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WO2018047799A1 - Composé époxy, procédé de production d'un composé époxy, composition contenant un composé époxy, matériau de revêtement et produit durci - Google Patents

Composé époxy, procédé de production d'un composé époxy, composition contenant un composé époxy, matériau de revêtement et produit durci Download PDF

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Publication number
WO2018047799A1
WO2018047799A1 PCT/JP2017/031883 JP2017031883W WO2018047799A1 WO 2018047799 A1 WO2018047799 A1 WO 2018047799A1 JP 2017031883 W JP2017031883 W JP 2017031883W WO 2018047799 A1 WO2018047799 A1 WO 2018047799A1
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Prior art keywords
epoxy compound
epoxy
compound
group
weight
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English (en)
Japanese (ja)
Inventor
暁文 戸部
航 深山
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to an epoxy compound capable of forming a coating film excellent in light resistance, hardness and elution resistance, and a method for producing the same. Moreover, this invention relates to the epoxy compound containing composition, coating material, and hardened
  • Patent Document 1 describes a reaction product of an epoxy resin having a high halogen content and a hindered amine compound.
  • Patent Documents 2 to 4 disclose a composition of an epoxy resin and a hindered amine compound.
  • Japanese Laid-Open Patent Publication No. 8-165437 Japanese Unexamined Patent Publication No. 2009-108301 Japanese Unexamined Patent Publication No. 2016-113564 Japanese Laid-Open Patent Publication No. 9-176284
  • the coating film using the epoxy compound described in Patent Document 1 has insufficient light resistance.
  • coating films using the compositions described in Patent Documents 2 to 4 have low hardness and have problems such as bleeding out.
  • the present invention has been made in view of the above problems of the prior art. That is, the subject of this invention is providing the epoxy compound which can form the coating film excellent in light resistance, hardness, and elution resistance, and its manufacturing method. Moreover, this invention is providing the epoxy compound containing composition obtained by using this epoxy compound, a coating material, and hardened
  • R 1 to R 4 may be the same or different and each represents a hydrogen atom or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 4 carbon atoms.
  • X represents a divalent hydrocarbon group having 1 to 50 carbon atoms which may have a substituent.
  • X represents a divalent hydrocarbon group having 1 to 50 carbon atoms which may have a substituent.
  • [4] The epoxy compound according to any one of [1] to [3], including two or more different groups as the divalent group represented by the formula (2).
  • the X is a group having a structure represented by any of the following formulas (3) to (8), and each aromatic ring or cycloalkylene group in the following formulas (3) to (8) is The epoxy compound according to any one of [1] to [4], each of which may be substituted with an alkyl group.
  • R 5 and R 6 may be the same or different, and represent a hydrogen atom or an alkyl group.
  • R 7 and R 8 may be the same or different and represent a hydrogen atom or an alkyl group.
  • R 9 and R 10 may be the same or different and each represents a direct bond or an alkylene group having 1 to 5 carbon atoms.
  • R 11 and R 12 may be the same or different and represent a direct bond or an alkylene group having 1 to 5 carbon atoms.
  • a paint comprising the epoxy compound according to any one of [1] to [5].
  • [7] In any one of [1] to [5], including a step of reacting a piperidine ring-containing compound with an epoxy group-containing compound having a total amount of total chlorine and total bromine of 5% by weight or less. The manufacturing method of the epoxy compound of description.
  • An epoxy compound-containing composition comprising the epoxy compound according to any one of [1] to [5] and a curing agent.
  • the epoxy compound-containing composition according to [9] comprising 0.1 to 1000 parts by weight of the curing agent with respect to 100 parts by weight of the epoxy compound.
  • the curing agent is composed of polyfunctional phenols, polyisocyanate compounds, amine compounds, acid anhydride compounds, imidazole compounds, amide compounds, mercaptan compounds, cationic polymerization initiators, and organic phosphines.
  • the epoxy compound-containing composition according to [9] or [10] which is at least one selected from the group.
  • a paint comprising the epoxy compound-containing composition according to any one of [9] to [11].
  • a cured product obtained by curing the epoxy compound-containing composition according to any one of [9] to [11].
  • an epoxy compound capable of forming a coating film excellent in light resistance, hardness and elution resistance and a method for producing the same are provided.
  • cured material are provided.
  • the epoxy compound, the epoxy compound-containing composition and the cured product of the present invention can be applied in the fields of electrical / electronic materials, FRP (fiber reinforced resin), adhesives, paints, and the like. is there.
  • the epoxy compound of the present invention has a divalent group represented by the following formula (1) and a divalent group represented by the following formula (2), and has an epoxy equivalent of 200 g / equivalent or more and 200,000 g / An epoxy compound having an equivalent weight or less.
  • the coating film using the epoxy compound of the present invention has light resistance, hardness and elution resistance. Excellent in properties.
  • the epoxy equivalent is 200 g / equivalent or more and 200,000 g / equivalent or less, both flexibility and hardness of the coating film are excellent.
