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
  • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/18—Fireproof paints including high temperature resistant paints
• • 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
  • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
  • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
  • C08G79/025—Polyphosphazenes
• • 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
  • C08G59/20—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 epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
  • C08G59/245—Di-epoxy compounds carbocyclic 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
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • 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
• • 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
  • C08G59/68—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 catalysts used
  • C08G59/688—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 catalysts used containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/5399—Phosphorus bound to nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
  • C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
• • 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
  • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0066—Flame-proofing or flame-retarding additives

Definitions

• the present invention relates to an epoxy resin composition and a coating material.
• fire retardants such as boric acid compounds are usually injected into the wood to make it flame-retardant.
• boric acid compounds are usually injected into the wood to make it flame-retardant.
• this process causes the fire retardant to bleed out of the wood over time, resulting in the wood appearing white (efflorescence).
• a fire-resistant paint must be used to prevent the wood from losing its flame retardant properties.
• Fireproof paints are generally opaque and filled with inorganic substances, but there is also a strong demand for fireproof paints that can retain the grain of wood from an appearance perspective, and therefore highly transparent fireproof paints are in demand.
• Patent Document 1 discloses a flame-retardant coating composition containing a coating agent and a mixture of a specific stabilizer with steric hindrance and a conventional flame retardant.
• Patent Document 2 describes a fiber-reinforced sheet obtained by impregnating glass fibers with a resin composition containing a cyclic and/or chain-like phosphazene compound of a specific structure having a glycidyloxy group, a compound having two or more epoxy groups in one molecule, and a carboxylic acid or carboxylic acid anhydride as a curing agent, and curing the resin composition, and describes a transparent flame-retardant sheet with a small difference between the refractive index of the cured resin composition and the refractive index of the glass fibers, which has little coloring and is excellent in heat resistance, flame retardancy, and transparency.
• Patent Document 1 does not consider the transparency of the coating composition.
• Patent Document 2 discloses an epoxy resin composition for use in a transparent flame-retardant sheet, but the transparency of the sheet is improved by reducing the difference between the refractive index of the resin composition after curing and the refractive index of the glass fiber, and there is room for improvement in terms of improving the transparency of the epoxy resin composition alone.
• the objective of the present invention is to provide an epoxy resin composition capable of forming a coating film having excellent transparency and flame retardancy, and a paint containing the composition.
• an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent containing a specified diamine or a modified product thereof, and a specified amount or more of a phosphazene compound. That is, the present invention relates to the following.
• An epoxy resin composition comprising an epoxy resin (A), an epoxy resin curing agent (B) containing a diamine represented by the following general formula (1) or a modified product thereof (b1), and a phosphazene compound (C), wherein the total content of the components (A) to (C) in the epoxy resin composition is 85 mass% or more: NH2 - CH2 -X- CH2 - NH2 (1) (In the formula, X is a phenylene group or a cyclohexylene group.) [2] The epoxy resin composition according to the above [1], wherein the component (b1) contains a diamine represented by the general formula (1) or a styrene-modified product thereof.
• the present invention provides an epoxy resin composition capable of forming a coating film with excellent transparency and flame retardancy, and a paint containing the composition.
• the epoxy resin composition of the present invention (hereinafter, also simply referred to as “the composition (of the present invention)”) contains an epoxy resin (A), an epoxy resin curing agent (B) containing a diamine represented by the following general formula (1) or a modified product thereof (b1), and a phosphazene compound (C), and the total content of the components (A) to (C) in the epoxy resin composition is 85 mass% or more.
• the epoxy resin composition of the present invention has the above-mentioned configuration and is therefore capable of forming a coating film having excellent transparency and flame retardancy.
• the phosphazene compound which is the component (C) contains phosphorus and nitrogen atoms and is known as a compound having flame retardancy.
• a flame retardant when added to a resin composition, the transparency is likely to decrease, but the phosphazene compound is relatively easy to ensure transparency.
• an epoxy resin composition for paint it is not enough to use the phosphazene compound as a flame retardant alone to obtain transparency of the coating film formed.
