Classifications

• • 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
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium 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
  • C08G59/56—Amines together with other curing agents
• • 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
  • C08G59/5046—Amines heterocyclic
• • 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
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical

Definitions

• the present invention relates to an amino composition, a method for producing the same, an epoxy resin curing agent, an epoxy resin composition, and a cured product thereof.
• Epoxy resin compositions using polyamine compounds as epoxy resin curing agents are used in the paint field, such as anticorrosion paints for ships, bridges, land and sea railway 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 water and sewage linings, paving materials, and adhesives. Among these, it is important for epoxy resin compositions for paints that the resulting paint film has good appearance, water resistance, chemical resistance, and physical properties of the paint film.
• Xylylene diamine a type of aliphatic polyamine compound, has fast curing properties when used as an epoxy resin curing agent, and is also characterized by superior low-temperature curing properties and chemical resistance compared to other aliphatic polyamines. have.
• xylylene diamine easily absorbs carbon dioxide and water vapor in the atmosphere and produces carbamates, the coating film of an epoxy resin composition using xylylene diamine as an epoxy resin curing agent tends to whiten. There was a tendency for the appearance of the paint film to deteriorate.
• Patent Document 1 discloses that a predetermined maleic acid or fumaric acid derivative is reacted with a predetermined polyoxyalkylene amine in a specific ratio, and further a predetermined amount of a polyamine compound such as meta-xylylene diamine is added to react.
• the patent discloses an epoxy resin curing agent, and describes that the curing agent is not easily affected by carbon dioxide gas (stickiness and whitening of the surface of the cured product).
• Patent Document 2 describes a polyamine compound which is a reaction product of a compound having at least one glycidyl group in one molecule and a diamine such as xylylene diamine, a predetermined polyether-modified polysiloxane, and a predetermined amino group.
• a curing agent composition for epoxy resins containing a modified polysiloxane solves the problem of whitening caused by decreased water resistance and deterioration of appearance, and improves surface appearance such as transparency, drying property (easy to dry), It is disclosed that an epoxy resin composition having excellent adhesion to a substrate and excellent water resistance can be provided.
• epoxy resin curing agents that are modified polyamines have a high viscosity, so they are often diluted with a non-reactive diluent or the like before use.
• a non-reactive diluent there is a risk that the chemical resistance etc. of the coating film of the epoxy resin composition containing the curing agent may be reduced. Therefore, as a modified product of xylylene diamine having a low viscosity, an amino compound obtained by an addition reaction between a diamine such as xylylene diamine and an alkenyl compound such as styrene is also being considered (Patent Document 3).
• Patent Document 4 describes that an amine is a curing agent that is mixed into an adhesive that is polymerized and cured, and is a reaction product of a polyamine having two or more primary amino groups and furfural.
• Latent curing agents are disclosed.
• the reaction product is an imine (aldimine) and is different from an amino compound.
• the latent curing agent is an amine generated by hydrolysis of the aldimine, that is, the polyamine acts as a curing agent, and the reaction product itself, which is a modified product of the polyamine, acts as a curing agent. It does not act as an epoxy resin curing agent.
• Patent Document 5 discloses an agricultural and horticultural fungicide whose active ingredient is a compound obtained by reducing a compound obtained from 1 mole of xylylene diamine and 2 moles of an aldehyde with a predetermined structure. , there is no mention of the effect of using this compound as an epoxy resin curing agent.
• the amino compound which is a modified product of xylylene diamine described in Patent Document 3 has low viscosity and excellent water resistance, but the water-containing methanol resistance of the coating film of the epoxy resin composition obtained by using the amino compound as an epoxy resin curing agent is low. Regarding gender, there was still room for improvement.
• the object of the present invention is to provide an amino composition that has low viscosity and can form a coating film with excellent hydrous methanol resistance when used as an epoxy resin curing agent, a method for producing the same, an epoxy resin curing agent containing the composition, An object of the present invention is to provide an epoxy resin composition and a cured product thereof.
• an amino composition containing a modified diamine having a predetermined structure in a predetermined ratio can solve the above problems. That is, the present invention relates to the following.
• NH 2 -CH 2 -X-CH 2 -NH-R 1 (1) (In the formula, R 1 is a monovalent group represented by the following general formula (2).
• X is a phenylene group.
