CN103304790A - Polyester resin for outdoor aluminum profile heat transfer printing powder coating and preparation method thereof - Google Patents
Polyester resin for outdoor aluminum profile heat transfer printing powder coating and preparation method thereof Download PDFInfo
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- CN103304790A CN103304790A CN2013102218213A CN201310221821A CN103304790A CN 103304790 A CN103304790 A CN 103304790A CN 2013102218213 A CN2013102218213 A CN 2013102218213A CN 201310221821 A CN201310221821 A CN 201310221821A CN 103304790 A CN103304790 A CN 103304790A
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Abstract
The invention relates to a polyester resin for an outdoor aluminum profile heat transfer printing powder coating and a preparation method thereof. The polyester resin is characterized by comprising 10-40 percent of neopentyl glycol, 0-10 percent of 2-butyl-2-ethyl-1,3-propylene glycol, 0-10 percent of 1,4-cyclohexanedimethanol, 20-60 percent of terephthalic acid, 0-16 percent of adipic acid, 0.05-0.2 percent of butyltin oxide, 0.02-0.15 percent of triphenyl phosphate, 0-5 percent of trimellitic anhydride, 0-20 percent of m-phthalic acid and 0-5 percent of curing accelerator. The polyester resin can be completely cured under the temperature of about 200 DEG C, the cured coating has high definition of the heat transfer printing pattern, the color is bright, the paper is easily torn, and glue water residue is avoided after paper tearing. In addition, the coating also has high gloss, excellent leveling property, high mechanical strength and excellent weather resistance.
Description
Technical field
The present invention relates to a kind of is outdoor hot transfer printing polyester resin for powder coating of solidifying agent and preparation method thereof with three-glycidyl ester group isocyanuric acid ester (TGIC), this material is the main raw material(s) of making environment-friendly powder coating, belongs to field of material synthesis technology.
Background technology
Powder coating is a kind of environmentally friendly product, and color and coating variety of all shapes and colors can be provided.Growing field begins to use powder coating.Along with the develop rapidly of aluminium section bar industry, the powder coating that is applied to aluminium section bar has become the important branch of powder coating, and replaces electrocoating paint and fluorine carbon lacquer gradually.Along with the appearance of transfer technique, aluminium section bar proprietary powder coatings kind is more rich and varied.
Aluminium section bar need have superpower weathering resistance and ornamental, so the aluminium shape surface processing is essential.The surface treatment of aluminium section bar comprises powder coating spraying, the spraying of fluorine carbon lacquer and wood grain processing based on organic coating.Wood grain is handled and is carried out on the powder coating surface, is divided into two kinds of water transfer printing and hot transfer printings.Hot transfer wood grain technology enters China from the phase at the end of the nineties in last century, obtains the development of advancing by leaps and bounds in recent years.The principal feature of this technology is that transferred image is bright in luster, levels are rich, hot transfer printing effect can compare favourably with printing, be that with the different of printing technology hot transfer printing is at high temperature to make printing ink be subjected to heat sublimation, can once become figure by multicolor patterns, need not chromatography, namely form the beautiful pattern of color after sublimating, printing ink can infiltrate the inside of powder coating 40 ~ 60um.So hot transfer printing product is durable in use, pattern transferring can not come off, chaps and fade, and can not change the original glossiness of product, wear resistance, weathering resistance, resistance to acids and bases etc. because of hot transfer process.The surface decoration effect is just played in hot transfer printing, has now basically formed perfect hot transfer printing corollary system, comprises the manufacturing of powder coating, spraying coating process, hot transfer apparatus, heat-transferring printing paper and transfer film.
The aluminium section bar caloric transfer printing technology adopts polyester/TGIC type powder coating usually, because the powder coating of this system has the excellent pattern transfer performance, in this system, the structure of vibrin and performance to it to the sharpness of thermally transferred pattern, heat-transferring printing paper peel off and the stability of thermally transferred pattern plays conclusive effect.Therefore, the synthetic vibrin that is exclusively used in the outdoor aluminium section bar powder coating of manufacturing is very necessary.
