CN102219873B - Triallyl isocyanurate modified aqueous hydroxyl acrylic resin and preparation method thereof - Google Patents
Triallyl isocyanurate modified aqueous hydroxyl acrylic resin and preparation method thereof Download PDFInfo
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Abstract
The invention provides a triallyl isocyanurate modified aqueous hydroxyl acrylic resin and a preparation method thereof. The preparation method is characterized in that an allyl monomer with a special structure is introduced in the composition of a polymerized monomer, and simultaneously the allyl monomer is required to be dropwise added by using a two-step method. Aqueous double-component varnish and top coat can be prepared by mixing the aqueous hydroxyl acrylic resin with fatty polyisocyanurate, thus the aqueous hydroxyl acrylic resin prepared by the method has the advantages of excellent water tolerance, weather resistance and stain resistance, can be widely used for automobile repair, large-size transportation coating and industrial coating.
Description
Technical field
The present invention relates to organic synthesis and coating industry in the chemical industry field, specifically, relate to a kind of triallyl isocyanate modified water-soluble Hydroxylated acrylic resin of preparing water-borne coatings and preparation method thereof that is applicable to.
Background technology
Progress along with society, the raising day by day of people's living standard, environmental protection more and more is subject to people's attention, become the development trend of current all trades and professions, country has also put into effect many policies and regulations the discharging of hazardous and noxious substances has strictly been controlled, coating industry is no exception, and consequently, the demand to water-borne coatings on Coating Market increases gradually.The development and application of water-borne acrylic resin coating starts from the 1950's, has obtained developing rapidly to the beginning of the seventies.The development Water-borne Acrylic Coating can replace water with most of organic volatile solvent under the condition of the various characteristic properties that guarantee acrylic coating, reduce the use of volatile solvent, thereby reaches the purpose of decrease topsoil.Its flash-point of mixture of hydrophilic solvent and water is high more a lot of than the flash-point of solvent itself, the mixture of solvent and water generally do not continue to prolong combustion when reaching flash-point and very fast oneself put out, thereby improved security.Thereby compare with traditional solvent based coating, water-borne coatings has use safety, and price is low, saving resource and the energy, the advantages such as environmental contamination reduction and public hazards become the main development direction of current coatings industry.Water-borne acrylic resin has the performances such as good weathering resistance, resistance to acids and bases, anti-staining property, has become a kind of important coating variety.The exploitation of water-borne acrylic resin in recent years, application cause people's attention day by day, constantly expand in the application of industrial coating, civilian paint field.
Summary of the invention
The present invention not only is intended to solve the general relatively poor problem of water based acrylic resin water tolerance, has also further overcome when acid number is identical, drips the poor weak point of the existing package stability of resin of Acrylic Acid Monomer preparation with single stage method.
The present invention realizes like this, it is a kind of water based acrylic resin of cyanacrylate modification, its feed composition comprises: acrylic monomer, styrene monomer, allyl monomer, strong solvent, initiator, solubility promoter and neutralizing agent, it is characterized in that, described acrylic monomer is the mixture of Acrylic Acid Monomer and acrylic acid derivative monomer; Described allyl monomer is cyanacrylate; Described strong solvent is tertiary monocarboxylic acid derivatives active solvent; Described initiator is the peroxide initiator; Described solubility promoter is the mixture of pure ether solvent and petrolic solvent; Described neutralizing agent is the amine neutralizing agent, and in mass parts, the proportioning of each feed composition is as follows:
The feed composition mass parts
Acrylic Acid Monomer 20～70;
Styrene monomer 15～35;
Allyl monomer 1～3;
Strong solvent 10～50;
Initiator 1～5;
Solubility promoter 10～30;
Neutralizing agent 1～10.
Acrylic monomer described here is the mixture of Acrylic Acid Monomer and acrylic acid derivative monomer, and Acrylic Acid Monomer is selected from one or both in vinylformic acid, methacrylic acid; The acrylic acid derivative monomer is selected from one or more the mixture in methyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl methylacrylate and Rocryl 410.That is to say, except the higher acrylic monomer of selective polymerization activity, also comprised the acrylic acid derivative of hydroxyl in the acrylic acid or the like raw material, like this can to hydroxyl acrylic aqueous dispersion wetting ability and stability are preferably arranged.
