CN1373785A - Solvent composition - Google Patents
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- CN1373785A CN1373785A CN00812851A CN00812851A CN1373785A CN 1373785 A CN1373785 A CN 1373785A CN 00812851 A CN00812851 A CN 00812851A CN 00812851 A CN00812851 A CN 00812851A CN 1373785 A CN1373785 A CN 1373785A
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- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/095—Oxygen containing compounds
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- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- Medicinal Chemistry (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
Description
本发明涉及一种溶剂组合物和该溶剂组合物作为以下物质的稀释剂的用途：一种或多种环氧树脂，和/或一种或多种环氧树脂固化剂，和/或一种或多种固化催化剂，和/或一种或多种固化抑制剂。The present invention relates to a solvent composition and the use of the solvent composition as a diluent for one or more epoxy resins, and/or one or more epoxy resin curing agents, and/or one or more curing catalysts, and/or one or more curing inhibitors.
发明背景Background of the invention
现有技术已知使用有机溶剂来降低液体环氧树脂或其液体固化剂的粘度，或使有机溶剂中的固体树脂和/或固化剂增溶，以便于加工环氧树脂和/或固化剂。It is known in the prior art to use organic solvents to reduce the viscosity of liquid epoxy resins or their liquid curing agents, or to solubilize solid resins and/or curing agents in organic solvents to facilitate processing of epoxy resins and/or curing agents.
优良的环氧树脂固化剂如双氰胺的溶剂，为二甲基甲酰胺和乙二醇一甲醚。但是，二甲基甲酰胺或乙二醇一甲醚的使用已引起了工业卫生学关注。Excellent solvents for epoxy resin curing agents such as dicyandiamide are dimethylformamide and ethylene glycol monomethyl ether. However, the use of dimethylformamide or ethylene glycol monomethyl ether has raised industrial hygiene concerns.
因此，本发明目的在于发现新的溶剂，其用于溶解环氧树脂、环氧树脂固化剂、固化催化剂或固化抑制剂，或用于降低这些化合物的粘度。It was therefore an object of the present invention to find new solvents for dissolving epoxy resins, epoxy resin curing agents, curing catalysts or curing inhibitors, or for reducing the viscosity of these compounds.
环氧树脂的已知用途是和其它物质一起生产电层压材料、玻璃层压材料和涂料。在典型的方法中，将在有机溶剂如酮中的环氧树脂溶液，和环氧树脂固化剂如双氰胺的溶液混合来生产作各种应用的环氧树脂组合物。在使用已知的双氰胺溶剂，如丙二醇一甲醚时，难以在混合双氰胺溶液与环氧树脂溶液后将双氰胺保存在溶液中。Known uses of epoxy resins are among other substances to produce electrical laminates, glass laminates and coatings. In a typical method, an epoxy resin solution in an organic solvent, such as ketone, and a solution of an epoxy resin curing agent, such as dicyandiamide, are mixed to produce epoxy resin compositions for various applications. When using known dicyandiamide solvents such as propylene glycol monomethyl ether, it is difficult to keep dicyandiamide in solution after mixing the dicyandiamide solution with the epoxy resin solution.
因此，本发明的优选的目的在于发现新的溶剂，在此溶剂中，环氧树脂固化剂如双氰胺即使在固化剂溶液与环氧树脂溶液混合后仍能充分地溶解。It is therefore a preferred object of the present invention to find new solvents in which epoxy resin curing agents such as dicyandiamide are sufficiently soluble even after the curing agent solution is mixed with the epoxy resin solution.
发明概述Summary of the invention
本发明的一方面提供了一种溶剂组合物，该溶剂组合物包含：One aspect of the present invention provides a solvent composition comprising:
a)乙二醇一醚或二醚和a) Ethylene glycol mono- or diether and
b)含有碳酸酯基的有机低分子量化合物。b) Organic low molecular weight compounds containing carbonate groups.
本发明的另一方面提供了一种包含在上述溶剂组合物中的组合物，其含有选自以下的一种或多种化合物：i)环氧树脂，ii)环氧树脂固化剂，iii)固化催化剂和iv)固化抑制剂。Another aspect of the present invention provides a composition contained in the above solvent composition, which contains one or more compounds selected from: i) epoxy resin, ii) epoxy resin curing agent, iii) Cure Catalyst and iv) Cure Inhibitor.
本发明的另一方面提供了在一种溶剂组合物中的包含选自以下的一种或多种化合物的组合物的制备方法：i)环氧树脂，ii)环氧树脂固化剂，iii)固化催化剂，和iv)固化抑制剂，Another aspect of the present invention provides a method for the preparation of a composition comprising one or more compounds selected from the group consisting of: i) epoxy resins, ii) epoxy resin curing agents, iii) in a solvent composition a curing catalyst, and iv) a curing inhibitor,
通过使一种或多种的这些化合物与以下化合物接触By contacting one or more of these compounds with
a)乙二醇一醚或二醚和a) Ethylene glycol mono- or diether and
b)含有碳酸酯基的有机低分子量化合物。b) Organic low molecular weight compounds containing carbonate groups.
本发明的另一方面提供了a)乙二醇一醚或二醚和b)含有碳酸酯基的有机低分子量化合物作为一种或多种选自以下的化合物的稀释剂的用途：i)环氧树脂，ii)环氧树脂固化剂，iii)固化催化剂和iv)固化抑制剂。发明详述Another aspect of the present invention provides the use of a) ethylene glycol mono- or diether and b) organic low molecular weight compounds containing carbonate groups as diluents for one or more compounds selected from: i) ring epoxy resin, ii) epoxy resin curing agent, iii) curing catalyst and iv) curing inhibitor. Detailed description of the invention
本发明的溶剂组合物优选包含：The solvent composition of the present invention preferably comprises:
a)至少45％，优选至少50％，更优选至少60％，最优选60-90％的乙二醇一醚或二醚；和a) at least 45%, preferably at least 50%, more preferably at least 60%, most preferably 60-90% ethylene glycol mono- or diether; and
b)1-30％，优选1-25％，更优选1-20％，最优选5-15％的含有碳酸酯基的有机低分子量化合物；和任选的b) 1-30%, preferably 1-25%, more preferably 1-20%, most preferably 5-15% of organic low molecular weight compounds containing carbonate groups; and optionally
c)至多25％，优选至多20％，更优选2-15％，最优选5-12％的除了乙二醇一醚或二醚之外的质子液体，以a)、b)和c)的总重量为基准。c) up to 25%, preferably up to 20%, more preferably 2-15%, most preferably 5-12% of protic liquids other than glycol mono- or diethers, in terms of a), b) and c) The total weight is the basis.