Summary of the invention
First purpose of the present invention is to overcome the deficiencies in the prior art and provide a kind of and can be under about 200 ℃ condition solidify fully, no glue was residual after filming after the curing had thermally transferred pattern sharpness height, bright in luster, easy paper-tear picture and paper-tear picture, in addition, film also have the gloss height, the levelling excellence, physical strength is good and the vibrin of the hot transfer printing powder coating of outdoor aluminium section bar that has excellent weather resistance.
Second purpose of the present invention provides the preparation method of the vibrin of the hot transfer printing powder coating of a kind of outdoor aluminium section bar.
In order to reach above-mentioned first purpose, the present invention realizes like this, it is the vibrin of the hot transfer printing powder coating of a kind of outdoor aluminium section bar, it is characterized in that comprising the neopentyl glycol of 10-40%, 2-butyl-2-ethyl-1 of 0-10%, ammediol, 1 of 0-10%, the 4-cyclohexanedimethanol, the terephthalic acid of 20-60%, the hexanodioic acid of 0-16%, the Mono-n-butyltin of 0.05-0.2%, the triphenyl phosphite of 0.02-0.15%, the trimellitic acid 1,2-anhydride of 0-5%, the m-phthalic acid of 0-20% and the curing catalyst of 0-5%.
Described curing catalyst is one or more the mixture in imidazoles, glyoxal ethyline, three-(dimethylamino methyl) phenol, trolamine, the xylidine.
In order to reach above-mentioned first purpose, the present invention is achieved in that it is the preparation method of the vibrin of the hot transfer printing powder coating of a kind of outdoor aluminium section bar, is characterized in that comprising the steps:
Step 1
In the reactor that has heating unit, agitator and condensing tower, press the neopentyl glycol that mass ratio adds 10-40%, 2-butyl-2-ethyl-1 of 0-10%, ammediol, the 1,4 cyclohexane dimethanol of 0-10% is warming up to 80-130 ℃ of heated and stirred to fusing;
Step 2
The terephthalic acid, the hexanodioic acid of 0-16% and the Mono-n-butyltin of 0.05-0.2% that add 20-60% continue temperature reaction under the logical nitrogen, produce esterification water to 180 ℃-200 ℃ beginning esterifications and polycondensation and distillate; Be warmed up to 220 ℃-240 ℃ gradually by 180 ℃-200 ℃, add the triphenyl phosphite of 0.02-0.15%, continue to be warming up to 250 ℃-260 ℃, be incubated to reaction solution and become clarification fully;
Step 3
Be cooled to 200 ℃-220 ℃, add the trimellitic acid 1,2-anhydride of 0-5% and the m-phthalic acid of 0-20% then; Be warming up to 230 ℃-240 ℃ gradually, insulation reaction 1-4 hour; Be cooled to 210 ℃-220 ℃ then, the vacuum polycondensation removes the esterification water in the reaction mass;
Step 4
The control temperature is 180 ℃-205 ℃, discharging after the curing catalyst of adding 0-5% stirs, and gained vibrin outward appearance is faint yellow transparent solid, acid number is 25-75mgKOH/g, second-order transition temperature is 20-80 ℃, and viscosity is 20-60 pool (broolfield cone-and-plate viscometer, 200 ℃).
The present invention's advantage compared with prior art is as follows:
(1) prepared vibrin glass transition temp is higher, and hydroxyl value is low;
(2) powder coating by this terminal carboxyl polyester resin and three-glycidyl ester group isocyanuric acid ester (TGIC) preparation solidifies under 200 ℃ condition fully, filming has good hot transfer printing effect, and no glue is residual etc. behind its thermally transferred pattern sharpness height, bright in luster, easy paper-tear picture and the paper-tear picture;
(3) under 200 ℃ condition, finish curing by the powder coating of this terminal carboxyl polyester resin and three-glycidyl ester group isocyanuric acid ester (TGIC) preparation, film also have the gloss height, the levelling excellence, physical strength is good and the performance that has excellent weather resistance.
(4) this vibrin is easily realized industrialized mass production.
Embodiment
Below the specific embodiment of the present invention is further specified.Need to prove at this, understand the present invention for the explanation of these embodiments for helping, but do not constitute limitation of the invention.In addition, below in each embodiment of described the present invention involved technical characterictic just can not make up mutually as long as constitute conflict each other.