The present invention has also selected styrene monomer in synthetic raw material, this is to have excellent dryness, hardness, gloss, fullness ratio, chemoresistance and water tolerance after the cold coating film forming due to styrene monomer.Applicable styrene monomer is selected from a kind of in meta-vinyl toluene, p-methylstyrene, vinylbenzene or their mixture.
The strong solvent of selecting in the present invention is the tertiary monocarboxylic acid derivative, can be selected from a kind of in tertiary carbonic acid glycidyl ester, tertiary ethylene carbonate or their mixture.Wherein especially take tertiary carbonic acid glycidyl ester as good.The effect of tertiary monocarboxylic acid group is to provide low viscosity and good pigment wettability, the compatibility with non-polar solvent, good anti-UV, excellent chemical resistant properties, height hydrophobic nature and crosslinked sterically hindered protection; And that oh group can provide is crosslinked, interlayer adheres to and with the compatibility of polarity coating.Introduce tertiary carbonic acid glycidyl ester (Shell Co. Ltd, Cardura E-10p) in resin of the present invention some excellent performances can be provided, as high solvent compatibility and low viscosity, improve simultaneously acid resistance and outdoor weather resisteant.
According to the present invention, what the initiation of resin polymerization process was adopted is peroxide initiator, and applicable superoxide is selected from a kind of in peroxidized t-butyl perbenzoate, peroxidation two tert-pentyls or their mixture.For this reaction system, selecting is that the high-temperature initiator peroxidized t-butyl perbenzoate is particularly suitable.
The solubility promoter that uses in this building-up reactions is the mixture of pure ether solvent and petrolic solvent, optional a kind of in butyl glycol ether, propandiol butyl ether of alcohol ether solvent or their mixture, petrolic solvent can be selected from a kind of in S-100, S-200 or their mixture.A better scheme is to select butyl glycol ether and S-100 solvent complex, when two kinds of solvent burden ratios are 1: 1, and account for the total solids quality 15～18% the time for best, at this moment the synthetic resin viscosity that obtains is moderate, the good stability of resin after emulsification.
The present invention compared with prior art, a key character is: the present invention has introduced allyl monomer in the polymerizable acrylic monomer process, is wherein good with cyanacrylate (Triallyl isocyanurate, be called for short TAIC) especially.Its structure is as follows:
This is a kind of multi-functional olefinic monomer that contains fragrant heterocycle, is mainly used in multi-purpose linking agent and properties-correcting agent.TAIC has three allyl functionality, has the general general character of aliphatics alkene, can participate in multiple addition reaction, homopolymerization and copolyreaction, Prins reaction etc.Performance is very stable at normal temperatures, and under superoxide caused, TAIC was than the easier polymerization reaction take place of other allyl group, and it can make the performance of polymkeric substance be improved, and comprises mechanical property, thermotolerance, water tolerance and weathering resistance etc.
The cyanacrylate that adds in the present invention can carry out radical polymerization with Acrylic Acid Monomer, water based acrylic resin is carried out modification, because it contains the structure of three special allyl functionality, can form macromolecular dendritic structure after copolymerization, increased the molecular weight of resin, improved the cross-linking density that resin and aliphatic isocyanates solidify, the performance of filming is improved, particularly water tolerance, be significantly improved.The addition of TAIC is that 1～3% of total solids quality is advisable, when add solid amount 2.5% the time, best to the improved performance of acrylic resin.
Preparation method according to water based acrylic resin of the present invention is characterised in that, vinylformic acid is divided into the dropping of two steps when synthetic resins, that is: the first step is that all monomers except Acrylic Acid Monomer and the Acrylic Acid Monomer of part and the mixture of initiator are dripped polymerization; Second step is remaining Acrylic Acid Monomer to be mixed with a part of initiator again to drip.Concrete steps comprise:
(1) add solubility promoter and strong solvent in the reactor that stirring rake, thermometer and condenser are housed, logical nitrogen stirs and is warming up to 150～155 ℃;
(2) drip first mix monomer at this temperature, comprise part propylene acid mono and whole acrylic acid derivative monomer, styrene monomer, allyl monomer and part initiator, wherein, Acrylic Acid Monomer accounts for 80～90 quality % of its total amount, initiator accounts for 77～84 quality % of its total amount, time for adding is 4～5h, insulation 0.3～0.6h also is cooled to 145 ℃ of left and right, add the second batch monomer, comprise remaining Acrylic Acid Monomer and part initiator, wherein, Acrylic Acid Monomer accounts for 10～20 quality % of its total amount, initiator accounts for 5～8 quality % of its total amount, time for adding is 10～15min, then add rapidly remaining initiator, 11～16 quality % for total amount of initiator, insulation 1.5～2.5h, make prepolymer,
(3) above-mentioned prepolymer is cooled to 70～75 ℃, add lentamente in three batches neutralizing agent, first is 20～30 quality % of total amount, second batch is 30～40 quality % of total amount, the 3rd batch is 30～40 quality % of total amount, in stirring and after 20～40min, slowly drips deionized water emulsification, time for adding is about 1.5～2.5h, then fully stirs 0.5～1.5h discharging.
