WO2017047036A1 - Curing catalyst for epoxy resin - Google Patents
Curing catalyst for epoxy resin Download PDFInfo
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- WO2017047036A1 WO2017047036A1 PCT/JP2016/004038 JP2016004038W WO2017047036A1 WO 2017047036 A1 WO2017047036 A1 WO 2017047036A1 JP 2016004038 W JP2016004038 W JP 2016004038W WO 2017047036 A1 WO2017047036 A1 WO 2017047036A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- the present invention relates to a novel epoxy resin curing catalyst, a composition for forming a cured resin using the curing catalyst, a method for producing a cured resin using the composition for forming a cured resin, and the curing obtained by the method. It relates to resin.
- Epoxy resins are widely used in various fields because they have excellent mechanical and thermal properties.
- a curing agent for curing such an epoxy resin imidazole is used.
- the epoxy resin-imidazole mixed solution has a problem that the onset of curing is early and the stability of one solution is extremely poor.
- an imidazolic acid addition salt obtained by adding hydroxybenzoic acid to imidazole (see Patent Document 1) or a tetrakisphenol compound (for example, 1,1,2,2-tetrakis (4-hydroxy) is used. It has been proposed to use an inclusion body of phenyl) ethane (hereinafter referred to as TEP)) and imidazole (see Patent Document 2).
- TEP phenyl ethane
- An object of the present invention is to provide a curing catalyst capable of effectively curing a resin by suppressing a curing reaction at a low temperature to improve one-component stability and performing a heat treatment. is there. Moreover, the subject of this invention provides the cured resin forming composition using this curing catalyst, the manufacturing method of the cured resin using this cured resin forming composition, and the cured resin obtained by this manufacturing method There is.
- each X 1 independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or Represents a cyano group.
- m represents any integer from 0 to 4
- n represents any integer from 0 to 4.
- X 2 each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or a cyano group.
- Fluorene compound represented by Formula (II) (Wherein R 1 represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, or an unsubstituted or substituted C6-10 aryl group. R 2 to R 4 each independently represents a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, a nitro group, or a cyano group. To express.
- Curing catalyst (4) Composition for forming an epoxy cured resin containing the following component (A), component (B), and component (C) (A) epoxy resin; (B) Formula (I) (In the formula, each X 1 independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or Represents a cyano group. m represents any integer from 0 to 4, and n represents any integer from 0 to 4.
- X 2 each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or a cyano group.
- . p represents any integer from 0 to 4
- q represents any integer from 0 to 4.
- R 2 to R 4 each independently represents a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, a nitro group, or a cyano group.
- Imidazole compound represented by (5) The fluorene compound represented by the formula (I) as the component (B) is contained in an amount of 0.01 mol or more per 1 mol of the imidazole compound represented by the formula (II) as the component (C) ( 4)
- the composition for epoxy cured resin formation as described in 4), (6) 0.01 to 1.0 mol of the imidazole compound represented by the formula (II) as the component (C) is contained per 1 mol of the epoxy ring of the epoxy resin as the component (A) (4) Or the composition for epoxy cured resin formation as described in (5), (7)
- the resin can be effectively cured by suppressing the curing reaction at a low temperature and improving the one-component stability and performing the heat treatment.
- FIG. 1 It is a figure which shows the DSC measurement result of the composition A for epoxy cured resin formation obtained in Example 1, and the composition G for epoxy cured resin formation obtained in the comparative example 1.
- FIG. 2 It is a figure which shows the DSC measurement result of the composition B for epoxy cured resin formation obtained in Example 2, and the composition G for epoxy cured resin formation obtained by the comparative example 1.
- FIG. 2 It is a figure which shows the DSC measurement result of the composition C for epoxy cured resin formation obtained in Example 3, and the composition G for epoxy cured resin formation obtained in the comparative example 1.
- FIG. It is a figure which shows the DSC measurement result of the composition D for epoxy cured resin formation obtained in Example 4, and the composition G for epoxy cured resin formation obtained in the comparative example 1.
- FIG. 1 It is a figure which shows the DSC measurement result of the composition E for epoxy cured resin formation obtained in Example 5, and the composition G for epoxy cured resin formation obtained in the comparative example 1.
- FIG. It is a figure which shows the DSC measurement result of the composition F for epoxy cured resin formation obtained in Example 6, and the composition G for epoxy cured resin formation obtained in Comparative Example 1.
- the term “unsubstituted” means only a group serving as a mother nucleus.
- the term “having a substituent” means that any hydrogen atom of a group serving as a mother nucleus is substituted with a group having the same or different structure from the mother nucleus. Accordingly, the “substituent” is another group bonded to a group serving as a mother nucleus.
- the number of substituents may be one, or two or more. Two or more substituents may be the same or different. Terms such as “C1-6” indicate that the group serving as the mother nucleus has 1 to 6 carbon atoms. This number of carbon atoms does not include the number of carbon atoms present in the substituent. For example, a butyl group having an ethoxy group as a substituent is classified as a C2 alkoxy C4 alkyl group.
- the “substituent” is not particularly limited as long as it is chemically acceptable and has the effects of the present invention.
- groups that can be “substituents” are shown below.
- Halogeno groups such as fluoro, chloro, bromo and iodo groups
- C1-6 such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc.
- alkyl group An alkyl group; Vinyl group, 1-propenyl group, 2-propenyl group (allyl group), 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, etc.
- a C2-6 alkenyl group of C2-6 alkynyl groups such as ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group;
- a C3-8 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group;
- a C6-10 aryl group such as a phenyl group or a naphthyl group;
- a C6-10 aryl C1-6 alkyl group such as a benzyl group or a phenethyl group; 3-6 membered heterocyclyl group;
- Hydroxyl group C1-6 alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group; C2-6 alkenyloxy groups such as vinyloxy group, allyloxy group, propenyloxy group, butenyloxy group; C6-10 aryloxy groups such as phenoxy group and naphthoxy group; A C6-10 aryl C1-6 alkoxy group such as a benzyloxy group or a phenethyloxy group; A 3-6 membered heterocyclyloxy group; A 3-6 membered heterocyclyl C1-6 alkoxy group; C1-6 haloalkyl groups such as chloromethyl group, chloroethyl group, trifluoromethyl group, 1,2-dichloro-n-propyl group, 1-fluoro-n-butyl group, perfluoro-n-pentyl
- a C1-6 alkylamino group such as a methylamino group, a dimethylamino group, a diethylamino group
- C6-10 arylamino groups such as anilino group and naphthylamino group
- a C6-10 aryl C1-6 alkylamino group such as a benzylamino group or a phenethylamino group
- a mercapto group C1-6 alkylthio groups such as methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, t-butylthio group
- a C1-6 alkylsulfonyl group such as a methylsulfonyl group, an ethylsulfonyl group, a t-butylsulfonyl
- any hydrogen atom in the substituent may be substituted with a group having a different structure.
- examples of the “substituent” include a halogeno group, a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, a C1-6 haloalkoxy group, a cyano group, and a nitro group.
- the “3- to 6-membered heterocyclyl group” is a cyclic group containing 1 to 4 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom as constituent atoms of the ring.
- Examples of the “3- to 6-membered heterocyclyl group” include a 3- to 6-membered saturated heterocyclyl group, a 5- to 6-membered heteroaryl group, and a 5- to 6-membered partially unsaturated heterocyclyl group.
- Examples of the 3- to 6-membered saturated heterocyclyl group include aziridinyl group, epoxy group, pyrrolidinyl group, tetrahydrofuranyl group, thiazolidinyl group, piperidyl group, piperazinyl group, morpholinyl group, dioxolanyl group, dioxanyl group and the like.
- Examples of 5-membered heteroaryl groups include pyrrolyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl Can do.
- Examples of the 6-membered heteroaryl group include a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, and a triazinyl group.
- Examples of the 5-membered partially unsaturated heterocyclyl group include a pyrrolinyl group, a dihydrofuranyl group, an imidazolinyl group, a pyrazolinyl group, and an oxazolinyl group.
- Examples of the 6-membered partially unsaturated heterocyclyl group include an isoxazolinyl group and a dihydropyranyl group.
- each X 1 independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, or a nitro group. Or a cyano group.
- m represents any integer from 0 to 4
- n represents any integer from 0 to 4.
- X 2 each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or a cyano group.