Embodiment one
Step 1
In the reactor of being furnished with heating unit, agitator and condensing tower, press the neopentyl glycol of mass ratio adding 30% and 2-butyl-2-ethyl-1 of 2.15%, ammediol is warming up to 130 ℃ of heated and stirred fusings;
Step 2
Add 45% terephthalic acid, 7% hexanodioic acid and 0.1% Mono-n-butyltin, continue temperature reaction under the logical nitrogen, produce esterification water to 180 ℃ of beginning esterifications and polycondensation and distillate; Be warmed up to 204 ℃ gradually by 180 ℃, add 0.15% triphenyl phosphite, continue to be warming up to 250 ℃, be incubated to reaction solution and become clarification fully;
Step 3
Be cooled to 220 ℃, add 14% m-phthalic acid then; Be warming up to 230 ℃ gradually, insulation reaction 2 hours is cooled to 220 ℃ then, and vacuum polycondensation 0.5 hour removes the esterification water in the reaction mass;
Step 4
Be cooled to 205 ℃, the curing catalyst of adding 1.6%, the back discharging stirs, obtaining acid number is 32.8 mgKOH/g, viscosity is 46P (broolfield cone-and-plate viscometer, 200 ℃), and second-order transition temperature is 63 ℃, the number average relative molecular mass is 3241, and outward appearance is the vibrin of faint yellow transparent solid.
In the present embodiment, described curing catalyst is imidazoles; Also can be according to practical situation with one or more the mixture in glyoxal ethyline, three-(dimethylamino methyl) phenol, trolamine, xylidine instead of imidazoles.
Embodiment two
Step 1
In the reactor of being furnished with heating unit, agitator and condensing tower, to press mass ratio and add 20% neopentyl glycol, 2-butyl-2-ethyl-1 of 5.4%, ammediol and 10% 1,4 cyclohexane dimethanol are warming up to 110 ℃ of heated and stirred fusings;
Step 2
Add 40% terephthalic acid, 8% hexanodioic acid and 0.09% Mono-n-butyltin, continue temperature reaction under the logical nitrogen, produce esterification water to 190 ℃ of beginning esterifications and polycondensation and distillate; Be warmed up to 230 ℃ gradually by 190 ℃, add 0.11% triphenyl phosphite, continue to be warming up to 255 ℃, be incubated to the ester reaction solution and become clarification fully;
Step 3
Be cooled to 210 ℃, add 2.2% trimellitic acid 1,2-anhydride and 12% m-phthalic acid then; Be warming up to 240 ℃ gradually, insulation reaction 1 hour is cooled to 210 ℃ then, and vacuum polycondensation 1 hour removes the esterification water in the reaction mass;
Step 4
Be cooled to 200 ℃, add 2.2% curing catalyst, discharging after the back discharging that stirs stirs.Obtaining acid number is 30.6mgKOH/g, and viscosity is 52.8P (broolfield cone-and-plate viscometer, 200 ℃), and second-order transition temperature is 70 ℃, and the number average relative molecular mass is 3610, and outward appearance is the vibrin of faint yellow transparent solid.
In the present embodiment, described curing catalyst is glyoxal ethyline; Also can be according to practical situation with one or more the mixture in imidazoles, three-(dimethylamino methyl) phenol, trolamine, xylidine instead of imidazoles.
Embodiment three
Step 1
In the reactor of being furnished with heating unit, agitator and condensing tower, press the neopentyl glycol of mass ratio adding 40% and 2-butyl-2-ethyl-1 of 4.53%, ammediol is warming up to 90 ℃ of heated and stirred fusings;
Step 2
Add 25% terephthalic acid, 5% hexanodioic acid and 0.05% Mono-n-butyltin, continue temperature reaction under the logical nitrogen, produce esterification water to 200 ℃ of beginning esterifications and polycondensation and distillate; Be warmed up to 240 ℃ gradually by 200 ℃, add 0.02% triphenyl phosphite, continue to be warming up to 260 ℃, be incubated to reaction solution and become clarification fully;
Step 3
Be cooled to 205 ℃, add 4.2% trimellitic acid 1,2-anhydride and 20% m-phthalic acid then; Be warming up to 235 ℃ gradually, insulation reaction 3 hours is cooled to 215 ℃ then, and vacuum polycondensation 45 minutes removes the esterification water in the reaction mass;
Step 4
Be cooled to 180 ℃, add 1.2% curing catalyst, discharging after the back discharging that stirs stirs.Obtaining acid number is 34mgKOH/g, and viscosity is 47.2P (broolfield cone-and-plate viscometer, 200 ℃), and second-order transition temperature is 61 ℃, and the number average relative molecular mass is 3325, and outward appearance is the vibrin of faint yellow transparent solid.
