Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of 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
  • C08G59/18—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
  • C08G59/50—Amines
  • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
• • 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
  • C08G59/50—Amines
  • C08G59/5033—Amines aromatic
• • 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
  • C08G59/50—Amines

Definitions

• the present invention relates to epoxy resin compositions and cured products thereof.
• Epoxy resin compositions using a polyamine compound as an epoxy resin curing agent are used in the field of paints such as anticorrosion paints for ships, bridges, land and sea iron structures, lining, reinforcement and repair materials for concrete structures, flooring materials for buildings, It is also used in civil engineering and construction fields such as linings for water supply and sewerage, paving materials, and adhesives. Among these, it is important that epoxy resin compositions for coatings give good physical properties such as appearance, water resistance, chemical resistance and impact resistance.
• Xylylenediamine which is a type of aliphatic polyamine compound, is fast-curing when used as a curing agent for epoxy resins, and is characterized by its excellent low-temperature curability and chemical resistance compared to other aliphatic polyamines. have.
• xylylenediamine absorbs carbon dioxide and water vapor in the atmosphere and tends to form a carbamate, a coating film formed from an epoxy resin composition using xylylenediamine as an epoxy resin curing agent is whitened. There was a tendency that the appearance of the coating film deteriorated.
• US Pat. No. 5,300,000 discloses a wet surface or water curable epoxy comprising a reaction product of a polyamine with an adduct forming agent (excluding glycidyl ethers, carboxylic acids and lactams), activated alumina or silica alumina, and an epoxy resin.
• a resin composition is disclosed, and an adduct obtained by reacting meta-xylylenediamine and propylene oxide is described as the reaction product of a polyamine and an adduct-forming agent. It also describes that the epoxy resin composition does not cause amine blushing and has flexibility.
• Patent Document 2 discloses an epoxy resin curing agent which is a reaction product of meta-xylylenediamine and ethylene oxide as an epoxy resin curing agent used for the gas barrier layer of the gas barrier laminate.
• Patent Documents 1 and 2 disclose an epoxy resin curing agent which is a reaction product of meta-xylylenediamine and alkylene oxide.
• an epoxy resin curing agent which is a reaction product of meta-xylylenediamine and alkylene oxide.
• the appearance of the coating film obtained using the epoxy resin composition is good, and from the viewpoint of improving impact resistance, the coating film obtained has good elongation. is also required.
• An object of the present invention is to provide an epoxy resin composition capable of forming a coating film having good appearance (transparency and gloss) and good elongation, and a cured product thereof.
• an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent containing a reaction composition containing a reaction product of xylylenediamine and an alkylene oxide, and a non-reactive diluent solves the above problems.
• the present invention relates to the following. [1] An epoxy resin composition containing an epoxy resin, an epoxy resin curing agent containing a reaction composition (A) containing a reaction product of xylylenediamine and an alkylene oxide, and a non-reactive diluent. [2] A cured product of the epoxy resin composition described in [1] above.
• an epoxy resin composition capable of forming a coating film with good appearance (transparency and gloss) and good elongation, and a cured product thereof.
• the epoxy resin composition of the present invention is an epoxy resin containing an epoxy resin, a reaction composition (A) containing a reaction product of xylylenediamine and an alkylene oxide (hereinafter also simply referred to as "reaction composition (A)"). Contains a hardener and a non-reactive diluent.
• reaction composition (A) a reaction product of xylylenediamine and an alkylene oxide
• reaction composition (A) containing a reaction product of xylylenediamine and an alkylene oxide
• the reaction composition (A) may contain an unreacted raw material such as xylylenediamine, and the xylylenediamine may form a carbamate.
• reaction composition (A) has a high solubility of the carbamate of xylylenediamine, whitening of the coating film due to the formation of the carbamate can be suppressed, and as a result, a coating film having a good appearance can be formed. It is possible.
• the combination of the epoxy resin curing agent containing the reactive composition (A) and the non-reactive diluent improves the elongation of the coating film, which is the cured product of the epoxy resin composition of the present invention. .
• the epoxy resin which is the main ingredient of the epoxy resin composition, may be any of saturated or unsaturated aliphatic compounds, alicyclic compounds, aromatic compounds, and heterocyclic compounds. From the viewpoint of obtaining a cured product with high water resistance, an epoxy resin containing an aromatic ring or an alicyclic structure in the molecule is preferable.