- p represents any integer from 0 to 4
- q represents any integer from 0 to 4.
- halogeno group examples include a fluoro group, a chloro group, a bromo group, and an iodo group.
- the “C1-6 alkyl group” in X 1 and X 2 may be linear or branched.
- Examples of the C1-6 alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, i-propyl group, i-butyl group, s-butyl group, t -Butyl group, i-pentyl group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, i-hexyl group and the like can be mentioned.
- the substituent on the “C1-6 alkyl group” is preferably a halogeno group, a hydroxyl group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, a C6-10 aryl group, or a cyano group.
- C1-6 alkyl group having a substituent specifically, Fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, 2,2,2-trifluoroethyl group, 2, 2,2-trichloroethyl group, pentafluoroethyl group, 4-fluorobutyl group, 4-chlorobutyl group, 3,3,3-trifluoropropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl
- a C1-6 haloalkyl group such as a group, perfluorohexyl group, perchlorohexyl group, 2,4,6-trichlorohexyl group; Hydroxy C1-6 alkyl groups such as hydroxymethyl group, 2-hydroxyethyl group; Methoxymethyl group, ethoxymethyl group, methoxyethyl
- C1-6 alkoxy group in X 1 and X 2 , a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, an i-propoxy group, Examples include i-butoxy group, s-butoxy group, t-butoxy group, i-hexyloxy group and the like.
- the substituent on the “C1-6 alkoxy group” is preferably a halogeno group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, or a C6-10 aryl group.
- substituted C1-6 alkoxy group examples include chloromethoxy group, dichloromethoxy group, difluoromethoxy group, trichloromethoxy group, trifluoromethoxy group, 1-fluoroethoxy group, 1,1- Examples thereof include C1-6 haloalkoxy groups such as difluoroethoxy group, 2,2,2-trifluoroethoxy group, and pentafluoroethoxy group.
- fluorene compound represented by the formula (I) include 9,9-bis (4-hydroxyphenyl) fluorene ⁇ 9,9-Bis (4-hydroxyphenyl) fluorene>, 9,9-bis ( 4-hydroxy-3-methylphenyl) fluorene ⁇ 9,9-Bis (4-hydroxy-3-methylphenyl) fluorene>, 2,7-dibromo-9,9-bis (4-hydroxyphenyl) fluorene ⁇ 2,7 -Dibromo-9,9-bis (4-hydroxyphenyl) fluorene>, 9,9-bis (3-amino-4-hydroxyphenyl) fluorene ⁇ 9,9-Bis (3-amino-4-hydroxyphenyl) fluorene>, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene ⁇ 9,9-Bis (4-hydroxy-3,5-dimethylphenyl) fluorene>, 9,9-bis (4-hydroxy-2, 6-d
- R 1 represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, or an unsubstituted or substituted C6-10 aryl group.
- Examples of the “C1-6 alkyl group” for R 1 include the same groups as those exemplified for X 1 above.
- the substituent on the “C1-6 alkyl group” is preferably a halogeno group, a hydroxyl group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, a C6-10 aryl group, or a cyano group.
- the “C6-10 aryl group” in R 1 may be monocyclic or polycyclic. In the polycyclic aryl group, if at least one ring is an aromatic ring, the remaining ring may be a saturated alicyclic ring, an unsaturated alicyclic ring, or an aromatic ring. Examples of the “C6-10 aryl group” in R 1 include a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group.
- Examples of the substituent on the “C6-10 aryl group” include halogeno group, C1-6 alkyl group, hydroxyl group, C1-6 alkoxy group, C1-6 haloalkoxy group, cyano group, nitro group and the like.
- R 2 to R 4 each independently represent a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, nitro Represents a group or a cyano group.
- halogeno group examples include a halogeno group, a hydroxyl group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, a C6-10 aryl group, or a cyano group.
- substituent on the “C6-10 aryl group” include halogeno group, C1-6 alkyl group, hydroxyl group, C1-6 alkoxy group, C1-6 haloalkoxy group, cyano group, nitro group and the like.
- imidazole compound represented by the formula (II) include imidazole, 2-ethyl-4-methylimidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 1-benzyl-2- Methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl Examples include -2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and the like.
- the epoxy resin curing catalyst of the present invention comprises a fluorene compound represented by formula (I) and an imidazole compound represented by formula (II) as main components.
- the epoxy resin curing catalyst of the present invention can be used as a resin curing agent such as a polyester resin, an epoxy resin, an epoxy-polyester resin, or a urethane resin, and can be particularly preferably used as a curing agent for an epoxy resin.
- the blending ratio of the fluorene compound represented by the formula (I) and the imidazole compound represented by the formula (II) in the epoxy resin curing catalyst of the present invention is 1 mol of the fluorene compound represented by the formula (I).
- the imidazole compound represented by the formula (II) is preferably 0.01 mol or more.
- the upper limit is not particularly present and may be a ratio of 0.01 mol or more as long as it satisfies economic reasons.
- the range for obtaining a sufficient effect is preferably 0.1 to 10 mol.
- Epoxy cured resin forming composition The composition for forming an epoxy cured resin of the present invention is not particularly limited as long as it contains an epoxy resin and the curing catalyst of the present invention, and is as described above.
- epoxy resin various conventionally known polyepoxy compounds can be used.
- the ratio of the epoxy resin and the imidazole compound represented by the formula (II) in the epoxy cured resin forming composition of the present invention is the ratio of the imidazole compound represented by the formula (II) to 1 mol of the epoxy ring of the epoxy resin.
- the content is preferably 0.01 to 1.0 mol, more preferably 0.1 to 1.0 mol, and still more preferably 0.3 to 1.0 mol.
- Solvents include water, methanol, ethanol, isopropyl alcohol, ethyl acetate, methyl acetate, diethyl ether, dimethyl ether, tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, acetonitrile, benzene, toluene, hexane, chloroform, dichloromethane, tetrachloride. Carbon or the like can be used.
- the epoxy resin curing catalyst of the present invention is a heat treatment or heating reflux with stirring as necessary after adding the fluorene compound represented by formula (I) and the imidazole compound represented by formula (II) to the solvent.
- the fluorene compound represented by the formula (I) and the imidazole compound represented by the formula (II) may be dissolved in the solvent and then mixed with each other. preferable.
- the composition for forming an epoxy cured resin of the present invention can be produced by mixing an epoxy resin, a compound represented by the formula (I), and a compound represented by the formula (II). Usually, the mixture is heated to about room temperature to about 100 ° C. so that a mixed state is formed. In the production of an epoxy cured resin, the stability of one liquid at this temperature is important.
- composition of the present invention for the purpose of imparting desired properties.
- Curing Catalyst for Epoxy Resin In addition to the above curing catalyst, a known curing catalyst can be used in combination with the composition of the present invention.
- curing agent Further known curing agents for curing the epoxy resin can be used.
- compounds having two phenolic hydroxyl groups in one molecule such as resorcin, catechol, bisphenol A, bisphenol F; phenol novolak resin, cresol novolak resin, cresol aralkyl resin, phenol aralkyl resin, biphenyl aralkyl resin, dicyclopentadiene
- Polyphenol resin such as a type phenol resin and a naphthol aralkyl resin; and the like.
- a filler may be blended in order to control the viscosity and physical properties of the cured product.
- an insulating inorganic filler, whisker, or resin filler can be used.
- the insulating inorganic filler include glass, silica, alumina, titanium oxide, carbon black, mica, and boron nitride.
- whiskers include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, and boron nitride.
- a polyurethane resin, a polyimide resin, or the like can be used as the resin filler.
- metal particles such as gold, silver, copper, nickel, solder, and conductive fillers such as carbon can also be used when constituting an adhesive for joining electronic components.
- the method for producing the epoxy curable resin of the present invention is not particularly limited as long as it is a method of curing the epoxy curable resin-forming composition by heat treatment.
- the heating temperature of the heat treatment is 60 It is preferably from 250 to 250 ° C., and preferably from 100 to 200 ° C., and it is preferably cured at such temperature for a short time.
- composition for forming an epoxy curable resin of the present invention is not particularly limited, and examples thereof include underfill, thermosetting prepreg, casting material, structural adhesive, and powder coating. Can do.
- electrical materials, printed circuit board prepregs, semiconductor / electronic component sealing materials, electronic component adhesives, conductive adhesives, resist inks, insulating materials, and the like can be given.