溶剂组合物的组分a)为乙二醇一醚，或乙二醇二醚，或一种或多种一醚和/或二醚的混合物。一醚较二醚优选。Component a) of the solvent composition is ethylene glycol monoether, or ethylene glycol diether, or a mixture of one or more monoethers and/or diethers. Monoethers are preferred over diethers.
优选的乙二醇一醚为丙二醇或丁二醇一醚，最优选式I表示的醚Preferred ethylene glycol monoethers are propylene glycol or butylene glycol monoethers, most preferably the ethers represented by formula I
R1O-(CH2-CHR3O)n-R2 (I)R 1 O-(CH 2 -CHR 3 O) n -R 2 (I)
其中，in,
取代基R1和R2之一为具有1-12，优选1-6个，更优选1-4个碳原子的烷基，而取代基R1和R2之另一为氢， One of the substituents R and R is an alkyl group having 1-12, preferably 1-6, more preferably 1-4 carbon atoms, while the other of the substituents R and R is hydrogen,
R3在每种情况下独立地为乙基，或优选为甲基，而R 3 is in each case independently ethyl, or preferably methyl, and
n为1-4，优选为1、2或3。n is 1-4, preferably 1, 2 or 3.
烷基可以是支链或非支链的。烷基的实例为甲基、乙基、正丙基、异丙基、丁基如正丁基或异丁基、和戊基、己基、辛基、癸基或十二烷基。丙基和丁基中优选正丙基和正丁基。优选R1和R2之一为甲基或正丁基。Alkyl groups may be branched or unbranched. Examples of alkyl groups are methyl, ethyl, n-propyl, isopropyl, butyl, such as n-butyl or isobutyl, and pentyl, hexyl, octyl, decyl or dodecyl. Among propyl and butyl, n-propyl and n-butyl are preferred. Preferably one of R1 and R2 is methyl or n-butyl.
式I的优选的一醚为丙二醇一正丁醚，一缩二丙二醇一甲醚，一缩二丙二醇一正丁醚，最优选丙二醇一甲醚。Preferred monoethers of formula I are propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-butyl ether, most preferably propylene glycol monomethyl ether.
还可以使用对应的丙二醇或丁二醇二醚，其中，两个取代基R1和R2为烷基。It is also possible to use the corresponding propylene glycol or butanediol diethers in which the two substituents R1 and R2 are alkyl groups.
溶剂组合物的组分b)为含有碳酸酯基的有机低分子量化合物。本文所用的术语“低分子量”指至多200，优选至多150，最优选至多120的分子量。例如有用的组分b)为碳酸亚乙酯或碳酸丁烯酯。优选的组分b)为碳酸异丙烯酯。Component b) of the solvent composition is an organic low molecular weight compound containing carbonate groups. The term "low molecular weight" as used herein refers to a molecular weight of at most 200, preferably at most 150, most preferably at most 120. Useful components b) are, for example, ethylene carbonate or butylene carbonate. A preferred component b) is propylene carbonate.
溶剂组合物的任选组分c)为除了乙二醇一醚或二醚之外的质子液体，或者两种或多种此质子液体的混合物。“液体”指室温和大气压下为液体的化合物。最优选的质子液体为水。其它的质子液体为醇或二醇，如甲醇、乙醇、乙二醇或丙二醇。Optional component c) of the solvent composition is a protic liquid other than a glycol mono- or diether, or a mixture of two or more such protic liquids. "Liquid" refers to a compound that is a liquid at room temperature and atmospheric pressure. The most preferred protic liquid is water. Other protic liquids are alcohols or glycols, such as methanol, ethanol, ethylene glycol or propylene glycol.
如果溶剂组合物的组分b)为碳酸异丙烯酯或碳酸丁烯酯，则适合在本发明溶剂组合物中包含组分c)。如果溶剂组合物的组分b)为碳酸亚乙酯，则此溶剂组合物为固化剂如双氰胺的优良溶剂，此时可含或不含组分c)。Component c) is suitably included in the solvent composition according to the invention if component b) of the solvent composition is propylene carbonate or butylene carbonate. If component b) of the solvent composition is ethylene carbonate, this solvent composition is an excellent solvent for curing agents such as dicyandiamide, with or without component c).
根据本发明溶剂组合物的目的用途，除了组分a)、b)和c)以外，此溶剂组合物优选含有一种或多种其它溶剂，优选酮，如丙酮、甲乙酮或甲基异丁基酮；或酰胺，如二甲基甲酰胺。它们的用量也取决于此溶剂组合物的目的用途。Depending on the intended use of the solvent composition according to the invention, in addition to components a), b) and c), this solvent composition preferably contains one or more other solvents, preferably ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketones; or amides such as dimethylformamide. Their amounts also depend on the intended use of the solvent composition.
如果本发明溶剂组合物用于稀释环氧树脂，则组分a)、b)和c)的总量一般为至少40％，优选至少50％，更优选至少60％，而一种或多种其它溶剂的量一般为至多60％，优选至多50％，更优选至多40％，以溶剂组合物中溶剂的总重量为基准。If the solvent composition of the present invention is used to dilute epoxy resins, the total amount of components a), b) and c) is generally at least 40%, preferably at least 50%, more preferably at least 60%, and one or more The amount of other solvents is generally up to 60%, preferably up to 50%, more preferably up to 40%, based on the total weight of solvents in the solvent composition.
如果溶剂组合物用作环氧树脂固化剂、固化催化剂或固化抑制剂的稀释剂，则组分a)、b)和c)的总重量一般为至少60％，优选至少75％，更优选至少90％，而一种或多种其它溶剂的量一般为至多40％，优选至多25％，更优选至多10％，以溶剂组合物中溶剂的总重量为基准。If the solvent composition is used as a diluent for epoxy resin curing agents, curing catalysts or curing inhibitors, the total weight of components a), b) and c) is generally at least 60%, preferably at least 75%, more preferably at least 90%, and the amount of one or more other solvents is generally at most 40%, preferably at most 25%, more preferably at most 10%, based on the total weight of the solvent in the solvent composition.