• Specific examples of the epoxy resin include an epoxy resin having a glycidylamino group derived from metaxylylenediamine, an epoxy resin having a glycidylamino group derived from paraxylylenediamine, and 1,3-bis(aminomethyl).
• the above epoxy resins can be used in combination of two or more.
• the epoxy resin derived from meta-xylylenediamine is used as an epoxy resin from the viewpoint of forming a coating film having good appearance and elongation, improving the curing speed, and improving the water resistance of the resulting coating film.
• Epoxy resins having glycidylamino groups, epoxy resins having glycidylamino groups derived from paraxylylenediamine, epoxy resins having glycidyloxy groups derived from bisphenol A, and glycidyloxy groups derived from bisphenol F Glycidyl derived from bisphenol A, preferably containing at least one selected from the group consisting of epoxy resins as a main component, from the viewpoint of the ability to form a coating film with good appearance and elongation, and from the viewpoint of availability and economy.
• the main component is an epoxy resin having an oxy group.
• the term "main component" as used herein means that other components may be included within the scope of the present invention, preferably 50 to 100% by mass, more preferably 70 to 100% by mass of the total. , more preferably 90 to 100% by mass.
• the epoxy resin which is the main agent, may contain a reactive diluent other than the epoxy resin from the viewpoint of improving handling properties.
• the reactive diluent include low-molecular-weight compounds having at least one epoxy group, such as aromatic monoglycidyl ethers such as phenyl glycidyl ether and cresyl glycidyl ether; butyl glycidyl ether, hexyl glycidyl ether, octyl glycidyl ether; , decyl glycidyl ether, lauryl glycidyl ether, tetradecyl glycidyl ether and other alkyl monoglycidyl ethers; 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6 Examples include digly
• the epoxy resin curing agent used in the epoxy resin composition contains a reaction composition (A) containing a reaction product of xylylenediamine and alkylene oxide.
• the epoxy resin curing agent contains the reaction composition (A)
• the appearance (transparency and gloss) of the resulting coating film is improved.
• the effect of improving the elongation of the coating film can be obtained.
• Reaction composition (A) comprises the reactant of xylylenediamine and alkylene oxide.
• reactant of xylylenediamine and alkylene oxide means an addition reaction product (adduct) of xylylenediamine and alkylene oxide.
• the reaction product of xylylenediamine and alkylene oxide includes an addition reaction product (1:1 adduct) of 1 mol of xylylenediamine and 1 mol of alkylene oxide, and a 1:2 mixture of xylylenediamine and alkylene oxide. Adducts, multi-adducts such as 1:3 adducts are also included.
• reaction composition (A) containing a reaction product of xylylenediamine and alkylene oxide means a reaction product obtained by the reaction of xylylenediamine and alkylene oxide, which, in addition to the above adduct, includes xylylene It may contain unreacted raw materials such as diamine.
• xylylenediamine examples include orthoxylylenediamine, metaxylylenediamine (MXDA), and paraxylylenediamine (PXDA).
• MXDA metaxylylenediamine
• PXDA paraxylylenediamine
• meta-xylylenediamine and para-xylylenediamine is preferable from the viewpoint of forming a coating film with good appearance, and from the viewpoint of being able to form a coating film with good appearance and elongation. Therefore, meta-xylylenediamine is more preferred.
• the alkylene oxide is preferably an alkylene oxide having 2 to 6 carbon atoms, more preferably an alkylene oxide having 2 to 4 carbon atoms, from the viewpoint of forming a coating film having good appearance and elongation, and the group consisting of ethylene oxide and propylene oxide. At least one selected from is more preferable, and from the viewpoint of improving the water resistance of the resulting coating film, it is more preferable that it contains ethylene oxide, and it is still more preferable that it is ethylene oxide.
• An alkylene oxide can be used individually by 1 type or in combination of 2 or more types.
• the reaction molar ratio of xylylenediamine and alkylene oxide is within a range in which the reaction composition (A) has sufficient active hydrogen derived from amino groups to function as an epoxy resin curing agent.
• the reaction composition (A) preferably contains xylylenediamine and an alkylene oxide.