- the method for producing the epoxy curable resin of the present invention is not particularly limited as long as it is a method of curing the epoxy curable resin-forming composition by heat treatment.
- the heating temperature of the heat treatment is 60 It is preferably from 250 to 250 ° C., and preferably from 100 to 200 ° C., and it is preferably cured at such temperature for a short time.
- Example 1 (Preparation of composition A for epoxy cured resin formation) 200 mg (1.82 mmol) of 2-ethyl-4-methylimidazole (hereinafter, 2E4MZ) as a curing catalyst with respect to 5 g of epoxy resin (trade name: Epototo (registered trademark) YD-128, manufactured by Toho Kasei Co., Ltd.) After adding 63.0 mg (0.181 mmol) of 9,9-bis (4-hydroxyphenyl) fluorene, the mixture was kneaded at 25 ° C. for 10 minutes to obtain an epoxy cured resin forming composition A.
- 2E4MZ 2-ethyl-4-methylimidazole
- DSC measurement of composition A for epoxy cured resin formation Using a DSC measuring apparatus (DSC1, manufactured by METTLER TOLEDO), 9.4 mg of the epoxy cured resin forming composition A was weighed in an aluminum container, and purged with nitrogen (flow rate of nitrogen: 50 mL / min) at 30 ° C. To 250 ° C. (temperature increase rate: 10 k / min), and heat generation based on the curing reaction of the epoxy cured resin forming composition A was measured. The measurement results with time and temperature on the horizontal axis are shown in FIG.
- Example 2 (Preparation of composition B for forming epoxy cured resin)
- E2MZ as a curing catalyst
- 9,9-bis (4-hydroxyphenyl) fluorene as 158.0 mg (0.453 mmol) were used.
- An epoxy cured resin forming composition B was obtained in the same manner except that each was added.
- Example 3 (Preparation of epoxy cured resin forming composition C)
- the same preparation was carried out except that the amount of 9,9-bis (4-hydroxyphenyl) fluorene was changed to 318.0 mg (0.907 mmol).
- an epoxy cured resin forming composition C was obtained.
- Example 4 (Preparation of composition D for epoxy cured resin formation)
- the same preparation was carried out except that the amount of 9,9-bis (4-hydroxyphenyl) fluorene was changed to 635.0 mg (1.815 mmol).
- an epoxy cured resin forming composition D was obtained.
- Example 5 (Preparation of composition E for epoxy cured resin formation)
- the same preparation was performed except that the amount of 9,9-bis (4-hydroxyphenyl) fluorene added was changed to 1.27 g (3.63 mmol).
- an epoxy cured resin forming composition E was obtained.
- Example 6 (Preparation of composition F for forming an epoxy cured resin)
- the same preparation was carried out except that the amount of 9,9-bis (4-hydroxyphenyl) fluorene was changed to 3.17 g (9.08 mmol).
- a composition F for forming an epoxy cured resin was obtained.
- the curing time of each composition for forming an epoxy cured resin was calculated based on the exothermic peak in the DSC measurement shown in FIG. 1 to FIG.
- the curing time was determined by subtracting the curing start time from the curing end time, with the time at which the exothermic peak separated from the baseline as the curing start time and the return time as the curing end time. From Table 1, it became clear that in any case where the bisphenol fluorene compound was added, the curing time was shortened, and the bisphenol fluorene compound greatly contributed to the rapid curing of the epoxy resin.
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Abstract
The present invention addresses the problem of providing a curing catalyst that suppresses a curing reaction at a low temperature to improve one-pack stability, and can effectively cure a resin by applying heat treatment. The curing catalyst for an epoxy resin according to the present invention contains a fluorene compound represented by formula (I) and an imidazole compound represented by formula (II).
Description
本発明は、新規なエポキシ樹脂用硬化触媒、該硬化触媒を用いた硬化樹脂形成用組成物、該硬化樹脂形成用組成物を用いた硬化樹脂の製造方法、及び該製造方法により得られた硬化樹脂に関する。
本願は、２０１５年９月１６日に出願された日本国特許出願第２０１５－１８２６８９号に対し優先権を主張し、その内容をここに援用する。 The present invention relates to a novel epoxy resin curing catalyst, a composition for forming a cured resin using the curing catalyst, a method for producing a cured resin using the composition for forming a cured resin, and the curing obtained by the method. It relates to resin.
This application claims priority to Japanese Patent Application No. 2015-182689 filed on Sep. 16, 2015, the contents of which are incorporated herein by reference.
本願は、２０１５年９月１６日に出願された日本国特許出願第２０１５－１８２６８９号に対し優先権を主張し、その内容をここに援用する。 The present invention relates to a novel epoxy resin curing catalyst, a composition for forming a cured resin using the curing catalyst, a method for producing a cured resin using the composition for forming a cured resin, and the curing obtained by the method. It relates to resin.
This application claims priority to Japanese Patent Application No. 2015-182689 filed on Sep. 16, 2015, the contents of which are incorporated herein by reference.
エポキシ樹脂は、優れた機械特性、熱特性を有するため様々な分野で広く用いられている。かかるエポキシ樹脂を硬化させるための硬化剤として、イミダゾールが用いられているが、エポキシ樹脂－イミダゾールの混合液は、硬化の開始が早く、一液安定性が極めて悪いという問題がある。
Epoxy resins are widely used in various fields because they have excellent mechanical and thermal properties. As a curing agent for curing such an epoxy resin, imidazole is used. However, the epoxy resin-imidazole mixed solution has a problem that the onset of curing is early and the stability of one solution is extremely poor.
そこで、硬化剤として、イミダゾールにヒドロキシ安息香酸を付加したイミダゾール酸付加塩を用いること（特許文献１参照。）や、テトラキスフェノール系化合物（例えば、１，１，２，２－テトラキス（４－ヒドロキシフェニル）エタン（以下、ＴＥＰという。））とイミダゾールとの包接体を用いること（特許文献２参照。）が提案されている。かかるイミダゾール酸付加塩や包接体は、一定の効果を奏するものであるが、これと同等の機能を有するものや更に機能の向上したものの開発が望まれている。
Therefore, as the curing agent, an imidazolic acid addition salt obtained by adding hydroxybenzoic acid to imidazole (see Patent Document 1) or a tetrakisphenol compound (for example, 1,1,2,2-tetrakis (4-hydroxy) is used. It has been proposed to use an inclusion body of phenyl) ethane (hereinafter referred to as TEP)) and imidazole (see Patent Document 2). Such imidazole acid addition salts and clathrates have a certain effect, but development of those having the same function or further improved functions is desired.
本発明の課題は、低温での硬化反応を抑制して、一液安定性の向上を図ると共に、加熱処理を施すことにより、効果的に樹脂を硬化させることができる硬化触媒を提供することにある。また、本発明の課題は、かかる硬化触媒を用いた硬化樹脂形成用組成物、該硬化樹脂形成用組成物を用いた硬化樹脂の製造方法、及び該製造方法により得られた硬化樹脂を提供することにある。
An object of the present invention is to provide a curing catalyst capable of effectively curing a resin by suppressing a curing reaction at a low temperature to improve one-component stability and performing a heat treatment. is there. Moreover, the subject of this invention provides the cured resin forming composition using this curing catalyst, the manufacturing method of the cured resin using this cured resin forming composition, and the cured resin obtained by this manufacturing method There is.
本発明者らは、上記課題を解決すべく鋭意研究した結果、特定のフルオレン化合物と特定のイミダゾール化合物との組み合わせを硬化触媒として用いることにより、上記課題を解決できることを見出し、本発明を完成するに至った。
As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a combination of a specific fluorene compound and a specific imidazole compound as a curing catalyst, and the present invention is completed. It came to.