• the present inventors have found that by using a combination of an epoxy resin curing agent (B) containing a specific component (b1) and a phosphazene compound in an epoxy resin composition, flame retardancy can be imparted without impairing transparency.
• the component (b1) has a ring structure, which contributes to improving flame retardancy, and further, the compatibility between the component (b1) and the component (C) is good, so that good transparency and flame retardancy can be obtained.
• the total content of the components (A) to (C) in the epoxy resin composition is 85 mass% or more, the effects of the present invention can be effectively exerted, and a coating film having excellent transparency and flame retardancy can be formed.
• the epoxy resin (A) which is the main component of the epoxy resin composition, may be any of a saturated or unsaturated aliphatic compound, an alicyclic compound, an aromatic compound, and a heterocyclic compound. From the viewpoint of obtaining a coating film having high water resistance and chemical resistance, an epoxy resin containing an aromatic ring or an alicyclic structure in the molecule is preferred.
• the epoxy resin (A) include at least one resin selected from the group consisting of epoxy resins having a glycidylamino group derived from meta-xylylenediamine, epoxy resins having a glycidylamino group derived from para-xylylenediamine, epoxy resins having a glycidylamino group derived from 1,3-bis(aminomethyl)cyclohexane, epoxy resins having a glycidylamino group derived from 1,4-bis(aminomethyl)cyclohexane, epoxy resins having a glycidylamino group derived from diaminodiphenylmethane, epoxy resins having a glycidylamino group and/or a glycidyloxy group derived from para-aminophenol, epoxy resins having a glycidyloxy group derived from bisphenol A, epoxy resins having a glycidyloxy group derived from bisphenol A,
• the epoxy resin (A) is preferably one having as a main component at least one selected from the group consisting of epoxy resins having a glycidylamino group derived from meta-xylylenediamine, epoxy resins having a glycidylamino group derived from para-xylylenediamine, epoxy resins having a glycidyloxy group derived from bisphenol A, and epoxy resins having a glycidyloxy group derived from bisphenol F, and from the viewpoint of obtaining a coating film having high transparency, flame retardancy, chemical resistance, etc., availability and economical aspects, one having as a main component an epoxy resin having a glycidyloxy group derived from bisphenol A is more preferred.
• main component means that other components may be contained within a range that does not deviate from the spirit of the present invention, and preferably means 50 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 90 to 100% by mass of the total.
• the epoxy resin (A) may be either a solid epoxy resin or a liquid epoxy resin.
• solid epoxy resin means an epoxy resin that is solid at room temperature (25°C)
• liquid epoxy resin means an epoxy resin that is liquid at room temperature (25°C).
• the epoxy equivalent of the epoxy resin (A) is preferably 150 g/equivalent or more from the viewpoint of obtaining a coating film with high transparency, flame retardancy, chemical resistance, etc., and is preferably 1000 g/equivalent or less from the viewpoint of curability, more preferably 800 g/equivalent or less, even more preferably 500 g/equivalent or less, even more preferably 300 g/equivalent or less, and even more preferably 250 g/equivalent or less.
• the epoxy resin curing agent (B) contains a diamine represented by the following general formula (1) or a modified product thereof (b1). NH2 - CH2 -X- CH2 - NH2 (1) (In the formula, X is a phenylene group or a cyclohexylene group.)
• the diamine represented by the general formula (1) used as component (b1) is a compound in which X in the formula (1) is a phenylene group or a cyclohexylene group.
• X is at least one selected from the group consisting of a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, and a 1,4-cyclohexylene group.
• X is preferably a phenylene group, more preferably at least one selected from the group consisting of a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group, and even more preferably a 1,3-phenylene group.
• the cyclohexylene group includes both cis and trans isomers.
• the diamine represented by the general formula (1) examples include xylylenediamines such as ortho-xylylenediamine, meta-xylylenediamine (MXDA), and para-xylylenediamine (PXDA); and bis(aminomethyl)cyclohexanes such as 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, and 1,4-bis(aminomethyl)cyclohexane.
• the diamine represented by the general formula (1) is preferably xylylenediamine, and more preferably metaxylylenediamine.
