WO2022109791A1 - Copolymère de polyester à base d'eau, son procédé de préparation et son application - Google Patents

Copolymère de polyester à base d'eau, son procédé de préparation et son application Download PDF

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Publication number
WO2022109791A1
WO2022109791A1 PCT/CN2020/131177 CN2020131177W WO2022109791A1 WO 2022109791 A1 WO2022109791 A1 WO 2022109791A1 CN 2020131177 W CN2020131177 W CN 2020131177W WO 2022109791 A1 WO2022109791 A1 WO 2022109791A1
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WIPO (PCT)
Prior art keywords
acid
water
polyester copolymer
based polyester
sol
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PCT/CN2020/131177
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English (en)
Chinese (zh)
Inventor
陆均杰
李勇
谢静
刘亮
顾宇昕
张捷
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擎天材料科技有限公司
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Priority to PCT/CN2020/131177 priority Critical patent/WO2022109791A1/fr
Priority to KR1020237012782A priority patent/KR20230069199A/ko
Priority to CN202080003836.0A priority patent/CN112654658B/zh
Publication of WO2022109791A1 publication Critical patent/WO2022109791A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6886—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/87—Non-metals or inter-compounds thereof
    • 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
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings

Definitions

  • the invention belongs to the technical field of coatings, and particularly relates to an aqueous polyester copolymer and a preparation method and application thereof.
  • Polyester resin is a type of polyester resin with the characteristics of plump appearance, good adhesion, good flexibility and good mechanical properties. It can be used as the main film-forming material in water-based thermosetting compositions, and is widely used in coatings and inks, adhesive sealing, fibers and films. materials for applications such as processing. Outstanding processability and adhesion advantages are maintained for high molecular weight polyesters and their cured coatings. However, for high molecular weight polyesters used in waterborne coatings, especially for high glass transition temperature (Tg) systems, it is difficult for common high molecular weight polyesters to achieve ideal water dispersibility and storage stability.
  • Tg glass transition temperature
  • polycondensation is the key process for synthesizing high-molecular-weight polyesters.
  • the catalysts used in the polycondensation process are mainly tin and antimony. These two types of catalytic systems have relatively mature technology and moderate catalytic speed. It has certain toxicity with antimony catalysts, and there is a risk of dissolving harmful substances during the use of the cured coating of its catalytic system.
  • Titanate catalysts commonly used in titanium catalysts have high catalytic activity and non-toxicity, but their poor hydrolytic stability is not conducive to the storage stability of water-based coatings and the stability of hydrolysis resistance of cured coatings; the thermal degradation reaction catalysis of titanate If the activity is too high, the performance of the polyester polymer will also decrease, and the hue will easily turn yellow.
  • the surface hydroxyl-rich titanium dioxide has quite strong Lewis acidity and high catalytic activity, but the long-term stability of its activity is insufficient.
  • the improvement method mainly uses silicon oxide, alkali metal or alkaline earth metal modified titanium dioxide to improve the long-term catalytic activity, but the structural change weakens its catalytic activity, which is not conducive to the application of polycondensation catalysis. Therefore, the catalytic synthesis of high-molecular water-based polyester also requires the use of environmentally friendly catalysts with higher catalytic activity and longer activity stability.
  • the obtaining of high molecular weight waterborne polyester copolymer also needs to optimize its structure and composition, and control the type and quantity of functional groups, which are the key performance requirements to realize its waterborne coating application.
  • the proportion and distribution of hydrophilic groups can be adjusted by adding reactive hydrophilic groups such as carboxyl groups and introducing strong hydrophilic groups such as sulfonic acid groups in the polyester, thereby effectively improving the water dispersibility and stability of the resin.
  • the type and content of hydrophilic groups in the polyester polymer not only affect the molecular weight and distribution of the polyester during the polycondensation process, but also the reaction residues of the groups further affect the curing degree of the coating, resulting in the processability and retort resistance of the cured coating. (Boiling water resistance), solvent resistance and other comprehensive performance decreased.
