CN103554381A - Water-based acrylic acid modified saturated polyester resin and preparation method thereof - Google Patents

Water-based acrylic acid modified saturated polyester resin and preparation method thereof Download PDF

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Publication number
CN103554381A
CN103554381A CN201310495773.7A CN201310495773A CN103554381A CN 103554381 A CN103554381 A CN 103554381A CN 201310495773 A CN201310495773 A CN 201310495773A CN 103554381 A CN103554381 A CN 103554381A
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Prior art keywords
acid
mixture
acrylate
polyester resin
acrylic acid
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CN201310495773.7A
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Chinese (zh)
Inventor
陈明
秦文
王英
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LANGFANG JINHWEILI INDUSTRIAL COATINGS Co Ltd
BEIJING JINHWEILI APPLIED CHEMICAL PRODUCTS Co Ltd
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LANGFANG JINHWEILI INDUSTRIAL COATINGS Co Ltd
BEIJING JINHWEILI APPLIED CHEMICAL PRODUCTS Co Ltd
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Priority to CN201310495773.7A priority Critical patent/CN103554381A/en
Publication of CN103554381A publication Critical patent/CN103554381A/en
Priority to CN201410559256.6A priority patent/CN104761684A/en
Priority to CN201410559258.5A priority patent/CN104761685A/en
Priority to PCT/CN2014/089104 priority patent/WO2015058681A1/en
Priority to PCT/CN2014/089109 priority patent/WO2015058685A1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention relates to a water-based acrylic acid modified saturated polyester resin and a preparation method thereof. The water-based acrylic acid modified saturated polyester resin is prepared from the following raw materials in percentage by weight: 5-40% of polyatomic acid, 3-40% of polyhydric alcohol, 0.5-5% of cosolvent, 5-20% of acrylic monomer I, 0.5-5% of acrylic monomer II, 0.01-5% of initiator, 0.5-5% of neutralizer,2-20% of glycidyl tertiary carboxylic ester and 40-50% of distilled water. The water-based acrylic acid modified saturated polyester resin prepared by the invention has the advantages of excellent stability, high solids, low viscosity and low content of VOC (Volatile Organic Compounds) and is mainly applicable to amino-baking paint for waterborne coatings.

