CN100406494C - Epoxy modified polyester resin for paint of coil back surface and its preparation method - Google Patents
Epoxy modified polyester resin for paint of coil back surface and its preparation method Download PDFInfo
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- CN100406494C CN100406494C CNB2006101192108A CN200610119210A CN100406494C CN 100406494 C CN100406494 C CN 100406494C CN B2006101192108 A CNB2006101192108 A CN B2006101192108A CN 200610119210 A CN200610119210 A CN 200610119210A CN 100406494 C CN100406494 C CN 100406494C
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Abstract
The invention discloses an epoxy modified polyester resin and making method of coil backing paint, which comprises the following steps: polymerizing polyol composition, polyacid composition acted by organic tin as catalyst; adding epoxy resin to open loop; diluting through solvent. The invention possesses excellent adhesive force for metal base, which makes foamer on the paint film over 90.
Description
Technical field
The present invention relates to epoxy modified polyester resin for paint of coil back surface and preparation method thereof.
Background technology
At present, the foamable paint of coil back surface of supplying on the market has two types, and a kind of is epoxy type, and another kind is a polyurethane-type.Epoxy type back side lacquer has stronger hardness, and solidity to corrosion is good, and metal substrate is had excellent sticking power, but has the shortcoming of snappiness difference.Polyurethane-type back side lacquer has outstanding snappiness and ageing, but has the shortcoming of difference of hardness.
Summary of the invention
The invention provides a kind of epoxy modified polyester resin for paint of coil back surface and preparation method thereof.This epoxy modified polyester resin is by introducing epoxide group at vibrin one end, overcome the defective that exists in the prior art, provide a kind of metal base is had good adhesion, the paint film that generates has excellent flexibility and hardness, after the lacquer foaming of the back side, adhesive aggregation can reach the epoxy modified polyester resin that the paint of coil back surface more than 90% is used at the whipping agent on the paint film.
Technical scheme of the present invention is as follows:
Epoxy modified polyester resin for paint of coil back surface of the present invention be by polyol blends, polyprotonic acid mixture after polymerization reaches certain acid number under the effect of organotin catalysts, add Resins, epoxy again and carry out ring-opening polymerization, make with the solvent latting drown then, each component and weight % content are:
Component weight %
Polyol blends 18-27
Polyprotonic acid mixture 23-33
Organotin catalysts 0.2-0.3
Resins, epoxy 3-8
Solvent 40.7-52.8
The component of described polyol blends and weight % content are
Component weight %
Neopentyl glycol 50-65
Methyl propanediol 15-28
Tertiary carbonic acid glycidyl ester 15-25
The component of described polyprotonic acid mixture and weight % content are
Component weight %
Hexanodioic acid 10-25
M-phthalic acid 45-60
Terephthalic acid 10-23
Trimellitic acid 1,2-anhydride 0-10
Tetra hydro Phthalic anhydride 5-15
Described catalyzer is an organotin catalysts, is selected from dibutyl tin laurate, dimethyl oxalic acid tin or dibutyl tin acetate etc.
Described Resins, epoxy is selected from oxirane value and is 0.02～0.22 Resins, epoxy.
The component of described solvent and weight % content are
Component weight %
Dimethylbenzene 0-5
The heavy aromatic solvent 55-65 that contains C9-C10
1-Methoxy-2-propyl acetate 15-25
Pimelinketone 5-15
Diester 0-15
Described diester is made up of with weight ratio dimethyl succinate, Methyl glutarate and dimethyl adipate at 1: 1: 1.
The heavy aromatic solvent of the described C9-C10 of containing is that U.S. Exxon company produces " Solvesso150 sym-trimethylbenzene product ".
The preparation method of epoxy modified polyester resin for paint of coil back surface of the present invention is as follows: polyprotonic acid mixture, polyol blends are added reactor, slowly be heated to 150-200 ℃, treat to add organotin catalysts after the fusion, continue to be heated to 220-240 ℃, reaction times was controlled at 5-8 hour, reach acid number 10-20mgKOH/g until reaction, add Resins, epoxy again, 150-160 ℃ of reaction 1-2 hour, reach acid number 2-10mgKOH/g until reaction, use the solvent latting drown at last to solids content 45-55%.
