CN102875739A - Epoxy resin modified styrene-acrylic emulsion and preparation method thereof - Google Patents
Epoxy resin modified styrene-acrylic emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses epoxy resin modified styrene-acrylic emulsion and a preparation method thereof. The epoxy resin modified styrene-acrylic emulsion comprises, by weight, 20-44 parts of (methyl) acrylate, 50-74 parts of (methyl) styrene, 6-10 parts of (methyl) acyclic acid, 3-10 parts of epoxy resin, 0.7-4.5 parts of emulsifier, 0.4-4.5 parts of initiator, 0.2-2 parts of buffer agent, 2-8 crosslinking monomer, 4-10 parts of aqueous alkali and 90-290 parts of water. The epoxy resin modified styrene-acrylic emulsion is high in fiber binding force and fine in film-forming property and water resistance. The epoxy resin modified styrene-acrylic emulsion is applied to paint of coated paper. Compared with common emulsion, the epoxy resin modified styrene-acrylic emulsion can evidently improve surface strength and gloss of paper. The epoxy resin modified styrene-acrylic emulsion is high in performance, environment-friendly and applicable to surface sizing of papermaking coating printing.
Description
Technical field
The present invention relates to a kind of epoxy resin modification benzene emulsion, be applied to coated paper coatings.
Background technology
Emulsion is widely used in the bonding of paper coating, and is in application process, more and more higher to the performance requriements of emulsion.Along with improvement and the development of emulsion applications Technology, require emulsion to have good technique suitability, wherein, the most important or cohesiveness of benzene emulsion.Emulsion applications can obviously improve the surface strength of paper in paper coating, improve the glossiness of paper.
Chinese patent CN101280035A discloses a kind of preparation method of emulsion, and the emulsion applications for preparing is in paper coating, and coating is mobile, but surface strength of paper is relatively poor and the water tolerance of emulsion own is relatively poor after the paper coating.
Summary of the invention
Purpose of the present invention discloses a kind of epoxy resin modification benzene emulsion, the defective that exists to overcome prior art.
Described epoxy resin modification benzene emulsion is to adopt the component that comprises following weight part to prepare:
Described (methyl) acrylate is selected from least a in methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, ethyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, methacrylic acid-2-ethylhexyl, acrylic or methacrylic acid C8～C16 alkyl ester;
Described cross-linking monomer is selected from least a in vinylformic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate or the methacrylic acid-2-hydroxypropyl acrylate.
Said Resins, epoxy is selected from middle E-44 Resins, epoxy (propanepoxy resin, the oxirane value average index is 0.44mol/100g), E-42 Resins, epoxy (propanepoxy resin, the oxirane value average index is 0.44mol/100g), E-20 Resins, epoxy (propanepoxy resin, the oxirane value average index is 0.20mol/100g), E-12 Resins, epoxy (propanepoxy resin, the oxirane value average index is 0.12mol/100g), E-06 Resins, epoxy (propanepoxy resin, the oxirane value average index is 0.06mol/100g), in the E-03 Resins, epoxy (propanepoxy resin, oxirane value average index are 0.03mol/100g) one or more; Said emulsifying agent is the mixture of anionic emulsifier and nonionic emulsifying agent; Weight ratio is 1:5～5:1;
Said initiator is selected from least a in Potassium Persulphate, Sodium Persulfate, the ammonium persulphate;
Described buffer reagent is selected from sodium bicarbonate, yellow soda ash, sodium-acetate or Sodium phosphate dibasic.