Description

A kind of aqueous acrylic modified saturated polyester resin and preparation method thereof
Technical field
The present invention relates to a kind of aqueous acrylic modified saturated polyester resin and preparation method thereof, belong to chemical field.
Background technology
Water-borne coatings is subject to applying more and more widely as a kind of low VOC content coating.And water-borne coatings is because its construction is solid containing lower, be difficult to reach the high-decoration effect of dissolubility type.Water-base resin is as the filmogen of water-borne coatings, and the solid of its water dispersion plays a decisive role on the performance of paint film with on affecting environment containing, viscosity and VOC content.The weathering resistance that saturated polyester has high gloss, high plumpness, excellence is applied in medium-to-high grade amino-stoving varnish and polyurethane finish.Yet at present water-based saturated polyester resin product exists construction admittedly containing low, facile hydrolysis, defect that VOC content is high.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of aqueous acrylic modified saturated polyester resin and preparation method thereof, aqueous acrylic modified saturated polyester resin prepared by the present invention has the characteristic of excellent stability, high solid, low viscosity and low VOC content, have great importance, this resin is mainly used in water-borne coatings amino-stoving varnish.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of aqueous acrylic modified saturated polyester resin, by the percentage composition of raw material gross weight, by following raw material, formed: 5～40% polyprotonic acid, 3～40%% polyvalent alcohol, 0.5～5% solubility promoter, 5～20% Acrylic Acid Monomer I, 0.5～5% Acrylic Acid Monomer II, 0.01～5% initiator, 0.5～5% neutralizing agent, 2～20% tertiary carbonic acid glycidyl ester (E10P, purchased from Mitugao New Material Group), 40～50% distilled water.Wherein, described Acrylic Acid Monomer I is one or more the mixture in isobornyl methacrylate, methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, vinylbenzene, butyl acrylate, butyl methacrylate, butyl methacrylate, lauryl acrylate, lauryl methacrylate(LMA), ethyl acrylate, methacrylic acid-2-ethylhexyl, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester;
Described Acrylic Acid Monomer II is one or more the mixture in vinylformic acid, methacrylic acid, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester, methyl acrylate, methyl methacrylate.
On the basis of technique scheme, the present invention can also do following improvement.
Further, described polyprotonic acid is one or more the mixture in hexanodioic acid, 1, 4-succinic acid, hexanodioic acid, m-phthalic acid, terephthalic acid, 1,4 cyclohexanedicarboxylic acid, trimellitic acid 1,2-anhydride, HHPA, MALEIC ANHYDRIDE, fumaric acid;
Further, described polyvalent alcohol is 1, ammediol, neopentyl glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, 1,4 cyclohexane dimethanol, hydroxypivalyl hydroxypivalate, 2,2,4-trimethylammonium-1, the mixture of one or more in 3 pentanediols, 2-butyl-2-ethyl-1,3-PD, tetramethylolmethane, TriMethylolPropane(TMP), trimethylolethane.
Further, described solubility promoter is one or more the mixture in propylene glycol monobutyl ether, Virahol, isopropylcarbinol, propyl carbinol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, Diethylene Glycol butyl ether, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, dipropylene glycol methyl ether;
Further, described initiator is one or more the mixture in Diisopropyl azodicarboxylate, benzoyl peroxide, tertbutyl peroxide, ditertiary butyl peroxide, two t-amyl peroxy things, isopropyl benzene hydroperoxide, peroxidized t-butyl perbenzoate, the peroxidation trimethylacetic acid tert-butyl ester;
Further, described neutralizing agent is triethylamine, 2-amino-2-methyl-1-propanol, trolamine, diethanolamine, N, the mixture of one or more in N-dimethylethanolamine, ammoniacal liquor.
The present invention also provides the preparation method of aqueous acrylic modified saturated polyester resin as above, comprising:
1) in the reactor that whipping appts, reflux condensate device, Dropping feeder and temperature regulating device are housed, drop into polyprotonic acid, tertiary carbonic acid glycidyl ester (E10P), polyvalent alcohol, pass into nitrogen, slowly be heated to 110～190 ℃, insulation 0.5～3h, slowly be warming up to 200～250 ℃, insulation 3～6h, adding refluxing xylene to acid number is 0～20mgKOH/g, reaction process control is heated up in a steamer a temperature and is less than 100 ℃;
2) be cooled to 80～190 ℃, add solubility promoter;
3) be cooled to 80～190 ℃, drip and account for the initiator of initiator total amount 50～90% and the mixture of Acrylic Acid Monomer I, 3.5～4h drips off;
4) 80～190 ℃ of droppings account for the initiator of initiator total amount 3～20% and the mixture of Acrylic Acid Monomer II, and 0.5～1h drips off;