• ⁇ is 1/0.2 to 1/4, more preferably 1/0.2 to 1/3, more preferably 1/0.2 to 1/2, even more preferably 1/0.5 to 1/2 , and more preferably a composition obtained by reacting at a molar ratio (xylylenediamine/alkylene oxide) of 1/0.8 to 1/1.2.
• the reaction composition (A) can be produced by reacting xylylenediamine and alkylene oxide under heating conditions.
• xylylenediamine is charged into a reaction vessel, and while stirring, preferably 50 to 150° C., more preferably 70 to 130° C., alkylene oxide is blown in or added dropwise to complete the addition. After that, it can be produced by reacting for 0.5 to 12 hours while continuing heating.
• the reaction is preferably carried out in an inert gas atmosphere such as nitrogen gas.
• the obtained reaction solution can be used as it is as the reaction composition (A). If necessary, the reaction solution may be purified to remove unreacted raw materials before use as the reaction composition (A).
• the epoxy resin curing agent can also contain curing agent components other than the reaction composition (A).
• the curing agent component include components known as epoxy resin curing agents, but polyamines other than the reaction composition (A) are preferred from the viewpoint of improving the curing speed.
• the polyamine is not particularly limited as long as it is a compound having at least two amino groups in the molecule.
• IPDA
• ketimine obtained by reacting the above amine with a ketone compound; and the like.
• ketimine obtained by reacting the above amine with a ketone compound; and the like.
• the content of the reaction composition (A) in all the curing agent components contained in the epoxy resin curing agent is preferably 50% by mass or more, more preferably 60% by mass or more, from the viewpoint of obtaining the effects of the present invention. More preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more and 100% by mass or less.
• the curing agent component in the curing agent means a component contained in the curing agent that has two or more active hydrogens capable of reacting with the epoxy groups in the epoxy resin.
• the mass % of the composition refers to the content of the reaction composition relative to the total amount of curable components contained in the curing agent.
• the active hydrogen equivalent of the epoxy resin curing agent is preferably 40 or more, more preferably 50, from the viewpoints of forming a coating film with good appearance, improving the curing speed, and improving the water resistance of the resulting coating film. Above, more preferably 55 or more, preferably 150 or less, more preferably 120 or less, even more preferably 110 or less, still more preferably 100 or less from the viewpoint of improving curability.
• the active hydrogen equivalent (hereinafter also referred to as "AHEW”) in the present specification is the mass per mole of active hydrogen derived from amino groups in the epoxy resin curing agent. AHEW of the epoxy resin curing agent can be calculated from the amine value.
• the content ratio of the epoxy resin and the epoxy resin curing agent in the epoxy resin composition of the present invention is the ratio of the number of active hydrogens derived from amino groups in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin (epoxy resin).
• the number of active hydrogens derived from amino groups in the curing agent/the number of epoxy groups in the epoxy resin is preferably 1/0.5 to 1/2, more preferably 1/0.75 to 1/1.5, and still more preferably is an amount of 1/0.8 to 1/1.2.
• the epoxy resin composition contains a non-reactive diluent from the viewpoint of improving handling properties and improving the elongation of the resulting coating film.
• a non-reactive diluent improves the water resistance of the coating film.
• non-reactive diluents include benzyl alcohol, furfuryl alcohol, tetrafurfuryl alcohol, aromatic hydrocarbon formaldehyde resins, and the like, and one or more of these can be used.
• Aromatic hydrocarbon formaldehyde resin is a resin obtained by reacting an aromatic hydrocarbon with formaldehyde.
• the xylene formaldehyde resin is preferred as the aromatic hydrocarbon formaldehyde resin from the viewpoint of improving the elongation of the resulting coating film.
• aromatic hydrocarbon formaldehyde resins include, for example, “Nikanol Y-50”, “Nikanol Y-100”, “Nikanol Y-300”, “Nikanol Y- 1000", “Nikanol L”, “Nikanol LL”, “Nikanol LLL”, “Nikanol G”, “Nikanol H”, “Nikanol H-80” and the like.
• the non-reactive diluent contains benzyl alcohol
• the content of benzyl alcohol in the non-reactive diluent is preferably 20% by mass or more, more preferably 30% by mass, from the viewpoint of improving the elongation of the resulting coating film.