Said alkali aqueous solution is selected from least a in aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, the ammonium hydroxide aqueous solution, and weight concentration is 28～32%;
The anionic emulsifier agent is selected from least a in C10～C20 sodium alkyl benzene sulfonate, C10～C20 sodium alkyl naphthalene sulfonate, C10～C20 sodium alkyl sulfate, dialkyl group-2-sodium sulfosuccinate, dicyclohexyl-2-sodium sulfosuccinate, Succinic Acid sodium sulfonate, sodium oleate, potassium oleate, the Emulphor FM;
Nonionic emulsifying agent is selected from Witconol AL 69-66, anhydrous sorbitol tristearate (this dish 65), glycol fatty acid ester, propylene glycol fatty acid ester, anhydrous sorbitol list hard fatty acid ester (this dish 60), sorbitan monooleate (span 80), the Diethylene Glycol fatty acid ester, anhydrous sorbitol monopalmitate (this dish 40), the polyoxytrimethylene hard fatty acid ester, sorbitan mono-laurate (this dish 20), the polyoxyethylene hard fatty acid ester, the lauric acid polyoxyethylene ester, polyoxyethylene (4) anhydrous sorbitol list hard fatty acid ester (Tween61), polyoxyethylene (5) sorbitan monooleate (sorbimacrogol oleate100), polyoxyethylene (20) anhydrous sorbitol tristearate (polysorbate65), polyoxyethylene (20) Witconol AL 69-66 (polysorbate85), the polyoxyethylene monoleate, fatty alcohol amine polyoxyethylene ether, alkylphenol polyoxyethylene, the polyoxyethylene mono-laurate, polyoxyethylene castor oil, polyoxyethylene (4) sorbitan mono-laurate (tween 21), polyoxyethylene (20) anhydrous sorbitol list hard fatty acid ester (polysorbate60), polyoxyethylene (20) sorbitan monooleate (tween 80), polyoxyethylene (20) anhydrous sorbitol monopalmitate (polysorbate40), at least a in polyoxyethylene (20) sorbitan mono-laurate (polysorbas20).
The method of described epoxy resin modification benzene emulsion comprises the steps:
(1) with (methyl) acrylate, (methyl) vinylbenzene, (methyl) vinylformic acid and Resins, epoxy mixed dissolution;
(2) water with mixed solution, cross-linking monomer, emulsifying agent and the gross weight 80～90% of step (1) mixes, and obtains the mix monomer pre-emulsion;
(3) mix monomer pre-emulsion, buffer reagent, the emulsifying agent of gross weight 20～60% and the water of surplus with the step (2) of gross weight 5～20% mixes, be warming up to 60 ℃～95 ℃, then the initiator that adds gross weight 20～50% reacted 10～30 minutes, obtained seed emulsion;
(4) with the mix monomer pre-emulsion of step (2) remainder and the initiator of remainder, in 1～3 hour, splash into simultaneously respectively in the described seed emulsion, 60 ℃～95 ℃ were reacted 1～3 hour;
(5) 50～80 ℃ of insulations 1～2 hour are cooled to 20～30 ℃, with alkali aqueous solution neutralization, filter, and make the weight solid content and be 30～50% epoxy resin modification benzene emulsion.
Described epoxy resin modification benzene emulsion can be applicable to coated paper coatings;
Hydroxyl, carboxyl isoreactivity group that the present invention introduces make the epoxy resin modification benzene emulsion have the multiple performances such as bridging property, color stuffing consistency, polarity; Add the thiazolinyl carboxylic acid monomer, obtain the polymer segment of carboxylate-containing, improve the Investigation of stabilized dispersion of nano of emulsion particle in water, thereby reduce emulsifier, improved the water tolerance of filming.Among the present invention, add a small amount of Resins, epoxy, unexpected, be applied in the coating of White Board, obviously improve surface strength and the glossiness of paper.This may because, Resins, epoxy has epoxy group(ing), ether even contains two keys, the cementability that shows, erosion resistance etc.Resins, epoxy is used for the phenylpropyl alcohol modification, the advantage grafting of Resins, epoxy in benzene emulsion, has been improved the use propertieies such as intensity, cementability, film forming properties, hardness of film of product.