In the present embodiment, described curing catalyst is three-(dimethylamino methyl) phenol; Also can be according to practical situation with one or more the mixture in the imidazoles, glyoxal ethyline, trolamine, xylidine instead of imidazoles.
Embodiment four
Step 1
In the reactor of being furnished with heating unit, agitator and condensing tower, to press mass ratio and add 10% neopentyl glycol, 2-butyl-2-ethyl-1 of 8.35%, ammediol and 10% 1,4 cyclohexane dimethanol are warming up to 80 ℃ of heated and stirred fusings;
Step 2
Add 50% terephthalic acid, 4.2% hexanodioic acid and 0.2% Mono-n-butyltin, continue temperature reaction under the logical nitrogen, produce esterification water to 185 ℃ of beginning esterifications and polycondensation and distillate; Be warmed up to 240 ℃ gradually by 185 ℃, add 0.15% triphenyl phosphite, continue to be warming up to 250 ℃, insulation reaction liquid becomes clarification fully;
Step 3
Be cooled to 200 ℃, add 5% trimellitic acid 1,2-anhydride and 10.5% m-phthalic acid then; Be warming up to 230 ℃ gradually, insulation reaction 4 hours is cooled to 220 ℃ then, and vacuum polycondensation 0.5 hour removes the esterification water in the reaction mass;
Step 4
Be cooled to 195 ℃, add 1.6% curing catalyst, discharging after the back discharging that stirs stirs.Obtaining acid number is 36.8mgKOH/g, and viscosity is 41P (broolfield cone-and-plate viscometer, 200 ℃), and second-order transition temperature is 62 ℃, and the number average relative molecular mass is 4010, and outward appearance is the vibrin of faint yellow transparent solid.
In the present embodiment, described curing catalyst is trolamine; Also can be according to practical situation with one or more the mixture in the imidazoles, glyoxal ethyline, three-(dimethylamino methyl) phenol, xylidine instead of imidazoles.
More than embodiments of the present invention are made detailed invention, but the present invention is not limited to described embodiment.For those of ordinary skill in the art, can carry out multiple variation, modification, replacement and distortion to these embodiments without departing from the principles and spirit of the present invention and still fall within protection scope of the present invention.
Claims (3)
1. the vibrin of the hot transfer printing powder coating of outdoor aluminium section bar, it is characterized in that comprising the neopentyl glycol of 10-40%, 2-butyl-2-ethyl-1 of 0-10%, ammediol, 1 of 0-10%, the 4-cyclohexanedimethanol, the terephthalic acid of 20-60%, the hexanodioic acid of 0-16%, the Mono-n-butyltin of 0.05-0.2%, the triphenyl phosphite of 0.02-0.15%, the trimellitic acid 1,2-anhydride of 0-5%, the m-phthalic acid of 0-20% and the curing catalyst of 0-5%.
2. the vibrin of the hot transfer printing powder coating of outdoor aluminium section bar according to claim 1 is characterized in that described curing catalyst is one or more the mixture in imidazoles, glyoxal ethyline, three-(dimethylamino methyl) phenol, trolamine, the xylidine.