• R 2 to R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms that may have a hydroxy group. * indicates the presence or absence of a ⁇ bond.
• R 1 -NH-CH 2 -X-CH 2 -NH-R 1 (3) (In the formula, R 1 and X are the same as above.)
• Step (1) A process for obtaining an imine by reacting a diamine represented by the following general formula (4) with an aldehyde compound represented by the following general formula (5)
• Step (2) Obtaining an imine by reacting the diamine represented by the following general formula (4) Step of reducing imine NH 2 -CH 2 -X-CH 2 -NH 2 (4) (In the formula, X is the same as above.) (In the formula, R 2 to R 4 are the same as above.)
• step (1) In the step (1), 0.8 to 1.8 mol of the aldehyde compound represented by the general formula (5) is reacted with 1 mol of the diamine represented by the general formula (4); 5].
• an amino composition having low viscosity and capable of forming a coating film with excellent hydrous methanol resistance when used as an epoxy resin curing agent, and a method for producing the same, an epoxy resin curing agent containing the composition, Epoxy resin compositions and cured products thereof can be provided.
• the amino composition of the present invention is an amino composition containing an amino compound (A) represented by the following general formula (1) and an amino compound (B) represented by the following general formula (3), comprising:
• the molar ratio [(A)/(B)] of the amino compound (A) and the amino compound (B) in the composition is 10/90 to 99/1.
• NH 2 -CH 2 -X-CH 2 -NH-R 1 (1) (In the formula, R 1 is a monovalent group represented by the following general formula (2).
• X is a phenylene group.
• the broken line indicates the presence or absence of a ⁇ bond, and R 2 to R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms that may have a hydroxy group. * indicates the presence or absence of a ⁇ bond. (Indicates a bond.) R 1 -NH-CH 2 -X-CH 2 -NH-R 1 (3) (In the formula, R 1 and X are the same as above.)
• the epoxy resin curing agent containing the amino composition of the present invention has low viscosity, and furthermore, when the epoxy resin composition containing the epoxy resin curing agent is used, a coating film with excellent hydrous methanol resistance is formed. be able to.
• the reason why the above effects are obtained by the amino composition of the present invention is not clear, but it is thought to be as follows.
• the amino composition of the present invention is obtained, for example, by reducing a reaction product (imine) of xylylene diamine and furfural or a derivative thereof, and from this point of view, it is a type of modified product of xylylene diamine. I can say that.
• xylylene diamine is used as a reaction raw material for the amino composition, and further, an aromatic substituent such as a furan ring is introduced as a substituent for the amino group in xylylene diamine, thereby improving hydrophobicity. This is thought to improve the water resistance of the coating film. Additionally, when xylylene diamine is modified with an epoxy compound or the like, the viscosity generally increases, but it is thought that the increase in viscosity can be suppressed by modifying xylylene diamine with furfural or a derivative thereof.
• the amino composition of the present invention does not require the addition of a non-reactive diluent or the like to reduce the viscosity, it is possible to use the amino composition as a non-reactive diluent in the coating film of an epoxy resin composition using the amino composition as an epoxy resin curing agent. It is thought that the decrease in water-containing methanol resistance resulting from the inclusion of a reactive diluent can be suppressed.
• the amino composition of the present invention contains the amino compound (A) represented by the general formula (1) and the amino compound (B) represented by the general formula (3) in a predetermined ratio.
• the amino compound (A) is a compound obtained by reducing imine, which is a reaction product of the diamine and aldehyde compound reacted at a molar ratio of 1/1 (hereinafter, the compound may be referred to as a "1-adduct").
• the amino compound (B) is a compound obtained by reducing imine, which is a reaction product of the diamine and aldehyde compound reacted at a molar ratio of 1/2 (hereinafter, the compound is referred to as a "di-adduct").
• Patent Document 5 discloses an amino compound (B) which is a compound obtained by reducing a reaction product in which xylylene diamine and furfural react at a molar ratio of 1/2.
• the amino composition of the present invention containing a high proportion of the amino compound (A), which is a mono-adduct, is more difficult to cure when used as an epoxy resin curing agent than the amino compound (B), which is a di-adduct.
• the resulting epoxy resin composition has excellent methanol resistance.
• the amino composition of the present invention contains an amino compound (A) represented by the following general formula (1).
• R 1 is a monovalent group represented by the following general formula (2).
• X is a phenylene group.