The technical indicator and the measured result of epoxy modified polyester resin are as follows:
| Project | Index | Measured result |
| Quality solids content % | 45-55 | 45-55 |
| Viscosity second | 10-25 | 12-23 |
| Acid number mgKOH/g | 2-10 | 4.8-8.5 |
| Molecular weight | 4000-7000 | 4500-6100 |
| Second-order transition temperature ℃ | 25-65 | 32-60 |
| Hydroxyl value mgKOH/g | 50-80 | 53-73 |
Epoxy modified polyester resin for paint of coil back surface of the present invention be acid number by the control polyester portion at 10-20mgKOH/g, adjust the add-on of Resins, epoxy, control 40-60% Resins, epoxy is at 150-160 ℃ of epoxide group ring-opening polymerization.Owing to insert part epoxy, after the masked isocyanate resin crosslinks, hardness of paint film is good, and metal base is had good sticking power and excellent flexibility, has solved market product epoxy type back side lacquer and has had the shortcoming that snappiness is poor, difference of hardness is coated with lacquer at the polyurethane-type back side.After the lacquer foaming of the back side, adhesive aggregation can reach more than 90% at the whipping agent on the paint film.It not only can use to paint can also use at the coil back surface that can foam at common coil back surface and paint, and is the multi-usage epoxy modified polyester resin.
Embodiment:
Embodiment 1, neopentyl glycol with 148 kilograms, 60 kilograms tertiary carbonic acid glycidyl ester, 58 kilograms methyl propanediol, 77 kilograms hexanodioic acid, 180 kilograms m-phthalic acid, 51 kilograms terephthalic acid, 18 kilograms of trimellitic acid 1,2-anhydrides, 18 kilograms of Tetra hydro Phthalic anhydrides add reactor, slowly are heated to 160 ℃, treat to add 3 kilograms of dibutyltin dilaurate catalysts after the fusion, continue to be heated to 225 ℃, the reaction times was controlled at 6.5 hours, and final reaction reaches acid number 20-19mgKOH/g, 71.6 kilograms of aquifer yields, add 30 kilograms of dimethylbenzene then, be cooled to 175 ℃ and add 68 kilograms of oxirane value 0.02～0.045 Resins, epoxy, 150-160 ℃ of reaction 1 hour, below acid number 9mgKOH/g, add 417 kilograms of heavy aromatic solvents that contain C9-C10,180 kilograms of 1-Methoxy-2-propyl acetates, 110 kilograms of pimelinketone latting drowns are to solids content 45%, filter packing.
Performance test is as follows:
| Project | Test result |
| Quality solids content % | 45 |
| Viscosity second | 12 |
| Acid number mgKOH/g | 8.5 |
| Molecular weight | 6100 |
| Second-order transition temperature ℃ | 60 |
| Hydroxyl value mgKOH/g | 53 |
Embodiment 2, neopentyl glycol with 160 kilograms, 40 kilograms tertiary carbonic acid glycidyl ester, 65 kilograms methyl propanediol, 57 kilograms hexanodioic acid, 199 kilograms m-phthalic acid, 36 kilograms of terephthalic acids, 30 kilograms of trimellitic acid 1,2-anhydrides, 33 kilograms of Tetra hydro Phthalic anhydrides add reactor, slowly be heated to 170 ℃, treat to add 3.5 kilograms of dimethyl oxalic acid tin catalysts after the fusion, continue to be heated to 230 ℃, the reaction times was controlled at 7 hours, final reaction reaches acid number 16-15mgKOH/g, 74.6 kilograms of aquifer yields add 30 kilograms of dimethylbenzene then, are cooled to 175 ℃ and add 68 kilograms of oxirane value 0.09～0.14 Resins, epoxy, 150-160 ℃ of reaction 1.5 hours, below acid number 7mgKOH/g, add 370 kilograms of heavy aromatic solvents that contain C9-C10,95 kilograms of 1-Methoxy-2-propyl acetates, 65 kilograms of pimelinketone, 56.9 kilogram diester latting drown filters packing to solids content 50%.
