WO1993012156A1 - Epoxy phosphate ester resin, its production and coating composition containing the resin - Google Patents

Epoxy phosphate ester resin, its production and coating composition containing the resin Download PDF

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Publication number
WO1993012156A1
WO1993012156A1 PCT/US1992/010197 US9210197W WO9312156A1 WO 1993012156 A1 WO1993012156 A1 WO 1993012156A1 US 9210197 W US9210197 W US 9210197W WO 9312156 A1 WO9312156 A1 WO 9312156A1
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WO
WIPO (PCT)
Prior art keywords
epoxy
resin
phosphate ester
phosphoric acid
epoxy phosphate
Prior art date
Application number
PCT/US1992/010197
Other languages
English (en)
French (fr)
Inventor
Yoshimitsu Yabu
Original Assignee
The Dow Chemical Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to CA002101244A priority Critical patent/CA2101244A1/en
Priority to US08/090,027 priority patent/US5389704A/en
Priority to AU32261/93A priority patent/AU658710B2/en
Priority to BR9205627A priority patent/BR9205627A/pt
Publication of WO1993012156A1 publication Critical patent/WO1993012156A1/en
Priority to NO93932894A priority patent/NO932894L/no

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Classifications

    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1405—Polycondensates modified by chemical after-treatment with inorganic compounds
    • C08G59/1422—Polycondensates modified by chemical after-treatment with inorganic compounds containing phosphorus