• R 2 to R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms that may have a hydroxy group. * indicates the presence or absence of a ⁇ bond. (Indicates a bond.)
• X is a phenylene group, and is either a 1,2-phenylene group, a 1,3-phenylene group, or a 1,4-phenylene group. From the viewpoints of low viscosity, rapid curing when used as an epoxy resin curing agent, hardness, appearance, water resistance, and improved hydrous methanol resistance of the resulting epoxy resin composition, X is preferably 1, A 3-phenylene group or a 1,4-phenylene group, more preferably a 1,3-phenylene group.
• the broken line indicates the presence or absence of a ⁇ bond. Although it is preferable that a ⁇ bond is present in the broken line, it may also include a line in which a ⁇ bond is partially reduced so that a ⁇ bond is absent.
• the alkyl group in R 2 to R 4 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.
• R 2 to R 4 are selected from the viewpoints of low viscosity, rapid curing when used as an epoxy resin curing agent, hardness of the coating film of the resulting epoxy resin composition, appearance, water resistance, and improvement in water-containing methanol resistance.
• R 2 to R 4 are hydrogen atoms, or R 2 is a methyl group In which R 3 and R 4 are hydrogen atoms, and even more preferably all of R 2 to R 4 are hydrogen atoms.
• the amino composition of the present invention contains an amino compound (B) represented by the following general formula (3).
• R 1 -NH-CH 2 -X-CH 2 -NH-R 1 (3) (In the formula, R 1 and X are the same as above.)
• R 1 is a monovalent group represented by the general formula (2), and its preferred embodiments are also the same as above.
• X is a phenylene group, and is either a 1,2-phenylene group, a 1,3-phenylene group, or a 1,4-phenylene group.
• X is preferably 1, A 3-phenylene group or a 1,4-phenylene group, more preferably a 1,3-phenylene group.
• the molar ratio of the amino compound (A) to the amino compound (B) in the amino composition [(A)/(B)] is from the viewpoints of low viscosity, fast curing property when used as an epoxy resin curing agent, and improvement in hardness, appearance, water resistance, and hydrous methanol resistance of the coating film of the obtained epoxy resin composition, and is preferably 20/80 to 99/1, more preferably 30/70 to 99/1, even more preferably 40/60 to 99/1, and still more preferably 50/50 to 99/1.
• the above molar ratio can be determined by the method described in the Examples.
• the amino composition contains, in addition to the amino compound (A) and the amino compound (B), by-products and unreacted raw materials such as diamine (xylylene diamine) represented by the general formula (4) described below. You may do so.
• the total content of the amino compound (A) and the amino compound (B) is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, Even more preferably it is 98% by mass or more and 100% by mass or less.
• the content of xylylene diamine, which is an unreacted raw material, in the amino composition is preferably determined from the viewpoint of improving the hardness, appearance, water resistance, and hydrous methanol resistance of the resulting epoxy resin composition. It is 5% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less.
• the total content of the amino compound (A) and the amino compound (B) in the amino composition and the content of xylylenediamine, which is an unreacted raw material, can be measured by gas chromatography (GC) analysis method. can.
• GC gas chromatography
• the viscosity of the amino composition at 25° C. is preferably 500 mPa ⁇ s or less, more preferably 300 mPa ⁇ s or less, even more preferably 200 mPa ⁇ s or less, even more preferably It is 100 mPa ⁇ s or less, more preferably 90 mPa ⁇ s or less, and usually 10 mPa ⁇ s or more.
• the viscosity of the amino composition at 25° C. can be measured using an E-type viscometer, specifically by the method described in the Examples.
• the method for producing an amino composition of the present invention preferably includes the following steps (1) and (2) in order.
• step (1) the diamine represented by the general formula (4) is reacted with the aldehyde compound represented by the general formula (5) to obtain an imine.
• X is a phenylene group, and is either a 1,2-phenylene group, a 1,3-phenylene group, or a 1,4-phenylene group. From the viewpoints of low viscosity, rapid curing when used as an epoxy resin curing agent, hardness, appearance, water resistance, and improved hydrous methanol resistance of the resulting epoxy resin composition, X is preferably 1, A 3-phenylene group or a 1,4-phenylene group, more preferably a 1,3-phenylene group.