最优选地，本发明溶剂组合物基本上由组分a)、b)和c)组成。Most preferably, the solvent composition of the present invention consists essentially of components a), b) and c).
此溶剂组合物可以含有其它添加剂，例如粘度改性剂，如N-甲基吡咯烷酮，增稠剂，如高分子量聚亚烷基二醇，或增塑剂，如邻苯二甲酸二辛酯或氯化石蜡。如果存在这些添加剂的话，其数量优选为0.1-20％，更优选1-10％，以组分a)、b)和c)的总重量为基准。The solvent composition may contain other additives such as viscosity modifiers such as N-methylpyrrolidone, thickeners such as high molecular weight polyalkylene glycols, or plasticizers such as dioctyl phthalate or Chlorinated paraffins. These additives, if present, are preferably present in amounts of 0.1-20%, more preferably 1-10%, based on the total weight of components a), b) and c).
本发明溶剂组合物可以包含固体颗粒，如填料。但是，此溶剂组合物包含不大于150％，优选不大于100％的固体颗粒，以组分a)、b)和c)的总重量为基准。有用的填料包括有机和无机填料，如蜜胺树脂、木粉填料、碳黑或石墨、滑石、碳酸钙、磷酸盐如缩聚磷酸铵、飘尘、三羟化铝、氢氧化镁、玻璃纤维、大理石粉、水泥粉、粘土、长石、二氧化硅或玻璃、煅烧二氧化硅、氧化铝、氧化镁、氧化锌、硫酸钡、硅酸铝、硅酸钙、二氧化钛、钛酸盐、玻璃微球体或白垩。有用的阻燃剂填料和添加剂，如硫化合物、磷化合物、硼化合物、硅化合物和多核芳香化合物如在以下文献中所述：“国际塑料可燃性手册”(International Plastics Flammability Handbook)，Jurgen Troitzach，1983，ISBN 0-02-949770-1 Macmillan Publishing Co.，Inc.，New York，P46-53和“工业化学乌尔曼百科全书”(Ullmann′s Encyclopedia of IndustrialChemistry)，全卷，124-126页。The solvent compositions of the present invention may contain solid particles, such as fillers. However, the solvent composition comprises not more than 150%, preferably not more than 100%, solid particles, based on the total weight of components a), b) and c). Useful fillers include organic and inorganic fillers such as melamine resins, wood flour fillers, carbon black or graphite, talc, calcium carbonate, phosphates such as condensed ammonium phosphate, fly ash, aluminum trihydroxide, magnesium hydroxide, glass fibers, marble powder, cement powder, clay, feldspar, silica or glass, calcined silica, aluminum oxide, magnesium oxide, zinc oxide, barium sulfate, aluminum silicate, calcium silicate, titanium dioxide, titanate, glass microspheres or chalk. Useful flame retardant fillers and additives such as sulfur compounds, phosphorus compounds, boron compounds, silicon compounds and polynuclear aromatic compounds are described in: "International Plastics Flammability Handbook", Jurgen Troitzach, 1983, ISBN 0-02-949770-1 Macmillan Publishing Co., Inc., New York, P46-53 and "Ullmann's Encyclopedia of Industrial Chemistry", full volume, pp. 124-126 .
可以以已知的方式生产本发明溶剂组合物。一般在1℃-80℃，优选15℃-40℃的温度下，将溶剂组合物的组分以上述的比率混合，直至得到均匀的混合物。The solvent compositions of the invention can be produced in a known manner. The components of the solvent composition are mixed in the ratios mentioned above, generally at a temperature of from 1°C to 80°C, preferably from 15°C to 40°C, until a homogeneous mixture is obtained.
本发明溶剂组合物是一种很有用的用于一种或多种选自以下的化合物的稀释剂：i)环氧树脂，ii)环氧树脂固化剂，iii)固化催化剂，和iv)固化抑制剂。该稀释剂可以用作降低一种或多种液体化合物的粘度的试剂或用作溶剂。The solvent composition of the present invention is a useful diluent for one or more compounds selected from i) epoxy resins, ii) epoxy resin curing agents, iii) curing catalysts, and iv) curing Inhibitors. The diluent can be used as an agent to reduce the viscosity of one or more liquid compounds or as a solvent.
优选用本发明溶剂组合物稀释环氧树脂固化剂，任选的固化催化剂和任选的固化抑制剂。这种混合优选与用有机溶剂稀释的环氧树脂混合。The epoxy resin curing agent, optional curing catalyst and optional curing inhibitor are preferably diluted with the solvent composition of the present invention. This blend is preferably blended with an epoxy resin diluted with an organic solvent.
在现有技术中已知环氧树脂固化剂，它通常还被称为环氧固化剂。有用的固化剂类如酰胺，酸酐，如苯乙烯/马来酸酐，三氟化硼络合物，双氰胺，取代的双氰胺，聚酯树脂，酚醛清漆或酚固化剂，它们为含有一个以上芳香羟基的化合物。现有技术中已知的另一类固化剂包括预活化的环氧树脂与胺或酐或双氰胺或酚醛树酯的加合物。优选的酚固化剂为在欧洲专利说明书0,240,565第6-8页所述。其它已知的固化剂为伯或仲胺，酰肼或肼，优选多官能的，更优选二至六官能伯胺，酰胺和酰肼。这些固化剂在美国专利4,789,690第5栏，第47-68行和第6栏第14-19行中列出。Epoxy resin curing agents are known in the prior art, which are often also referred to as epoxy curing agents. Useful curing agents such as amides, anhydrides such as styrene/maleic anhydride, boron trifluoride complexes, dicyandiamides, substituted dicyandiamides, polyester resins, novolaks or phenolic curing agents, which are Compounds with more than one aromatic hydroxyl group. Another class of curing agents known in the art comprises adducts of preactivated epoxy resins with amines or anhydrides or dicyandiamide or phenolic resins. Preferred phenolic curing agents are described on pages 6-8 of European Patent Specification 0,240,565. Other known curing agents are primary or secondary amines, hydrazides or hydrazines, preferably polyfunctional, more preferably di- to hexafunctional primary amines, amides and hydrazides. These curing agents are listed in US Patent 4,789,690 at column 5, lines 47-68 and column 6, lines 14-19.