Definitions

  • the present invention relates to a water- soluble epoxy phosphate ester resin which can be used as a water-borne coating material, its production process and a coating composition containing the resin.
  • Epoxy resins have been used in a wide variety of applications such as coating applications, for example, because of their superiority in corrosion resistance, chemical resistance and flexibility.
  • the epoxy resins are usually diluted with an organic solvent to decrease their viscosities.
  • Hei 1-055,299 discfoses an epoxy phosphate ester resin prepared by reacting an epoxy resin with phosphoric acid, and then hydrolyzing the phosphoric acid modified epoxy resin for monoesterification.
  • the resultant resin perse can be made water dispersible.
  • the resins have unduly large particle size when dispersed in water, resulting in poor dispersion stability. Accordingly, if the amount of organic solvent used is restricted, sufficient dispersion stability cannot be obtained.
  • a completely transparent aqueous solution cannot be obtained.
  • relatively low molecular weight epoxy resins having a weight average molecular weight of 340 to 4,000 there is a problem that they are difficultto hydrolyze and their viscosities increase when dispersed in water.
  • composition having good coating properties such as a good anti-rust property and good flexibility.
  • an epoxy phosphate ester resin which comprises (1) reacting an epoxy resin having an average of greaterthan one vicinal epoxy group with a phosphoric acid source material to obtain an epoxy phosphate ester; and (2) further reacting the obtained epoxy phosphate ester with a phosphoric acid source material.
  • Another aspect of the present invention pertains to an epoxy phosphate ester resin prepared by the above process.
  • Another aspect of the present invention relates to a coating composition comprising:
  • water-soluble epoxy phosphate ester resins having low viscosity can be obtained while restricting the amount of free phosphoric acid, diesters of phosphoric acid and triesters of phosphoric acid to a minimum levef.
  • the water-soluble resins of the present invention can be used to form a more stable aqueous solution when compared with conventional epoxy
  • the water-borne coating compositions according to the present invention provides a resultant coating film with improved corrosion resistance and flexibility as compared with a conventional paint such as an acrylic resin-based paint. Accordingly, the coating compositions of the present invention can be effectively used, particularly, in the fields of coating applications such as spray coating and roll coating.
  • any known epoxy resins having an average of more than one epoxy group per molecule can be used.
  • Suitable epoxy resins include, for example, those having an epoxy equi alent weight of from 170 to 3,500, more suitably from about 175 to 1,000, and a weight average molecular weight of from 340 to 18,000, more suitably from 340 to 5,000.
  • Preferred epoxy resins which can be used herein are those having two vicinal epoxy groups such as diglycidyl ethers of bisphe ⁇ ol A, bisphenol K, bisphenol F, bisphenol S, bisphenol AD, aliphatic phenols and mixtures thereof.
  • the most preferred epoxy resin are diglycidyl ethers of bisphenol A and diglycidyl ethers of aliphatic phenols.
  • the epoxy resins are not limited to the above-mentioned epoxy resins, but include any known epoxy resins. Such epoxy resins are well described in, for example, U.S. Patent Nos. 4,289,812, 4,397,970, 4,868,059 and 5,070,174, and "The Handbook of Epoxy Resins" by H. Lee and K. Neville, published in 1967 by McGraw-Hill, New York, all of which are incorporated herein by reference. As commercially available epoxy resins, D.E.R.TM 331 L; D.E.R. TM 383J; D.E.R.TM 661 ;
  • the epoxy resins which can be used in the present invention may be prepared by the reaction of a commercially available epoxy resin and a phenolic compound having an average of more than one hydroxyl group.
  • the epoxy resin and the phenolic compound may be used in an amount to provide an epoxy: phenolic component ratio by weight of preferably from 60:40 to 99: 1 , more preferably from 75:25 to 99: 1.
  • the next reaction i.e., phosphorylation is difficult to conduct.
  • any known catalyst can be used.
  • Such known catalysts include, for example, imidazoles such as 2-methylimidazole; tertiary amines such as triethylamine, tripropylamine and tributylamine; phosphonium salts such as ethyltriphenylphosphonium chloride, ethyltriphenyl phosphonium bromide and ethyltriphenylphosphonium acetate-acetic acid complex; and ammonium salts such as benzyltrimethylammonium chloride and benzyltrimethylammonium hydroxide.
  • known catalysts other than the above-mentioned catalysts can be used. Such catalysts include those described in, for example, U.S. Patent Nos. 4,289,812; 4,397,970 and 4,868,059, all of which are incorporated herein by reference.
  • acidic catalysts are (preferable.
  • the amount of the catalysts used generally ranges from 0.001 , preferably 0.01 to 1 , preferably to 0.3 percent by weight, based on the total solid weight of the reaction mixture.
  • the above-mentioned epoxy resin is reacted with a phosphoric acid source material and the reaction product obtained is further reacted with a phosphoric acid source material.
  • the obtained product is then subjected to hydrolysis treatmentto produce an epoxy phosphate monoester resin.