• the modified product of the diamine represented by the general formula (1) used as component (b1) includes an epoxy modified product obtained by reacting the diamine represented by the general formula (1) with an epoxy compound having at least one epoxy group; a reaction product obtained by reacting the diamine represented by the general formula (1) with an unsaturated hydrocarbon compound; a carboxylic acid modified product obtained by reacting the diamine represented by the general formula (1) with a carboxylic acid or a derivative thereof; a Mannich modified product obtained by reacting the diamine represented by the general formula (1) with a phenol compound and an aldehyde compound; a ketimine (ketimine) obtained by reacting the diamine represented by the general formula (1) with a ketone compound; a phosphorus modified product obtained by reacting the diamine represented by the general formula (1) with a phosphorus-containing compound; and the like. These can be used alone or in combination of two or more.
• the phosphorus-modified product obtained by reacting the diamine represented by the above general formula (1) with a phosphorus-containing compound includes, for example, the phosphorus-modified product represented by the following general formula (3).
• R 11 represents a hydrocarbon group
• X represents a phenylene group or a cyclohexylene group
• n is a number from 1 to 5.
• Examples of the hydrocarbon group in R 11 in the general formula (3) include an alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.
• R 1 is preferably an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms.
• the aryl group include a phenyl group, a toluyl group, a mesityl group, a biphenyl group, and a naphthyl group, and the phenyl group is preferred.
• X in the general formula (3) is the same as defined above.
• the modified product of the diamine represented by the general formula (1) is preferably at least one selected from the group consisting of an epoxy modified product obtained by reacting the diamine represented by the general formula (1) with an epoxy compound having at least one epoxy group, and a reaction product obtained by reacting the diamine represented by the general formula (1) with an unsaturated hydrocarbon compound, and more preferably a reaction product obtained by reacting the diamine represented by the general formula (1) with an unsaturated hydrocarbon compound.
• the reaction composition referred to here is a composition obtained by reacting the diamine represented by the general formula (1) with an unsaturated hydrocarbon compound, and contains at least a reaction product (adduct) between the diamine represented by the general formula (1) and the unsaturated hydrocarbon compound.
• the reaction composition may contain unreacted raw materials, by-products, etc. in addition to the adduct.
• Examples of the unsaturated hydrocarbon compound in the reaction product obtained by reacting the diamine represented by the general formula (1) with an unsaturated hydrocarbon compound include unsaturated aliphatic hydrocarbon compounds having 2 to 10 carbon atoms and aromatic hydrocarbon compounds having an ethylenically unsaturated bond having 2 to 10 carbon atoms, and examples thereof include at least one selected from the group consisting of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, isobutylene, 2-pentene, 3-methyl-1-butene, 2-methyl-2-butene, 2,3-dimethyl-2-butene, cyclohexene, cyclohexadiene, styrene, and divinylbenzene.
• the unsaturated hydrocarbon compound is preferably an aromatic hydrocarbon compound having an ethylenically unsaturated bond, such as styrene or divinylbenzene, and more preferably styrene.
• the modified product of the diamine represented by the general formula (1) used as component (b1) is preferably a reaction product obtained by reacting the diamine represented by the general formula (1) with an aromatic hydrocarbon compound having an ethylenically unsaturated bond, and more preferably a styrene modified product of the diamine represented by the general formula (1).
• component (b1) preferably contains a diamine represented by the general formula (1) or a styrene-modified product thereof, more preferably contains at least one selected from the group consisting of xylylenediamine and a styrene-modified product of xylylenediamine, even more preferably contains at least one selected from the group consisting of metaxylylenediamine and a styrene-modified product of metaxylylenediamine, and even more preferably contains metaxylylenediamine.
• component (b1) preferably contains a diamine represented by the general formula (1) or a styrene-modified product thereof, more preferably contains at least one selected from the group consisting of xylylenediamine and a styrene-modified product of xylylenediamine, even more preferably contains at least one selected from the group consisting of metaxylylenediamine and a styrene-modified product of
• the content of the diamine represented by the general formula (1) or its styrene-modified product in component (b1) is, from the viewpoint of obtaining a coating film having high transparency and flame retardancy, preferably 30 mass% or more, more preferably 50 mass% or more, even more preferably 60 mass% or more, still more preferably 70 mass% or more, still more preferably 80 mass% or more, and still more preferably 90 mass% or more, and 100 mass% or less.