• the content of the non-reactive diluent in the epoxy resin composition is preferably 100 parts by mass of the epoxy resin curing agent from the viewpoint of improving handling properties and improving the water resistance and elongation of the resulting coating film. is 10 to 500 parts by mass, more preferably 20 to 500 parts by mass, more preferably 30 to 450 parts by mass, even more preferably 40 to 450 parts by mass, even more preferably 50 to 420 parts by mass, even more preferably 60 420 parts by mass, more preferably 65 to 400 parts by mass.
• the content of the epoxy resin and epoxy resin curing agent in the epoxy resin composition is such that the ratio of the number of active hydrogens derived from amino groups in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin is preferably within the above range.
• the following range is preferable.
• the content of the epoxy resin in the epoxy resin composition is preferably 30% by mass or more, more preferably 35% by mass or more, and preferably 70% by mass or less.
• the content of the epoxy resin curing agent in the epoxy resin composition is preferably 10% by mass or more, more preferably 12% by mass or more, and preferably 35% by mass or less, more preferably 30% by mass or less.
• the content of the epoxy resin curing agent in the epoxy resin composition is preferably 20 to 60 parts by mass, more preferably 30 to 60 parts by mass, based on 100 parts by mass of the epoxy resin as the main ingredient.
• the content of the reaction composition (A) in the epoxy resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 35% by mass or less. Preferably, it is 30% by mass or less.
• the content of the non-reactive diluent in the epoxy resin composition is preferably 1% by mass or more, more preferably 2% by mass, from the viewpoint of improving handleability and improving the water resistance and elongation of the resulting coating film. % by mass or more, more preferably 5% by mass or more, preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less.
• the total content of the epoxy resin and the epoxy resin curing agent in the epoxy resin composition is preferably 40% by mass or more, more preferably 50% by mass or more, and preferably 99% by mass. 95% by mass or less, more preferably 95% by mass or less.
• the total content of the epoxy resin, epoxy resin curing agent, and non-reactive diluent in the epoxy resin composition is preferably 40% by mass or more, more preferably 50% by mass or more, from the viewpoint of obtaining the effects of the present invention. More preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more and 100% by mass or less.
• the epoxy resin composition may further contain a curing accelerator from the viewpoint of improving the curing speed and improving the hardness of the coating film.
• Curing accelerators include, for example, phenol compounds, organic acids, organic acid salts, tertiary amines, quaternary ammonium salts, imidazoles, organophosphorus compounds, quaternary phosphonium salts, diazabicycloalkenes, and organic metal salts. compounds, boron compounds, metal halides, and the like.
• Phenol compounds include phenol, cresol, hydroquinone, 1-naphthol, 2-naphthol, resorcinol, phenol novolak resin, p-isopropylphenol, t-butylphenol, nonylphenol, bisphenol A and the like.
• organic acids include carboxylic acid compounds and sulfonic acid compounds.
• Carboxylic acid compounds include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butanoic acid, 2-ethylhexanoic acid, and benzoic acid; hydroxycarboxylic acids such as lactic acid and salicylic acid; oxalic acid, malonic acid, maleic acid, and itaconic acid.
• sulfonic acid compounds include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and trifluoromethanesulfonic acid.
• organic acid salts include salts of the above organic acids, such as imidazole salts, substituted imidazole salts, diazabicycloundecene (DBU) salts, and diazabicyclononene of the above carboxylic acid compounds or sulfonic acid compounds.
• DBN diazabicyclooctane
• DABCO diazabicyclooctane
• tetraethylammonium salts tetrabutylammonium salts, and the like.
• Tertiary amines include triethylenediamine, triethanolamine, benzyldimethylamine, dimethylcyclohexylamine, 2-(dimethylaminomethyl)phenol and the like.
• Quaternary ammonium salts include tetraethylammonium bromide, tetrabutylammonium bromide and the like.
• Examples of imidazoles include 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole. etc.
• organic phosphorus compounds include triphenylphosphine, diphenylphosphine, tributylphosphine, and triphenylphosphite.
• Quaternary phosphonium salts include tetraphenylphosphonium bromide, tetra-n-butylphosphonium bromide and the like.
• diazabicycloalkenes include 1,8-diazabicyclo[5.4.0]undecene-7.