  • Phosphoric acid source materials which can be employed in the present invention include, for example, 100 percent phosphoric acid, the semi-hydrate (2H3PO4 ⁇ 2O) and aqueous solutions containing at (east 18 weight percent HP3O4 (at least 1 mole H3P ⁇ 4 per 25 moles of water).
  • the various condensed forms (polymeric, partial anhydrides) of phosphoric acid, pyrophosphoric acid, orthophosphoric acid and triphosphoric acid can also be used.
  • the phosphoric acid source material may be added dropwise to the epoxy component at, for example, 50°C to 150°C for a period of from 1 , preferably 5 to 1 0, preferably to 15 minutes. Afterthe dropwise addition, the reaction mixture may be heated and stirred for 1 to 120 minutes. If desired, these procedures may be repeated as many times as necessary.
  • Water-dispersible epoxy phosphate ester resins can be obtained even if the whole amount of phosphoric [acid source material for the two-step reaction is simultaneously reacted in a single step with an epoxy resin.
  • the reaction products have high viscosity and also contain unreacted phosphoric acid, triesters and diesters of phosphoric acid, resulting in poor stability when dispersed in an aqueous solution.
  • Suitable solvents for use herein include organic solvents having good compatibility with an epoxy resin and a boiling point higher than 110°C, especially higherthan 140°C.
  • organic solvents used herein are glycol type solvents such as ethylene glycol and propylene glycol; glycol monoether type solvents such as ethyiene glycol monoethyl ether, ethylene glycol onobutyl ether, dipropylene glycol methyl ether, diethylene glycol butyl ether, propylene glycol n-butyl ether; acetate type solvents such as propylene glycol monomethyl ether acetate, butyl acetate and propylene glycol methyl ether acetate; alcohol type solvents such as n-butanol, amyl alcohol and cyclohexanol; ketone type solvents such as cyclohexanone and diisobutyl ketone; and aromatic solvents such as xylene and SOLVESSOTM 100 (supplied by Exx
  • the non-volatiles concentration of the diluted reaction system is preferably from 50 to 100 percent, based on the total reaction mixture. The higher solids concentration is preferable within the viscosity range where the reaction mixture is not gelled.
  • an epoxy resin in the first reaction step may be reacted with a phosphoric acid source material in an amount to provide from 0.2 to 0.4, preferably from 0.25 to 0.35 hydroxyl group per epoxy group; and in the second reaction step the obtained epoxy phosphate ester is reacted with a phosphoric acid source material in an amount to provide from 0.05 to 0.4, preferably from 0.05 to 0.20 hydroxyl group per epoxy group.
  • the amount of the phosphoric acid source material used for one reaction may preferably range from 0.1 to 6.0 percent by weight, more preferably from 0.3 to 5.5 percent by weight, most preferably from 0.4 to 4.8 based on the total solid content of the reaction mixture. If the amount of the phosphoric acid source material used is less than 0.1 percent by weight, the resultant resins have a large amount of unreacted epoxy groups, resulting in increased viscosity or poor dispersion stability when dispersed in water. If the amount of unreacted epoxy groups exceeds 6.0 percent by weight, gelation may occur during the reaction or free phosphoric acid will be formed during the next reaction step.
  • the phosphoric acid source materials per se can be added dropwise. However, it is effective to use the phosphoric acid source material diluted with a hydroxylic solvent such as the above-mentioned glycol monoether type
  • a hydroxylic solvent such as the above-mentioned glycol monoether type
  • the use of the hydroxyl group-containing solvents prevents self-condensation of the phosphoric acid source materials, resulting in a more uniform reaction.
  • These solvents can be used in an amount to provide a molar ratio of the solvent to the phosphoric acid source material of at least 2: 1, preferably at least 4: 1.
  • the epoxy phosphate ester resins prepared as above are mainly in the form of triesters or diesters, and thus can be changed to monoesters by subjecting them to partial hydrolysis to reduce them to monoesters. Monoesterif ication reduces the viscosity of the resultant hydrolyzed modified epoxy phosphate ester resin to make handling easier.
  • the phosphate groups existing at the end of molecules can provide good corrosion resistance inherently possessed by the phosphoric acid.
  • the phosphoric acid residues may catalyze curing of the resultant coated film and provide flexibility to the coated film.
  • the hydrolyzed, modified epoxy phosphate ester resins may contain a small quantity of diesters, triesters and free phosphoric acid in addition to monoesters, but normally contain almost no epoxy groups.
  • the epoxy phosphate ester resins can be made water-soluble by adding at least one amine compound to the resin to adjust its pH to between 6 and 11, adding dropwise water, and then stirring the obtained product. If the pH of the adjusted epoxy phosphate ester resin is outside the pH range of 6 to 11, the resultant solution may have poor stability.
  • the present invention include those described in U.S. Patent Nos.4,289,812 and 4,397,970; for example, alkanol amines such as N,N-dimethylethanol amine. Particularly preferred is an amine mixture prepared by mixing N,N-dimethylethanoi amine and diethanol amine at a weight ratio of between 50:50 and 70:30.
  • neutralization can be effected at room temperature.
  • the reaction mixture can be heated at a temperature below the boiling point of the amine compound used.