Performance test is as follows:
| Project | Test result |
| Quality solids content % | 50 |
| Viscosity second | 18 |
| Acid number mgKOH/g | 6.7 |
| Molecular weight | 5300 |
| Second-order transition temperature ℃ | 48 |
| Hydroxyl value mgKOH/g | 65 |
Embodiment 3, neopentyl glycol with 194 kilograms, 52 kilograms methyl propanediol, 54 kilograms of tertiary carbonic acid glycidyl esters, 80 kilograms hexanodioic acid, 180 kilograms m-phthalic acid, 87 kilograms terephthalic acid, 50 kilograms Tetra hydro Phthalic anhydride adds reactor, slowly is heated to 180 ℃, treats to add 3.8 kilograms of dibutyl tin acetate catalyzer after the fusion, continue to be heated to 235 ℃, reaction times was controlled at 8 hours, and final reaction reaches acid number 13-12mgKOH/g, 83.7 kilograms of aquifer yields, add 30 kilograms of dimethylbenzene then, be cooled to 175 ℃ and add 77 kilograms of oxirane value 0.18～0.22 Resins, epoxy, 150-160 ℃ of reaction 2 hours, below acid number 5mgKOH/g, add 360 kilograms of heavy aromatic solvents that contain C9-C10,115 kilograms of 1-Methoxy-2-propyl acetates, 45 kilograms of pimelinketone, 18.5 kilograms of diester latting drowns are to solids content 55%, filter packing.
Performance test is as follows:
| Project | Test result |
| Quality solids content % | 55 |
| Viscosity second | 23 |
| Acid number mgKOH/g | 4.8 |
| Molecular weight | 4500 |
| Second-order transition temperature ℃ | 32 |
| Hydroxyl value mgKOH/g | 73 |
Claims (2)
1. epoxy modified polyester resin for paint of coil back surface, it is characterized in that it is by polyol blends, the polymerization under the effect of organotin catalysts of polyprotonic acid mixture, add Resins, epoxy again and carry out ring-opening polymerization, make with the solvent latting drown then, each component and weight % content are:
Component weight %
Polyol blends 18-27
Polyprotonic acid mixture 23-33
Organotin catalysts 0.2-0.3
Resins, epoxy 3-8
Solvent 40.7-52.8;
The component of described polyol blends and weight % content are:
Component weight %
Neopentyl glycol 50-65
Methyl propanediol 15-28
Tertiary carbonic acid glycidyl ester 15-25;
The component of described polyprotonic acid mixture and weight % content are;
Component weight %
Hexanodioic acid 10-25
M-phthalic acid 45-60
Terephthalic acid 10-23
Trimellitic acid 1,2-anhydride 0-10
Tetra hydro Phthalic anhydride 5-15;
Described organotin catalysts is selected from dibutyl tin laurate, dimethyl oxalic acid tin or dibutyl tin acetate;
It is 0.02～0.22 Resins, epoxy that described Resins, epoxy is selected from oxirane value;
Described solvent component and weight % content are:
Component weight %
Dimethylbenzene 0-5
The heavy aromatic solvent 55-65 that contains C9-C10
1-Methoxy-2-propyl acetate 15-25
Pimelinketone 5-15
Diester 0-15;
Described diester is made up of with weight ratio dimethyl succinate, Methyl glutarate and dimethyl adipate at 1: 1: 1;
The heavy aromatic solvent of the described C9-C10 of containing is the Solvesso150 sym-trimethylbenzene product that U.S. Exxon company produces.