有用的固化剂还列在公开的欧洲专利申请EP-A-0,458,502第11页，第41-58行和第12页，第1-40行。其它优选的固化剂为氨腈或二氨腈、二羟基苯酚、双酚、卤化双酚、烷基化双酚、三酚、酚醛树脂、卤代酚醛酚醛清漆树脂、烷基化酚醛清漆树脂、烃酚树脂、烃卤代酚树脂、烃烷基化酚树脂，或其两种或更多种的组合。Useful curing agents are also listed on page 11, lines 41-58 and page 12, lines 1-40 of published European patent application EP-A-0,458,502. Other preferred curing agents are cyanamide or dicyanamide, dihydric phenols, bisphenols, halogenated bisphenols, alkylated bisphenols, trisphenols, phenolic resins, halogenated phenolic novolac resins, alkylated novolac resins, Hydrocarbon phenol resins, hydrocarbon halogenated phenol resins, hydrocarbon alkylated phenol resins, or combinations of two or more thereof.
本发明溶剂组合物特别用于溶解双氰胺，如取代的双氰胺或未取代的双氰胺(氰胍)。本发明溶剂组合物还用于溶解取代的双氰胺，如这样的双氰胺：其中，有某些但不是全部的结合至氮上的氢被烷基，优选C1-6烷基，更优选甲基、乙基或丙基取代；或被芳香基，优选苄基，更优选2-甲基苄基取代。优选双氰胺仅携带上述所列取代基的一种。最优选双氰胺未被取代。The solvent composition of the present invention is particularly useful for dissolving dicyandiamide, such as substituted dicyandiamide or unsubstituted dicyandiamide (cyanoguanidine). The solvent composition of the present invention is also useful for dissolving substituted dicyandiamides, such as dicyandiamides in which some, but not all, of the hydrogen bound to the nitrogen is replaced by an alkyl group, preferably a C 1-6 alkyl group, more Preferably methyl, ethyl or propyl; or substituted by aryl, preferably benzyl, more preferably 2-methylbenzyl. Preferably dicyandiamide carries only one of the substituents listed above. Most preferably dicyandiamide is unsubstituted.
本发明溶剂组合物用于溶解一种或多种上述的环氧树脂固化剂。本文所用的术语“固化剂”还包括用作环氧树脂固化剂的两种或更多种化合物的混合物。The solvent composition of the present invention is used to dissolve one or more of the above epoxy resin curing agents. The term "curing agent" as used herein also includes mixtures of two or more compounds used as curing agents for epoxy resins.
优选将占溶剂组合物重量的1-20％，更优选2-15％，最优选3-12％的固化剂溶于溶剂组合物。应该理解固化剂在本发明溶剂组合物中的溶解度取决于各种因素，如固化剂的类型、溶剂组合物的具体组成、附加溶解在溶剂组合物如固化催化剂或固化抑制剂中的化合物的数量和类型。在本发明的具体溶剂组合物中的具体固化剂的溶解度可以通过系列试验评价。Preferably 1-20%, more preferably 2-15%, most preferably 3-12% of the curing agent is dissolved in the solvent composition by weight of the solvent composition. It should be understood that the solubility of the curing agent in the solvent composition of the present invention depends on various factors, such as the type of curing agent, the specific composition of the solvent composition, the amount of additional compounds dissolved in the solvent composition such as curing catalyst or curing inhibitor and type. The solubility of a particular curing agent in a particular solvent composition of the invention can be evaluated by a series of tests.
增大固化剂和环氧树脂之间的反应速率的固化催化剂或固化促进剂在现有技术中是已知的。优选含有叔胺或含有杂环胺的化合物。某些固化催化剂本身可用作固化剂，如苯并胍脒，咪唑，苯并二甲胺，间苯二胺，或N，N，N′，N′-四甲基-1，3-丁二胺。优选的咪唑为2-甲基咪唑、2-乙基-4-甲基-咪唑或2-苯基咪唑。2-甲基咪唑、2-乙基-4-甲基咪唑和2-苯基咪唑为最优选的固化催化剂。其它可以溶解在本发明溶剂组合物中的固化催化剂为杂环氮化合物、磷化物、硫化物或含铵、鏻或锍的化合物。这些固化催化剂列在公开的欧洲专利申请EP-A-0,458,502第12页，第41-50行，第13-16页和第17页，第1-22行。本发明溶剂组合物用于溶解一种或多种上述固化催化剂。本文所用的术语“固化催化剂”还包括两种或更多种影响环氧树脂和环氧固化剂之间反应速率的化合物。Curing catalysts or curing accelerators that increase the rate of reaction between curing agents and epoxy resins are known in the art. Preference is given to compounds containing tertiary amines or containing heterocyclic amines. Certain curing catalysts can be used as curing agents themselves, such as benzoguanidine amidine, imidazole, xylylenediamine, m-phenylenediamine, or N,N,N',N'-tetramethyl-1,3-butane diamine. Preferred imidazoles are 2-methylimidazole, 2-ethyl-4-methyl-imidazole or 2-phenylimidazole. 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole are the most preferred curing catalysts. Other curing catalysts which may be dissolved in the solvent composition of the present invention are heterocyclic nitrogen compounds, phosphides, sulfides or compounds containing ammonium, phosphonium or sulfonium. These curing catalysts are listed on page 12, lines 41-50, pages 13-16 and page 17, lines 1-22 of published European patent application EP-A-0,458,502. The solvent composition of the present invention is used to dissolve one or more of the curing catalysts described above. The term "curing catalyst" as used herein also includes two or more compounds that affect the rate of reaction between the epoxy resin and the epoxy curing agent.