water based acrylic resin according to the present invention's preparation can be dispersed into water-base resin well in water, this is mainly by in the carboxyl on molecular chain and salify, this resin is closer to dispersion, when identical acid number, it is relatively poor that single stage method drips the prepared resin wetting ability of mix monomer, package stability is bad, easily layering, and adopt two-step approach of the present invention to drip Acrylic Acid Monomer, wherein the vinylformic acid of second step dropping directly has been connected on the end group of molecular chain carboxylic group, make in more carboxyl and salify, increased the wetting ability of resin, also improved the package stability of resin.when the monomer consumption of carboxyl group is very few, mixed water based acrylic resin can contain the visible small-particle, show that the resin wetting ability is inadequate, and when this type of monomer is too much, although obtain the finely dispersed water based acrylic resin of oyster white, but after use cured with isocyanates film forming, blushing is arranged, this is can't shed from paint film because very good wetting ability causes moisture, but also can directly have influence on the water tolerance of paint film, therefore, the consumption of carboxyl group monomer is that 8～15% of synthesizing formula component total mass is advisable, at this moment after prepared water based acrylic resin film forming, over-all properties is best.
Acrylic resin of the present invention be by in amine and side chain on the carboxyl salify and be scattered in water, applicable amine neutralizing agent is selected from one or more the mixture in dimethylethanolamine, trolamine and ammoniacal liquor, and comparatively applicable is dimethylethanolamine.Degree of neutralization is expressed by pH value, and pH value directly affects the performance of variation, package stability and the paint film of viscosity.When being neutralized to PH and being 7.5～8.5, modest viscosity, be uniformly dispersed, gloss of film is good, fullness ratio is good.
By as seen above-mentioned, water based acrylic resin according to the cyanacrylate modification of the present invention preparation, its advantage is: emulsion particle diameter is little, preparation technology's simple and stable, the product period of storage is long, at room temperature can with the crosslinked film forming of water-based isocyanate solidifying agent, have good film-forming properties, excellent water tolerance, chemical proofing, can be widely used in car repair, high-grade water-borne wood coating and industrial coating.The typical performance of water-borne acrylic resin of the present invention is as shown in table 1:
The typical characteristics of table 1 Triallyl isocyanurate modified aqueous hydroxyl acrylic resin
Test item typical case performance
Appearance milky white is slightly transparent
Solid content, % 40～45
Viscosity, mPas 500～2000
PH value 7.5～8.5
Particle diameter, nm 100～200
Molecular weight distribution 1.7～2.4
Embodiment
Below by embodiment, the present invention is described in further detail, but the present invention is in no way limited to these embodiment.
Embodiment 1
The raw material that the preparation Triallyl isocyanurate modified aqueous hydroxyl acrylic resin is used forms as shown in table 2.