  • R 1 to R 4 may be the same or different and each represents a hydrogen atom or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 4 carbon atoms.
  • R 1 to R 4 may be the same or different and each represents a hydrogen atom or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 4 carbon atoms.
  • a hydrogen atom, a methyl group, or an ethyl group is preferable, and a methyl group is more preferable. More preferably, R 1 to R 4 are the same and are methyl groups.
  • the epoxy compound of the present invention is a divalent group represented by the above formula (1) from the viewpoint of handling properties during production of the epoxy compound and control of physical properties such as corrosion resistance and weather resistance when formed into a coating film. It is preferable to include two or more different groups.
  • X represents a divalent hydrocarbon group having 1 to 50 carbon atoms which may have a substituent.
  • X may have a substituent and has 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, more preferably 1 to 35 carbon atoms.
  • a divalent hydrocarbon group is shown.
  • X may be a linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group.
  • the cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group are collectively referred to as a hydrocarbon group having a cyclic structure.
  • X is preferably a hydrocarbon group containing a cyclic structure.
  • the epoxy compound of this invention is excellent in chemical resistance, adhesiveness, and a softness
  • the epoxy compound of the present invention is a divalent group represented by the above formula (2) from the viewpoint of handling properties during production of the epoxy compound and control of physical properties such as corrosion resistance and weather resistance when formed into a coating film. It is preferable to include two or more different groups.
  • X is preferably a group having a structure represented by any of the following formulas (3) to (8), and each aromatic ring or cyclohexylene group in the following formulas (3) to (8) is It may be substituted with an alkyl group.
  • R 5 and R 6 may be the same or different, and represent a hydrogen atom or an alkyl group.
  • R 7 and R 8 may be the same or different and represent a hydrogen atom or an alkyl group.
  • R 9 and R 10 may be the same or different and each represents a direct bond or an alkylene group having 1 to 5 carbon atoms.
  • R 11 and R 12 may be the same or different and represent a direct bond or an alkylene group having 1 to 5 carbon atoms.
  • R 5 and R 6 may be the same or different and each represents a hydrogen atom or an alkyl group.
  • R 5 and R 6 are preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • R 7 and R 8 may be the same or different and each represents a hydrogen atom or an alkyl group.
  • R 7 and R 8 are preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • R 9 and R 10 represent a direct bond or an alkylene group having 1 to 5 carbon atoms.
  • R 9 and R 10 are preferably a direct bond.
  • R 11 and R 12 represent a direct bond or an alkylene group having 1 to 5 carbon atoms.
  • R 11 and R 12 are preferably a direct bond.
  • the aromatic ring or cyclohexylene group represented by the formulas (3) to (8) has a substituent, the substituent is not particularly limited, and examples thereof include an alkyl group having 1 to 2 carbon atoms, The number of substituents per cyclohexylene group is preferably 2 or less.
  • the epoxy equivalent of the epoxy compound of the present invention is 200 g / equivalent or more, preferably 250 g / equivalent or more, more preferably 300 g / equivalent or more. Thereby, the flexibility can be further improved.
  • the epoxy equivalent of the epoxy compound of the present invention is 200,000 g / equivalent or less, preferably 100,000 g / equivalent or less, and preferably 50,000 g / equivalent or less from the viewpoint of compatibility with other materials. More preferably.
  • “epoxy equivalent” is defined as “mass of an epoxy compound containing one equivalent of an epoxy group” and can be measured according to JIS K7236.
  • the total of the total chlorine amount and the total bromine amount in the epoxy compound of the present invention is preferably 3 with respect to the epoxy compound from the viewpoint of improving the light resistance and weather resistance of the coating film using the epoxy compound of the present invention.
  • the lower limit is preferably 0% by weight, but may actually be 0.0001% by weight.
  • the chlorine and bromine in the epoxy compound of this invention mean what is contained with a partial form of a structure.
  • the method of bringing the total of the total chlorine amount and the total bromine amount of the epoxy compound of the present invention into the above range is not particularly limited, but for example, the total of the total chlorine amount and the total bromine amount as the epoxy group-containing compound (A) described later is The method of using the epoxy compound which is 5 weight% or less, Preferably it is 4 weight% or less is mentioned.
  • [Weight average molecular weight (Mw)] 240 or more are preferable, as for the weight average molecular weight (Mw) of the epoxy compound of this invention, 300 or more are more preferable, and 400 or more are especially preferable at the point which makes a softness
  • the weight average molecular weight (Mw) of the epoxy compound of the present invention is preferably 200,000 or less, more preferably 150,000 or less, and particularly preferably 100,000 or less from the viewpoint of compatibility with other materials.
  • the weight average molecular weight of an epoxy compound can be measured by the gel permeation chromatography method (GPC method). An example of a more detailed method will be described in the examples described later.