如果该溶剂组合物用于溶解固化催化剂，则一般将占溶剂组合物重量的0.1-40％，优选0.5-35％，更优选1-20％和最优选2-12％的固化催化剂溶于溶剂组合物。应该理解本发明溶剂组合物中固化催化剂的溶解度取决于多种因素，如固化催化剂的类型，溶剂组合物中任选存在的固化剂的数量和类型，溶剂组合物的具体组成，和可附加溶解于该溶剂组合物的化合物的数量和类型。在本发明具体的溶剂组合物中的具体固化催化剂的溶解度可以通过系列试验评价。在咪唑如2-甲基咪唑的情况下，优选将1-20％，更优选2-12％的咪唑溶于溶剂组合物，以溶剂组合物重量为基准。If the solvent composition is used to dissolve the curing catalyst, generally 0.1-40% by weight of the solvent composition, preferably 0.5-35%, more preferably 1-20% and most preferably 2-12% of the curing catalyst is dissolved in the solvent combination. It should be understood that the solubility of the curing catalyst in the solvent composition of the present invention depends on a variety of factors, such as the type of curing catalyst, the amount and type of curing agent optionally present in the solvent composition, the specific composition of the solvent composition, and additionally soluble The amount and type of compounds in the solvent composition. The solubility of a particular cure catalyst in a particular solvent composition of the invention can be evaluated by a series of tests. In the case of an imidazole such as 2-methylimidazole, preferably 1-20%, more preferably 2-12%, of imidazole is dissolved in the solvent composition, based on the weight of the solvent composition.
有用的固化抑制剂为硼酸、偏硼酸、硼酸酐或马来酸，或(偏)硼酸(酐)与至少一种具有微弱亲核阴离子的酸如氟硼酸(HBF4)的混合物。固化抑制剂如在公开的欧洲专利申请EP-A-0,458,502第17页，第18-50行和第18页，第1-38行所述。如果将固化抑制剂溶于溶剂组合物，则优选将占溶剂组合物重量的0.1-12％，更优选0.5-6％，最优选1-4％的数量溶于溶剂组合物。如果本发明溶剂组合物包含基本量的固化剂，如3-12％的双氰胺，则溶剂组合物中固化催化剂和/或固化抑制剂的溶解度一般较小，通常为0.1-3％，典型地为0.5-2％，以溶剂组合物的重量为基准。Useful cure inhibitors are boric acid, metaboric acid, boric anhydride or maleic acid, or mixtures of (meta)boric acid (anhydride) and at least one acid with a weak nucleophilic anion, such as fluoroboric acid (HBF 4 ). Cure inhibitors are as described on page 17, lines 18-50 and page 18, lines 1-38 of published European patent application EP-A-0,458,502. If the cure inhibitor is dissolved in the solvent composition, it is preferably dissolved in the solvent composition in an amount of 0.1-12%, more preferably 0.5-6%, most preferably 1-4% by weight of the solvent composition. If the solvent composition of the present invention comprises a substantial amount of curing agent, such as 3-12% of dicyandiamide, the solubility of the curing catalyst and/or curing inhibitor in the solvent composition is generally small, usually 0.1-3%, typically 0.5-2%, based on the weight of the solvent composition.
将所需量的固化剂和/或固化催化剂和/或固化抑制剂加到溶剂组合物，并优选搅拌所得的混合物直至得到澄清的溶液。可以一起或交替地将溶解的化合物加到本发明溶剂组合物中。或者，将各化合物各自溶解在溶剂组合物中，如果需要的话，混合所得的溶液。本发明所得溶液的优选组合物如上所述。The required amount of curing agent and/or curing catalyst and/or curing inhibitor is added to the solvent composition and the resulting mixture is preferably stirred until a clear solution is obtained. The dissolved compounds may be added to the solvent composition of the invention together or alternately. Alternatively, each compound is dissolved individually in the solvent composition, and the resulting solutions are mixed, if necessary. Preferred compositions of the resulting solutions of the present invention are as described above.
根据本发明的另一方面，首先将一种或多种选自环氧树脂固化剂、固化催化剂、固化抑制剂的化合物溶于组分a)或组分b)和任选的溶剂组合物的其它溶剂，然后加入组分b)或a)。例如，优选首先将双氰胺溶于乙二醇一醚或二醚a)和任选的组分c)，并在后一步骤加入组分b)。According to another aspect of the present invention, first one or more compounds selected from epoxy resin curing agents, curing catalysts, curing inhibitors are dissolved in component a) or component b) and optional solvent composition The other solvents are then added to component b) or a). For example, dicyandiamide is preferably first dissolved in ethylene glycol mono- or diether a) and optionally component c), and component b) is added in a later step.
本发明的另一优选的方面为一种包含在如上所述溶剂组合物中的环氧树脂和优选的以下一种或多种化合物的环氧树脂组合物，这些化合物选自环氧树脂固化剂、固化催化剂和固化抑制剂。Another preferred aspect of the present invention is an epoxy resin composition comprising an epoxy resin in a solvent composition as described above and preferably one or more of the following compounds selected from epoxy resin curing agents , curing catalysts and curing inhibitors.
可以以已知的方式制备环氧树脂组合物。根据优选的方法，将上述的在本发明溶剂组合物中的固化剂和/或固化催化剂和/或固化抑制剂溶液与环氧树脂混合。一般用溶剂稀释环氧树脂。虽然可以同时或在环氧树脂已与固化剂、固化催化剂和/或固化抑制剂的溶液混合之后加入环氧树脂的溶剂，但优选将环氧树脂与溶剂预混合。然后将环氧树脂溶液与固化剂、固化催化剂和/或固化抑制剂溶液混合，以生产环氧树脂组合物，这种环氧树脂组合物在现有技术中一般称为“单组分环氧树脂组合物”。The epoxy resin compositions can be prepared in a known manner. According to a preferred method, the above-mentioned solutions of curing agents and/or curing catalysts and/or curing inhibitors in the solvent composition of the invention are mixed with the epoxy resin. Epoxy resins are typically diluted with a solvent. The epoxy resin is preferably premixed with the solvent, although the solvent for the epoxy resin can be added simultaneously or after the epoxy resin has been mixed with the solution of curing agent, curing catalyst and/or curing inhibitor. The epoxy resin solution is then mixed with a curing agent, curing catalyst and/or curing inhibitor solution to produce an epoxy resin composition, which is generally referred to in the prior art as "one-component epoxy resin". resin composition".