Table 2 preparation Triallyl isocyanurate modified aqueous hydroxyl acrylic resin forms with raw material
| Component | Quality (g) |
| Tertiary carbonic acid glycidyl ester | 25.7 |
| Butyl glycol ether | 8 |
| The S-100 solvent | 8 |
[0044]
| Vinylformic acid | 9 |
| Butyl acrylate | 7.2 |
| Hydroxyethyl methylacrylate | 9.8 |
| Methyl methacrylate | 17.1 |
| Vinylbenzene | 19.1 |
| Cyanacrylate | 1.35 |
| Peroxidized t-butyl perbenzoate | 2.44 |
| Dimethylethanolamine | 2.6 |
| Deionized water | 93.6 |
Concrete preparation method is as follows: tertiary carbonic acid glycidyl ester, butyl glycol ether and S-100 solvent are added in the 500ml four-hole boiling flask that thermometer, whipping appts and condenser are housed, pass into the drying nitrogen protection, start stirring and be warming up to 150～155 ℃; Then begin to drip first mix monomer, comprise: vinylformic acid, butyl acrylate, hydroxyethyl methylacrylate, methyl methacrylate, vinylbenzene, cyanacrylate and peroxidized t-butyl perbenzoate, vinylformic acid 7.7g wherein, peroxidized t-butyl perbenzoate 2.05g, approximately dripping off in 4.5h, insulation 0.5h also is cooled to 145 ℃ of left and right; Add the second batch monomer, comprising: vinylformic acid 1.3g and peroxidized t-butyl perbenzoate 0.13g, approximately 15min drips off, and adds immediately peroxidized t-butyl perbenzoate 0.26g, and temperature remains on 145～150 ℃, insulation 2h, the survey acid number is 24mgKOH/g; Material is cooled to 70～75 ℃, according to acid number, adding lentamente in three batches degree of neutralization is that 50% dimethylethanolamine neutralizes, fully stir 30min, drip deionized water and carry out emulsification, approximately 2h adds, and adds appropriate 10% dimethyl ethanol amine aqueous solution and regulates pH value and viscosity (amount of dimethylethanolamine used herein is not calculated in the total amount of dimethylethanolamine), filters discharging after fully stirring 30～40min.
The water based acrylic resin solids content of above-mentioned cyanacrylate modification is 45%, and pH value is 8.2, and emulsion particle diameter is 100～200nm, and viscosity (rotational viscosimeter NDJ-1) is 1300mPas, molecular weight distribution 2.0; Be mixed with baked paint with this resin and melamine resin Cymel303 (cyanogen special company produce), this system is toasted under 120 ℃ and just can be solidified in 30 minutes, is applicable to single-component industrial baking coating.
Embodiment 2
The raw material for preparing in this example Triallyl isocyanurate modified aqueous hydroxyl acrylic resin forms as shown in table 3.As different from Example 1, improve the amount of cyanacrylate in the material component in this example, reduced acrylic acid amount.
Table 3 preparation Triallyl isocyanurate modified aqueous hydroxyl acrylic resin forms with raw material
| Component | Quality (g) |
| Tertiary carbonic acid glycidyl ester | 25.7 |
| Butyl glycol ether | 8 |
| The S-100 solvent | 8 |
| Vinylformic acid | 8.75 |
| Butyl acrylate | 7.2 |
| Hydroxyethyl methylacrylate | 9.8 |
| Methyl methacrylate | 17.1 |
| Vinylbenzene | 19.1 |
| Cyanacrylate | 1.8 |
[0051]
| Peroxidized t-butyl perbenzoate | 2.44 |
| Dimethylethanolamine | 2.8 |
| Deionized water | 108 |
Concrete preparation method is as follows: tertiary carbonic acid glycidyl ester, butyl glycol ether and S-100 solvent are added in the 500ml four-hole boiling flask that thermometer, whipping appts and condenser are housed, pass into the drying nitrogen protection, start stirring and be warming up to 150～155 ℃; Then begin to drip first mix monomer, comprise: vinylformic acid, butyl acrylate, hydroxyethyl methylacrylate, methyl methacrylate, vinylbenzene, cyanacrylate and peroxidized t-butyl perbenzoate, vinylformic acid 7.45g wherein, peroxidized t-butyl perbenzoate 2.05g, approximately dripping off in 4.5h, insulation 0.5h also is cooled to 145 ℃ of left and right; Add the second batch monomer, comprising: vinylformic acid 1.3g and peroxidized t-butyl perbenzoate 0.13g, approximately 15min drips off, and adds immediately peroxidized t-butyl perbenzoate 0.26g, and temperature remains on 145～150 ℃, insulation 2h, the survey acid number is 22mgKOH/g; Material is cooled to 70～75 ℃, according to acid number, adding lentamente in three batches degree of neutralization is that 50% dimethylethanolamine neutralizes, fully stir 30min, drip deionized water and carry out emulsification, approximately 2h adds, and adds appropriate 10% dimethyl ethanol amine aqueous solution and regulates pH value and viscosity (amount of dimethylethanolamine used herein is not calculated in the total amount of dimethylethanolamine), filters discharging after fully stirring 30～40min.