3. the preparation method of the vibrin of the hot transfer printing powder coating of outdoor aluminium section bar according to claim 1 is characterized in that comprising the steps:
Step 1
In the reactor that has heating unit, agitator and condensing tower, press the neopentyl glycol that mass ratio adds 10-40%, 2-butyl-2-ethyl-1 of 0-10%, ammediol, the 1,4 cyclohexane dimethanol of 0-10% is warming up to 80-130 ℃ of heated and stirred to fusing;
Step 2
The terephthalic acid, the hexanodioic acid of 0-16% and the Mono-n-butyltin of 0.05-0.2% that add 20-60% continue temperature reaction under the logical nitrogen, produce esterification water to 180 ℃-200 ℃ beginning esterifications and polycondensation and distillate; Be warmed up to 220 ℃-240 ℃ gradually by 180 ℃-200 ℃, add the triphenyl phosphite of 0.02-0.15%, continue to be warming up to 250 ℃-260 ℃, be incubated to reaction solution and become clarification fully;
Step 3
Be cooled to 200 ℃-220 ℃, add the trimellitic acid 1,2-anhydride of 0-5% and the m-phthalic acid of 0-20% then; Be warming up to 230 ℃-240 ℃ gradually, insulation reaction 1-4 hour; Be cooled to 210 ℃-220 ℃ then, the vacuum polycondensation removes the esterification water in the reaction mass;
Step 4
The control temperature is 180 ℃-205 ℃, discharging after the curing catalyst of adding 0-5% stirs, and gained vibrin outward appearance is faint yellow transparent solid, acid number is 25-75mgKOH/g, second-order transition temperature is 20-80 ℃, and viscosity is 20-60 pool (broolfield cone-and-plate viscometer, 200 ℃).
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103554453A (en) * | 2013-10-25 | 2014-02-05 | 滁州市全丰物资有限公司 | Polyester resin for industrial mechanical coating and production process thereof |
| CN103755934A (en) * | 2013-12-21 | 2014-04-30 | 安徽神剑新材料股份有限公司 | Method for preparing polyester resin used in frostless type powder coating |
| CN104356916A (en) * | 2014-11-21 | 2015-02-18 | 广东华江粉末科技有限公司 | High-gloss polyurethane heat transfer printing powder paint for aluminium profile and preparation method thereof |
| CN104559691A (en) * | 2014-12-25 | 2015-04-29 | 江苏兰陵高分子材料有限公司 | Polymer composite for heat transfer printing low-temperature crosslinking and preparation method thereof |
| CN107118337A (en) * | 2017-06-14 | 2017-09-01 | 陈丽 | A kind of preparation method of polyester resin for powder coating |
| CN107619471A (en) * | 2017-09-21 | 2018-01-23 | 浙江中法新材料有限公司 | High levelling polyester resin of high acid value of HAA solidifications and preparation method thereof |
| CN107810219A (en) * | 2015-06-17 | 2018-03-16 | 阿科玛法国公司 | Coating for metal foil has high solids content and the hydroxylating of high covering power and/or a polyester resin of carboxylated |
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| CN102277024A (en) * | 2011-07-06 | 2011-12-14 | 江苏盟晖涂装材料有限公司 | Construction powdery paint |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103554453A (en) * | 2013-10-25 | 2014-02-05 | 滁州市全丰物资有限公司 | Polyester resin for industrial mechanical coating and production process thereof |
| CN103554453B (en) * | 2013-10-25 | 2016-01-20 | 滁州市全丰物资有限公司 | A kind of industrial machinery coating vibrin and production technique thereof |
| CN103755934A (en) * | 2013-12-21 | 2014-04-30 | 安徽神剑新材料股份有限公司 | Method for preparing polyester resin used in frostless type powder coating |
| CN103755934B (en) * | 2013-12-21 | 2016-05-11 | 安徽神剑新材料股份有限公司 | A kind of preparation method of the mylar for frost-free type powdery paints |
| CN104356916A (en) * | 2014-11-21 | 2015-02-18 | 广东华江粉末科技有限公司 | High-gloss polyurethane heat transfer printing powder paint for aluminium profile and preparation method thereof |
| CN104559691A (en) * | 2014-12-25 | 2015-04-29 | 江苏兰陵高分子材料有限公司 | Polymer composite for heat transfer printing low-temperature crosslinking and preparation method thereof |
| CN107810219A (en) * | 2015-06-17 | 2018-03-16 | 阿科玛法国公司 | Coating for metal foil has high solids content and the hydroxylating of high covering power and/or a polyester resin of carboxylated |
| CN107118337A (en) * | 2017-06-14 | 2017-09-01 | 陈丽 | A kind of preparation method of polyester resin for powder coating |
| CN107619471A (en) * | 2017-09-21 | 2018-01-23 | 浙江中法新材料有限公司 | High levelling polyester resin of high acid value of HAA solidifications and preparation method thereof |
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Application publication date: 20130918 |