该环氧树脂组合物可以包含大量的环氧树脂，条件是可固化的话，优选用双氰胺固化。可固化的环氧树脂在现有技术中是已知的。这里所用的环氧树脂的例举性实施例如在以下文献中所述：H.Lee和K.Neville的“环氧树脂手册”(The Handbook of epoxy resins)，1967年由McGraw-Hill，New York出版，在附录4-1，第4-56页；和美国专利2,633,458、3,477,990、3,821,243、3,970,719、3,975,397、4,071,477和4,582,892；以及英国专利1,597,610。The epoxy resin composition may contain a substantial amount of epoxy resin, if curable, preferably with dicyandiamide. Curable epoxy resins are known in the art. Exemplary examples of epoxy resins used herein are described in H. Lee and K. Neville, "The Handbook of Epoxy Resins" (The Handbook of epoxy resins), McGraw-Hill, New York, 1967 Published, at Appendix 4-1, pp. 4-56; and US Patents 2,633,458, 3,477,990, 3,821,243, 3,970,719, 3,975,397, 4,071,477, and 4,582,892; and UK Patent 1,597,610.
有用的环氧树脂的溶剂或稀释剂在现有技术中是已知的。优选的实例为2-甲基-戊二醇(2，4)、甲苯、邻二氯苯、环己酮、环己醇或者，更优选，酮，如丙酮、甲乙酮或甲基异丁基酮。还将不同溶剂的混合物用于溶解环氧树脂。优选将环氧树脂溶于一种、两种、三种或更多种本发明溶剂组合物的组分中。一般来说，用适宜的溶剂将占环氧树脂和溶剂总重量的50-95％，优选60-90％，更优选70-85％环氧树脂溶解或稀释。Useful solvents or diluents for epoxy resins are known in the art. Preferred examples are 2-methyl-pentanediol (2,4), toluene, o-dichlorobenzene, cyclohexanone, cyclohexanol or, more preferably, ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone . A mixture of different solvents was also used to dissolve the epoxy resin. Preferably the epoxy resin is dissolved in one, two, three or more components of the solvent composition of the invention. Generally, 50-95%, preferably 60-90%, more preferably 70-85% of the total weight of epoxy resin and solvent is used to dissolve or dilute the epoxy resin.
该环氧树脂组合物优选包含0.05-10％，更优选0.1-6％，最优选0.5-4％的固化剂，如双氰胺，以环氧树脂的重量为基准。环氧树脂组合物优选还包含0.01-4％，更优选0.05-2％的固化催化剂，如2-甲基咪唑，以环氧树脂的重量为基准。环氧树脂组合物可以包含固化抑制剂，如硼酸，以将固化催化剂改性。这种固化抑制剂如果存在的话，其数量优选为至多4％，更优选至多2％，以环氧树脂的重量为基准。The epoxy resin composition preferably comprises 0.05-10%, more preferably 0.1-6%, most preferably 0.5-4% of a curing agent, such as dicyandiamide, based on the weight of the epoxy resin. The epoxy resin composition preferably also comprises 0.01-4%, more preferably 0.05-2%, of a curing catalyst, such as 2-methylimidazole, based on the weight of the epoxy resin. The epoxy resin composition may contain a cure inhibitor, such as boric acid, to modify the cure catalyst. Such cure inhibitors, if present, are preferably present in an amount of up to 4%, more preferably up to 2%, by weight of the epoxy resin.
在环氧树脂组合物中，组分i)环氧树脂，ii)环氧树脂固化剂，iii)固化催化剂，和iv)固化抑制剂的总重量一般为35-95％，优选45-75％，更优选50-70％，以环氧树脂组合物中存在的组分i)-iv)和溶剂的总重量为基准。In the epoxy resin composition, the total weight of components i) epoxy resin, ii) epoxy resin curing agent, iii) curing catalyst, and iv) curing inhibitor is generally 35-95%, preferably 45-75% , more preferably 50-70%, based on the total weight of components i)-iv) and solvent present in the epoxy resin composition.
环氧树脂组合物中溶剂全部用量可由本发明溶剂组合物组成。但是，该环氧树脂组合物还可以包含其它溶剂，如比推荐用于本发明溶剂组合物的更大量的酮。一般而言，环氧树脂组合物中存在的25-100％，优选40-100％，更优选40-60％的溶剂来自本发明溶剂组合物。剩余量为已知的环氧树脂的溶剂或稀释剂，如酮。The total amount of solvent used in the epoxy resin composition may consist of the solvent composition of the present invention. However, the epoxy resin composition may also contain other solvents, such as ketones in greater amounts than recommended for the solvent compositions of the present invention. Generally, 25-100%, preferably 40-100%, more preferably 40-60% of the solvent present in the epoxy resin composition comes from the solvent composition of the present invention. The remainder is known solvents or diluents for epoxy resins, such as ketones.
该环氧树脂组合物用于各种已知用途，如用于制备电层压材料和涂料。至少优选实施方案的环氧树脂组合物为均匀的，并一般具有足以使其良好浸渍加强材料如玻璃粗纱或加强垫的低粘度，以生产在加热时固化的加强型环氧组合物。用环氧树脂组合物浸渍加强材料和固化环氧树脂组合物的技术在现有技术中是已知的。The epoxy resin composition is used in various known applications, such as in the preparation of electrical laminates and coatings. The epoxy resin composition of at least the preferred embodiments is homogeneous and generally has a low viscosity sufficient to allow good impregnation of reinforcing materials such as glass rovings or reinforcing mats to produce a reinforced epoxy composition that cures upon heating. Techniques for impregnating reinforcing materials with epoxy resin compositions and for curing epoxy resin compositions are known in the art.
在包含本发明溶剂组合物的一种或多种选自以下的化合物的组合物中：i)环氧树脂，ii)环氧树脂固化剂，iii)固化催化剂，和iv)固化抑制剂，还可以包含除了上述以外的组分。如该组合物可包含固体颗粒，如填料。增大组合物阻燃性能的填料特别有用。但是，这种组合物含有不大于50％，优选不大于30％，最优选不大于25％的固体颗粒，以该组合物的总重为基准。In a composition comprising one or more compounds selected from the group consisting of: i) an epoxy resin, ii) an epoxy resin curing agent, iii) a curing catalyst, and iv) a curing inhibitor, of the solvent composition of the present invention, and Components other than the above may be contained. For example, the composition may contain solid particles, such as fillers. Fillers that increase the flame retardant properties of the composition are particularly useful. However, such compositions contain not more than 50%, preferably not more than 30%, most preferably not more than 25% solid particles, based on the total weight of the composition.