The water based acrylic resin solids content of above-mentioned cyanacrylate modification is 42%, and pH value is 8.4, and emulsion particle diameter is 100～200nm, and viscosity (rotational viscosimeter NDJ-1) is 1800mPas, molecular weight distribution 2.4; The aqueous double-component polyurethane finish paint that is mixed with this resin and aliphatic polymeric isocyanate Bayhydur3100 (Beyer Co., Ltd's product), after solidifying, paint film has good gloss and chemical proof, particularly after the consumption that has improved cyanacrylate, the water tolerance of paint film is significantly improved, this system can be applicable to car refinishing paint, and performance is as shown in table 4.
Table 4 coating property of embodiment 2 Triallyl isocyanurate modified aqueous hydroxyl acrylic resin systems
| Project | Detected result |
| Outward appearance | Surface free of pinholes and particle |
| 60 ° of gloss, % | 95 |
| Pencil hardness | 2H |
| Impact kgcm | 50 |
| Snappiness, mm | 1 |
| Sticking power, level | 0 |
| Drawing test, mm | 6 |
| Water tolerance (25 ± 1 ℃), h | 72h is without considerable change |
| Chemical proofing, 3% sulfuric acid, 2% sodium hydroxide, 5% acetic acid | The 15min appearance color is unchanged |
Embodiment 3
Compare with embodiment 1, improved the amount of cyanacrylate and initiator peroxidized t-butyl perbenzoate in this example, the raw materials used composition of preparation resin is as shown in table 5.
Table 5 preparation Triallyl isocyanurate modified aqueous hydroxyl acrylic resin forms with raw material
| Component | Quality (g) |
| Tertiary carbonic acid glycidyl ester | 25.7 |
| Butyl glycol ether | 8 |
| The S-100 solvent | 8 |
| Vinylformic acid | 9 |
| Butyl acrylate | 7.2 |
| Hydroxyethyl methylacrylate | 9.8 |
[0060]
| Methyl methacrylate | 17.1 |
| Vinylbenzene | 19.1 |
| Cyanacrylate | 2.3 |
| Peroxidized t-butyl perbenzoate | 3.2 |
| Dimethylethanolamine | 2.8 |
| Deionized water | 105 |
Concrete preparation method is as follows: tertiary carbonic acid glycidyl ester, butyl glycol ether and S-100 solvent are added in the 500ml four-hole boiling flask that thermometer, whipping appts and condenser are housed, pass into the drying nitrogen protection, start stirring and be warming up to 150～155 ℃; Then begin to drip first mix monomer, comprise: vinylformic acid, butyl acrylate, hydroxyethyl methylacrylate, methyl methacrylate, vinylbenzene, cyanacrylate and peroxidized t-butyl perbenzoate, vinylformic acid 7.7g wherein, peroxidized t-butyl perbenzoate 2.45g, approximately dripping off in 4.5h, insulation 0.5h also is cooled to 145 ℃ of left and right; Add the second batch monomer, comprising: vinylformic acid 1.3g and peroxidized t-butyl perbenzoate 0.25g, approximately 15min drips off, and adds immediately peroxidized t-butyl perbenzoate 0.5g, and temperature remains on 145～150 ℃, insulation 2h, the survey acid number is 24mgKOH/g; Material is cooled to 70～75 ℃, according to acid number, adding lentamente in three batches degree of neutralization is that 50% dimethylethanolamine neutralizes, fully stir 30min, drip deionized water and carry out emulsification, approximately 2h adds, and adds appropriate 10% dimethyl ethanol amine aqueous solution and regulates pH value and viscosity (amount of dimethylethanolamine used herein is not calculated in the total amount of dimethylethanolamine), filters discharging after fully stirring 30～40min.
The water based acrylic resin solids content of above-mentioned cyanacrylate modification is 43%, and pH value is 8.3, and emulsion particle diameter is 100～200nm, and viscosity (rotational viscosimeter NDJ-1) is 950mPas; Molecular weight distribution 1.7; This example is compared with embodiment 2, increased again the amount of cyanacrylate not reducing acrylic acid while, resin viscosity is increased, therefore increased the amount of initiator in this example, make molecular weight distribution more even, so just, can obtain the resin of high-solid lower-viscosity, and the increase of cyanacrylate has further improved water tolerance.