• a specific example of the diamine represented by the general formula (4) is at least one selected from the group consisting of ortho-xylylene diamine, meta-xylylene diamine, and para-xylylene diamine, and has low viscosity and is an epoxy resin curing agent.
• the group consisting of metaxylylene diamine and para-xylylene diamine is preferable.
• R 2 to R 4 in the general formula (5) are each independently an alkyl group having 1 to 4 carbon atoms which may have a hydrogen atom or a hydroxy group.
• the alkyl group in R 2 to R 4 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.
• R 2 to R 4 are the low viscosity of the obtained amino compound and amino composition, the fast curing property when used as an epoxy resin curing agent, the hardness, appearance, and water resistance of the coating film of the obtained epoxy resin composition; And from the viewpoint of improving water-containing methanol resistance, it is preferably a hydrogen atom, a methyl group, or a hydroxymethyl group, more preferably a hydrogen atom or a methyl group, and still more preferably all of R 2 to R 4 are hydrogen atoms. Or, R 2 is a methyl group, R 3 and R 4 are hydrogen atoms, and even more preferably, all of R 2 to R 4 are hydrogen atoms.
• aldehyde compound represented by the general formula (5) examples include furfural, 3-methylfurfural, 4-methylfurfural, 5-methylfurfural, 3-hydroxymethylfurfural, 4-hydroxymethylfurfural, and 5-hydroxymethylfurfural.
• the aldehyde compound represented by the general formula (5) is preferably furfural, 3-methylfurfural, 4-methylfurfural, 5-methylfurfural, 3-hydroxymethylfurfural, or 4-hydroxymethylfurfural. , 5-hydroxymethylfurfural, and 4,5-dimethylfurfural, more preferably at least one selected from the group consisting of furfural and 5-methylfurfural, and even more preferably Furfural.
• step (1) from the viewpoint of obtaining the amino compound represented by the general formula (1) and the amino composition containing the amino compound in high yield, 1 mole of the diamine represented by the general formula (4) is added.
• 0.8 to 1.8 mol, preferably 1.0 to 1.8 mol, more preferably 1.0 to 1.5 mol, even more preferably 1.0 to 1.3 mol is reacted.
• the reaction between the diamine represented by the general formula (4) and the aldehyde compound represented by the general formula (5) is preferably carried out under heating and stirring conditions.
• the reaction temperature is preferably in the range of 40 to 120°C, more preferably 50 to 95°C, from the viewpoint of improving reaction efficiency and suppressing thermal deterioration of the diamine and aldehyde compound as raw materials.
• the reaction time can be selected as appropriate, but is usually in the range of 15 minutes to 6 hours.
• the above reaction can be carried out in a reaction solvent, but may also be carried out without a solvent.
• the reaction in step (1) yields an imine that is a reaction product of the diamine represented by the general formula (4) and the aldehyde compound represented by the general formula (5).
• the reaction product obtained in step (1) may be purified, or may be directly subjected to step (2) without being purified.
• step (2) the imine obtained in step (1) is reduced and converted into an amine.
• the reduction of the imine is preferably carried out by hydrogenation under heating and pressurizing conditions in the presence of a catalyst.
• the catalyst used in step (2) include known hydrogenation catalysts, such as supported catalysts in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, etc.
• Homogeneous hydrogenation catalyst so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum; Ti, Ru, Rh, A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Zr is used.
• the temperature during the hydrogenation reaction is preferably 0°C or higher, more preferably 10°C or higher, even more preferably 20°C or higher, and preferably 200°C or higher, from the viewpoint of improving reaction efficiency and suppressing side reactions.
• the temperature is preferably 150°C or lower, more preferably 100°C or lower.
• the pressure during the hydrogenation reaction is preferably 0.01 MPaG or more, more preferably 0.1 MPaG or more, even more preferably 0.3 MPaG or more, from the viewpoint of improving reaction efficiency and suppressing side reactions, and Preferably it is 10 MPaG or less, more preferably 3 MPaG or less.
• the reaction time is not particularly limited, but is preferably 3 minutes or more, more preferably 10 minutes or more, even more preferably 30 minutes or more, and preferably 24 hours or less, more preferably 12 hours or less, and even more preferably 8 hours. It is as follows.
• the hydrogenation reaction may be performed in the presence of a solvent.