  • the epoxy compound of this invention can be manufactured by copolymerizing the epoxy group containing compound (A) mentioned later as a raw material of an epoxy compound, and a piperidine ring containing compound (B). Moreover, the epoxy compound of the present invention may be produced by copolymerizing an epoxy group-containing compound (A), a piperidine ring-containing compound (B), and a phenol compound (C), which will be described later, as a raw material for the epoxy compound. it can. In this copolymerization reaction, two or more kinds of the following epoxy group-containing compound (A), piperidine ring-containing compound (B) and phenol compound (C) can be used.
  • Epoxy group-containing compound (A) is a compound having two or more epoxy groups in the molecule.
  • the total amount of total chlorine and total bromine is 5% by weight or less, and a divalent group represented by the above formula (2) is introduced.
  • epoxy group-containing compound (A) used in the present invention for example, as a bifunctional epoxy group-containing compound, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, bisphenol Z diglycidyl ether, Bisphenol S diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol acetophenone diglycidyl ether, bisphenol trimethylcyclohexane diglycidyl ether, bisphenol fluorenediglycidyl ether, tetramethylbisphenol A diglycidyl ether, tetramethylbisphenol F diglycidyl ether, tetra-tert -Butyl bisphenol A diglycidyl ether, tetramethylbisphe Bisphenol-based diglycidyl ethers such as Biol diglycidyl ether; Biphenol-based diglycidyl ethers such as biphenol diglycidyl ether,
  • examples of the trifunctional or higher functional epoxy group-containing compound include the following.
  • the ⁇ type epoxy resin refers to a hydroxy group substituted with a glycidyl ether group.
  • epoxy group-containing compound from the viewpoint of preventing gelation during production.
  • epoxy group-containing compounds in which hydrogen is added to the aromatic ring of bisphenol diglycidyl ethers, biphenol diglycidyl ethers, bisphenol diglycidyl ethers, biphenol diglycidyl ethers It is preferable to use an epoxy group-containing compound obtained by adding hydrogen to the aromatic ring.
  • the epoxy group-containing compound (A) mentioned above can be used alone or in combination of two or more.
  • Preferred combinations include bisphenol diglycidyl ethers, biphenol diglycidyl ethers, epoxy group-containing compounds with hydrogen added to the aromatic ring of bisphenol diglycidyl ethers, and hydrogen added to the aromatic ring of biphenol diglycidyl ethers.
  • the piperidine ring-containing compound (B) is a compound having one or more piperidine rings in the molecule and one or more NH groups in the molecule and / or one or more OH groups in the molecule.
  • the piperidine ring-containing compound (B) used in the present invention is not particularly limited as long as it introduces a divalent group represented by the above formula (1), but preferably contains neither chlorine nor bromine.
  • examples of the compound having one NH group in the molecule include 2,2,6,6-tetramethyl-4-piperidyl methacrylate.
  • examples of the compound having one OH group in the molecule include dimethyl succinate 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate.
  • Examples of the compound having two NH groups in the molecule include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate.
  • Compounds having three or more NH groups in the molecule include tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate, poly [(6- Morpholino-S-triazine-2,4-diyl) [2,2,6,6-tetramethyl-4-piperidyl] imino] -hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) Imino] and the like.
  • a compound in which the total number of OH groups and NH groups is 2 is preferable from the viewpoint of polymerizability.
  • the piperidine ring-containing compound (B) mentioned above can be used alone or in combination of two or more.
  • preferred combinations include a compound having one OH group, a compound having two OH groups, a compound having one NH group, and a compound having two NH groups. It is a combination selected from.
  • the phenol compound (C) is a compound having two or more hydroxyl groups bonded to an aromatic ring. By copolymerizing the phenol compound (C), it is useful for adjusting the viscosity in the production process and controlling the physical properties of the resulting epoxy compound.
  • the phenolic compound (C) used in the present invention must contain neither chlorine nor bromine.
  • compounds having two hydroxyl groups bonded to an aromatic ring include bisphenol A, bisphenol F, bisphenol E, bisphenol Z, bisphenol S, bisphenol AD, bisphenol acetophenone, bisphenol trimethylcyclohexane, bisphenol fluorene, tetramethyl bisphenol A, tetra Bisphenols such as methyl bisphenol F, tetra-tert-butyl bisphenol A, tetramethyl bisphenol S; biphenols such as biphenol, tetramethyl biphenol, dimethyl biphenol, tetra-tert-butyl biphenol; hydroquinone, methyl hydroquinone, dibutyl hydroquinone, resorcin Benzene diols such as methylresorcin (where “benzene” “Alls” is a compound having one benzene ring, in which two hydroxyl groups are directly bonded to the benz
  • Examples of the compound having three or more hydroxyl groups bonded to an aromatic ring include ⁇ , ⁇ -bis (4-hydroxyphenyl) -4- (4-hydroxy- ⁇ , ⁇ -dimethylbenzyl) -ethylbenzene, 4,4 ′.