• the content of component (b1) in the epoxy resin hardener (B) is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and 100% by mass or less, from the viewpoint of obtaining a coating film with high transparency and flame retardancy.
• the epoxy resin curing agent (B) may contain a curing agent component other than the component (b1).
• the curing agent component means a component contained in the epoxy resin curing agent (B) that has two or more active hydrogens capable of reacting with the epoxy group in the epoxy resin.
• the curing agent components other than the component (b1) include amine-based curing agents other than the component (b1), phenol-based curing agents, acid anhydride-based curing agents, and hydrazide-based curing agents.
• the content of the hardener component in the epoxy resin hardener (B) is preferably 1% by mass or more, more preferably 5% by mass or more.
• the upper limit of the content may be within a range that does not impair the effects of the present invention, and is preferably 70% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and even more preferably 10% by mass or less.
• the active hydrogen equivalent of the epoxy resin curing agent (B) is preferably 20 or more, more preferably 30 or more, from the viewpoint of obtaining good coating properties, and is preferably 150 or less, from the viewpoint of improving curing properties.
• the active hydrogen equivalent (hereinafter also referred to as "AHEW”) is the mass per mole of active hydrogen in the epoxy resin curing agent.
• the phosphazene compound means a compound having a structure in which phosphorus atoms and nitrogen atoms are bonded alternately.
• the phosphazene compound (C) (hereinafter also simply referred to as “component (C)”) may be either a chain phosphazene compound or a cyclic phosphazene compound, and from the viewpoint of obtaining a coating film having high transparency and flame retardancy, it is preferable that the compound contains a cyclic phosphazene compound.
• the content of the cyclic phosphazene compound in the phosphazene compound (C) is preferably 30 mass% or more, more preferably 50 mass% or more, even more preferably 60 mass% or more, still more preferably 70 mass% or more, still more preferably 80 mass% or more, and still more preferably 90 mass% or more, and is 100 mass% or less.
• the cyclic phosphazene compound may be a compound represented by the following general formula (2).
• R and R' each independently represent a fluorine atom, an alkoxy group having 1 to 12 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms which may have a substituent; and n is a number from 3 to 8.
• n is preferably 3 to 6, more preferably 3 to 4, and even more preferably 3.
• cyclic phosphazene compound a compound represented by the following general formula (2-1) is preferably mentioned.
• R 1 to R 6 each independently represent a fluorine atom, an alkoxy group having 1 to 12 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms which may have a substituent.
• the number of carbon atoms in the alkoxy group in R 1 to R 6 is preferably 1 to 8, more preferably 2 to 6, and even more preferably 2 to 4.
• Specific examples of preferred alkoxy groups include methoxy groups, ethoxy groups, various propoxy groups, various butoxy groups, etc.
• the term "various" refers to linear and all branched groups, and the same applies hereinafter.
• the aryloxy group in R 1 to R 6 is a group represented by -OR 7 (R 7 is an aryl group), and may have a substituent on the aromatic ring of the aryl group.
• substituent include a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a vinyl group, and an epoxy group-containing group, and is preferably a cyano group.
• the aryloxy group for R 1 to R 6 preferably has 6 to 10 carbon atoms, and more preferably 6 to 8 carbon atoms.
• R 1 to R 6 are preferably a fluorine atom, an alkoxy group having 1 to 4 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms which may have a cyano group, more preferably an aryloxy group having 6 to 12 carbon atoms which may have a cyano group, and even more preferably a phenoxy group.
• R 1 to R 6 may be the same or different, but it is even more preferable that all of them are phenoxy groups.
• cyclic phosphazene compound used as the phosphazene compound (C) include the compounds represented by the following formulas (2-2) to (2-5), and the compound represented by the formula (2-2) is preferred.
