add 6.5 parts of N, N-dimethylethanolamine neutralizes, in and the time be 1 hour, after neutralization, under the high speed shear of 2000 revs/min, add 150 parts of deionized water water inlets to disperse, jitter time is 1.5 hours, after dispersion, can obtain the water-based hydroxyl acrylate resin of appearance milky white.
Embodiment 4
In a polymerization reaction kettle that disposes agitator, temperature controller, prolong, nitrogen ingress pipe, add 40 parts of ethyl acetate, be heated to 85 DEG C.Then the mixture of 40 parts of vinylbenzene, 30 parts of Rocryl 410s, 19 parts of butyl acrylates, 6 parts of vinylformic acid, 1.0 parts of lauryl mercaptans, 2.6 parts of benzoyl peroxides was added gradually in polymerization reaction kettle in 3 hours.After dropwising, the vinyl hydroxy silicone oil of 5 parts of molecular weight 8000 and 0.2 part of benzoyl peroxide were added in reactor in 0.5 hour.85 DEG C of insulations 1 hour, again add 0.5 part of benzoyl peroxide, then temperature to the 95 DEG C insulation 2 hours that raises gradually.
Then, reduce temperature to 60 DEG C, add 7.4 parts of N, N-dimethylethanolamine neutralizes, in and the time be 30 minutes, after neutralization, under the high speed shear of 2000 revs/min, add 130 parts of deionized water water inlets to disperse, jitter time is 2 hours, after dispersion, can obtain outward appearance clear water Hydroxylated acrylic resin.
Properties for above-described embodiment and comparative example preparing product is tested, and test result is as shown in following table 2, table 3:
Table 2
Above-mentioned table 2 is the water-based hydroxyl acrylic acid dispersion resin being obtained by comparative example and embodiment,
Wherein, before hydroxyl silicon the third resin dispersion of preparing through above-mentioned each comparative example and embodiment is tested, first it is processed.Particularly, itself and Bayer isocyanate curing agent 3100 are carried out to mixture.When mixture, according to different Bayer cyanate NCO group, the ratio of the contained OH group molar ratio of hydroxyl silicon the third resin dispersion 0.95:1～1.15:1 is uniformly mixed, uniform coating is on BOPP film.Then dry at 45～65 DEG C, then carry out the thermofixation processing in later stage.Then test accordingly.
Table 3
Show according to the test result of comparative example and embodiment, water based acrylic resin prepared by the preparation method of the smooth high gloss resin of water-based scratch resistance of the present invention is compared with comparative example, its scratch resistant performance excellence, can resistance to finger scratch, and all can't see film surface damage from various angles.
In sum, the preparation method of the smooth high gloss resin of scratch resistance of the present invention adopts the reaction solvent that the feature of environmental protection is high, and its step is simple, mild condition.And the scratch resistance resin printing effect of preparing is good, slipping is high, transparency is high, glossiness is good, safe, has excellent scratch resistance and wide application field.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned example embodiment, and in the situation that not deviating from spirit of the present invention or essential characteristic, can realize the present invention with other specific form.Therefore, no matter from which point, all should regard embodiment as exemplary, and be nonrestrictive, scope of the present invention is limited by claims instead of above-mentioned explanation, is therefore intended to all changes that drop in the implication and the scope that are equal to important document of claim to include in the present invention.Any Reference numeral in claim should be considered as limiting related claim.
In addition, be to be understood that, although this specification sheets is described according to embodiment, but be not that each embodiment only comprises an independently technical scheme, this narrating mode of specification sheets is only for clarity sake, those skilled in the art should make specification sheets as a whole, and the technical scheme in each embodiment also can, through suitably closing, form other embodiments that it will be appreciated by those skilled in the art that.
Claims (13)
1. a preparation method for the smooth high gloss resin of scratch resistance, is characterized in that, described preparation method comprises the steps:
S1., reaction solvent is provided, and partial reaction solvent is joined in reactor, be heated to 40～140 DEG C, described reaction solvent is selected from one or more in alkane solvents, esters solvent, alcoholic solvent, alcohol ether solvent, alcoholic solvent;
S2., molecular weight regulator and initiator are provided, to the initiator, remaining reaction solvent and the some monomers that add molecular weight regulator, part in reactor,
Described some monomers comprise: being selected from vinylbenzene or α-vinylbenzene or skeleton symbol is H
2cCH
3cOOR
1compound in one or more hard monomer, being selected from skeleton symbol is H
2cCHCOOR
2compound in one or more soft monomer, and to be selected from Viscoat 295 or Phthalic acid, diallyl ester or skeleton symbol be H
2cCH
3cOOR
3, or skeleton symbol be CH
2cR
4cOR
5compound in one or more function monomer;
S3. in 0.5～1h, in reactor, drip two of bonding silicone oil, described pair of of bonding silicone molecule weight range is selected from 3000～80000, and the described pair of of bonding silicone oil is selected from one or more in hydroxyl vinyl silicone oil or unsaturated polyether organic silicone oil or unsaturated polyester organic silicone oil or vinyl silicone oil compounds;
S4. drip two of bonding silicone oil, after being incubated under temperature of reaction, in 0.5～1h, add gradually remaining initiator, and the temperature that raises is to carrying out after secondary insulation higher than 8～12 DEG C of temperature of reaction, obtains the Hydroxylated acrylic resin of the smooth high gloss of solvent-borne type scratch resistance.