  • the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a water-based polyester copolymer and a preparation method and application thereof.
  • the water-based polyester copolymer can be used to prepare a water-based coating, and the coating formed after curing has excellent processability, boiling water resistance and stability.
  • the polyols include spiro diols, diols with no less than 5 carbon atoms on the main chain; the diols with no less than 5 carbon atoms on the main chain are selected from 3-methyl- 1,5-pentanediol and/or 2-methyl-2,4-pentanediol;
  • the polybasic acid includes aromatic polybasic acid, sulfonic acid group-containing dibasic acid (ester), fatty acid and alicyclic acid;
  • the environmental protection catalyst is prepared by complex reaction of titanate, silicate and amine compound;
  • the amine compound is selected from (R)-spirocyclic diamine, caprolactam or N,N-dimethylamide at least one of;
  • 70-100% of the total amount of terminal carboxyl groups in the aqueous polyester copolymer is derived from the terminal carboxyl groups of fatty acids and/or alicyclic acids.
  • the inventors of the present application found that the spiro diol with a relatively stable rigid structure was introduced into the polyester polymer with strong hydrophilic group and excellent in water dispersibility, and the spiro ring of the segment could inhibit the polymerization and curing of the polymer.
  • the volume shrinkage of the process avoids the deformation and steric hindrance failure of the polymer at high temperature and high humidity, and ensures the cooking resistance of the water-based polyester polymer;
  • the water-based polyester copolymer has both processability and retort resistance, and achieves a balance of comprehensive properties.
  • the present invention helps to improve the affinity of the composite catalyst and the polymer and improve the catalytic efficiency by introducing the silicate into the environment-friendly catalyst during the synthesis process of the polyester copolymer; and also helps to suppress the structural phase transition and avoid the activity reduction. ; On the other hand, it helps to slow down thermal degradation and maintain catalyst activity. Further introduce amine organic compounds containing sterically hindered structure to improve the electronic environment of Ti, improve its catalytic activity and long-term stability of activity, and meet the needs of environmentally friendly catalytic synthesis of water-based polyesters.
  • the molar content of the spiro diol in the polyol is 10-70 mol%. More preferably, the molar content of the spiro diol in the polyol is 10-65 mol%. Most preferably, the molar content of the spiro diol in the polyol is 10-60 mol%.
  • the molar content of the dihydric alcohol with not less than 5 carbon atoms on the main chain of the polyhydric alcohol is 0.05-80 mol%. More preferably, the molar content of the dihydric alcohol having no less than 5 carbon atoms in the main chain of the polyhydric alcohol is 0.05-70 mol%. Most preferably, the molar content of the dihydric alcohol having no less than 5 carbon atoms in the main chain of the polyhydric alcohol is 0.05-60 mol%.
  • the polyol further includes bisphenol A, and the bisphenol A is selected from hydroxyethylated bisphenol A and/or hydroxypropylated bisphenol A.
  • the introduction of bisphenol A has a positive effect on improving the chemical resistance of waterborne polyester copolymers.
  • the molar content of bisphenol A in the polyol is 0.05-25 mol%. More preferably, the molar content of bisphenol A in the polyol is 2-25 mol%.
  • the polyol further includes 2-ethyl-2-butyl-1,3-propanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, neopentyl glycol, At least one of 1,4-butanediol, diethylene glycol, trimethylolpropane, trimethylolethane or pentaerythritol.
  • the sulfonic acid group-containing dibasic acid is selected from the group consisting of sodium isophthalate-5-sulfonate, lithium isophthalate-5-sulfonate, and dimethyl isophthalate-5-sulfonate At least one of sodium or bishydroxyethyl isophthalate-5-sodium sulfonate.
  • the molar content of the sulfonic acid group-containing dibasic acid (ester) in the aqueous polyester copolymer is 0.1-30 mol%. More preferably, the molar content of the sulfonic acid group-containing dibasic acid (ester) in the aqueous polyester copolymer is 0.1-25 mol%.
  • Sulfonic acid group-containing dibasic acid (ester) is an important component to effectively improve the water solubility and leveling of the resin; however, as a highly hydrophilic group, the introduction of the sulfonic acid group into the polyester copolymer will affect the cooking resistance of the coating. performance, so its content needs to be controlled.