• the solvent is not particularly limited as long as it does not inhibit the hydrogenation reaction, but aliphatic hydrocarbons such as pentane, hexane, isopentane, heptane, octane, and isooctane; cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc. Examples include alicyclic hydrocarbons; hydrocarbon solvents such as aromatic hydrocarbons such as toluene, ethylbenzene, and xylene. These may be used alone or in combination of two or more.
• the catalyst is removed from the resulting reaction solution, and if necessary, purification by distillation or the like can be performed to obtain the amino compound or amino composition of the present invention.
• the method for producing the amino composition is not limited to the above method.
• a method of deammonizing the diamine represented by the general formula (4) and the amine represented by the following general formula (6) in the presence of a catalyst Produced by a method of reacting an alcohol represented by 7) in the presence of a catalyst in a hydrogen atmosphere; a method of reacting a diamine represented by the general formula (4) with a chloride represented by the following general formula (8); You can also.
• preferably 0.8 to 1.8 mol, more preferably 0.8 to 1.8 mol, each of the compounds represented by the general formulas (6) to (8) are added to 1 mol of the diamine represented by the general formula (4).
• the reaction amount is 1.0 to 1.8 mol, more preferably 1.0 to 1.5 mol, even more preferably 1.0 to 1.3 mol.
• R 2 to R 4 are the same as above.
• the epoxy resin curing agent of the present invention contains the amino composition of the present invention.
• the epoxy resin curing agent has low viscosity, and when used in an epoxy resin composition, it can form a coating film with excellent water-containing methanol resistance.
• the content of the amino composition in the epoxy resin curing agent is determined from the viewpoints of low viscosity, fast curing, hardness of the coating film of the resulting epoxy resin composition, appearance, water resistance, and improvement of water-containing methanol resistance.
• the epoxy resin curing agent of the present invention can also contain other curing agent components in addition to the amino composition.
• the curing agent component refers to a component contained in an epoxy resin curing agent that has two or more active hydrogens capable of reacting with the epoxy groups in the epoxy resin.
• the other curing agent components include amine curing agents, phenol curing agents, acid anhydride curing agents, etc., and amine curing agents are preferred from the viewpoint of rapid curing.
• the amine curing agent include polyamine compounds other than the above-mentioned amino compositions or modified products thereof.
• the polyamine compound is not particularly limited as long as it is a compound having at least two amino groups in the molecule.
• polyamine compound or modified product thereof examples include chain aliphatic polyamine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, 2-methylpentamethylenediamine, and trimethylhexamethylenediamine.
• chain aliphatic polyamine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, 2-methylpentamethylenediamine, and trimethylhexamethylenediamine.
• Polyamine compounds polyamine compounds having a heterocyclic structure such as N-aminomethylpiperazine and N-aminoethylpiperazine; polyether polyamine compounds; the above polyamine compounds and epoxy compounds having at least one epoxy group, unsaturated hydrocarbon compounds , carboxylic acid or a derivative thereof; Mannich reaction product obtained by reacting the above polyamine compound with a phenol compound and an aldehyde compound; Ketoimine (ketimine) obtained by reacting the above polyamine compound with a ketone compound. ); etc. These can be used alone or in combination of two or more.
• the content of the other curing agent components in the epoxy resin curing agent 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, still more preferably 40% by mass or less, even more preferably 30% by mass.
• the content is more preferably 20% by mass or less.
• the epoxy resin curing agent of the present invention may further contain a known curing accelerator, non-reactive diluent, and the like.
• curing accelerators include phenolic compounds, organic acids, organic acid salts, tertiary amines, quaternary ammonium salts, imidazoles, organic phosphorus compounds, quaternary phosphonium salts, diazabicycloalkenes, and organic metal salts. compounds, boron compounds, metal halides, and the like.
• the non-reactive diluent include benzyl alcohol, furfuryl alcohol, tetrafurfuryl alcohol, aromatic hydrocarbon formaldehyde resin, and one or more of these may be used.
• the epoxy resin curing agent of the present invention preferably has a low content of non-reactive diluent from the viewpoint of improving the hydrous methanol resistance of the coating film of the resulting epoxy resin composition.
• the content of the non-reactive diluent in the epoxy resin curing agent is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, even more preferably 1% by mass or less, Even more preferably, it is 0% by mass.