2. the preparation method of the smooth high gloss resin of scratch resistance according to claim 1, is characterized in that, described alkane solvents comprises: normal hexane, normal heptane, octane, long chain alkane or their mixture; Described esters solvent comprises: vinyl acetic monomer, N-BUTYL ACETATE; Described alcoholic solvent comprises: Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol; Described alcohol ether solvent comprises: butyl glycol ether, propandiol butyl ether, propylene glycol monomethyl ether; Described solvent of ether ester type comprises: 2-Butoxyethyl acetate, 1-Methoxy-2-propyl acetate, ethylene glycol ether acetate.
3. the preparation method of the smooth high gloss resin of scratch resistance according to claim 1, it is characterized in that, described initiator is selected from one or more in following material: benzoyl peroxide, peroxidation 2 ethyl hexanoic acid tert-pentyl ester, the peroxidation 2 ethyl hexanoic acid tert-butyl ester, 1, two (tert-pentyl peroxide) the cyclic group alkane of 1-, 1, two (the tert-pentyl peroxides)-3 of 1-, 3, 5-trimethyl-cyclohexane, peroxidation acetic acid tert-pentyl ester, peroxide acid tert-amyl acetate, peroxidation 3, 3, the 5 tri-methyl hexanoic acid tert-butyl esters, peroxidized t-butyl perbenzoate, 3, two (t-butyl peroxy) ethyl hexanoates of 3-, dicumyl peroxide, di-t-butyl peroxide, peroxidation two tert-pentyls, tertbutyl peroxide, t-amyl peroxy hydrogen, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile).
4. the preparation method of the smooth high gloss resin of scratch resistance according to claim 1, it is characterized in that, described step S2 also comprises: in reactor, add reductive agent, described reductive agent is selected from one or more in following material: sodium bisulfite, rongalite, ferrous sulfate.
5. the preparation method of the smooth high gloss resin of scratch resistance according to claim 1, is characterized in that, described molecular weight regulator is: Dodecyl Mercaptan, 2 mercapto ethanol or the mixing of the two.
6. the preparation method of the smooth high gloss resin of scratch resistance according to claim 1, is characterized in that, in described step S1, the reaction solvent joining in reactor is 0.1～10wt% of reaction solvent total amount.
7. the preparation method of the smooth high gloss resin of scratch resistance according to claim 1, is characterized in that, described skeleton symbol is H
2cCH
3cOOR
1compound comprise: methyl methacrylate, isobornyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA.
8. the preparation method of the smooth high gloss resin of scratch resistance according to claim 1, is characterized in that, described skeleton symbol is H
2cCHCOOR
2compound comprise: butyl acrylate, Isooctyl acrylate monomer, ethyl propenoate.
9. the preparation method of the smooth high gloss resin of scratch resistance according to claim 1, is characterized in that, described skeleton symbol is H
2cCH
3cOOR
3compound comprise: methacrylic acid, hydroxyethyl methylacrylate, Rocryl 410, glycidyl methacrylate.
10. the preparation method of the smooth high gloss resin of scratch resistance according to claim 1, is characterized in that, described skeleton symbol is CH
2cR
4cOR
5compound comprise: vinylformic acid, acrylamide, Methacrylamide, N hydroxymethyl acrylamide.
The preparation method of the smooth high gloss resin of 11. scratch resistance according to claim 1, is characterized in that, the ratio of described hard monomer, soft monomer and function monomer obtains by FOX equation, and described FOX equation is:
The preparation method of the smooth high gloss resin of 12. scratch resistance according to claim 1, it is characterized in that, described molecular weight regulator and some monomers adopt the mode dripping to join in reactor, and the time for adding of described molecular weight regulator and some monomers is 3～5h.
13. according to the preparation method of the smooth high gloss resin of scratch resistance described in claim 1～12 any one, it is characterized in that, also comprises step:
S5. in the Hydroxylated acrylic resin of the smooth high gloss of described solvent-borne type scratch resistance, add neutralizing agent, in and the time be 15-60min, neutral temperature is 50-100 DEG C, adds deionized water high speed dispersion, the time is 1-3h, thereby obtain water based acrylic resin.
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