Described epoxy resin modification benzene emulsion has with fibrous binding force higher, good film-forming properties and water tolerance advantage.Be applied to the coating of White Board, compare with ordinary emulsion, can obviously improve surface strength and the glossiness of paper, can satisfy the papermaking paint printing with the product of top sizing with high-performance, environmental protection for a kind of.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited to this.
Embodiment 1
With the mixed aqueous solution that adds the 2g 2-hydroxyethyl methacrylate and formed by 0.25g Sodium dodecylbenzene sulfonate, 0.1g polyoxyethylene (20) sorbitan monooleate (tween 80), 60g deionized water in the mixture behind the abundant mixed dissolution under 20g n-butyl acrylate, 74g vinylbenzene and 6g vinylformic acid, 8g Resins, epoxy (E-42) normal temperature, then stir on the machine at JB90-D type powerful motor, rotating speed with 1000rpm stirred 30 minutes, obtained monomer pre-emulsion;
The 0.2g sodium bicarbonate is being housed, 0.25g Sodium dodecylbenzene sulfonate, 0.1g polyoxyethylene (20) sorbitan monooleate (tween 80), add the above-mentioned pre-emulsion of 15g in the four-hole bottle of 176g deionized water, be warmed up to 60 ℃, adding 0.1g Potassium Persulphate is dissolved in the aqueous solution of 10g deionized water, react to emulsion change basket, drip simultaneously the aqueous solution that remaining pre-emulsion and 0.3g Potassium Persulphate are dissolved in the 10g deionized water, after 3h drips off, be incubated 1 hour, after being cooled to room temperature, adding 4g weight concentration is 28% ammonium hydroxide aqueous solution adjusting pH, 100 eye mesh screens filter and namely get normal temperature epoxy resin modified benzene emulsion, weight solid content: 30.23wt%, pH=7.18 (using PHS-3C Accurate pH instrumentation to get).
Embodiment 2
To add 1g vinylformic acid-2-hydroxyl ethyl ester and 0.1g dialkyl group-2-sodium sulfosuccinate in the mixture behind the abundant mixed dissolution under 40g ethyl propenoate, 50g vinyl toluene and 10g methacrylic acid, 4g Resins, epoxy (E-20) normal temperature, 0.4g the mixed aqueous solution that sorbitan mono-laurate (this dish 20), 1.5g polyoxyethylene monoleate, 60g deionized water form, then stir on the machine at JB90-D type powerful motor, rotating speed with 1500rpm stirred 30 minutes, obtained monomer pre-emulsion.
The 2g Sodium phosphate dibasic is being housed, 1.5g dodecyl sodium naphthalene sulfonate, 1g sorbitan mono-laurate (this dish 20), 26.7g add the above-mentioned pre-emulsion of 15g in the four-hole bottle of deionized water, be warmed up to 95 ℃, adding 1g Sodium Persulfate is dissolved in the aqueous solution of 10g deionized water, react to emulsion change basket, drip simultaneously the aqueous solution that remaining pre-emulsion and 3g Sodium Persulfate are dissolved in the 10g deionized water, after 1h drips off, 80 ℃ are incubated 1 hour, after being cooled to room temperature, adding 10g weight concentration is 32% aqueous sodium hydroxide solution adjusting pH, 100 eye mesh screens filter and namely get normal temperature epoxy resin modified benzene emulsion, weight solid content: 50.18wt%, pH=9.86 (using PHS-3C Accurate pH instrumentation to get).
Embodiment 3
With the 10g methyl methacrylate, the 34g ethyl acrylate, the 48g vinyl toluene, fully add 1.5g methacrylic acid-2-hydroxypropyl acrylate in the mixture behind the mixed dissolution under 8g methacrylic acid and 10g Resins, epoxy (E-20) normal temperature and by 0.1g Succinic Acid sodium sulfonate, 0.2g polyoxytrimethylene hard fatty acid ester, 0.5g sodium lauryl sulphate, 0.2g the mixed aqueous solution that sorbitan monooleate (span 80) and 60g deionized water form, then stir on the machine at JB90-D type powerful motor, rotating speed with 2000rpm stirred 20 minutes, obtained monomer pre-emulsion.