すなわち本発明は、
（１）式（Ｉ）
（式中、Ｘ１は、それぞれ独立に、ハロゲノ基、無置換若しくは置換基を有するＣ１～６アルキル基、水酸基、無置換若しくは置換基を有するＣ１～６アルコキシ基、アミノ基、ニトロ基、又はシアノ基を表す。
ｍは０～４のいずれかの整数を表し、ｎは０～４のいずれかの整数を表す。
Ｘ２は、それぞれ独立に、ハロゲノ基、無置換若しくは置換基を有するＣ１～６アルキル基、水酸基、無置換若しくは置換基を有するＣ１～６アルコキシ基、アミノ基、ニトロ基、又はシアノ基を表す。
ｐは０～４のいずれかの整数を表し、ｑは０～４のいずれかの整数を表す。）で表されるフルオレン化合物と、
式（II）
（式中、Ｒ１は、水素原子、無置換若しくは置換基を有するＣ１～６アルキル基、又は無置換若しくは置換基を有するＣ６～１０アリール基を表す。
Ｒ２～Ｒ４は、それぞれ独立に、水素原子、ハロゲノ基、無置換若しくは置換基を有するＣ１～６アルキル基、無置換若しくは置換基を有するＣ６～１０アリール基、ニトロ基、又はシアノ基を表す。）で表されるイミダゾール化合物を含有するエポキシ樹脂用硬化触媒、
（２）式（Ｉ）で表されるフルオレン化合物が、９,９－ビス（４－ヒドロキシフェニル）フルオレンである（１）に記載のエポキシ樹脂用硬化触媒、
（３）式（II）で表されるイミダゾール化合物１モルに対して、式（Ｉ）で表されるフルオレン化合物を０．０１モル以上含有する（１）又は（２）に記載のエポキシ樹脂用硬化触媒、
（４）下記（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分を含有するエポキシ硬化樹脂形成用組成物
（Ａ）エポキシ樹脂；
（Ｂ）式（Ｉ）
（式中、Ｘ１は、それぞれ独立に、ハロゲノ基、無置換若しくは置換基を有するＣ１～６アルキル基、水酸基、無置換若しくは置換基を有するＣ１～６アルコキシ基、アミノ基、ニトロ基、又はシアノ基を表す。
ｍは０～４のいずれかの整数を表し、ｎは０～４のいずれかの整数を表す。
Ｘ２は、それぞれ独立に、ハロゲノ基、無置換若しくは置換基を有するＣ１～６アルキル基、水酸基、無置換若しくは置換基を有するＣ１～６アルコキシ基、アミノ基、ニトロ基、又はシアノ基を表す。
ｐは０～４のいずれかの整数を表し、ｑは０～４のいずれかの整数を表す。）で表されるフルオレン化合物；
（Ｃ）式（II）
（式中、Ｒ１は、水素原子、無置換若しくは置換基を有するＣ１～６アルキル基、又は無置換若しくは置換基を有するＣ６～１０アリール基を表す。
Ｒ２～Ｒ４は、それぞれ独立に、水素原子、ハロゲノ基、無置換若しくは置換基を有するＣ１～６アルキル基、無置換若しくは置換基を有するＣ６～１０アリール基、ニトロ基、又はシアノ基を表す。）で表されるイミダゾール化合物、
（５）（Ｃ）成分である式（II）で表されるイミダゾール化合物１モルに対して、（Ｂ）成分である式（Ｉ）で表されるフルオレン化合物を０．０１モル以上含有する（４）に記載のエポキシ硬化樹脂形成用組成物、
（６）（Ａ）成分であるエポキシ樹脂のエポキシ環１モルに対して、（Ｃ）成分である式（II）で表されるイミダゾール化合物を０．０１～１．０モル含有する（４）又は（５）に記載のエポキシ硬化樹脂形成用組成物、
（７）（Ｂ）成分である式（Ｉ）で表されるフルオレン化合物が、９,９－ビス（４－ヒドロキシフェニル）フルオレンである（４）～（６）のいずれか記載のエポキシ硬化樹脂形成用組成物、
（８）（４）～（７）のいずれか記載のエポキシ硬化樹脂形成用組成物を加熱処理して硬化して、エポキシ硬化樹脂を製造する方法、及び
（９）（４）～（７）のいずれか記載のエポキシ硬化樹脂形成用組成物を加熱処理して硬化して得られたエポキシ硬化樹脂に関する。 That is, the present invention
(1) Formula (I)
(In the formula, each X 1 independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or Represents a cyano group.
m represents any integer from 0 to 4, and n represents any integer from 0 to 4.
X 2 each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or a cyano group. .
p represents any integer from 0 to 4, and q represents any integer from 0 to 4. Fluorene compound represented by
Formula (II)
(Wherein R 1 represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, or an unsubstituted or substituted C6-10 aryl group.
R 2 to R 4 each independently represents a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, a nitro group, or a cyano group. To express. A curing catalyst for epoxy resins containing an imidazole compound represented by:
(2) The epoxy resin curing catalyst according to (1), wherein the fluorene compound represented by the formula (I) is 9,9-bis (4-hydroxyphenyl) fluorene,
(3) The epoxy resin according to (1) or (2), containing 0.01 mol or more of the fluorene compound represented by the formula (I) with respect to 1 mol of the imidazole compound represented by the formula (II). Curing catalyst,
(4) Composition for forming an epoxy cured resin containing the following component (A), component (B), and component (C) (A) epoxy resin;
(B) Formula (I)
(In the formula, each X 1 independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or Represents a cyano group.
m represents any integer from 0 to 4, and n represents any integer from 0 to 4.
X 2 each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or a cyano group. .
p represents any integer from 0 to 4, and q represents any integer from 0 to 4. Fluorene compound represented by:
(C) Formula (II)
(Wherein R 1 represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, or an unsubstituted or substituted C6-10 aryl group.
R 2 to R 4 each independently represents a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, a nitro group, or a cyano group. To express. Imidazole compound represented by
(5) The fluorene compound represented by the formula (I) as the component (B) is contained in an amount of 0.01 mol or more per 1 mol of the imidazole compound represented by the formula (II) as the component (C) ( 4) The composition for epoxy cured resin formation as described in 4),
(6) 0.01 to 1.0 mol of the imidazole compound represented by the formula (II) as the component (C) is contained per 1 mol of the epoxy ring of the epoxy resin as the component (A) (4) Or the composition for epoxy cured resin formation as described in (5),
(7) The epoxy curable resin according to any one of (4) to (6), wherein the fluorene compound represented by formula (I) as component (B) is 9,9-bis (4-hydroxyphenyl) fluorene Forming composition,
(8) A method for producing an epoxy cured resin by heat-treating the composition for forming an epoxy cured resin according to any one of (4) to (7), and (9) (4) to (7) The epoxy cured resin obtained by heat-processing and hardening the composition for epoxy cured resin formation of any one of these.
（１）式（Ｉ）
ｍは０～４のいずれかの整数を表し、ｎは０～４のいずれかの整数を表す。
Ｘ２は、それぞれ独立に、ハロゲノ基、無置換若しくは置換基を有するＣ１～６アルキル基、水酸基、無置換若しくは置換基を有するＣ１～６アルコキシ基、アミノ基、ニトロ基、又はシアノ基を表す。
ｐは０～４のいずれかの整数を表し、ｑは０～４のいずれかの整数を表す。）で表されるフルオレン化合物と、
式（II）
Ｒ２～Ｒ４は、それぞれ独立に、水素原子、ハロゲノ基、無置換若しくは置換基を有するＣ１～６アルキル基、無置換若しくは置換基を有するＣ６～１０アリール基、ニトロ基、又はシアノ基を表す。）で表されるイミダゾール化合物を含有するエポキシ樹脂用硬化触媒、
（２）式（Ｉ）で表されるフルオレン化合物が、９,９－ビス（４－ヒドロキシフェニル）フルオレンである（１）に記載のエポキシ樹脂用硬化触媒、
（３）式（II）で表されるイミダゾール化合物１モルに対して、式（Ｉ）で表されるフルオレン化合物を０．０１モル以上含有する（１）又は（２）に記載のエポキシ樹脂用硬化触媒、
（４）下記（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分を含有するエポキシ硬化樹脂形成用組成物
（Ａ）エポキシ樹脂；
（Ｂ）式（Ｉ）
ｍは０～４のいずれかの整数を表し、ｎは０～４のいずれかの整数を表す。
Ｘ２は、それぞれ独立に、ハロゲノ基、無置換若しくは置換基を有するＣ１～６アルキル基、水酸基、無置換若しくは置換基を有するＣ１～６アルコキシ基、アミノ基、ニトロ基、又はシアノ基を表す。
ｐは０～４のいずれかの整数を表し、ｑは０～４のいずれかの整数を表す。）で表されるフルオレン化合物；
（Ｃ）式（II）
Ｒ２～Ｒ４は、それぞれ独立に、水素原子、ハロゲノ基、無置換若しくは置換基を有するＣ１～６アルキル基、無置換若しくは置換基を有するＣ６～１０アリール基、ニトロ基、又はシアノ基を表す。）で表されるイミダゾール化合物、
（５）（Ｃ）成分である式（II）で表されるイミダゾール化合物１モルに対して、（Ｂ）成分である式（Ｉ）で表されるフルオレン化合物を０．０１モル以上含有する（４）に記載のエポキシ硬化樹脂形成用組成物、
（６）（Ａ）成分であるエポキシ樹脂のエポキシ環１モルに対して、（Ｃ）成分である式（II）で表されるイミダゾール化合物を０．０１～１．０モル含有する（４）又は（５）に記載のエポキシ硬化樹脂形成用組成物、
（７）（Ｂ）成分である式（Ｉ）で表されるフルオレン化合物が、９,９－ビス（４－ヒドロキシフェニル）フルオレンである（４）～（６）のいずれか記載のエポキシ硬化樹脂形成用組成物、
（８）（４）～（７）のいずれか記載のエポキシ硬化樹脂形成用組成物を加熱処理して硬化して、エポキシ硬化樹脂を製造する方法、及び
（９）（４）～（７）のいずれか記載のエポキシ硬化樹脂形成用組成物を加熱処理して硬化して得られたエポキシ硬化樹脂に関する。 That is, the present invention
(1) Formula (I)
m represents any integer from 0 to 4, and n represents any integer from 0 to 4.