2. the preparation method of the described epoxy modified polyester resin for paint of coil back surface of claim 1, it is characterized in that the polyprotonic acid mixture, polyol blends is heated to 150-200 ℃, add organotin catalysts again, continue to be heated to 220-240 ℃, reaction times 5-8 hour, add Resins, epoxy again, at 150-160 ℃ of reaction times 1-2 hour, use the solvent latting drown then to solids content 45-55%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101192108A CN100406494C (en) | 2006-12-06 | 2006-12-06 | Epoxy modified polyester resin for paint of coil back surface and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101192108A CN100406494C (en) | 2006-12-06 | 2006-12-06 | Epoxy modified polyester resin for paint of coil back surface and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1970601A CN1970601A (en) | 2007-05-30 |
| CN100406494C true CN100406494C (en) | 2008-07-30 |
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| CNB2006101192108A Expired - Fee Related CN100406494C (en) | 2006-12-06 | 2006-12-06 | Epoxy modified polyester resin for paint of coil back surface and its preparation method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993422A (en) * | 2012-11-30 | 2013-03-27 | 无锡市虎皇漆业有限公司 | Epoxy modified saturated polyester resin for undercoat of coil coating and undercoat of coil coating |
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| CN101245132B (en) * | 2008-02-29 | 2011-06-08 | 浙江天女集团制漆有限公司 | Functional resin for paint and manufacture method thereof |
| CN102060979B (en) * | 2010-11-29 | 2012-12-12 | 上海涂料有限公司振华造漆厂 | Novel epoxy modified resin for anti-corrosion primer and one-step preparation method thereof |
| CN102115527A (en) * | 2010-12-10 | 2011-07-06 | 天津市新宇彩板有限公司 | Neopentyl glycol resin |
| CN103113814A (en) * | 2011-11-16 | 2013-05-22 | 上海富臣化工有限公司 | Adhesion enhancement priming paint used for surface of gold and silver foil, and preparation method and application thereof |
| CN109721717B (en) * | 2017-10-31 | 2021-12-10 | 万华化学（广东）有限公司 | Waterborne epoxy modified saturated polyester resin and preparation method and application thereof |
| CN108302284A (en) * | 2018-02-06 | 2018-07-20 | 中国石油工程建设有限公司华北分公司 | A kind of underground heat-insulated oil pipe and preparation method thereof |
| CN108441090B (en) * | 2018-02-28 | 2020-06-30 | 东莞市大兴化工有限公司 | Coil coating and preparation method thereof |
| CN109734887A (en) * | 2018-12-29 | 2019-05-10 | 中山市柏顿涂料有限公司 | A kind of high temperature resistance polyester resin and preparation method thereof |
| CN110845710B (en) * | 2019-12-13 | 2022-03-25 | 立邦工业涂料(上海)有限公司 | Epoxy modified polyester resin and preparation method and application thereof |
| CN112778529A (en) * | 2020-12-30 | 2021-05-11 | 万博新材料科技（南通）有限公司 | Preparation method of polyester modified epoxy resin for coil primer |
| CN114276526B (en) * | 2021-12-30 | 2023-10-13 | 山东凯威尔新材料有限公司 | Polyester resin for metal coil steel finishing paint and preparation method thereof |
| CN115637098B (en) * | 2022-10-31 | 2023-11-03 | 江苏三木化工股份有限公司 | Preparation method of epoxy modified saturated polyester for coil back paint |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993422A (en) * | 2012-11-30 | 2013-03-27 | 无锡市虎皇漆业有限公司 | Epoxy modified saturated polyester resin for undercoat of coil coating and undercoat of coil coating |
| CN102993422B (en) * | 2012-11-30 | 2015-01-28 | 无锡市虎皇漆业有限公司 | Epoxy modified saturated polyester resin for undercoat of coil coating and undercoat of coil coating |
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| Publication number | Publication date |
|---|---|
| CN1970601A (en) | 2007-05-30 |
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Owner name: SHANGHAI COATINGS CO., LTD. Free format text: FORMER OWNER: SHANGHAI ZHENHUA PAINT FACTORY Effective date: 20100129 |
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Effective date of registration: 20100129 Address after: No. 345 South Shaanxi Road, Shanghai Patentee after: Shanghai Paint Co., Ltd. Address before: No. 1167, Gulang Road, Shanghai Patentee before: Shanghai Chenhua Paint MFG. Co. |
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Granted publication date: 20080730 Termination date: 20111206 |