本文所用的术语“包含”指“包括”。不应将术语“包含”理解为“由……组成”。As used herein, the term "comprises" means "includes". The term "comprising" should not be read as "consisting of".
通过以下实施例进一步说明本发明，不应将这些实施例理解为对本发明保护范围的限定。所有的份数和百分数是以重量计的，除非另外指出。实施例1-8和对比例A-CThe present invention is further illustrated by the following examples, which should not be construed as limiting the protection scope of the present invention. All parts and percentages are by weight unless otherwise indicated. Examples 1-8 and Comparative Examples A-C
制备在各种单独的溶剂和溶剂组合物中的双氰胺(＂DICY＂)溶液。浓度列在下表I中。室温(RT)下目测检查所生产的溶液是否澄清。下表I中将澄清的溶液指示为＂Y＂(是)。不澄清的溶液指示为＂N＂(不)。测试室温下澄清的溶液在5℃下存储24小时后是否保持澄清。Solutions of dicyandiamide ("DICY") were prepared in various individual solvents and solvent combinations. Concentrations are listed in Table I below. The resulting solution was visually inspected at room temperature (RT) for clarity. Clear solutions are indicated as "Y" (yes) in Table I below. A solution that is not clear is indicated as "N" (not). It was tested whether solutions that were clear at room temperature remained clear after storage at 5°C for 24 hours.
此外，表I显示了溶液是否含有有害或有毒的化学物质，这种有害或有毒的化学物质是由EU标准定义的，它是根据Council Directive67/548/EEC(危险物质指令)的附件I的一种分类。In addition, Table I shows whether the solution contains hazardous or toxic chemical substances, which are defined by EU standards, which are based on Annex I of Council Directive67/548/EEC (Dangerous Substances Directive) category.
表I
表I中实施例2-8的DICY(双氰胺)溶液是澄清的，且不含上述EU标准定义的有害或有毒的化学物质。对比例B也如此。但是，如在以下表4中的对比例O和P所示，包含丙二醇一甲醚和水，但不含碳酸酯的溶剂组合物对所选的环氧树脂变化敏感。实施例1和5之间的比较说明，如果该溶剂组合物包含碳酸异丙烯酯的话，在本发明溶剂组合物中包含第三组分c)如水是有利的。实施例9-20和对比例D-PThe DICY (dicyandiamide) solutions of Examples 2-8 in Table 1 are clear and do not contain harmful or toxic chemicals as defined by the above EU standards. The same is true for Comparative Example B. However, as shown in Comparative Examples O and P in Table 4 below, solvent compositions comprising propylene glycol monomethyl ether and water, but no carbonate, were sensitive to changes in the epoxy resin selected. The comparison between Examples 1 and 5 shows that it is advantageous to include a third component c) such as water in the solvent composition of the invention if the solvent composition comprises propylene carbonate. Embodiment 9-20 and comparative example D-P
制备在各个单独的溶剂和溶剂组合物中的双氰胺(＂DICY＂)溶液。将该溶液与环氧树脂溶液混合。在实施例9-13和对比例D-J中，将环氧树脂溶于丙二醇一甲醚或乙二醇一甲醚。在实施例14-18和对比例K和L中，将环氧树脂溶于甲乙酮。在实施例19和20和对比例M-P中，将环氧树脂为溶于丙酮。Solutions of dicyandiamide ("DICY") were prepared in each individual solvent and solvent composition. This solution was mixed with the epoxy resin solution. In Examples 9-13 and Comparative Examples D-J, the epoxy resin was dissolved in propylene glycol monomethyl ether or ethylene glycol monomethyl ether. In Examples 14-18 and Comparative Examples K and L, the epoxy resin was dissolved in methyl ethyl ketone. In Examples 19 and 20 and Comparative Examples M-P, the epoxy resin was dissolved in acetone.
除了实施例20和对比例P，使用在甲乙酮中的溴化环氧树脂，这种树脂可以从陶氏化学公司(Dow Chemical Company)购得，其商标为D.E.R.539 EK80。在实施例20和对比例P中，使用在丙酮中的溴化环氧树脂，该树脂可以从陶氏化学公司购得，其商标为D.E.R.592A80。In addition to Example 20 and Comparative Example P, a brominated epoxy resin in methyl ethyl ketone, commercially available from the Dow Chemical Company under the trademark D.E.R. 539 EK80, was used. In Example 20 and Comparative Example P, a brominated epoxy resin in acetone available from The Dow Chemical Company under the designation D.E.R. 592A80 was used.
在下表2-4中列出了最终掺合物的组成。如果最终的掺合物在室温下是澄清的和均匀的话，则将它归类为与环氧树脂相容，并将其表示为＂Y＂。否则，如果所得的掺合物为混浊的或含有两相，则将它表示为＂N＂。The compositions of the final blends are listed in Tables 2-4 below. If the final blend is clear and homogeneous at room temperature, it is classified as compatible with the epoxy resin and designated as "Y". Otherwise, if the resulting blend was cloudy or contained two phases, it was designated as "N".
生产层压材料并目测检查双氰胺晶体是否可见，如果是可见的，则检查可见程度。将层压材料分类为不可接受的层压质量(＂U＂)、可接受的层压质量(＂ACC＂)、标准层压质量(＂ST＂)和高级层压质量(＂SUP＂)。Laminates were produced and visually inspected to see if dicyandiamide crystals were visible, and if so, to check the degree of visibility. Laminates were classified as unacceptable laminate quality ("U"), acceptable laminate quality ("ACC"), standard laminate quality ("ST"), and superior laminate quality ("SUP").
表2-4还列出溶液是否含有由EU标准定义的有害或有毒的化学物质，它是根据Council Directive 67/548/EEC(危险物质指令)的附件I的一种分类。Table 2-4 also lists whether the solution contains harmful or toxic chemical substances defined by EU standards, which is a classification according to Annex I of Council Directive 67/548/EEC (Dangerous Substances Directive).