• organic metal salt compounds include zinc octylate and tin octylate.
• Boron compounds include boron trifluoride and triphenylborate.
• zinc chloride, stannic chloride, etc. are mentioned as a metal halide.
• a hardening accelerator can be used individually by 1 type or in combination of 2 or more types.
• the curing accelerator is preferably at least one selected from the group consisting of phenol compounds, organic acids, and organic phosphorus compounds, from the viewpoint of solubility in the epoxy resin composition and improvement of the curing speed.
• a compound is more preferred, and at least one selected from the group consisting of phenol, cresol, p-isopropylphenol, t-butylphenol, nonylphenol, and bisphenol A is more preferred, and t-butylphenol is even more preferred.
• the content of the curing accelerator in the epoxy resin composition is 100 mass of the epoxy resin curing agent from the viewpoint of improving the curing speed and improving the hardness of the coating film. parts, preferably 10 to 50 parts by mass, more preferably 15 to 40 parts by mass, even more preferably 20 to 40 parts by mass, and even more preferably 25 to 40 parts by mass.
• the epoxy resin composition of the present invention may further contain other components such as fillers, modifying components such as plasticizers, flow control components such as thixotropic agents, pigments, leveling agents, tackifiers, and elastomer fine particles. may be included depending on
• the epoxy resin composition of the present invention may contain solvents (water and volatile solvents) other than non-reactive diluents, but the content thereof is preferably 5% by mass or less in the epoxy resin composition. , more preferably 2% by mass or less, and still more preferably 1% by mass or less.
• the method for producing the epoxy resin composition of the present invention is not particularly limited. can be manufactured.
• the mixing order of each component contained in the epoxy resin composition is not particularly limited, and after the epoxy resin curing agent is prepared, it may be mixed with the epoxy resin. And other components and epoxy resin may be mixed at the same time to prepare.
• the epoxy resin composition is prepared by preparing an epoxy resin curing agent composition containing an epoxy resin curing agent and a non-reactive diluent, and then adding the epoxy resin curing agent composition and the main agent It is preferable to prepare by mixing with an epoxy resin.
• an epoxy resin curing agent composition containing an epoxy resin curing agent, a non-reactive diluent, and a curing accelerator is prepared, and then the epoxy resin curing agent is prepared. It is preferable to prepare by mixing the composition with an epoxy resin as a main agent.
• the cured product of the epoxy resin composition of the present invention (hereinafter also simply referred to as "the cured product of the present invention") is obtained by curing the epoxy resin composition by a known method. Curing conditions for the epoxy resin composition are appropriately selected according to the application and form, and are not particularly limited. The form of the cured product of the present invention is also not particularly limited, and can be selected depending on the application. From the viewpoint of forming a coating film with good appearance, the cured product of the epoxy resin composition is preferably a film-like cured product.
• a coating film, which is a cured product of the epoxy resin composition of the present invention has good appearance (transparency and gloss), and also has good water resistance and elongation.
• the epoxy resin composition of the present invention can form a coating film with good appearance (transparency and gloss), it can be used for, for example, marine paints, heavy duty anticorrosion paints, tank paints, pipe interior paints, exterior paints, and flooring materials. It is suitably used for coating applications such as commercial coatings.
• the present invention will be described in detail below with examples and comparative examples, but the present invention is not limited to the following examples.
• the epoxy resin curing agent, the epoxy resin composition, and the cured products thereof were evaluated according to the following methods.
• ⁇ Dry touch> A zinc phosphate-treated steel plate (manufactured by Paltec Co., Ltd.; SPCC-SD PB-N144 0.8 ⁇ 70 ⁇ 150 mm) was used as the base material. 23°C, 50% R.I. H. Under these conditions, the epoxy resin composition of each example was applied onto a substrate using an applicator to form a coating film (film thickness immediately after application: 200 ⁇ m). This coating film was heated at 23° C. and 50% R.I. H. It was stored under these conditions, and after one day had passed, it was evaluated by touch with a finger according to the following criteria. The results are shown in Tables 1-2.