• the active hydrogen equivalent of the epoxy resin curing agent is preferably 80 or more from the viewpoint of low viscosity, fast curing, and improving the hardness, appearance, water resistance, and hydrous methanol resistance of the resulting epoxy resin composition. From the viewpoint of improving curability, it is preferably 150 or less, more preferably 120 or less.
• the active hydrogen equivalent (hereinafter also referred to as "AHEW”) in this specification is the mass per mole of active hydrogen derived from an amino group of the epoxy resin curing agent.
• the AHEW of the curing agent can be calculated from the amine value.
• Epoxy resin composition contains an epoxy resin and the epoxy resin curing agent.
• the epoxy resin composition has a fast curing speed, and the resulting coating film has excellent hardness, water resistance, and water-containing methanol resistance.
• 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 improving the curing rate and forming a coating film with high hardness, appearance, water resistance, and water-containing methanol resistance, epoxy resins containing an aromatic ring or alicyclic structure in the molecule are preferred. Specific examples of the epoxy resin include epoxy resins having a glycidylamino group derived from metaxylylene diamine, epoxy resins having a glycidylamino group derived from paraxylylene diamine, and 1,3-bis(aminomethyl).
• At least one resin selected from epoxy resins having glycidyloxy groups derived from resorcinol and epoxy resins having glycidyloxy groups derived from resorcinol can be used.
• the above epoxy resins can also be used in combination of two or more.
• the epoxy resins include epoxy resins having glycidylamino groups derived from metaxylylene diamine, At least one selected from the group consisting of an epoxy resin having a glycidylamino group derived from xylylene diamine, an epoxy resin having a glycidyloxy group derived from bisphenol A, and an epoxy resin having a glycidyloxy group derived from bisphenol F.
• main component is an epoxy resin having a derived glycidyloxy group.
• main component here means that other components may be included without departing from the spirit of the present invention, and is preferably 50 to 100% by mass, more preferably 70 to 100% by mass of the whole. , more preferably 90 to 100% by mass.
• the epoxy resin as the main ingredient may contain a reactive diluent other than the above-mentioned epoxy resin from the viewpoint of improving handling properties.
• the reactive diluent include low-molecular 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, and octyl glycidyl ether.
• alkyl monoglycidyl ethers such as decyl glycidyl ether, lauryl glycidyl ether, and tetradecyl glycidyl ether; 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6 - Diglycidyl ethers of aliphatic diols such as hexanediol diglycidyl ether are exemplified.
• the above-mentioned reactive diluents can be used alone or in combination of two or more.
• 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 curing agent (number of active hydrogens derived from amino groups in the resin/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 even more preferably 1 /0.8 to 1/1.2.
• 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. Although there are no limitations, the following ranges are preferred from the viewpoint of improving the curing speed and forming a coating film with high hardness, appearance, water resistance, and water-containing methanol resistance.
• the content of the epoxy resin in the epoxy resin composition is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, and is preferably 80% by mass or less, more preferably 75% by mass or less.
• the content of the epoxy resin curing agent in the epoxy resin composition is preferably 20% by mass or more, more preferably 25% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably It is 40% 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, and still more preferably 40 to 60 parts by mass, based on 100 parts by mass of the epoxy resin as the main ingredient. It is 60 parts by mass.
• the total content of the epoxy resin and the epoxy resin curing agent in the epoxy resin composition is preferably 40% from the viewpoint of improving low viscosity, fast curing, hardness of the coating film, appearance, water resistance, and hydrous methanol resistance.
• % by mass or more more preferably 50% by mass or more, still 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 more. mass% or less.
• the epoxy resin composition of the present invention may further contain other components such as fillers, modifying components such as plasticizers, flow adjusting components such as thixotropic agents, pigments, leveling agents, tackifiers, and elastomer fine particles. It may be included depending on the situation.
• the epoxy resin composition of the present invention may contain the non-reactive diluent and a solvent other than the non-reactive diluent (water and volatile solvent), but the content thereof is determined by the composition of the epoxy resin composition. It is preferably 5% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less.
• the epoxy resin composition can be produced by mixing an epoxy resin, an epoxy resin curing agent, and other components as necessary using known methods and equipment.
• the mixing order of each component contained in the epoxy resin composition and after preparing the epoxy resin curing agent, it may be mixed with the epoxy resin, and each component constituting the epoxy resin curing agent, Alternatively, the epoxy resin may be prepared by simultaneously mixing other components with the epoxy resin.