  • the epoxy phosphate ester resin may be incorporated with, for example, an acrylic resin and/or a polyester resin, a curing agent, water and/or an organic solvent to prepare a coating composition.
  • Acrylic resins which can be used in the present invention include any acrylic resin known as a coating material, such as a polymer of alkyl acrylate or methacrylate and a monomer copolymerizable therewith.
  • Suitable alkyl (meth)acrylate polymers include, for example, those prepared from methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate and a monomer copolymerizable with these esters.
  • Suitable copolymerizable monomers used herein include, for example, (meth)acrylic acid, maleicacid, itaconi acid, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, acryl-amide, N-methylol acryl-amide, styrene, vinyltoluene, acrylonitrile and vinyiacetate.
  • Polyester resins which can be used in the present invention include polyester resins known as coating materials, which are prepared from a suitable alcohol component and a suitable acid component.
  • Suitable alcohol components include, for example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, butanediol, 1 ,5-pentanediol, 1,6-hexanediol, 1-4-cydohexanedimethanol, glycerol, anthrol,trimethyfoiethane, hexanetriol and pentaerythritol.
  • Suitable acid components include, for example, phthalic acid, tetrahydrophthalicacid, hexahydrophthalicacid, trimellitic acid, pyromellitic acid, isophthalic acid, terephthalic acid, maleic acid, f umar ⁇ c acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, succinic acid and anhydrides of these acids.
  • Curing agents which can be incorporated into the composition for solvent-borne coatings according to the present invention include, for example, amino resins such as melamine-formaldehyde and urea-formaldehyde; alkyl-etherified amino resins such as those prepared from the etherification of the above amino resins with lower alcohols such as methanol or ethanol; polyisocyanates such as isophorone diisocyanate and m-xylene diisocyanate; blocked isocyanates such as those formed by introducing blocking agents such as alcohols, including methanol, or phenols, including cresol, into the above polyisocyanates; and alkyl-etherified phenol resins such as an aryl ether monomethylol phenol.
  • amino resins such as melamine-formaldehyde and urea-formaldehyde
  • alkyl-etherified amino resins such as those prepared from the etherification of the above amino resins with lower alcohols such as methanol or ethanol
  • any known water-soluble curing agents can be used.
  • the epoxy resins of the present invention can be used as raw materials for water- borne coating compositions, which are considered preferable from an [environmental view point, as well as raw materials for solvent-borne coating compositions.
  • the epoxy phosphate ester resins of the present invention can be incorporated with water and known water-soluble curing agents to prepare a water-borne coating composition.
  • the epoxy phosphate ester resins of the present invention can also be used to prepare a solvent-borne coating composition.
  • Suitable organic solvents which can be used as diluent to adjust viscosity include, for example, the above-mentioned glycol-type solvents, glycol monoether-type solvents, alcohol-type solvents, aromatic- type solvents and ketone-type solvents (such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone). These solvents can be used alone or in combination.
  • the epoxy phosphate ester resins of the present invention can be used in combination with a known epoxy resin as long as the resin mixture keeps good performance derived from the epoxy phosphate ester resins.
  • the preferable component ratio of a coating composition of the present invention is as follows:
  • water and/or an organic solvent may be added to provide a volatiles content of, for example, from 10, preferably 15 to 80, preferably 40 percent by weight.
  • these coating compositions may comprise an appropriate amount of a pigment, plasticizer, coloring agent, flow modifier and/or curing accelerator. Examples and Comparative Examples
  • a reaction vessel equipped with a condenser was charged with 777 parts of a diglycidyl ether of bisphenol A (D.E.R.TM 331 resin: trademark of The Dow Chemical Company), 323 parts of bisphenol A and 0.2 parts of a catalyst, a 70 percent methanol solution of ethyltriphenylphosphonium acetate-acetic acid complex.
  • the reaction was carried out in a nitrogen current at 175°C for 1 hour.
  • a mixed solvent containing DOWANOLTM PM (propylene glycol methyl ether) and DOWANOLTM DPM (dipropylene glycol methyl ether) (1 :1 weightratio) was then added to the reaction mixture to adjust the solids concentration to 90 percent and to cool the reaction mixture to 125°C. Then, 20 parts of a solution prepared by diluting superphosphoricacid having a concentration of 105 percent in 4 times as many moles of the same mixed [solvent (DOWANOLTM PM and DOWANOLTM DPM 1 : 1 weight ratio) as phosphoric acid, were added dropwise to the reaction product over a period of 30 minutes. To the reaction product obtained, 20 parts of the same superphosphoric acid solution were added in the same way as above for further reaction, under the same conditions.
  • DOWANOLTM PM propylene glycol methyl ether
  • DOWANOLTM DPM dipropylene glycol methyl ether
  • Example 1 As in Example 1 , a coating composition, indicated in Table 1 , of 25 percent volatiles content was prepared.
  • Example 3 In the same fashion, 100 parts of D.E.R.TM 331 diglycidyl ether supplied by The
  • Example 1 As in Example 1, a coating composition, indicated in Table 1 , of 25 percent volatiles content was prepared.