  • the aromatic polybasic acid is selected from at least one of phthalic acid, terephthalic acid, isophthalic acid, trimellitic anhydride, 2-hydroxyisophthalic acid or 2,6-dihydroxyisophthalic acid kind.
  • Aromatic polybasic acid with rigid structure of benzene ring can improve the hardness of water-based polyester copolymer.
  • the molar content of the aromatic polybasic acid in the polybasic acid is 20-80 mol%. More preferably, the molar content of the aromatic polybasic acid in the polybasic acid is 20-70 mol%.
  • the amount of aromatic polyacid is too high, the polyester coating will be too rigid and brittle, which is not conducive to achieving excellent flexibility (post-processing), and the excessive amount of aromatic polyacid will also affect the storage performance. Therefore, the above dosage range is a better choice.
  • the fatty acid is selected from at least one of adipic acid, suberic acid or sebacic acid.
  • the alicyclic acid is selected from cyclohexanedicarboxylic acid and/or cyclobutyldicarboxylic acid.
  • the titanate is selected from at least one of n-butyl titanate, n-propyl titanate, isopropyl titanate or tetraoctyl titanate.
  • the amine compound includes at least (R)-spirocyclic diamine.
  • the silicate is selected from ethyl orthosilicate and/or propyl orthosilicate. More preferably, the silicate is a mixture of ethyl orthosilicate and propyl orthosilicate.
  • the preparation method of the environmental protection catalyst comprises the following steps:
  • titanate is placed in an aqueous hydrochloric acid solution for hydrolysis to obtain sol A;
  • silicate is placed in an ethanol-containing aqueous hydrochloric acid solution for hydrolysis to obtain sol B; sol A and sol B are mixed to obtain sol C;
  • the hydrochloric acid concentration of the hydrochloric acid aqueous solution is 0.005-0.03 mol/L; more preferably, the hydrochloric acid concentration of the hydrochloric acid aqueous solution is 0.005-0.025 mol/L.
  • the molar ratio of titanium element to silicon element in the sol C in step (1) is (1-10): (1-10). More preferably, the molar ratio of titanium element to silicon element in the sol C of step (1) is (1-8): (1-8). Most preferably, the molar ratio of titanium element to silicon element in the sol C of step (1) is (1-6): (1-6).
  • the concentration of the amine compound is 0.05-0.5 mol/L. More preferably, the concentration of the amine compound is 0.05-0.4 mol/L. Most preferably, the concentration of the amine compound is 0.05-0.3 mol/L.
  • the particle size distribution of the environment-friendly catalyst obtained after pulverization in step (2) is D95 ⁇ 5 ⁇ m. More preferably, the particle size distribution of the environment-friendly catalyst obtained after pulverization in step (2) is D98 ⁇ 5 ⁇ m. Most preferably, the particle size distribution of the environment-friendly catalyst obtained after pulverization in step (2) is D98 ⁇ 3 ⁇ m.
  • the number average molecular weight of the aqueous polyester copolymer is 8-25KDa. More preferably, the number average molecular weight of the aqueous polyester copolymer is 8-22KDa.
  • the intrinsic viscosity of the aqueous polyester copolymer is 0.1-0.8 dL/g. More preferably, the intrinsic viscosity of the aqueous polyester copolymer is 0.1-0.7 dL/g.
  • the glass transition temperature of the aqueous polyester copolymer is 15-60°C. More preferably, the glass transition temperature range of the aqueous polyester copolymer is 15-55°C.
  • 75-100% of the total amount of terminal carboxyl groups in the aqueous polyester copolymer comes from the terminal carboxyl groups of fatty acids and/or alicyclic acids. More preferably, 80-100% of the total amount of terminal carboxyl groups in the aqueous polyester copolymer is derived from the terminal carboxyl groups of fatty acids and/or alicyclic acids.
  • the preparation method of above-mentioned aqueous polyester copolymer comprises the following steps:
  • step (2) under the temperature of maintaining step (1), add remaining spirocyclic diol and part of fatty acid to react;
  • control conditions for the completion of the reaction in step (1) are: the acid value of the system is reduced to below 20 mgKOH/g.
  • control condition for the completion of the reaction in step (2) is: the acid value of the system is reduced to below 25 mgKOH/g.
  • control condition for the completion of the reaction in step (3) is: the acid value of the system is reduced to below 40 mgKOH/g.
  • the vacuum degree of vacuum polycondensation in step (4) is ⁇ 500Pa.
  • an aqueous organic solvent is added to the aqueous polyester copolymer for application.