• phosphazene compound (C) Commercially available products can also be used as the phosphazene compound (C). Examples of commercially available products include “FP-100” (hexaphenoxycyclotriphosphazene; compound represented by formula (2-2)), “FP-110” and “FP-300B” (compound represented by formula (2-3)) manufactured by Fushimi Pharmaceutical Co., Ltd., “HICHICOLIN E” (compound represented by formula (2-4)) and “HICHICOLIN O” (compound represented by formula (2-5)) manufactured by Nippon Chemical Industry Co., Ltd., and "SPE-100", “SPB-100”, “SPM-100” and “SPS-100” manufactured by Otsuka Chemical Co., Ltd.
• FP-100 hexaphenoxycyclotriphosphazene
• FP-300B compound represented by formula (2-3)
• HICHICOLIN E compound represented by formula (2-4)
• HICHICOLIN O compound represented by formula (2-5)
• the ratio of the number of active hydrogens in the epoxy resin curing agent (B) to the number of epoxy groups in the epoxy resin (A) is preferably 1/0.5 to 1/2, more preferably 1/0.75 to 1/1.5, and even more preferably 1/0.8 to 1/1.2.
• the content of epoxy resin (A) in the epoxy resin composition is not limited as long as the above (number of active hydrogens in epoxy resin hardener (B)/number of epoxy groups in epoxy resin (A)) is preferably within the above range, but is preferably 30 to 80% by mass, more preferably 40 to 80% by mass, and even more preferably 50 to 75% by mass.
• the content of the epoxy resin curing agent (B) in the epoxy resin composition is not limited as long as the above (number of active hydrogens in the epoxy resin curing agent (B)/number of epoxy groups in the epoxy resin (A)) is preferably within the above range, but is preferably 5 to 40 mass%, more preferably 10 to 30 mass%, and even more preferably 10 to 20 mass%.
• the content of the phosphazene compound (C) in the epoxy resin composition is preferably 0.1 to 10 mass%, more preferably 0.2 to 8.0 mass%, even more preferably 0.5 to 5.0 mass%, even more preferably 0.5 to 2.5 mass%, even more preferably 1.0 to 2.4 mass%, and even more preferably 1.0 to 2.2 mass%, in terms of the phosphorus atom content in the composition.
• the content of the phosphazene compound (C) in the epoxy resin composition is preferably 1.0 to 30 mass%, more preferably 2.0 to 30 mass%, even more preferably 4.0 to 20 mass%, and even more preferably 5.0 to 20 mass%, from the viewpoint of obtaining a coating film with high transparency and flame retardancy.
• the epoxy resin composition may further contain other components depending on the application, such as a curing accelerator, a non-reactive diluent such as benzyl alcohol, a filler, a modifying component such as a plasticizer, a flow adjusting component such as a thixotropic agent, a pigment, a leveling agent, a tackifier, and elastomer fine particles.
• a curing accelerator such as benzyl alcohol
• a filler such as benzyl alcohol
• a modifying component such as a plasticizer
• a flow adjusting component such as a thixotropic agent, a pigment, a leveling agent, a tackifier, and elastomer fine particles.
• the total content of components (A) to (C) in the epoxy resin composition is 85 mass % or more, preferably 90 mass % or more, more preferably 95 mass % or more, and even more preferably 98 mass % or more, and is 100 mass % or less.
• the epoxy resin composition of the present invention has a small content of water and organic solvent.
• the content of water and organic solvent in the epoxy resin composition is preferably 10% by mass or less, more preferably 5.0% by mass or less, even more preferably 3.0% by mass or less, still more preferably 2.0% by mass or less, and still more preferably 1.0% by mass or less.
• the epoxy resin composition of the present invention contains a small amount of thermoplastic resin such as polyphenylene ether.
• the content of the thermoplastic resin in the epoxy resin composition is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 5.0% by mass or less, still more preferably 2.0% by mass or less, and even more preferably 1.0% by mass or less.