  • a coating composition was prepared in the same way as in Example 3 except that the kind of acrylic resin was changed as indicated in Table 1.
  • Reference Example A reaction vessel equipped with a condenser was charged with 388 parts of an aliphatic diglycidyl ether (D.E.R.TM 331 : trademark of The Dow Chemical Company), 1 12 parts of bisphenol A and 0.1 parts of a 70 percent methanol solution of ethyltriphenylphosphonium acetate-acetic acid complex. The reaction was carried out in a nitrogen current at 175°C for 1 hour. Thereafter, a mixed solvent containing DOWANOLTM PM and DOWANOLTM DPM (1 : 1 weight ratio) was added to the reaction mixture to adjust a solid concentration to 70 percent and to cool the reaction mixture to 125°C.
  • DOWANOLTM PM and DOWANOLTM DPM (1 : 1 weight ratio
  • Comparative Example 1 The emulsion type acrylic resin (AR-1) used in Examples 1 to 3 was incorporated with a melamine curing agent as indicated in Table 1. To the mixture, deionized water was added for dilution of the volatiles content to 25 percent, to prepare a coating composition.
  • Example 4 The emulsion type acrylic resin (AR-2) used in Example 4 was incorporated with a melamine curing agent as indicated in Table 1. Deionized water was added to the mixture for dilution so thatthe volatiles content became 25 percent, to prepare a coating composition.
  • AR-1 Emulsion type acrylic resin having a MW of 20,000.
  • AR-2 Water-soluble acrylic resin having a MW of 9,600.
  • CYMELTM 303 Melamine hardener supplied by Mitsui-Cyanamid.
  • the coating compositions prepared as above were coated on a tin-plated steel sheet, and heated to 180°C for 10 minutes for heat curing. Then, the properties of the resultant coated films were evaluated. In the experiment, pigment was not used in order to evaluate the properties of the resins themselves.
  • a coated specimen (3 cm X 3 cm) is bent so that the coated surface appears outside, and a plurality of tin plates (spacer) having the same thickness asthat of the specimen are inserted inside of the bent specimen. Then, the bent specimen is pressed. The bent specimen is re-pressed after the number of the spacers is reduced, one by one, until a crack occurs in the coated film. The minimum number of the spacers where a crack did not occur is regarded as an index of flexibility.
  • a specimen is subjected to a rubbing test using a rubbing tester with xylene at a load of 2 pounds.
  • the maximum number of rubbing is set as 100 times.
  • Pencil hardness is measured before and after a coated specimen is immersed in a boiling water for a period of 2 hours.
  • the pencil hardness test is conducted in accordance with JIS K-5400.
  • the epoxy phosphate ester resins of the present invention exhibitan improved curing time, corrosion resistance, chemical resistance, flexibility and hardness, and can provide a transparent aqueous solution when the solution is neutralized.
  • the resins exhibit good stability when dissolved in water.
  • the coating compositions of the present invention can be effectively used in coating applications such as spray coating and roll coating.
  • the coating compositions show good performance in the fields of can coating, coil coating and post coating.
  • the coating compositions according to the present invention can be effectively used as coating materials on steel based plates or sheets such as a tin-plated steel (TPS) sheet, tin-free steel (TFS) sheet and galvanized steel sheet; and non-steel based plates or sheets such as an aluminum sheet.
  • steel based plates or sheets such as a tin-plated steel (TPS) sheet, tin-free steel (TFS) sheet and galvanized steel sheet; and non-steel based plates or sheets such as an aluminum sheet.
  • the resin compositions of the present invention can be effectively used as primers for substrates.
  • conventional coating materials may be coated thereon as top coating layers.
  • coating materials fortop coatings include, for example, an alkyd resin- based paint, polyester resin-based paint, thermosetting acrylic resin-based paint, vinyl resin- based paint and silicon resin-based paint.
  • the resin compositions of the present invention can be used as coating materials for top coating when an aqueous solution of the resin composition is blended with a water-soluble or water-dispersible acrylic resin or polyester resin. Therefore, the epoxy resins of the present invention can be used as additive for an acrylic resin-based paint or a polyester resin- based paint, in which an epoxy resin was not previously used.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Epoxy Resins (AREA)
PCT/US1992/010197 1991-12-16 1992-11-30 Epoxy phosphate ester resin, its production and coating composition containing the resin WO1993012156A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CA002101244A CA2101244A1 (en) 1991-12-16 1992-11-30 Epoxy phosphate ester resin, its production and coating composition containing the resin
US08/090,027 US5389704A (en) 1991-12-16 1992-11-30 Epoxy phosphate ester resin, its production and coating composition containing the resin
AU32261/93A AU658710B2 (en) 1991-12-16 1992-11-30 Epoxy phosphate ester resin, its production and coating composition containing the resin
BR9205627A BR9205627A (pt) 1991-12-16 1992-11-30 Processo para preparar uma resina de éster de fosfato de epóxi, resina de éster de fosfato de epóxi e composição de revestimento.
NO93932894A NO932894L (no) 1991-12-16 1993-08-13 Epoksyfosfatesterharpiks, dens fremstilling og belegningspreparat som inneholder harpiksen