X 2 each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or a cyano group. .
p represents any integer from 0 to 4, and q represents any integer from 0 to 4. Fluorene compound represented by
Formula (II)
R 2 to R 4 each independently represents a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, a nitro group, or a cyano group. To express. A curing catalyst for epoxy resins containing an imidazole compound represented by:
(2) The epoxy resin curing catalyst according to (1), wherein the fluorene compound represented by the formula (I) is 9,9-bis (4-hydroxyphenyl) fluorene,
(3) The epoxy resin according to (1) or (2), containing 0.01 mol or more of the fluorene compound represented by the formula (I) with respect to 1 mol of the imidazole compound represented by the formula (II). Curing catalyst,
(4) Composition for forming an epoxy cured resin containing the following component (A), component (B), and component (C) (A) epoxy resin;
(B) Formula (I)
m represents any integer from 0 to 4, and n represents any integer from 0 to 4.
X 2 each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or a cyano group. .
p represents any integer from 0 to 4, and q represents any integer from 0 to 4. Fluorene compound represented by:
(C) Formula (II)
R 2 to R 4 each independently represents a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, a nitro group, or a cyano group. To express. Imidazole compound represented by
(5) The fluorene compound represented by the formula (I) as the component (B) is contained in an amount of 0.01 mol or more per 1 mol of the imidazole compound represented by the formula (II) as the component (C) ( 4) The composition for epoxy cured resin formation as described in 4),
(6) 0.01 to 1.0 mol of the imidazole compound represented by the formula (II) as the component (C) is contained per 1 mol of the epoxy ring of the epoxy resin as the component (A) (4) Or the composition for epoxy cured resin formation as described in (5),
(7) The epoxy curable resin according to any one of (4) to (6), wherein the fluorene compound represented by formula (I) as component (B) is 9,9-bis (4-hydroxyphenyl) fluorene Forming composition,
(8) A method for producing an epoxy cured resin by heat-treating the composition for forming an epoxy cured resin according to any one of (4) to (7), and (9) (4) to (7) The epoxy cured resin obtained by heat-processing and hardening the composition for epoxy cured resin formation of any one of these.
本発明の硬化触媒によれば、低温での硬化反応を抑制して、一液安定性の向上を図ると共に、加熱処理を施すことにより、効果的に樹脂を硬化させることができる。
According to the curing catalyst of the present invention, the resin can be effectively cured by suppressing the curing reaction at a low temperature and improving the one-component stability and performing the heat treatment.
〔フルオレン化合物〕
式（Ｉ）で表されるフルオレン化合物について説明する。まず、本発明において、「無置換の」の用語は、母核となる基のみであることを意味する。「置換基を有する」との記載がなく母核となる基の名称のみで記載しているときは、別段の断りがない限り「無置換の」の意味である。
一方、「置換基を有する」の用語は、母核となる基のいずれかの水素原子が、母核と同一または異なる構造の基で置換されていることを意味する。従って、「置換基」は、母核となる基に結合した他の基である。置換基は１つであってもよいし、２つ以上であってもよい。２つ以上の置換基は同一であってもよいし、異なるものであってもよい。
「Ｃ１～６」などの用語は、母核となる基の炭素原子数が１～６個などであることを表している。この炭素原子数は、置換基の中に在る炭素原子の数を含まない。例えば、置換基としてエトキシ基を有するブチル基は、Ｃ２アルコキシＣ４アルキル基に分類する。 [Fluorene compound]
The fluorene compound represented by the formula (I) will be described. First, in the present invention, the term “unsubstituted” means only a group serving as a mother nucleus. When there is no description of “having a substituent” and only the name of the group serving as a mother nucleus is used, it means “unsubstituted” unless otherwise specified.
On the other hand, the term “having a substituent” means that any hydrogen atom of a group serving as a mother nucleus is substituted with a group having the same or different structure from the mother nucleus. Accordingly, the “substituent” is another group bonded to a group serving as a mother nucleus. The number of substituents may be one, or two or more. Two or more substituents may be the same or different.
Terms such as “C1-6” indicate that the group serving as the mother nucleus has 1 to 6 carbon atoms. This number of carbon atoms does not include the number of carbon atoms present in the substituent. For example, a butyl group having an ethoxy group as a substituent is classified as a C2 alkoxy C4 alkyl group.
式（Ｉ）で表されるフルオレン化合物について説明する。まず、本発明において、「無置換の」の用語は、母核となる基のみであることを意味する。「置換基を有する」との記載がなく母核となる基の名称のみで記載しているときは、別段の断りがない限り「無置換の」の意味である。
一方、「置換基を有する」の用語は、母核となる基のいずれかの水素原子が、母核と同一または異なる構造の基で置換されていることを意味する。従って、「置換基」は、母核となる基に結合した他の基である。置換基は１つであってもよいし、２つ以上であってもよい。２つ以上の置換基は同一であってもよいし、異なるものであってもよい。
「Ｃ１～６」などの用語は、母核となる基の炭素原子数が１～６個などであることを表している。この炭素原子数は、置換基の中に在る炭素原子の数を含まない。例えば、置換基としてエトキシ基を有するブチル基は、Ｃ２アルコキシＣ４アルキル基に分類する。 [Fluorene compound]
The fluorene compound represented by the formula (I) will be described. First, in the present invention, the term “unsubstituted” means only a group serving as a mother nucleus. When there is no description of “having a substituent” and only the name of the group serving as a mother nucleus is used, it means “unsubstituted” unless otherwise specified.
On the other hand, the term “having a substituent” means that any hydrogen atom of a group serving as a mother nucleus is substituted with a group having the same or different structure from the mother nucleus. Accordingly, the “substituent” is another group bonded to a group serving as a mother nucleus. The number of substituents may be one, or two or more. Two or more substituents may be the same or different.
Terms such as “C1-6” indicate that the group serving as the mother nucleus has 1 to 6 carbon atoms. This number of carbon atoms does not include the number of carbon atoms present in the substituent. For example, a butyl group having an ethoxy group as a substituent is classified as a C2 alkoxy C4 alkyl group.
「置換基」は化学的に許容され、本発明の効果を有する限りにおいて特に制限されない。以下に「置換基」となり得る基を例示する。
フルオロ基、クロロ基、ブロモ基、イオド基などのハロゲノ基；
メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｓ－ブチル基、ｉ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基などのＣ１～６アルキル基；
ビニル基、１－プロペニル基、２－プロペニル基（アリル基）、１－ブテニル基、２－ブテニル基、３－ブテニル基、１－メチル－２－プロペニル基、２－メチル－２－プロペニル基などのＣ２～６アルケニル基；
エチニル基、１－プロピニル基、２－プロピニル基、１－ブチニル基、２－ブチニル基、３－ブチニル基、１－メチル－２－プロピニル基などのＣ２～６アルキニル基；
シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基などのＣ３～８シクロアルキル基；
フェニル基、ナフチル基などのＣ６～１０アリール基；
ベンジル基、フェネチル基などのＣ６～１０アリールＣ１～６アルキル基；
３～６員ヘテロシクリル基；
３～６員へテロシクリルＣ１～６アルキル基； The “substituent” is not particularly limited as long as it is chemically acceptable and has the effects of the present invention. Examples of groups that can be “substituents” are shown below.