  • the compounding ratio of the containing compound (B) and the phenol compound (C) is preferably a compounding ratio at which the theoretical epoxy equivalent of the resulting epoxy compound is 200,000 g / equivalent or less, and a compounding ratio of 150,000 g / equivalent or less.
  • the ratio is more preferably 100,000 g / equivalent or less, particularly preferably in view of ensuring compatibility with other materials.
  • the lower limit of the theoretical epoxy equivalent exceeds 100 g / equivalent, and is preferably 120 g / equivalent or more, particularly 150 g / equivalent or more, particularly 200 g / equivalent or more. .
  • the compounding ratio of the epoxy group-containing compound (A) and the piperidine ring-containing compound (B) is, for example, 1 to 100 parts by weight of the piperidine ring-containing compound (B) with respect to 100 parts by weight of the epoxy group-containing compound (A). can do.
  • a compounding ratio of an epoxy group-containing compound (A), a piperidine ring-containing compound (B), and a phenol compound (C) for example, a piperidine ring-containing compound (100 parts by weight with respect to 100 parts by weight of the epoxy group-containing compound (A)) B) 1 to 100 parts by weight, phenol compound (C) 1 to 100 parts by weight.
  • epoxy equivalent means that the epoxy group-containing compound (A), piperidine ring-containing compound (B), and phenol compound (C) all have an epoxy group, NH group and / or OH group of 1: 1. It means the epoxy equivalent of the reaction product when reacted.
  • epoxy equivalent is defined as “mass of an epoxy compound containing one equivalent of an epoxy group” and can be measured according to JIS K7236.
  • Catalyst (D) In the reaction step for producing the epoxy compound of the present invention, a catalyst (D) may be used.
  • the catalyst (D) is not particularly limited as long as it is usually used as a catalyst for the advance method in the epoxy resin production method.
  • Examples of the catalyst (D) include alkali metal compounds, organic phosphorus compounds, tertiary amines, quaternary ammonium salts, cyclic amines, imidazoles and the like.
  • alkali metal compound examples include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide; alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride and potassium chloride; sodium Examples thereof include alkali metal alkoxides such as methoxide and sodium ethoxide; alkali metal hydrides such as alkali metal phenoxide, sodium hydride and lithium hydride; alkali metal salts of organic acids such as sodium acetate and sodium stearate.
  • alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide
  • alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride and potassium chloride
  • sodium Examples thereof include alkali metal alkoxides such as methoxide and sodium ethoxide; alkali metal hydrides such as alkali metal phenoxide, sodium hydride and lithium hydride; alkali metal salt
  • organic phosphorus compound examples include triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri-2,4-xylylphosphine, tri-2,5- Xylylphosphine, tri-3,5-xylylphosphine, tris (p-tert-butylphenyl) phosphine, tris (p-methoxyphenyl) phosphine, tris (p-tert-butoxyphenyl) phosphine, tri (pn) -Octylphenyl) phosphine, tri (pn-nonylphenyl) phosphine, triallylphosphine, tributylphosphine, trimethylphosphine, tribenzylphosphine, triisobutylphosphine, tri-tert-butylphosphine
  • tertiary amines include triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, N, N-dimethylbenzylamine and the like.
  • the quaternary ammonium salt include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium bromide, Tetrapropylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide, benzyltributylammonium chloride Ride, and phenyl trimethylammonium chloride and the like.
  • cyclic amines include 1,8-diazabicyclo (5,4,0) -7-undecene, 1,5-diazabicyclo (4,3,0) -5-nonene.
  • imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like.
  • the catalyst (D) mentioned above may be used alone or in combination of two or more.
  • the amount used is preferably 10,000 ppm by weight or less, for example, 10 to 5000 ppm by weight, based on the amount of the epoxy group-containing compound (A) used.
  • reaction solvent (E) In the reaction step for producing the epoxy compound of the present invention, a reaction solvent (E) may be used.
  • the reaction solvent (E) is not particularly limited as long as it dissolves the raw material, but is usually an organic solvent.
  • organic solvent examples include aromatic solvents, ketone solvents, amide solvents, glycol ether solvents, and the like.
  • aromatic solvent examples include benzene, toluene, xylene and the like.
  • ketone solvent examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclopentanone, cyclohexanone, acetylacetone and the like.
  • amide solvent examples include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone and the like.
  • glycol ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Examples thereof include mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate and the like.
  • reaction solvent (E) mentioned above may be used alone or in combination of two or more.
  • the reaction can be continued by further adding a reaction solvent (E).
  • reaction conditions The reaction between the epoxy group-containing compound (A) and the piperidine ring-containing compound (B), or the reaction between the epoxy group-containing compound (A), the piperidine ring-containing compound (B) and the phenol compound (C) is carried out at normal pressure. , Pressurization, and reduced pressure.