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP35184891A JPH05163330A (ja) 1991-12-16 1991-12-16 エポキシ燐酸エステル樹脂、その製造方法、及びその樹脂を含む塗料組成物
JP03/351848 1991-12-16

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WO1993012156A1 true WO1993012156A1 (en) 1993-06-24

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EP (1) EP0571606A1 (enrdf_load_stackoverflow)
JP (1) JPH05163330A (enrdf_load_stackoverflow)
AU (1) AU658710B2 (enrdf_load_stackoverflow)
BR (1) BR9205627A (enrdf_load_stackoverflow)
CA (1) CA2101244A1 (enrdf_load_stackoverflow)
TW (1) TW219943B (enrdf_load_stackoverflow)
WO (1) WO1993012156A1 (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1087751C (zh) * 1998-04-09 2002-07-17 中国科学院化学研究所 一种环氧树脂组合物
EP1310534A1 (en) * 2001-11-07 2003-05-14 Sigma Coatings S.A. Treating primer for coil coating

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KR101625516B1 (ko) * 2008-02-08 2016-05-30 램 리써치 코포레이션 플라즈마 프로세싱 장치 및 플라즈마 프로세싱 장치에서 반도체 기판을 처리하는 방법
JP5859726B2 (ja) * 2010-10-05 2016-02-16 日本鋳鉄管株式会社 外面防食塗装を施した管路構成部材の製造方法
KR101525867B1 (ko) * 2013-08-29 2015-06-03 (주)에프티씨코리아 수용성 변성 에폭시 에스테르 수지 조성물의 제조방법 및 이에 의해 제조된 수용성 수지 조성물
WO2019055128A1 (en) * 2017-09-12 2019-03-21 Dow Global Technologies Llc EPOXY ADHESIVES REINFORCED WITH A COMPONENT
WO2023073470A1 (en) * 2021-10-26 2023-05-04 3M Innovative Properties Company Flame retardant pressure-sensitive adhesive and method of making

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0174628A2 (en) * 1984-09-10 1986-03-19 Ppg Industries, Inc. Blends of phosphates epoxy and acidic resins and the use thereof in coating compositions
US4600754A (en) * 1983-05-18 1986-07-15 Scm Corporation Phosphate epoxy acrylic copolymers
EP0188689A2 (en) * 1984-11-23 1986-07-30 Ppg Industries, Inc. An aqueous composition comprising a phosphated epoxy and non-self dispersible resin, and method of making it

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4600754A (en) * 1983-05-18 1986-07-15 Scm Corporation Phosphate epoxy acrylic copolymers
EP0174628A2 (en) * 1984-09-10 1986-03-19 Ppg Industries, Inc. Blends of phosphates epoxy and acidic resins and the use thereof in coating compositions
EP0188689A2 (en) * 1984-11-23 1986-07-30 Ppg Industries, Inc. An aqueous composition comprising a phosphated epoxy and non-self dispersible resin, and method of making it

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1087751C (zh) * 1998-04-09 2002-07-17 中国科学院化学研究所 一种环氧树脂组合物
EP1310534A1 (en) * 2001-11-07 2003-05-14 Sigma Coatings S.A. Treating primer for coil coating

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JPH05163330A (ja) 1993-06-29
AU658710B2 (en) 1995-04-27
CA2101244A1 (en) 1993-06-17
EP0571606A1 (en) 1993-12-01
TW219943B (enrdf_load_stackoverflow) 1994-02-01
AU3226193A (en) 1993-07-19
BR9205627A (pt) 1994-11-08

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