• the cured product of the epoxy resin composition of the present invention (hereinafter also simply referred to as "cured product of the present invention") is obtained by curing the above-mentioned epoxy resin composition by a known method. Curing conditions for the epoxy resin composition are appropriately selected depending on 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 intended use. From the viewpoint of being able to form a coating film with high hardness, appearance, water resistance, and water-containing methanol resistance, the cured product of the epoxy resin composition is preferably a film-like cured product.
• the epoxy resin composition of the present invention can form a coating film with high hardness, appearance, water resistance, and water-containing methanol resistance, it can be used, for example, in marine paints, heavy-duty anticorrosion paints, tank paints, pipe interior paints, and exterior paints. Suitable for use in coatings such as paints and floor coatings.
• 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 Examples below.
• the amino composition was analyzed and evaluated by the following method.
• GC analysis The content ratio of each component in the amino composition was measured by GC analysis.
• the measurement conditions are as follows. Equipment: “7890B GC” manufactured by Agilent Technologies Co., Ltd. Column: “CP-Sil 8 CB for Amines” manufactured by Agilent Technologies (length 30 m, film thickness 0.25 ⁇ m, inner diameter 0.25 mm) Column temperature: 40°C 10 minutes ⁇ 20°C/min temperature increase ⁇ 250°C 10 minutes ⁇ 20°C/min temperature increase ⁇ 300°C 10 minutes Carrier gas: Helium Carrier gas flow rate: 2.2553 mL/min Inlet pressure: 22. 474psi (constant pressure mode) Detector: FID Inlet temperature: 250°C Detector temperature: 310°C
• composition analysis of amino composition (molar ratio of amino compound (A) and amino compound (B))>
• the molar ratio of the amino compound (A) and the amino compound (B) in the amino composition can be determined by performing 1 H-NMR analysis under the above conditions and determining the integral value of protons corresponding to the benzylic position of each amino compound. From the results, the molar ratio of amino compound (A) and amino compound (B) was calculated.
• AHEW active hydrogen equivalent
• the AHEW of the amino composition is determined by determining the total amine value, secondary and tertiary amine values using an automatic potentiometric titrator "AT-710S" manufactured by Kyoto Electronics Co., Ltd., and determining the AHEW from the results. Calculated. Total amine value was measured using 0.1 mol/L perchloric acid/acetic acid solution (manufactured by Kanto Chemical Co., Ltd.), and secondary/tertiary amine value was measured using 0.1 mol/L hydrochloric acid (2-propanol). did.
• ⁇ Pencil hardness> The epoxy resin composition was applied onto the base material (zinc phosphate treated steel plate) in the same manner as described above to form a coating film (thickness immediately after application: 200 ⁇ m). This coating film was heated at 23°C and 50% R. H. The pencil hardness was measured in accordance with JIS K5600-5-4:1999 after 1 and 7 days of storage under the following conditions. The results are shown in Table 2.
• test piece was immersed in a 90% aqueous methanol solution at 23° C., and after one week, the appearance of the test piece was visually observed and the resistance to hydrous methanol was evaluated according to the following criteria.
• the results are shown in Table 2.
• G Slight decrease in gloss
• F Rough surface and decrease in gloss
• P Blisters appear or the coating dissolves
• Example 1 Manufacture of amino composition A [Step (1)] In a separable flask with an internal volume of 300 ml equipped with a stirrer, a thermometer, a nitrogen introduction tube, a dropping funnel, and a cooling tube, 40.0 g (0.3 28.2 g (0.3 mol) of furfural (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 15 to 20 minutes while stirring under a nitrogen stream. After the dropwise addition was completed, the temperature was raised to 80°C and a reaction was carried out for 30 minutes. 1 H-NMR of the reaction product was measured, and it was confirmed that the 1 H peak derived from the aldehyde group of furfural had disappeared, indicating that the reaction was complete.
• furfural manufactured by Tokyo Chemical Industry Co., Ltd.
• Step (2) In an autoclave (capacity 230 mL, material: SUS 316 L) equipped with a stirrer and a heater, 29.7 g of the imine obtained in step (1), 30 g of toluene, and a 5% Pd/C catalyst (NE Chemcat) as a hydrogenation catalyst were placed. Co., Ltd.; STD type) 0.3 g was charged, and the gas phase was replaced with hydrogen.