  • the reaction temperature is usually 60 to 240 ° C. If the reaction temperature is not less than the lower limit, the reaction is likely to proceed, and if the reaction temperature is not more than the upper limit, the side reaction is unlikely to proceed.
  • the temperature is preferably 80 to 220 ° C, more preferably 100 to 200 ° C, and still more preferably 120 to 180 ° C, from the viewpoint of obtaining a high-purity epoxy compound.
  • the reaction time is not particularly limited, but is usually 0.5 to 24 hours, preferably 1 to 22 hours, more preferably 1.5 to 20 hours, and further preferably 2 to 10 hours.
  • the reaction time is not more than the above upper limit, it is preferable from the viewpoint of improving production efficiency, and when it is not less than the above lower limit, it is preferable from the viewpoint of reducing unreacted components.
  • the compound (B) is less likely to undergo a copolymerization reaction due to its structure, and on the other hand, due to the presence of nitrogen atoms, there is a concern that the reaction may be gelled if the reaction conditions are made more severe.
  • the reaction conditions are made more severe.
  • unreacted components are reduced even when copolymerization of the compounds (A) and (B) or copolymerization of the compounds (A), (B) and (C).
  • a pure epoxy compound can be obtained.
  • the solid content concentration may be adjusted by mixing the diluting solvent (F) after completion of the reaction.
  • the dilution solvent (F) may be any solvent as long as it can dissolve the epoxy compound, but is usually an organic solvent. Specific examples of the organic solvent can be the same as those mentioned as the reaction solvent (E).
  • the terms “solvent” and “solvent” are used as the “solvent” when used in the reaction of the epoxy compound, and as the “solvent” as used after the completion of the reaction. Alternatively, different types may be used.
  • Epoxy compound-containing composition contains at least the above-described epoxy compound of the present invention and a curing agent. Moreover, the epoxy compound containing composition of this invention can mix
  • the curing agent used in the epoxy compound-containing composition of the present invention is a substance that contributes to a crosslinking reaction and / or chain length extension reaction between epoxy groups of the epoxy compound.
  • a curing accelerator is a substance that contributes to a crosslinking reaction and / or chain extension reaction between epoxy groups of an epoxy compound, it is regarded as a curing agent. To do.
  • the content of the curing agent in the epoxy compound-containing composition of the present invention is preferably 0.1 to 1000 parts by weight, more preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the epoxy compound of the present invention. More preferably 0.1 to 80 parts by weight, particularly preferably 0.1 to 60 parts by weight.
  • curing agent is preferably 0 with respect to 100 weight part of all the epoxy compound components. 0.1 to 1000 parts by weight, more preferably 0.1 to 100 parts by weight, still more preferably 0.1 to 80 parts by weight, and particularly preferably 0.1 to 60 parts by weight. More preferable content of the curing agent is as described below according to the kind of the curing agent.
  • solid content means a component excluding a solvent, and includes not only a solid epoxy compound but also a semi-solid or viscous liquid material. Further, the “total epoxy compound component” means the total of the epoxy compound of the present invention and other epoxy compounds described later.
  • epoxy compound-containing composition of the present invention polyfunctional phenols, polyisocyanate compounds, amine compounds, acid anhydride compounds, imidazole compounds, amide compounds, mercaptan compounds, cationic polymerization initiation It is preferable to use at least one member selected from the group consisting of an agent and organic phosphines.
  • polyfunctional phenols examples include bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol AD, bisphenol Z, tetrabromobisphenol A, and the like; 4,4′-biphenol, 3,3 ′, 5, Biphenols such as 5′-tetramethyl-4,4′-biphenol; catechol, resorcin, hydroquinone, dihydroxynaphthalene; and hydrogen atoms bonded to the aromatic ring of these compounds are halogen groups, alkyl groups, aryl groups, ethers And those substituted with a non-interfering substituent such as an organic substituent containing a hetero element such as a group, an ester group, sulfur, phosphorus or silicon.
  • these polyfunctional phenols and monofunctional phenols such as phenol, cresol and alkylphenol and novolaks and resols which are polycondensates of aldehydes can be mentioned.
  • polyisocyanate compounds include tolylene diisocyanate, methylcyclohexane diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dimer acid diisocyanate, trimethylhexamethylene diisocyanate, And polyisocyanate compounds such as lysine triisocyanate.
  • polyisocyanate compound obtained by reacting these polyisocyanate compounds with a compound having at least two active hydrogen atoms such as an amino group, a hydroxyl group, a carboxyl group and water, or 3 to 3 of the above polyisocyanate compounds.
  • a pentamer etc. can be mentioned.
  • Examples of amine compounds include aliphatic primary, secondary, tertiary amines, aromatic primary, secondary, tertiary amines, cyclic amines, guanidines, urea derivatives, and the like. Ethylenetetramine, diaminodiphenylmethane, diaminodiphenyl ether, metaxylenediamine, dicyandiamide, 1,8-diazabicyclo (5,4,0) -7-undecene, 1,5-diazabicyclo (4,3,0) -5-nonene, dimethyl Examples include urea and guanylurea.