The 0.5g sodium bicarbonate is being housed, 0.2g potassium oleate, 0.8g Diethylene Glycol fatty acid ester, 0.3g sodium lauryl sulphate, 94.9g add the above-mentioned pre-emulsion of 15g in the four-hole bottle of deionized water, be warmed up to 75 ℃, adding 0.8g Potassium Persulphate is dissolved in the aqueous solution of 10g deionized water, react to emulsion change basket, drip simultaneously the aqueous solution that remaining pre-emulsion and 1.5g Potassium Persulphate are dissolved in the 10g deionized water, 1.5h after dripping off, be incubated 1 hour, after being cooled to room temperature, the adding weight concentration is 30% potassium hydroxide aqueous solution adjusting pH, 100 eye mesh screens filter and namely get normal temperature epoxy resin modified benzene emulsion, weight solid content: 40.18wt%, pH=8.41 (using PHS-3C Accurate pH instrumentation to get).
Embodiment 4
Comparative Examples: the emulsion of pressing the method preparation of CN101280035A
With embodiment 1～3 and Comparative Examples, by following formulated coating
95 grades of water-ground limestone 400g
Brazil china clay 100g
Emulsion (dry weight) 50g
Deionized water is an amount of, and adjusting the coating weight solid content is 65%.
Experimentation: 1) 95 grades of water-ground limestones, Brazilian china clay and appropriate amount of deionized water are added high speed dispersor, the rear high speed dispersion 20～30min that stirs, qualified to fineness, add emulsion under the low speed, after stirring, discharging, 100 eye mesh screens filter.2) will adopt the coating of embodiment 1～5 and Comparative Examples emulsion preparation to be coated with at the 75g/m2 art base paper with the 10# spreading rod, glue spread 20g/m2, for subsequent use.3) coating rolling condition: get respectively above-mentioned coating pattern with twice of the hard press polish of small-sized rolling press (0.3Mpa, 85 ℃).For subsequent use.
A) adopt IGT printability instrument (Japanese KRK) to detect above-mentioned White Board:
Criterion: surface strength shows that more greatly the emulsion effect is better
| Surface strength m/s | |
| Comparative Examples | 0.65 |
| Embodiment 1 | 0.97 |
| Embodiment 2 | 0.88 |
| Embodiment 3 | 0.92 |
B) paper to be measured was placed 24 hours under the constant-temperature constant-humidity environment of 25 ℃ of temperature, relative humidity 60%, detected sheet gloss with the Ou Yi JKGZ-1 of company vancometer.
| Sample | Glossiness/Gs |
| Blank | 30.0 |
| The contrast sample | 45.0 |
| Embodiment 1 | 68.2 |
| Embodiment 2 | 65.0 |
| Embodiment 3 | 67.0 |
Can find out from above-mentioned application result: use the styrene-acrylate emulsion for surface coatings of coated paper of the embodiment of the invention 1～3 preparation, compare with Comparative Examples, be applied to the painting coating of White Board, can significantly improve surface strength and the coating glossiness of White Board.
Claims (6)
1. the epoxy resin modification benzene emulsion is characterized in that, is to adopt the component that comprises following weight part to prepare:
2. epoxy resin modification benzene emulsion according to claim 1, it is characterized in that, described (methyl) acrylate is selected from least a in methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, ethyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, methacrylic acid-2-ethylhexyl, acrylic or methacrylic acid C8～C16 alkyl ester;
Described cross-linking monomer is selected from least a in vinylformic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate or the methacrylic acid-2-hydroxypropyl acrylate;
Said Resins, epoxy is selected from one or more in E-44 Resins, epoxy, E-42 Resins, epoxy, E-20 Resins, epoxy, E-12 Resins, epoxy, E-06 Resins, epoxy, the E-03 Resins, epoxy;
Said emulsifying agent is the mixture of anionic emulsifier and nonionic emulsifying agent; Weight ratio is 1:5～5:1.