• reaction composition (A1) containing reactant of meta-xylylenediamine and ethylene oxide (reaction molar ratio 1/1)) 136.19 g (1 mol) of meta-xylylenediamine (MXDA, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was charged into a reaction vessel, and the temperature was raised to 80° C. while stirring under a nitrogen stream. While continuing to stir, 44.05 g (1 mol) of ethylene oxide was blown into the reaction vessel over 5 hours, and after the completion of the blowing, the mixture was stirred at 80 to 120° C. for 1 hour to react, and the reaction composition (A1) (MXDA) was obtained. -EO (1/1)).
• the active hydrogen equivalent weight (AHEW) derived from the amino group of the reaction composition (A1) was 60.
• reaction composition (A2) containing reaction product of meta-xylylenediamine and propylene oxide (reaction molar ratio 1/1)) 136.19 g (1 mol) of meta-xylylenediamine (MXDA, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was charged into a reaction vessel, and the temperature was raised to 80° C. while stirring under a nitrogen stream. While continuing to stir, 58.1 g (1 mol) of propylene oxide was added dropwise into the reaction vessel over 5 hours, and after the completion of the dropwise addition, the mixture was stirred at 80 to 120°C for 1 hour to react to obtain a reaction composition (A2). (MXDA-PO(1/1)) was obtained. The AHEW derived from the amino group of the reaction composition (A2) was 67.
• Production Example 3 (Production of reaction composition (A3) containing reactant of meta-xylylenediamine and ethylene oxide (reaction molar ratio 1/1.5)) In Production Example 1, except that the amount of ethylene oxide used was changed to 66.1 g (1.5 mol), the same operation as in Production Example 1 was carried out to obtain a reaction composition (A3) (MXDA-EO (1/1 .5)) was obtained. The AHEW derived from the amino group of the reaction composition (A3) was 82.
• Production Example 4 (Production of reaction composition (A4) containing reactant of meta-xylylenediamine and ethylene oxide (reaction molar ratio 1/2)) In Production Example 1, except that the amount of ethylene oxide used was changed to 88.1 g (2 mol), the same operation as in Production Example 1 was performed to obtain a reaction composition (A4) (MXDA-EO (1/2)). got The AHEW derived from the amino group of the reaction composition (A4) was 112.
• Example 1 (Preparation and Evaluation of Epoxy Resin Curing Agent Composition and Epoxy Resin Composition) [Preparation of epoxy resin curing agent composition]
• benzyl alcohol which is a non-reactive diluent, was added in an amount of 40% by mass of the total to dilute, and the concentration of the reaction composition (A1) was 60% by mass to obtain an epoxy resin curing agent.
• the amino group-derived AHEW of the epoxy resin curing agent composition was 101.
• Epoxy Resin Composition As the epoxy resin, which is the main ingredient of the epoxy resin composition, a polyfunctional epoxy resin (“jER828” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 186 g/equivalent) having a glycidyloxy group derived from bisphenol A was used. The ratio of the number of active hydrogens derived from amino groups in the curing agent composition to the number of epoxy groups in the epoxy resin (the number of active hydrogens derived from amino groups in the curing agent composition /number of epoxy groups in the epoxy resin) was blended and mixed in the amount ratio shown in Table 1 to prepare an epoxy resin composition. Using the obtained epoxy resin composition, various evaluations were performed by the methods described above. Table 1 shows the results.
• the epoxy resin composition of the present invention provides coating films with good transparency, gloss, and elongation. Moreover, the curing speed of the epoxy resin composition was not significantly impaired, and the water resistance of the coating film was good. On the other hand, according to the comparison between Examples 1 to 14 and Comparative Examples 1 to 4, even if an epoxy resin curing agent containing the reaction composition (A) is used, an epoxy resin composition containing no non-reactive diluent In the product, the elongation of the coating film was significantly reduced. Furthermore, the curing speed of the epoxy resin composition and the water resistance of the coating film tended to decrease. The epoxy resin composition of Comparative Example 4 was slow to cure and the coating film was sticky, so the Erichsen test could not be performed. Further, as shown in Comparative Examples 5 to 7, when an epoxy resin curing agent containing no reaction composition (A) was used, the effect of improving elongation of the coating film was not obtained even when a non-reactive diluent was used. .
• an epoxy resin composition capable of forming a coating film with good appearance (transparency and gloss) and elongation, and a cured product thereof.

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• 2023
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