  • Examples of the acid anhydride compound include phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, and a condensate of maleic anhydride and an unsaturated compound.
  • Examples of imidazole compounds include 1-isobutyl-2-methylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, benzimidazole and the like. It is done.
  • the imidazole compound also functions as a curing accelerator described later, but in the present invention, it is classified as a curing agent.
  • amide compounds include dicyandiamide and its derivatives, polyamide resins, and the like.
  • mercaptan compounds include butyl mercaptan, dodecyl mercaptan, hexyl mercaptan, pentaerythritol tetrakis (3-mercaptopropionate), 1,1 ′-[isopropylidenebis (p-phenyleneoxy) bis [3-mercaptopropane -2-ol] and the like.
  • Cationic polymerization initiators generate cations by heat or active energy ray irradiation, and include aromatic onium salts.
  • aromatic onium salts include anionic components such as SbF 6 ⁇ , BF 4 ⁇ , AsF 6 ⁇ , PF 6 ⁇ , CF 3 SO 3 2 ⁇ , B (C 6 F 5 ) 4 ⁇ and iodine, sulfur, nitrogen, phosphorus, etc.
  • a compound comprising an aromatic cation component containing the above atoms In particular, diaryl iodonium salts and triaryl sulfonium salts are preferred.
  • organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine and the like
  • phosphonium salts include tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenyl.
  • Examples include borate, tetrabutylphosphonium / tetrabutylborate, and examples of the tetraphenylboron salt include 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, and the like.
  • the functional groups in the curing agent with respect to all epoxy groups in the epoxy compound-containing composition (hydroxy groups of polyfunctional phenols, amine compounds)
  • the amino group or the acid anhydride group of the acid anhydride compound) is preferably used so as to be in the range of 0.8 to 1.5.
  • the number of isocyanate groups in the polyisocyanate compound relative to the number of hydroxyl groups in the epoxy compound-containing composition is in the range of 1: 0.01 to 1: 1.5 in an equivalent ratio. It is preferable to use it.
  • an imidazole compound When used as the curing agent, it is preferably used in the range of 0.5 to 10 parts by weight with respect to 100 parts by weight of the total epoxy compound component as a solid content in the epoxy compound-containing composition.
  • an amide compound When an amide compound is used as the curing agent, it is preferably used in a range of 0.1 to 20% by weight with respect to the total amount of all the epoxy compound components and the amide compound as a solid content in the epoxy compound-containing composition. .
  • a mercaptan-based compound When a mercaptan-based compound is used as the curing agent, it is preferably used in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the total epoxy compound component as a solid content in the epoxy compound-containing composition.
  • a cationic polymerization initiator When a cationic polymerization initiator is used as the curing agent, it is preferably used in the range of 0.01 to 15 parts by weight with respect to 100 parts by weight of the total epoxy compound component as a solid content in the epoxy compound-containing composition.
  • organic phosphines When organic phosphines are used as the curing agent, it is preferably used in the range of 0.1 to 20% by weight based on the total amount of all epoxy compound components and organic phosphines as a solid content in the epoxy compound-containing composition. .
  • organic acid dihydrazide, boron halide amine complex and the like can be used as the curing agent in the epoxy compound-containing composition of the present invention.
  • These curing agents may be used alone or in combination of two or more.
  • an epoxy compound other than the epoxy compound of the present invention (sometimes referred to as “other epoxy compound” in the present specification) can be used.
  • epoxy compounds include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin. , Glycidyl ether type epoxy resin such as tetrabromobisphenol A type epoxy resin, other polyfunctional phenol type epoxy resin, epoxy resin hydrogenated to the aromatic ring of the above aromatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy Examples thereof include epoxy compounds such as resins, linear aliphatic epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins. The other epoxy compounds mentioned above may be used alone or in combination of two or more.
  • the ratio of the other epoxy compounds in the total epoxy compound component as a solid content in the epoxy compound-containing composition is The amount is preferably 1% by weight or more, more preferably 5% by weight or more, and preferably 99% by weight or less, more preferably 95% by weight or less.
  • the ratio of the other epoxy compound is not less than the above lower limit value, the effect of improving physical properties by blending the other epoxy compound can be sufficiently obtained.
  • the ratio of the other epoxy compound is not more than the above upper limit, the light resistance and the coating film hardness improving effect by the epoxy compound of the present invention can be obtained.
  • the epoxy compound-containing composition of the present invention may be diluted by blending a solvent in order to appropriately adjust the viscosity of the epoxy compound-containing composition during handling such as coating film formation.
  • the solvent is used to ensure the handleability and workability in the molding of the epoxy compound-containing composition, and the amount used is not particularly limited.
  • the term “solvent” and the term “solvent” are distinguished from each other depending on the form of use, but the same or different ones may be used independently.