Halogeno groups such as fluoro, chloro, bromo and iodo groups;
C1-6 such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc. An alkyl group;
Vinyl group, 1-propenyl group, 2-propenyl group (allyl group), 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, etc. A C2-6 alkenyl group of
C2-6 alkynyl groups such as ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group;
A C3-8 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group;
A C6-10 aryl group such as a phenyl group or a naphthyl group;
A C6-10 aryl C1-6 alkyl group such as a benzyl group or a phenethyl group;
3-6 membered heterocyclyl group;
A 3-6 membered heterocyclyl C1-6 alkyl group;
フルオロ基、クロロ基、ブロモ基、イオド基などのハロゲノ基；
メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｓ－ブチル基、ｉ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基などのＣ１～６アルキル基；
ビニル基、１－プロペニル基、２－プロペニル基（アリル基）、１－ブテニル基、２－ブテニル基、３－ブテニル基、１－メチル－２－プロペニル基、２－メチル－２－プロペニル基などのＣ２～６アルケニル基；
エチニル基、１－プロピニル基、２－プロピニル基、１－ブチニル基、２－ブチニル基、３－ブチニル基、１－メチル－２－プロピニル基などのＣ２～６アルキニル基；
シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基などのＣ３～８シクロアルキル基；
フェニル基、ナフチル基などのＣ６～１０アリール基；
ベンジル基、フェネチル基などのＣ６～１０アリールＣ１～６アルキル基；
３～６員ヘテロシクリル基；
３～６員へテロシクリルＣ１～６アルキル基； The “substituent” is not particularly limited as long as it is chemically acceptable and has the effects of the present invention. Examples of groups that can be “substituents” are shown below.
Halogeno groups such as fluoro, chloro, bromo and iodo groups;
C1-6 such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc. An alkyl group;
Vinyl group, 1-propenyl group, 2-propenyl group (allyl group), 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, etc. A C2-6 alkenyl group of
C2-6 alkynyl groups such as ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group;
A C3-8 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group;
A C6-10 aryl group such as a phenyl group or a naphthyl group;
A C6-10 aryl C1-6 alkyl group such as a benzyl group or a phenethyl group;
3-6 membered heterocyclyl group;
A 3-6 membered heterocyclyl C1-6 alkyl group;
水酸基；
メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉ－プロポキシ基、ｎ－ブトキシ基、ｓ－ブトキシ基、ｉ－ブトキシ基、ｔ－ブトキシ基などのＣ１～６アルコキシ基；
ビニルオキシ基、アリルオキシ基、プロペニルオキシ基、ブテニルオキシ基などのＣ２～６アルケニルオキシ基；
フェノキシ基、ナフトキシ基などのＣ６～１０アリールオキシ基；
ベンジルオキシ基、フェネチルオキシ基などのＣ６～１０アリールＣ１～６アルコキシ基；
３～６員ヘテロシクリルオキシ基；
３～６員へテロシクリルＣ１～６アルコキシ基；
クロロメチル基、クロロエチル基、トリフルオロメチル基、１，２－ジクロロ－ｎ－プロピル基、１－フルオロ－ｎ－ブチル基、パーフルオロ－ｎ－ペンチル基などのＣ１～６ハロアルキル基；
トリフルオロメトキシ基、２－クロロ－ｎ－プロポキシ基、２，３－ジクロロブトキシ基などのＣ１～６ハロアルコキシ基； Hydroxyl group;
C1-6 alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group;
C2-6 alkenyloxy groups such as vinyloxy group, allyloxy group, propenyloxy group, butenyloxy group;
C6-10 aryloxy groups such as phenoxy group and naphthoxy group;
A C6-10 aryl C1-6 alkoxy group such as a benzyloxy group or a phenethyloxy group;
A 3-6 membered heterocyclyloxy group;
A 3-6 membered heterocyclyl C1-6 alkoxy group;
C1-6 haloalkyl groups such as chloromethyl group, chloroethyl group, trifluoromethyl group, 1,2-dichloro-n-propyl group, 1-fluoro-n-butyl group, perfluoro-n-pentyl group;
A C1-6 haloalkoxy group such as a trifluoromethoxy group, 2-chloro-n-propoxy group, 2,3-dichlorobutoxy group;
メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉ－プロポキシ基、ｎ－ブトキシ基、ｓ－ブトキシ基、ｉ－ブトキシ基、ｔ－ブトキシ基などのＣ１～６アルコキシ基；
ビニルオキシ基、アリルオキシ基、プロペニルオキシ基、ブテニルオキシ基などのＣ２～６アルケニルオキシ基；
フェノキシ基、ナフトキシ基などのＣ６～１０アリールオキシ基；
ベンジルオキシ基、フェネチルオキシ基などのＣ６～１０アリールＣ１～６アルコキシ基；
３～６員ヘテロシクリルオキシ基；
３～６員へテロシクリルＣ１～６アルコキシ基；
クロロメチル基、クロロエチル基、トリフルオロメチル基、１，２－ジクロロ－ｎ－プロピル基、１－フルオロ－ｎ－ブチル基、パーフルオロ－ｎ－ペンチル基などのＣ１～６ハロアルキル基；
トリフルオロメトキシ基、２－クロロ－ｎ－プロポキシ基、２，３－ジクロロブトキシ基などのＣ１～６ハロアルコキシ基； Hydroxyl group;
C1-6 alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group;
C2-6 alkenyloxy groups such as vinyloxy group, allyloxy group, propenyloxy group, butenyloxy group;
C6-10 aryloxy groups such as phenoxy group and naphthoxy group;
A C6-10 aryl C1-6 alkoxy group such as a benzyloxy group or a phenethyloxy group;
A 3-6 membered heterocyclyloxy group;
A 3-6 membered heterocyclyl C1-6 alkoxy group;
C1-6 haloalkyl groups such as chloromethyl group, chloroethyl group, trifluoromethyl group, 1,2-dichloro-n-propyl group, 1-fluoro-n-butyl group, perfluoro-n-pentyl group;
A C1-6 haloalkoxy group such as a trifluoromethoxy group, 2-chloro-n-propoxy group, 2,3-dichlorobutoxy group;
アミノ基；
メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基などのＣ１～６アルキルアミノ基；
アニリノ基、ナフチルアミノ基などのＣ６～１０アリールアミノ基；
ベンジルアミノ基、フェネチルアミノ基などのＣ６～１０アリールＣ１～６アルキルアミノ基；
メルカプト基；
メチルチオ基、エチルチオ基、ｎ－プロピルチオ基、ｉ－プロピルチオ基、ｎ－ブチルチオ基、ｉ－ブチルチオ基、ｓ－ブチルチオ基、ｔ－ブチルチオ基などのＣ１～６アルキルチオ基；
メチルスルホニル基、エチルスルホニル基、ｔ－ブチルスルホニル基などのＣ１～６アルキルスルホニル基；
フェニルチオ基、ナフチルチオ基などのＣ６～１０アリールチオ基；
３～６員へテロシクリルチオ基；
フェニルスルホニル基などのＣ６～１０アリールスルホニル基；
３～６員へテロシクリルスルホニル基；
シアノ基；
ニトロ基。
また、これらの「置換基」は、当該置換基中のいずれかの水素原子が、異なる構造の基で置換されていてもよい。その場合の「置換基」としては、ハロゲノ基、Ｃ１～６アルキル基、Ｃ１～６ハロアルキル基、Ｃ１～６アルコキシ基、Ｃ１～６ハロアルコキシ基、シアノ基、ニトロ基などを挙げることができる。 An amino group;
A C1-6 alkylamino group such as a methylamino group, a dimethylamino group, a diethylamino group;
C6-10 arylamino groups such as anilino group and naphthylamino group;
A C6-10 aryl C1-6 alkylamino group such as a benzylamino group or a phenethylamino group;
A mercapto group;
C1-6 alkylthio groups such as methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, t-butylthio group;
A C1-6 alkylsulfonyl group such as a methylsulfonyl group, an ethylsulfonyl group, a t-butylsulfonyl group;
A C6-10 arylthio group such as a phenylthio group or a naphthylthio group;
A 3-6 membered heterocyclylthio group;
A C6-10 arylsulfonyl group such as a phenylsulfonyl group;
A 3-6 membered heterocyclylsulfonyl group;
A cyano group;
Nitro group.