  • the aqueous organic solvent includes but is not limited to the following specific types: ethylene glycol monobutyl ether (BCS), ethylene glycol tert-butyl ether (ETB), diethylene glycol butyl ether (BDG), dipropylene glycol butyl ether (DPnB) ), propylene glycol methyl ether (PM), dipropylene glycol methyl ether (DPM).
  • the water-based polyester copolymer can be used as the main film-forming substance in the water-based paint, and undergoes a curing and cross-linking reaction with melamine compounds, isocyanate compounds and other components to form a cured coating.
  • the formed cured coating has excellent processability and boiling water resistance. sex.
  • the melamine compound can be selected from at least one of hexamethoxymethyl melamine, tetramethoxymethyl benzyl melamine, butoxy/methoxyl partially substituted melamine;
  • the isocyanate compound can be selected from diphenylmethanediol At least one of isocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and a corresponding blocked isocyanate compound.
  • the main application scope of the water-based polyester copolymer of the present invention is water-based paint.
  • water When water is used as a solvent, the water-solubility, hydrolysis resistance and high-temperature cooking resistance of the polyester copolymer are highly required.
  • the water-based polyester copolymer can meet the above requirements, and the cured coating formed by the prepared water-based paint has excellent processability, boiling water resistance and stability.
  • the preparation of the water-based polyester copolymer does not need to use a stabilizer, but based on the use characteristics of the water-based coating, in the present invention, the water-based polyester needs to use a water-based organic solvent (miscible with water) as a co-solvent, and the co-solvent is not Participates in the curing reaction and can be completely released from the coating after the baking process without residual risk.
  • a water-based organic solvent miscible with water
  • the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial channels unless otherwise specified, or can be obtained by existing known methods.
  • the present embodiment provides an environment-friendly catalyst CATA1, the preparation method of which includes the following steps:
  • sol A 3.15g of butyl titanate and n-propyl titanate composition were placed in 22mL hydrochloric acid aqueous solution (0.025mol/L) for hydrolysis to obtain sol A; 3.92g of propyl orthosilicate was placed in 23mL containing Hydrolysis in the hydrochloric acid aqueous solution (0.025mol/L) of ethanol to obtain sol B; sol A and sol B are mixed to obtain sol C; wherein the molar ratio of titanium element and silicon element in sol C is 4:6;
  • the present embodiment provides a kind of environmental protection catalyst CATA2, and its preparation method comprises the following steps:
  • sol A A total of 4.85g of the composition of butyl titanate and isopropyl titanate was placed in 26mL aqueous hydrochloric acid solution (0.025mol/L) for hydrolysis to obtain sol A; 5.1g of ethyl orthosilicate was placed in 23mL Hydrolysis in ethanol-containing hydrochloric acid aqueous solution (0.025mol/L) to obtain sol B; sol A and sol B are mixed to obtain sol C; wherein the molar ratio of titanium element and silicon element in sol C is 6:4;
  • This comparative example provides a kind of catalyst CATAO, and its preparation method comprises the following steps:
  • Embodiment 3-5 provides a kind of water-based polyester copolymer respectively, and its concrete preparation method comprises the following steps (wherein the raw material components and consumption used in each step are shown in Table 1):
  • step (2) under the temperature of maintaining step (1), add remaining spirocyclic diol and part of fatty acid to react, and react until the acid value of the system is reduced to below 25mgKOH/g;
  • the organic solvent ethylene glycol tert-butyl ether (ETB) was added to the prepared aqueous polyester copolymer to dilute to a solid content of 70%.
  • This comparative example provides a water-based polyester copolymer, the preparation method of which is basically the same as that of Examples 3-5, wherein the raw material components and amounts used in each step are shown in Table 1.
  • thermosetting water-based white paints were prepared according to the formula shown in Table 3.
  • thermosetting water-based coatings prepared from the water-based polyester copolymers in Examples 3-5 and Comparative Example 2 were named as thermosetting water-based coatings 1-4, respectively, and the above-mentioned thermosetting water-based white coatings were applied to tinplate by roller coating.
  • heat treatment heat treatment method: 220-260 °C, 1-2min
  • the initial performance of the cured coating and the performance after accelerated thermal storage were tested, and the test results are shown in Table 4:

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

Sont divulgués un copolymère de polyester à base d'eau, son procédé de préparation et son application. Le copolymère de polyester à base d'eau est principalement préparé avec les constituants suivants : un polyol, un acide polyprotique et un catalyseur écologique ; le polyol contient un diol spirocyclique et un diol dont le nombre d'atomes de carbone dans une chaîne principale est supérieur ou égal à 5 ; l'acide polyprotique contient un acide polyprotique aromatique, un acide polyprotique contenant un groupe acide sulfonique (ester), un acide gras et un acide alicyclique ; le catalyseur écologique est préparé par réaction de complexation d'un ester de titanate, d'un ester de silicate et d'un composé amine ; des groupes carboxyle terminaux dérivés de l'acide gras et/ou de l'acide alicyclique représentent 70 à 100 % de la quantité totale de groupes carboxyle terminaux dans le copolymère de polyester à base d'eau. Après la préparation d'un revêtement à base d'eau à l'aide du copolymère de polyester à base d'eau, un revêtement formé par durcissement présente de bonnes caractéristiques en termes d'aptitude au traitement, de résistance à l'eau bouillante et de stabilité.
PCT/CN2020/131177 2020-11-24 2020-11-24 Copolymère de polyester à base d'eau, son procédé de préparation et son application WO2022109791A1 (fr)

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Application Number Priority Date Filing Date Title
PCT/CN2020/131177 WO2022109791A1 (fr) 2020-11-24 2020-11-24 Copolymère de polyester à base d'eau, son procédé de préparation et son application
KR1020237012782A KR20230069199A (ko) 2020-11-24 2020-11-24 수성 폴리에스테르 공중합체, 그 제조방법 및 응용
CN202080003836.0A CN112654658B (zh) 2020-11-24 2020-11-24 一种水性聚酯共聚物及其制备方法与应用

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PCT/CN2020/131177 WO2022109791A1 (fr) 2020-11-24 2020-11-24 Copolymère de polyester à base d'eau, son procédé de préparation et son application

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WO2023065131A1 (fr) * 2021-10-20 2023-04-27 擎天材料科技有限公司 Copolymère de polyester saturé, son procédé de préparation et son utilisation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1424338A (zh) * 2001-12-12 2003-06-18 三菱瓦斯化学株式会社 聚酯树脂和模塑制品
US20100160549A1 (en) * 2008-12-18 2010-06-24 Eastman Chemical Company Polyester Compositions Which Comprise Spiro-Glycol, Cyclohexanedimethanol, and Terephthalic Acid
CN103764373A (zh) * 2011-08-25 2014-04-30 富士胶片株式会社 双轴拉伸聚酯膜及其制造方法以及太阳能电池模块
CN106046336A (zh) * 2016-07-15 2016-10-26 广州擎天材料科技有限公司 一种具有羟基酸封端的水溶性聚酯树脂及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1424338A (zh) * 2001-12-12 2003-06-18 三菱瓦斯化学株式会社 聚酯树脂和模塑制品
US20100160549A1 (en) * 2008-12-18 2010-06-24 Eastman Chemical Company Polyester Compositions Which Comprise Spiro-Glycol, Cyclohexanedimethanol, and Terephthalic Acid
CN103764373A (zh) * 2011-08-25 2014-04-30 富士胶片株式会社 双轴拉伸聚酯膜及其制造方法以及太阳能电池模块
CN106046336A (zh) * 2016-07-15 2016-10-26 广州擎天材料科技有限公司 一种具有羟基酸封端的水溶性聚酯树脂及其制备方法

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CN112654658A (zh) 2021-04-13
KR20230069199A (ko) 2023-05-18

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