  • a solvent which the epoxy compound of this invention can contain the 1 type (s) or 2 or more types of the organic solvent illustrated as reaction solvent (E) used for manufacture of the epoxy compound of this invention can be used.
  • the epoxy compound-containing composition of the present invention may contain other components in addition to the components listed above.
  • examples of other components include a curing accelerator (except for those corresponding to the curing agent), a coupling agent, a flame retardant, an antioxidant, a light stabilizer, a plasticizer, a reactive diluent, a pigment, An inorganic filler, an organic filler, etc. are mentioned.
  • the other components listed above can be used in appropriate combination depending on the desired physical properties of the epoxy compound-containing composition.
  • the coating material of this invention contains the epoxy compound of this invention, or the epoxy compound containing composition of this invention.
  • the paint of the present invention may be added with various additives that are added to the solvent and the usual paint, if necessary. It is obtained by mixing by the method.
  • the 1 type (s) or 2 or more types of the organic solvent illustrated as reaction solvent (E) used for manufacture of the epoxy compound of this invention can be used.
  • the additive include various stabilizers such as ultraviolet absorbers, antioxidants, weathering stabilizers and heat resistance inhibitors, colorants such as dyes, organic pigments and inorganic pigments, and conductivity imparting such as carbon black and ferrite. Agents, pigment dispersants, leveling agents, antifoaming agents, thickeners, preservatives, fungicides, rust inhibitors and wetting agents.
  • the cured product of the present invention can be obtained by curing the epoxy compound-containing composition of the present invention.
  • the term “curing” as used herein means that the epoxy compound is intentionally cured by heat and / or light or the like, and the degree of curing may be controlled by desired physical properties and applications.
  • the curing method of the epoxy compound-containing composition when curing the epoxy compound-containing composition of the present invention to obtain a cured product is different depending on the blending component and blending amount in the epoxy compound-containing composition, and the shape of the blend.
  • heating conditions of 50 to 200 ° C. for 5 seconds to 180 minutes can be mentioned. This heating is performed in a two-stage process of primary heating at 50 to 160 ° C. for 5 seconds to 30 minutes and secondary heating at 90 to 280 ° C. that is 40 to 120 ° C. higher than the primary heating temperature for 1 to 150 minutes.
  • the curing reaction of the epoxy compound-containing composition may be advanced to such an extent that the shape can be maintained by heating or the like.
  • the epoxy compound-containing composition contains a solvent, most of the solvent is removed by techniques such as heating, reduced pressure, and air drying, but 5% by weight or less of the solvent may be left in the semi-cured product. .
  • the epoxy compound of the present invention By using the epoxy compound of the present invention, a coating film excellent in light resistance, hardness and elution resistance can be formed. From this, the epoxy compound of this invention and the epoxy compound containing composition which mix
  • the present invention will be described more specifically based on examples, but the present invention is not limited to the following examples.
  • the value of various manufacturing conditions and evaluation results in the following examples has a meaning as a preferable value of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value.
  • a range defined by a combination of values of the following examples or values of the examples may be used.
  • Epoxy group-containing compound (A)] A-1 Bisphenol A diglycidyl ether (manufactured by Mitsubishi Chemical Corporation, jER (registered trademark) 828US, epoxy equivalent: 186 g / equivalent, total chlorine amount: 0.16% by weight)
  • B-1 Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinvin 770DF manufactured by BASF)
  • F-1 Methyl ethyl ketone (Tokyo Chemical Industry Co., Ltd.)
  • Evaluation methods in the following examples and comparative examples are as follows.
  • Example 1 1,200 parts by weight of bisphenol A diglycidyl ether (A-1), 24.9 parts by weight of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (B-1), bisphenol A (C-1 ) 460 parts by weight and 0.72 part by weight of tetramethylammonium chloride 50% aqueous solution (D-1) were placed in a 5 L flask and subjected to a polymerization reaction at 165 ° C. for 6 hours in a nitrogen gas atmosphere to obtain the desired epoxy compound. It was. This was dissolved in 1685 parts by weight of methyl ethyl ketone (F-1) (solid content 50% by weight).
  • F-1 methyl ethyl ketone
  • Example 2 200 parts by weight of bisphenol A diglycidyl ether (A-1), 14.5 parts by weight of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (B-1), bisphenol A (C-1 ) 72 parts by weight and 0.12 part by weight of a 50% aqueous solution of tetramethylammonium chloride (D-1) were placed in a 1 L flask and subjected to a polymerization reaction at 165 ° C. for 6 hours in a nitrogen gas atmosphere to obtain the desired epoxy compound. It was. This was dissolved in 287 parts by weight of methyl ethyl ketone (F-1) (solid content: 50% by weight).