In these “substituents”, any hydrogen atom in the substituent may be substituted with a group having a different structure. In this case, examples of the “substituent” include a halogeno group, a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, a C1-6 haloalkoxy group, a cyano group, and a nitro group.
メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基などのＣ１～６アルキルアミノ基；
アニリノ基、ナフチルアミノ基などのＣ６～１０アリールアミノ基；
ベンジルアミノ基、フェネチルアミノ基などのＣ６～１０アリールＣ１～６アルキルアミノ基；
メルカプト基；
メチルチオ基、エチルチオ基、ｎ－プロピルチオ基、ｉ－プロピルチオ基、ｎ－ブチルチオ基、ｉ－ブチルチオ基、ｓ－ブチルチオ基、ｔ－ブチルチオ基などのＣ１～６アルキルチオ基；
メチルスルホニル基、エチルスルホニル基、ｔ－ブチルスルホニル基などのＣ１～６アルキルスルホニル基；
フェニルチオ基、ナフチルチオ基などのＣ６～１０アリールチオ基；
３～６員へテロシクリルチオ基；
フェニルスルホニル基などのＣ６～１０アリールスルホニル基；
３～６員へテロシクリルスルホニル基；
シアノ基；
ニトロ基。
また、これらの「置換基」は、当該置換基中のいずれかの水素原子が、異なる構造の基で置換されていてもよい。その場合の「置換基」としては、ハロゲノ基、Ｃ１～６アルキル基、Ｃ１～６ハロアルキル基、Ｃ１～６アルコキシ基、Ｃ１～６ハロアルコキシ基、シアノ基、ニトロ基などを挙げることができる。 An amino group;
A C1-6 alkylamino group such as a methylamino group, a dimethylamino group, a diethylamino group;
C6-10 arylamino groups such as anilino group and naphthylamino group;
A C6-10 aryl C1-6 alkylamino group such as a benzylamino group or a phenethylamino group;
A mercapto group;
C1-6 alkylthio groups such as methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, t-butylthio group;
A C1-6 alkylsulfonyl group such as a methylsulfonyl group, an ethylsulfonyl group, a t-butylsulfonyl group;
A C6-10 arylthio group such as a phenylthio group or a naphthylthio group;
A 3-6 membered heterocyclylthio group;
A C6-10 arylsulfonyl group such as a phenylsulfonyl group;
A 3-6 membered heterocyclylsulfonyl group;
A cyano group;
Nitro group.
In these “substituents”, any hydrogen atom in the substituent may be substituted with a group having a different structure. In this case, examples of the “substituent” include a halogeno group, a C1-6 alkyl group, a C1-6 haloalkyl group, a C1-6 alkoxy group, a C1-6 haloalkoxy group, a cyano group, and a nitro group.
また、上記の「３～６員ヘテロシクリル基」とは、窒素原子、酸素原子および硫黄原子からなる群から選ばれる１～４個のヘテロ原子を環の構成原子として含む環状の基である。「３～６員ヘテロシクリル基」としては、３～６員飽和ヘテロシクリル基、５～６員ヘテロアリール基、５～６員部分不飽和ヘテロシクリル基などを挙げることができる。
In addition, the “3- to 6-membered heterocyclyl group” is a cyclic group containing 1 to 4 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom as constituent atoms of the ring. Examples of the “3- to 6-membered heterocyclyl group” include a 3- to 6-membered saturated heterocyclyl group, a 5- to 6-membered heteroaryl group, and a 5- to 6-membered partially unsaturated heterocyclyl group.
３～６員飽和ヘテロシクリル基としては、アジリジニル基、エポキシ基、ピロリジニル基、テトラヒドロフラニル基、チアゾリジニル基、ピペリジル基、ピペラジニル基、モルホリニル基、ジオキソラニル基、ジオキサニル基などを挙げることができる。
５員ヘテロアリール基としては、ピロリル基、フリル基、チエニル基、イミダゾリル基、ピラゾリル基、オキサゾリル基、イソオキサゾリル基、チアゾリル基、イソチアゾリル基、トリアゾリル基、オキサジアゾリル基、チアジアゾリル基、テトラゾリル基などを挙げることができる。
６員ヘテロアリール基としては、ピリジル基、ピラジニル基、ピリミジニル基、ピリダジニル基、トリアジニル基などを挙げることができる。
５員部分不飽和へテロシクリル基としては、ピロリニル基、ジヒドロフラニル基、イミダゾリニル基、ピラゾリニル基、オキサゾリニル基などを挙げることができる。
６員部分不飽和ヘテロシクリル基としては、イソオキサゾリニル基、ジヒドロピラニル基などを挙げることができる。 Examples of the 3- to 6-membered saturated heterocyclyl group include aziridinyl group, epoxy group, pyrrolidinyl group, tetrahydrofuranyl group, thiazolidinyl group, piperidyl group, piperazinyl group, morpholinyl group, dioxolanyl group, dioxanyl group and the like.
Examples of 5-membered heteroaryl groups include pyrrolyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl Can do.
Examples of the 6-membered heteroaryl group include a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, and a triazinyl group.
Examples of the 5-membered partially unsaturated heterocyclyl group include a pyrrolinyl group, a dihydrofuranyl group, an imidazolinyl group, a pyrazolinyl group, and an oxazolinyl group.
Examples of the 6-membered partially unsaturated heterocyclyl group include an isoxazolinyl group and a dihydropyranyl group.
５員ヘテロアリール基としては、ピロリル基、フリル基、チエニル基、イミダゾリル基、ピラゾリル基、オキサゾリル基、イソオキサゾリル基、チアゾリル基、イソチアゾリル基、トリアゾリル基、オキサジアゾリル基、チアジアゾリル基、テトラゾリル基などを挙げることができる。
６員ヘテロアリール基としては、ピリジル基、ピラジニル基、ピリミジニル基、ピリダジニル基、トリアジニル基などを挙げることができる。
５員部分不飽和へテロシクリル基としては、ピロリニル基、ジヒドロフラニル基、イミダゾリニル基、ピラゾリニル基、オキサゾリニル基などを挙げることができる。
６員部分不飽和ヘテロシクリル基としては、イソオキサゾリニル基、ジヒドロピラニル基などを挙げることができる。 Examples of the 3- to 6-membered saturated heterocyclyl group include aziridinyl group, epoxy group, pyrrolidinyl group, tetrahydrofuranyl group, thiazolidinyl group, piperidyl group, piperazinyl group, morpholinyl group, dioxolanyl group, dioxanyl group and the like.
Examples of 5-membered heteroaryl groups include pyrrolyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl Can do.
Examples of the 6-membered heteroaryl group include a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, and a triazinyl group.
Examples of the 5-membered partially unsaturated heterocyclyl group include a pyrrolinyl group, a dihydrofuranyl group, an imidazolinyl group, a pyrazolinyl group, and an oxazolinyl group.
Examples of the 6-membered partially unsaturated heterocyclyl group include an isoxazolinyl group and a dihydropyranyl group.
〔Ｘ１、Ｘ２〕
式（Ｉ）中、Ｘ１は、それぞれ独立に、ハロゲノ基、無置換若しくは置換基を有するＣ１～６アルキル基、水酸基、無置換若しくは置換基を有するＣ１～６アルコキシ基、アミノ基、ニトロ基、又はシアノ基を表す。ｍは０～４のいずれかの整数を表し、ｎは０～４のいずれかの整数を表す。
Ｘ２は、それぞれ独立に、ハロゲノ基、無置換若しくは置換基を有するＣ１～６アルキル基、水酸基、無置換若しくは置換基を有するＣ１～６アルコキシ基、アミノ基、ニトロ基、又はシアノ基を表す。ｐは０～４のいずれかの整数を表し、ｑは０～４のいずれかの整数を表す。 [X 1 , X 2 ]
In formula (I), each X 1 independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, or a nitro group. Or a cyano group. m represents any integer from 0 to 4, and n represents any integer from 0 to 4.