5) add residue initiator, 80～190 ℃ of insulation 4h;
6) temperature is controlled at 50～160 ℃, adds neutralizing agent, stirs 30min;
7) when the temperature of reactor is less than 100 ℃, slowly add distilled water, resin, admittedly containing being adjusted to 45～50%, is filtered to discharging, obtain aqueous acrylic modified saturated polyester resin.
Reaction principle of the present invention:
1. synthesize the vibrin with unsaturated link(age) and sterically hindered structure;
Grafting adjust TG Acrylic Acid Monomer and or functional Acrylic Acid Monomer;
Grafting provide water-soluble and or functional Acrylic Acid Monomer; form the outside hydrophilic spheroidal structure of class of intramolecule hydrophobic, this special structure was both protected ester is strong, can reduce the winding between molecular resin again; reduce the viscosity of resin, improve construction and admittedly contain.
The invention has the beneficial effects as follows:
Aqueous acrylic modified saturated polyester resin prepared by the present invention adopts tertiary carbonic acid glycidyl ester modification to increase the space steric hindrance group protection strong to ester, improves the anti-hydrolytic performance of resin.Substep drips Acrylic Acid Monomer, first drip to adjust TG Acrylic Acid Monomer and or functional Acrylic Acid Monomer, drip again provide water-soluble and or functional Acrylic Acid Monomer, form the outside hydrophilic spheroidal structure of class of intramolecule hydrophobic, realize acrylic resin saturated polyester resin is carried out to the viscosity that modification reduces resin, reduce the add-on of solubility promoter, improve construction and admittedly contain, fall low VOC content.
The water dispersion of aqueous acrylic modified saturated polyester resin prepared by the present invention is admittedly containing 45～50%, viscosity≤1000 centipoise, VOC content≤20g/kg(water dispersion), normal temperature storage 6 months is without layering, precipitation equistability problem, with this resin and amino-stoving varnish varnish 140～160 degree of methyl-etherified aminoresin or the preparation of high imino-resin completely, toast 20～30min or 110～130 degree baking 20～30min, gloss >=95,60 ° of angles, clarity (DOI) >=95 simultaneously.Also can be mixed with colored paint, decorative effect can with the comparing favourably of dissolubility type Amino-Polyester baking vanish, hardness is high, snappiness is good, has excellent water tolerance, solvent resistance, chemical-resistant and ageing resistance simultaneously.
Embodiment
Below principle of the present invention and feature are described, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Concrete implementation step is as follows:
1) in the reaction flask of 1L that whipping appts, reflux condensate device, Dropping feeder and temperature regulating device are housed, drop into polyprotonic acid, E10P, polyvalent alcohol, pass into nitrogen, slowly be heated to 190 ℃, insulation 1h, slowly be warming up to 250 ℃, insulation 6h, adds refluxing xylene to acid number 20mgKOH/g, and reaction process control is heated up in a steamer a temperature and is less than 100 ℃;
2) be cooled to 110 ℃, add solubility promoter;
3) 120 ℃ of mixtures that drip Acrylic Acid Monomer I and initiator I, 4h drips off;
4) 120 ℃ of mixtures that drip Acrylic Acid Monomer II and initiator II, 1h drips off;
5) add residue initiator III, 120 ℃ of insulation 4h, cooling;
6) in reaction flask, temperature is down to 80 ℃ and is added neutralizing agent, stirs 30min;
7) in reaction flask, temperature is down to 40 ℃ and is slowly added distilled water, and resin, admittedly containing being adjusted to 45～50%, is filtered to discharging, obtains aqueous acrylic modified saturated polyester resin.
Concrete proportioning is in Table 1
Table 1
Figure BDA0000399038570000061
By the special aminoresin 303 of the aqueous acrylic modified saturated polyester resin of above embodiment 1,2,3,4,5 preparations and cyanogen with (10-5): 1 or with cyanogen spy aminoresin 327 with (10-6): 1 mixes, add water viscosity be adjusted to-4 glasss of 30-40s(paintings) spray plate (base material is tinplate and sub-light welding glass plate), 140-150 degree baking 20-40min or 110-130 degree baking 20-40min.Lacquer formulation is as follows:
Table 2
Figure BDA0000399038570000071
Above flow agent BYK381 is the product purchased from German Bi Ke chemistry (BYK, bikehuaxue), and CYCAT600 is the product purchased from the special engineering materials of U.S.'s cyanogen (Cytec Industries Inc., CYTEC, qingtegongchengcailiao).
Obtain paint film property as follows:
Table 3
Remarks:
BYK clarity instrument: clarity is the objective criterion of lightness and gloss, BYK clarity instrument is the instrument of a measurement clarity of German Bi Ke chemical production, useful range 0～100, numerical value is larger, and clarity is better.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.