  • F-1 methyl ethyl ketone
  • Example 3 200 parts by weight of bisphenol A diglycidyl ether (A-1), 29.5 parts by weight of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (B-1), bisphenol A (C-1 ) 65 parts by weight of tetramethylammonium chloride 50% aqueous solution (D-1) 0.12 part by weight was placed in a 1 L flask and subjected to a polymerization reaction at 165 ° C. for 6 hours in a nitrogen gas atmosphere to obtain the desired epoxy compound. It was. This was dissolved in 295 parts by weight of methyl ethyl ketone (F-1) (solid content: 50% by weight).
  • F-1 methyl ethyl ketone
  • Example 4 175 parts by weight of bisphenol A diglycidyl ether (A-1), 145 parts by weight of bis (2,2,6,6-tetramethyl-4-piperidyl) (B-1) sebacate, 50% aqueous solution of tetramethylammonium chloride ( D-1) 0.105 part by weight was placed in a 1 L flask and subjected to a polymerization reaction at 165 ° C. for 6 hours in a nitrogen gas atmosphere to obtain the desired epoxy compound. This was dissolved in 320 parts by weight of methyl ethyl ketone (F-1) (solid content: 50% by weight).
  • Example 5 200 parts by weight of bisphenol A diglycidyl ether (A-1), 36 parts by weight of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (B-1), tetrabromobisphenol A (C-2 ) 125 parts by weight and 0.4 part by weight of a tetramethylammonium chloride 50% aqueous solution (D-1) are placed in a 1 L flask and subjected to a polymerization reaction at 165 ° C. for 6 hours in a nitrogen gas atmosphere to obtain the desired epoxy compound. It was. This was dissolved in 361 parts by weight of methyl ethyl ketone (F-1) (solid content 50% by weight).
  • F-1 methyl ethyl ketone
  • the coating film produced using the epoxy compound of Comparative Example 1 having no structure of Formula (1) had insufficient light resistance.
  • the coating film produced using the epoxy compound of Comparative Example 2 that does not have the structure of Formula (1) had insufficient elution resistance.
  • the epoxy compound of the present invention is considered to be capable of forming a coating film having good light resistance, hardness and elution resistance by having both groups of formula (1) and formula (2).
  • the coating film using the epoxy compound of the present invention has excellent weather resistance, hardness and elution resistance. Therefore, the epoxy compound of the present invention, the epoxy compound-containing composition containing the epoxy compound, and the cured product thereof are suitably used in the fields of paints, electrical / electronic materials, adhesives, fiber reinforced resins (FRP), and the like. be able to.

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Abstract

La présente invention concerne un composé époxy qui comprend un groupe divalent représenté par la formule (1) et un groupe divalent représenté par la formule (2), et qui a un poids équivalent en époxy de 200 g/équivalent à 200 000 g/équivalent (inclus). (Dans les formules (1) et (2), R1-R4 et X sont tels que définis dans la description.)
PCT/JP2017/031883 2016-09-06 2017-09-05 Composé époxy, procédé de production d'un composé époxy, composition contenant un composé époxy, matériau de revêtement et produit durci Ceased WO2018047799A1 (fr)

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Publication number Priority date Publication date Assignee Title
JPS5429400A (en) * 1977-08-08 1979-03-05 Sankyo Co Ltd Polymer comprising polyalkylpiperidine and its use as stabilizers
JPS54126249A (en) * 1978-02-08 1979-10-01 Ciba Geigy Ag Polyalkyl piperidine derivative of new sstriazine and stabilized polymer containing same
JPS56152462A (en) * 1980-03-28 1981-11-26 Ciba Geigy Ag Amide derivative of polyalkylpiperidine and its use
JPH0255726A (ja) * 1988-08-22 1990-02-26 Toshiba Silicone Co Ltd 加水分解性シリル基で分子鎖末端が閉塞されたポリエーテル、その製造方法およびそれを含有する室温硬化性組成物

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DK144796C (da) * 1975-03-21 1982-10-25 Montefibre Spa Stabiliseret alkenpolymerformstof eller-genstand og stabiliseringsmiddel til brug ved fremstillingen deraf
US8721946B2 (en) * 2008-01-25 2014-05-13 Borealis Ag Low-sticky additive package for automotive interior applications
WO2012036164A1 (fr) * 2010-09-15 2012-03-22 株式会社日本触媒 Composition utilisable comme initiateur de polymérisation à chaleur latente

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
JPS5429400A (en) * 1977-08-08 1979-03-05 Sankyo Co Ltd Polymer comprising polyalkylpiperidine and its use as stabilizers
JPS54126249A (en) * 1978-02-08 1979-10-01 Ciba Geigy Ag Polyalkyl piperidine derivative of new sstriazine and stabilized polymer containing same
JPS56152462A (en) * 1980-03-28 1981-11-26 Ciba Geigy Ag Amide derivative of polyalkylpiperidine and its use
JPH0255726A (ja) * 1988-08-22 1990-02-26 Toshiba Silicone Co Ltd 加水分解性シリル基で分子鎖末端が閉塞されたポリエーテル、その製造方法およびそれを含有する室温硬化性組成物

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