• amino composition A Using the obtained amino composition A, GC analysis and 1 H-NMR analysis were performed under the above conditions, and the composition ratios listed in Table 1 were calculated.
• the GC area ratio described in Table 1 means the area percentage of a component detected by gas chromatography.
• amino composition A the content of the amino compound represented by general formula (1) (amino compound (A)) was 73% in terms of GC area ratio, and the content of the amino compound represented by general formula (3) (amino compound (B)) was 73% in terms of GC area ratio.
• amino compound (A)) represented by general formula (1) in amino composition A was represented by the following structural formula (A1). It was found that the main component of the amino compound represented by general formula (3) (amino compound (B)) was a compound represented by the following structural formula (B1).
• the amino compound (A) contains, in addition to the compound represented by the following structural formula (A1), a trace amount of a compound in which some or all of the unsaturated bonds of the furan ring in the compound are reduced, and the amino compound (B) contained a trace amount of a compound in which part or all of the unsaturated bonds of the furan ring in the compound were reduced, in addition to the compound represented by the following structural formula (B1).
• Example 2 Manufacture of amino composition B
• step (1) of Example 1 the procedure was carried out except that the amount of metaxylylene diamine charged was changed to 40.9 g (0.3 mol) and the amount of furfural charged was changed to 43.2 g (0.45 mol).
• Amino composition B was produced in the same manner as in Example 1.
• the composition of amino composition B is shown in Table 1, and the viscosity and AHEW at 25°C are shown in Table 2.
• Preparation and evaluation of epoxy resin composition In Example 1, an epoxy resin composition was prepared and evaluated in the same manner as in Example 1, except that amino composition B was used in place of amino composition A. The results are shown in Table 2.
• Example 3 Manufacture of amino composition C
• step (1) of Example 1 the amount of metaxylylene diamine charged was changed to 40.9 g (0.3 mol), and 5-methylfurfural (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 33 was used instead of furfural.
• Amino composition C was produced in the same manner as in Example 1, except that .0 g (0.3 mol) was used.
• the composition of amino composition C is shown in Table 1, and the viscosity and AHEW at 25°C are shown in Table 2.
• amino compound (amino compound (A)) represented by general formula (1) in amino composition C was represented by the following structural formula (A2). It was found that the amino compound represented by the general formula (3) (amino compound (B)) is a compound represented by the following structural formula (B2).
• Comparative example 1 Manufacture of comparative amino composition D
• 40.8 g of metaxylylene diamine (Mitsubishi Gas Chemical Co., Ltd., MXDA) was charged into a 300 ml separable flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a dropping funnel, and a cooling tube.
• 22.3 g of a polyfunctional epoxy resin (“jER828” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 186 g/equivalent) having a glycidyloxy group derived from bisphenol A was added as an epoxy compound.
• Comparative example 2 As comparative amino composition E, a reaction product of styrene and metaxylylene diamine ("Gaskamine 240" manufactured by Mitsubishi Gas Chemical Co., Ltd., AHEW: 103) was used. Table 2 shows the viscosity of Comparative Amino Composition E at 25°C. In Example 1, an epoxy resin composition was prepared and evaluated in the same manner as in Example 1, except that Comparative Amino Composition E was used in place of Amino Composition A. The results are shown in Table 2.
• Comparative Example 3 (Preparation of Comparative Amino Composition F) Comparative amino composition F was produced in the same manner as in Example 1, except that in step (1) of Example 1, the amount of metaxylylenediamine charged was changed to 27.2 g (0.2 mol), the amount of furfural charged was changed to 39.4 g (0.4 mol), and 66.3 g of toluene was added as a solvent.
• the composition of comparative amino composition F is shown in Table 1, and its viscosity and AHEW at 25° C. are shown in Table 2.
• An epoxy resin composition was prepared and evaluated in the same manner as in Example 1, except that comparative amino composition F was used instead of amino composition A. The results are shown in Table 2.
• Table 2 shows that the epoxy resin curing agent containing the amino composition of the present invention has a low viscosity, and the coating film of the epoxy resin composition using the curing agent has excellent hydrous methanol resistance.
• an amino composition having low viscosity and capable of forming a coating film with excellent hydrous methanol resistance when used as an epoxy resin curing agent, and a method for producing the same, an epoxy resin curing agent containing the composition, Epoxy resin compositions and cured products thereof can be provided.

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