Claims (4)

1. an aqueous acrylic modified saturated polyester resin, is characterized in that, by the percentage composition of raw material gross weight, by following raw material, formed: 5～40% polyprotonic acid, 3～40% polyvalent alcohol, 0.5～5% solubility promoter, 5～20% Acrylic Acid Monomer I, 0.5～5% Acrylic Acid Monomer II, 0.01～5% initiator, 0.5～5% neutralizing agent, 2～20% tertiary carbonic acid glycidyl ester, 40～50% distilled water
Described Acrylic Acid Monomer I is isobornyl methacrylate, methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, vinylbenzene, butyl acrylate, butyl methacrylate, lauryl acrylate, lauryl methacrylate(LMA), ethyl acrylate, methacrylic acid-2-ethylhexyl, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, the mixture of one or more in vinylformic acid hydroxy butyl ester,
Described Acrylic Acid Monomer II is one or more the mixture in vinylformic acid, methacrylic acid, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester, methyl acrylate, methyl methacrylate.
2. aqueous acrylic modified saturated polyester resin according to claim 1, it is characterized in that, described polyprotonic acid is hexanodioic acid, 1, the mixture of one or more in 4-succinic acid, m-phthalic acid, terephthalic acid, 1,4 cyclohexanedicarboxylic acid, trimellitic acid 1,2-anhydride, HHPA, MALEIC ANHYDRIDE, fumaric acid;
Described polyvalent alcohol is 1, ammediol, neopentyl glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, 1,4-cyclohexanedimethanol, hydroxypivalyl hydroxypivalate, 2,2,4-trimethylammonium-1, the mixture of one or more in 3 pentanediols, 2-butyl-2-ethyl-1,3-PD, tetramethylolmethane, glycerol, TriMethylolPropane(TMP), trimethylolethane.
3. aqueous acrylic modified saturated polyester resin according to claim 1, it is characterized in that, described solubility promoter is one or more the mixture in propylene glycol monobutyl ether, Virahol, isopropylcarbinol, propyl carbinol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, Diethylene Glycol butyl ether, 1-Methoxy-2-propyl acetate, ethylene glycol ethyl ether, dipropylene glycol methyl ether;
Described initiator is one or more the mixture in Diisopropyl azodicarboxylate, benzoyl peroxide, tertbutyl peroxide, ditertiary butyl peroxide, two t-amyl peroxy things, isopropyl benzene hydroperoxide, peroxidized t-butyl perbenzoate, the peroxidation trimethylacetic acid tert-butyl ester;
Described neutralizing agent is triethylamine, 2-amino-2-methyl-1-propanol, trolamine, diethanolamine, N, the mixture of one or more in N-dimethylethanolamine, ammoniacal liquor.
4. a preparation method for the aqueous acrylic modified saturated polyester resin as described in as arbitrary in claim 1-3, is characterized in that, comprising:
1) in the reactor that whipping appts, reflux condensate device, Dropping feeder and temperature regulating device are housed, drop into polyprotonic acid, tertiary carbonic acid glycidyl ester, polyvalent alcohol, pass into nitrogen, slowly be heated to 110～190 ℃, insulation 0.5～3h, slowly be warming up to 200～250 ℃, insulation 3～6h, adding refluxing xylene to acid number is 0～20mgKOH/g, reaction process control is heated up in a steamer a temperature and is less than 100 ℃;
2) be cooled to 80～190 ℃, add solubility promoter;
3) be cooled to 80～190 ℃, drip and account for the initiator of initiator total amount 50～90% and the mixture of Acrylic Acid Monomer I, 3.5～4h drips off;
4) 80～190 ℃ of droppings account for the initiator of initiator total amount 3～20% and the mixture of Acrylic Acid Monomer II, and 0.5～1h drips off;
5) add residue initiator, 80～190 ℃ of insulation 4h;
6) temperature is controlled at 50～160 ℃, adds neutralizing agent, stirs 30min;
7) when temperature is less than 100 ℃ in reactor, slowly add distilled water, resin, admittedly containing being adjusted to 45～50%, filtered to discharging, obtain aqueous acrylic modified saturated polyester resin,
Wherein, by the percentage composition of raw material gross weight, aqueous acrylic modified saturated polyester resin is comprised of following raw material: 5～40% polyprotonic acid, 3～40%% polyvalent alcohol, 0.5～5% solubility promoter, 5～20% Acrylic Acid Monomer I, 0.5～5% Acrylic Acid Monomer II, 0.01～5% initiator, 0.5～5% neutralizing agent, 2～20% tertiary carbonic acid glycidyl ester, 40～50% distilled water;
Described Acrylic Acid Monomer I is isobornyl methacrylate, methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, vinylbenzene, butyl acrylate, butyl methacrylate, butyl methacrylate, lauryl acrylate, lauryl methacrylate(LMA), ethyl acrylate, methacrylic acid-2-ethylhexyl, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, the mixture of one or more in vinylformic acid hydroxy butyl ester,
Described Acrylic Acid Monomer II is one or more the mixture in vinylformic acid, methacrylic acid, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester, methyl acrylate, methyl methacrylate.
CN201310495773.7A 2013-10-21 2013-10-21 Water-based acrylic acid modified saturated polyester resin and preparation method thereof Pending CN103554381A (en)

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CN201310495773.7A CN103554381A (en) 2013-10-21 2013-10-21 Water-based acrylic acid modified saturated polyester resin and preparation method thereof
CN201410559256.6A CN104761684A (en) 2013-10-21 2014-10-20 Waterborne acrylic modified saturated polyester resin
CN201410559258.5A CN104761685A (en) 2013-10-21 2014-10-20 Preparation method of waterborne acrylic modified saturated polyester resin
PCT/CN2014/089104 WO2015058681A1 (en) 2013-10-21 2014-10-21 Preparation method for water-based acrylic-modified saturated polyester resin
PCT/CN2014/089109 WO2015058685A1 (en) 2013-10-21 2014-10-21 Aqueous acrylic acid modified saturated polyester resin

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