Table 6 uses the water tolerance of different amount cyanacrylate gained resins to compare
| Cyanacrylate, % | 1.5 | 2.0 | 2.5 |
| Water tolerance, h | 72h slightly bubbles, loss of gloss | 72h is without considerable change | 96h is without considerable change |
Claims (7)
1. the water based acrylic resin of a cyanacrylate modification, its raw material forms and comprises: acrylic monomer, styrene monomer, allyl monomer, strong solvent, initiator, solubility promoter and neutralizing agent, it is characterized in that, described allyl monomer is cyanacrylate; Described strong solvent is tertiary monocarboxylic acid derivatives active solvent; Described tertiary monocarboxylic acid derivatives active solvent is one or both the mixture that is selected from tertiary carbonic acid glycidyl ester, tertiary ethylene carbonate; Described initiator is the peroxide initiator; Described solubility promoter is the mixture of pure ether solvent and petrolic solvent; Described neutralizing agent is the amine neutralizing agent, and in mass parts, the proportioning of each feed composition is as follows:
The feed composition mass parts
Acrylic monomer 20～70;
Styrene monomer 15～35;
Allyl monomer 1～3;
Strong solvent 10～50;
Initiator 1～5;
Solubility promoter 10～30;
Neutralizing agent 1～10;
Described acrylic monomer is the mixture of Acrylic Acid Monomer and acrylic acid derivative monomer, Acrylic Acid Monomer is selected from one or both in vinylformic acid, methacrylic acid, and the acrylic acid derivative monomer is selected from one or more the mixture in hydroxyethyl methylacrylate and Rocryl 410.
2. water based acrylic resin according to claim 1, is characterized in that, described styrene monomer is selected from one or more the mixture in meta-vinyl toluene, p-methylstyrene and vinylbenzene.
3. water based acrylic resin according to claim 1, is characterized in that, described peroxide initiator is one or both the mixture that is selected from peroxidized t-butyl perbenzoate, peroxidation two tert-pentyls.
4. water based acrylic resin according to claim 1, it is characterized in that, described pure ether solvent is to be selected from a kind of in butyl glycol ether, propandiol butyl ether or their mixture, and petrolic solvent is one or more the mixture that is selected from S-100, S-200.
5. water based acrylic resin according to claim 4, is characterized in that, the mixture of described pure ether solvent and petrolic solvent is the mixture of butyl glycol ether and S-100.
6. water based acrylic resin according to claim 1, is characterized in that, described amine neutralizing agent is one or more the mixture that is selected from dimethylethanolamine, trolamine and ammoniacal liquor.
7. the preparation method according to water based acrylic resin claimed in claim 1, is characterized in that, vinylformic acid is divided into the dropping of two steps when synthetic resins, and concrete steps comprise:
(1) add solubility promoter and strong solvent in the reactor that stirring rake, thermometer and condenser are housed, logical nitrogen stirs and is warming up to 150～155 ℃;
(2) drip first monomer at this temperature, comprise part propylene acid mono and whole acrylic acid derivative monomer, styrene monomer, allyl monomer and part initiator, wherein, Acrylic Acid Monomer accounts for 80～90 quality % of its total amount, initiator accounts for 77～84 quality % of its total amount, time for adding is 4～5h, insulation 0.3～0.6h also is cooled to 145 ℃, add the second batch monomer, comprise remaining Acrylic Acid Monomer and part initiator, wherein, Acrylic Acid Monomer accounts for 10～20 quality % of its total amount, initiator accounts for 5～8 quality % of its total amount, time for adding is 10～15min, then add rapidly remaining initiator, 11～16 quality % for total amount of initiator, insulation 1.5～2.5h, make prepolymer,
(3) above-mentioned prepolymer is cooled to 70～75 ℃, add lentamente in three batches neutralizing agent, first is 20～30 quality % of total amount, second batch is 30～40 quality % of total amount, the 3rd batch is 30～40 quality % of total amount, in stirring and after 20～40min, slowly drips deionized water emulsification, time for adding is 1.5～2.5h, then fully stirs 0.5～1.5h discharging.
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