表II
＂-＂指：未试验"-" means: not tested
表III
＂-＂指：未试验"-" means: not tested
表IV
＂-＂指：未试验＂-＂means：not tested"-"means: not tested"-"means: not tested
*含有D.E.R.592 A80(商标)而不是D.E.R.539 EK80(商标) * Contains DER592 A80(TM) instead of DER539 EK80(TM)
实施例10-13、19和20的组合物都与环氧树脂相容，也就是说，即使在不存在二甲基甲酰胺的情况下，这些配方也是澄清和均匀的，其中二甲基甲酰胺根据上述的EU标准归类为有害或有毒的物质。The compositions of Examples 10-13, 19 and 20 are all compatible with epoxy resins, that is, the formulations are clear and homogeneous even in the absence of dimethylformamide, in which dimethylformamide Amides are classified as hazardous or toxic substances according to the aforementioned EU standards.
实施例9和10之间的比较说明，如果该溶剂组合物含有碳酸异丙烯酯的话，在本发明溶剂组合物中包含第三组分c)如水是有利的。实施例11和12说明，如果该溶剂组合物含有碳酸亚乙酯的话，该组合物在存在或不存在组分c)的情况下都与环氧树脂相容。The comparison between Examples 9 and 10 shows that it is advantageous to include a third component c) such as water in the solvent composition of the invention if the solvent composition contains propylene carbonate. Examples 11 and 12 illustrate that if the solvent composition contains ethylene carbonate, the composition is compatible with epoxy resins in the presence or absence of component c).
实施例14-18说明，如果将环氧树脂溶于甲乙酮，则最好保持水含量在更优选或最优选的范围内，即2-15％，最优选5-12％，以丙二醇一甲醚(组分a)、碳酸异丙烯酯(组分b)和水(组分c)的总重量为基准。对比例D-M和P的组合物要么与环氧树脂不相容，要么含有二甲基甲酰胺，而二甲基甲酰胺根据上述的EU标准归类为有害或有毒的物质。Examples 14-18 illustrate that if the epoxy resin is dissolved in methyl ethyl ketone, it is best to keep the water content in the more preferred or most preferred range, i.e. 2-15%, most preferably 5-12%, with propylene glycol monomethyl ether (component a), propylene carbonate (component b) and water (component c) based on the total weight. The compositions of comparative examples D-M and P are either incompatible with epoxy resins or contain dimethylformamide which is classified as a hazardous or toxic substance according to the aforementioned EU standards.
对比例O和P的组合物对所选择的环氧树脂的变化是敏感的。虽然对比例O的组合物与D.E.R.539 EK80(商标)环氧树脂是相容的，但对应的对比例P的组合物与D.E.R.592 A80环氧树脂不相容。实施例19和20之间的比较说明，本发明溶剂组合物，特别是包含丙二醇一甲醚、碳酸异丙烯酯和水的溶剂组合物与两种不同类型的环氧树脂相容。The compositions of Comparative Examples O and P are sensitive to changes in the epoxy resin chosen. While the composition of Comparative Example O was compatible with D.E.R. 539 EK80 (trade mark) epoxy resin, the corresponding composition of Comparative Example P was incompatible with D.E.R. 592 A80 epoxy resin. A comparison between Examples 19 and 20 demonstrates that the solvent compositions of the present invention, particularly those comprising propylene glycol monomethyl ether, propylene carbonate and water, are compatible with two different types of epoxy resins.
Claims (12)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US15582599P | 1999-09-23 | 1999-09-23 | |
| US60/155,825 | 1999-09-23 |
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| JP (1) | JP2003510388A (en) |
| KR (1) | KR20020033191A (en) |
| CN (1) | CN1373785A (en) |
| AU (1) | AU7370500A (en) |
| WO (1) | WO2001021687A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104220535A (en) * | 2012-03-19 | 2014-12-17 | 美利肯公司 | Carboxylate dyes |
| CN112724600A (en) * | 2020-12-28 | 2021-04-30 | 陕西生益科技有限公司 | Thermosetting resin composition, prepreg containing thermosetting resin composition, laminated board and printed circuit board |
| CN115197707A (en) * | 2022-07-29 | 2022-10-18 | 华南理工大学 | Trigger type infiltration-consolidation sand solidification material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS6136319A (en) * | 1984-07-30 | 1986-02-21 | Kansai Paint Co Ltd | Curing agent for thermosetting resin paint, its preparation and coating method |
| US5007969A (en) * | 1988-05-20 | 1991-04-16 | The Boeing Company | Low toxicity liquid solvent |
| DE3934940A1 (en) * | 1989-10-20 | 1991-04-25 | Gvt Giesserei Verfahrenstechni | BINDING AGENT TO SET FOUNDRY SAND |
| US5298081A (en) * | 1990-11-19 | 1994-03-29 | Texaco Chemical Company | Process for removing cured fiberglass resin from substrates |
| US5449474A (en) * | 1992-02-21 | 1995-09-12 | Inland Technology, Inc. | Low toxicity solvent composition |
| EP1052902A1 (en) * | 1998-02-06 | 2000-11-22 | Huntsman Petrochemical Corporation | Methomyl solvent systems |
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- 2000-09-08 JP JP2001525257A patent/JP2003510388A/en active Pending
- 2000-09-08 AU AU73705/00A patent/AU7370500A/en not_active Abandoned
- 2000-09-08 WO PCT/US2000/024915 patent/WO2001021687A1/en not_active Ceased
- 2000-09-08 EP EP00961802A patent/EP1230293A1/en not_active Withdrawn
- 2000-09-08 CN CN00812851A patent/CN1373785A/en active Pending
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104220535A (en) * | 2012-03-19 | 2014-12-17 | 美利肯公司 | Carboxylate dyes |
| CN104220535B (en) * | 2012-03-19 | 2017-03-22 | 美利肯公司 | Carboxylate dyes |
| CN112724600A (en) * | 2020-12-28 | 2021-04-30 | 陕西生益科技有限公司 | Thermosetting resin composition, prepreg containing thermosetting resin composition, laminated board and printed circuit board |
| CN115197707A (en) * | 2022-07-29 | 2022-10-18 | 华南理工大学 | Trigger type infiltration-consolidation sand solidification material and preparation method and application thereof |
| CN115197707B (en) * | 2022-07-29 | 2024-05-10 | 华南理工大学 | Trigger type infiltration-consolidation sand solidification material and preparation method and application thereof |
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| JP2003510388A (en) | 2003-03-18 |
| WO2001021687A1 (en) | 2001-03-29 |
| AU7370500A (en) | 2001-04-24 |
| EP1230293A1 (en) | 2002-08-14 |
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