• ⁇ Method for preparing epoxy resin composition There is no particular limitation on the method for preparing the epoxy resin composition, and the epoxy resin (A), the epoxy resin curing agent (B), the phosphazene compound (C), and other components as necessary can be mixed and prepared using a known method and device. There is also no particular limitation on the order of mixing the components contained in the epoxy resin composition, and after preparing the epoxy resin curing agent (B), this may be mixed with the epoxy resin (A) and the phosphazene compound (C), or the epoxy resin composition may be prepared by simultaneously mixing the components constituting the epoxy resin curing agent (B) and other components with the epoxy resin (A) and the phosphazene compound (C).
• the coating film which is the cured product of the epoxy resin composition of the present invention, can be obtained by curing the above-mentioned epoxy resin composition of the present invention by a known method.
• the curing conditions of the epoxy resin composition are appropriately selected depending on the application and form, and are not particularly limited.
• the coating film which is the cured product of the epoxy resin composition of the present invention has excellent transparency and flame retardancy, is resistant to whitening, and has a high oxygen index.
• the epoxy resin composition of the present invention has high flame retardancy.
• the oxygen index of a cured product of the epoxy resin composition having a thickness of 3 mm, measured in accordance with JIS K 7201:1995 is preferably 27 or more, more preferably 28 or more, even more preferably 30 or more, still more preferably 32 or more, and even more preferably 35 or more.
• the degree of flame retardancy can be confirmed by measuring the oxygen index.
• the oxygen index indicates the oxygen concentration required to continue combustion, and if it exceeds 21, combustion will not continue in air under normal conditions.
• an oxygen index of 27 or more is generally considered to indicate high flame retardancy.
• the oxygen index can be measured by the method described in the Examples.
• the present invention provides a coating material containing the epoxy resin composition.
• the coating material of the present invention contains the epoxy resin composition, and thereby the transparency and flame retardancy of the resulting coating film are improved.
• the coating material include wood coating materials used as interior and exterior materials and structural members of buildings, marine coating materials, heavy-duty anticorrosive coating materials, tank coating materials, pipe interior coating materials, exterior coating materials, and floor coating materials.
• the paint according to the present invention is preferably a transparent flame-retardant paint.
• the content of the epoxy resin composition in the coating material of the present invention is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more, but not more than 100% by mass.
• the epoxy resin composition can be suitably used for applications such as the coating material, adhesives, flooring materials, sealants, polymer cement mortar, gas barrier coatings, primers, screeds, top coats, sealing materials, crack repair materials, concrete materials, and the like.
• the present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
• the epoxy resin composition was evaluated according to the following methods.
• the epoxy resin composition of each example was heated at 80° C. for 1 hour to cure, and then molded into a test piece having dimensions of 70 mm ⁇ 6.5 mm ⁇ 3 mm thickness.
• the oxygen index of the test specimen was measured by a candle combustion tester type D (manufactured by Toyo Seiki Seisakusho) according to the method of JIS K 7201: 1995. A higher oxygen index means better flame retardancy.
• Example 1 (Preparation and Evaluation of Epoxy Resin Composition) A polyfunctional epoxy resin having a glycidyloxy group derived from bisphenol A ("jER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 186 g/equivalent) was used as the epoxy resin (A) which is the main component of the epoxy resin composition.
• metaxylylenediamine (MXDA, manufactured by Mitsubishi Gas Chemical Co., Ltd.) which is component (b1), was used as the epoxy resin curing agent (B), and a compound represented by the above formula (2-2) (hexaphenoxycyclotriphosphazene, "FP-100” manufactured by Fushimi Pharmaceutical Co., Ltd.) was used as the phosphazene compound (C).
• An epoxy resin composition was prepared by mixing the components (A) to (C) in amounts of mass % as shown in Table 1.
• the ratio of the number of active hydrogens in the curing agent (B) to the number of epoxy groups in the epoxy resin (A) was 1/1.
• the obtained epoxy resin composition was subjected to various evaluations by the above-mentioned methods. The results are shown in Table 1.
• an epoxy resin composition capable of forming a coating film having excellent transparency and flame retardancy, and a coating material containing the composition.

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• 2023
  • 2023-10-18 KR KR1020257019113A patent/KR20250124112A/ko active Pending
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