3. epoxy resin modification benzene emulsion according to claim 1 is characterized in that, said initiator is selected from least a in Potassium Persulphate, Sodium Persulfate, the ammonium persulphate; Described buffer reagent is selected from sodium bicarbonate, yellow soda ash, sodium-acetate or Sodium phosphate dibasic, and said alkali aqueous solution is selected from least a in aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, the ammonium hydroxide aqueous solution, and weight concentration is 28～32%.
4. epoxy resin modification benzene emulsion according to claim 2, it is characterized in that, the anionic emulsifier agent is selected from least a in C10～C20 sodium alkyl benzene sulfonate, C10～C20 sodium alkyl naphthalene sulfonate, C10～C20 sodium alkyl sulfate, dialkyl group-2-sodium sulfosuccinate, dicyclohexyl-2-sodium sulfosuccinate, Succinic Acid sodium sulfonate, sodium oleate, potassium oleate, the Emulphor FM;
Nonionic emulsifying agent is selected from Witconol AL 69-66, anhydrous sorbitol tristearate (this dish 65), glycol fatty acid ester, propylene glycol fatty acid ester, anhydrous sorbitol list hard fatty acid ester (this dish 60), sorbitan monooleate (span 80), the Diethylene Glycol fatty acid ester, anhydrous sorbitol monopalmitate (this dish 40), the polyoxytrimethylene hard fatty acid ester, sorbitan mono-laurate (this dish 20), the polyoxyethylene hard fatty acid ester, the lauric acid polyoxyethylene ester, polyoxyethylene (4) anhydrous sorbitol list hard fatty acid ester (Tween61), polyoxyethylene (5) sorbitan monooleate (sorbimacrogol oleate100), polyoxyethylene (20) anhydrous sorbitol tristearate (polysorbate65), polyoxyethylene (20) Witconol AL 69-66 (polysorbate85), the polyoxyethylene monoleate, fatty alcohol amine polyoxyethylene ether, alkylphenol polyoxyethylene, the polyoxyethylene mono-laurate, polyoxyethylene castor oil, polyoxyethylene (4) sorbitan mono-laurate (tween 21), polyoxyethylene (20) anhydrous sorbitol list hard fatty acid ester (polysorbate60), polyoxyethylene (20) sorbitan monooleate (tween 80), polyoxyethylene (20) anhydrous sorbitol monopalmitate (polysorbate40), at least a in polyoxyethylene (20) sorbitan mono-laurate (polysorbas20).
5. prepare the method for each described epoxy resin modification benzene emulsion of claim 1～4, it is characterized in that, comprise the steps:
(1) with (methyl) acrylate, (methyl) vinylbenzene, (methyl) vinylformic acid and Resins, epoxy mixed dissolution;
(2) mixed solution, cross-linking monomer, emulsifying agent and the water with step (1) mixes, and obtains the mix monomer pre-emulsion;
(3) emulsifying agent and the water with the mix monomer pre-emulsion of the step (2) of gross weight 5～20%, buffer reagent, gross weight 20～60% mixes, be warming up to 60 ℃～95 ℃, then the initiator that adds gross weight 20～50% reacted 10～30 minutes, obtained seed emulsion;
(4) with the mix monomer pre-emulsion of step (2) remainder and the initiator of remainder, in 1～3 hour, splash into simultaneously respectively in the described seed emulsion, 60 ℃～95 ℃ were reacted 1～3 hour;
(5) 50～80 ℃ of insulations 1～2 hour are cooled to 20～30 ℃, with alkali aqueous solution neutralization, filter, and make the weight solid content and be 30～50% epoxy resin modification benzene emulsion.
6. the application of each described epoxy resin modification benzene emulsion of claim 1～4 is used for coated paper coatings.
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