X 2 each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or a cyano group. . p represents any integer from 0 to 4, and q represents any integer from 0 to 4.
式（Ｉ）中、Ｘ１は、それぞれ独立に、ハロゲノ基、無置換若しくは置換基を有するＣ１～６アルキル基、水酸基、無置換若しくは置換基を有するＣ１～６アルコキシ基、アミノ基、ニトロ基、又はシアノ基を表す。ｍは０～４のいずれかの整数を表し、ｎは０～４のいずれかの整数を表す。
Ｘ２は、それぞれ独立に、ハロゲノ基、無置換若しくは置換基を有するＣ１～６アルキル基、水酸基、無置換若しくは置換基を有するＣ１～６アルコキシ基、アミノ基、ニトロ基、又はシアノ基を表す。ｐは０～４のいずれかの整数を表し、ｑは０～４のいずれかの整数を表す。 [X 1 , X 2 ]
In formula (I), each X 1 independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, or a nitro group. Or a cyano group. m represents any integer from 0 to 4, and n represents any integer from 0 to 4.
X 2 each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or a cyano group. . p represents any integer from 0 to 4, and q represents any integer from 0 to 4.
Ｘ１及びＸ２における、「ハロゲノ基」としては、フルオロ基、クロロ基、ブロモ基、イオド基などを挙げることができる。
Examples of the “halogeno group” in X 1 and X 2 include a fluoro group, a chloro group, a bromo group, and an iodo group.
Ｘ１及びＸ２における、「Ｃ１～６アルキル基」は、直鎖であってもよいし、分岐鎖であってもよい。Ｃ１～６アルキル基としては、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｉ－プロピル基、ｉ－ブチル基、ｓ－ブチル基、ｔ－ブチル基、ｉ－ペンチル基、ネオペンチル基、２－メチルブチル基、２，２－ジメチルプロピル基、ｉ－ヘキシル基などを挙げることができる。
「Ｃ１～６アルキル基」上の置換基としては、ハロゲノ基、水酸基、Ｃ１～６アルコキシ基、Ｃ３～８シクロアルキル基、Ｃ６～１０アリール基、又はシアノ基が好ましい。 The “C1-6 alkyl group” in X 1 and X 2 may be linear or branched. Examples of the C1-6 alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, i-propyl group, i-butyl group, s-butyl group, t -Butyl group, i-pentyl group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, i-hexyl group and the like can be mentioned.
The substituent on the “C1-6 alkyl group” is preferably a halogeno group, a hydroxyl group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, a C6-10 aryl group, or a cyano group.
「Ｃ１～６アルキル基」上の置換基としては、ハロゲノ基、水酸基、Ｃ１～６アルコキシ基、Ｃ３～８シクロアルキル基、Ｃ６～１０アリール基、又はシアノ基が好ましい。 The “C1-6 alkyl group” in X 1 and X 2 may be linear or branched. Examples of the C1-6 alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, i-propyl group, i-butyl group, s-butyl group, t -Butyl group, i-pentyl group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, i-hexyl group and the like can be mentioned.
The substituent on the “C1-6 alkyl group” is preferably a halogeno group, a hydroxyl group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, a C6-10 aryl group, or a cyano group.
「置換基を有するＣ１～６アルキル基」としては、具体的には、
フルオロメチル基、クロロメチル基、ブロモメチル基、ジフルオロメチル基、ジクロロメチル基、ジブロモメチル基、トリフルオロメチル基、トリクロロメチル基、トリブロモメチル基、２，２，２－トリフルオロエチル基、２，２，２－トリクロロエチル基、ペンタフルオロエチル基、４－フルオロブチル基、４－クロロブチル基、３，３，３－トリフルオロプロピル基、２，２，２－トリフルオロ－１－トリフルオロメチルエチル基、パーフロロヘキシル基、パークロロヘキシル基、２，４，６－トリクロロヘキシル基などのＣ１～６ハロアルキル基；
ヒドロキシメチル基、２－ヒドロキシエチル基などのヒドロキシＣ１～６アルキル基；
メトキシメチル基、エトキシメチル基、メトキシエチル基、エトキシエチル基、メトキシ－ｎ－プロピル基、エトキシメチル基、エトキシエチル基、ｎ－プロポキシメチル基、ｉ－プロポキシエチル基、ｓ－ブトキシメチル基、ｔ－ブトキシエチル基などのＣ１～６アルコキシＣ１～６アルキル基；
シクロプロピルメチル基、２－シクロプロピルエチル基、シクロペンチルメチル基、２－シクロヘキシルエチル基、２－シクロオクチルエチル基などのＣ３～８シクロアルキルＣ１～６アルキル基；
ベンジル基、フェネチル基などのＣ７～１１アラルキル基；
シアノメチル基、シアノエチル基などのシアノＣ１～６アルキル基；
などを挙げることができる。 As the “C1-6 alkyl group having a substituent”, specifically,
Fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, 2,2,2-trifluoroethyl group, 2, 2,2-trichloroethyl group, pentafluoroethyl group, 4-fluorobutyl group, 4-chlorobutyl group, 3,3,3-trifluoropropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl A C1-6 haloalkyl group such as a group, perfluorohexyl group, perchlorohexyl group, 2,4,6-trichlorohexyl group;
Hydroxy C1-6 alkyl groups such as hydroxymethyl group, 2-hydroxyethyl group;
Methoxymethyl group, ethoxymethyl group, methoxyethyl group, ethoxyethyl group, methoxy-n-propyl group, ethoxymethyl group, ethoxyethyl group, n-propoxymethyl group, i-propoxyethyl group, s-butoxymethyl group, t A C1-6 alkoxy C1-6 alkyl group such as a butoxyethyl group;
C3-8 cycloalkyl C1-6 alkyl groups such as cyclopropylmethyl group, 2-cyclopropylethyl group, cyclopentylmethyl group, 2-cyclohexylethyl group, 2-cyclooctylethyl group;
A C7-11 aralkyl group such as a benzyl group or a phenethyl group;
A cyano C1-6 alkyl group such as a cyanomethyl group and a cyanoethyl group;
And so on.
フルオロメチル基、クロロメチル基、ブロモメチル基、ジフルオロメチル基、ジクロロメチル基、ジブロモメチル基、トリフルオロメチル基、トリクロロメチル基、トリブロモメチル基、２，２，２－トリフルオロエチル基、２，２，２－トリクロロエチル基、ペンタフルオロエチル基、４－フルオロブチル基、４－クロロブチル基、３，３，３－トリフルオロプロピル基、２，２，２－トリフルオロ－１－トリフルオロメチルエチル基、パーフロロヘキシル基、パークロロヘキシル基、２，４，６－トリクロロヘキシル基などのＣ１～６ハロアルキル基；
ヒドロキシメチル基、２－ヒドロキシエチル基などのヒドロキシＣ１～６アルキル基；
メトキシメチル基、エトキシメチル基、メトキシエチル基、エトキシエチル基、メトキシ－ｎ－プロピル基、エトキシメチル基、エトキシエチル基、ｎ－プロポキシメチル基、ｉ－プロポキシエチル基、ｓ－ブトキシメチル基、ｔ－ブトキシエチル基などのＣ１～６アルコキシＣ１～６アルキル基；
シクロプロピルメチル基、２－シクロプロピルエチル基、シクロペンチルメチル基、２－シクロヘキシルエチル基、２－シクロオクチルエチル基などのＣ３～８シクロアルキルＣ１～６アルキル基；
ベンジル基、フェネチル基などのＣ７～１１アラルキル基；
シアノメチル基、シアノエチル基などのシアノＣ１～６アルキル基；
などを挙げることができる。 As the “C1-6 alkyl group having a substituent”, specifically,
Fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, 2,2,2-trifluoroethyl group, 2, 2,2-trichloroethyl group, pentafluoroethyl group, 4-fluorobutyl group, 4-chlorobutyl group, 3,3,3-trifluoropropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl A C1-6 haloalkyl group such as a group, perfluorohexyl group, perchlorohexyl group, 2,4,6-trichlorohexyl group;
Hydroxy C1-6 alkyl groups such as hydroxymethyl group, 2-hydroxyethyl group;
Methoxymethyl group, ethoxymethyl group, methoxyethyl group, ethoxyethyl group, methoxy-n-propyl group, ethoxymethyl group, ethoxyethyl group, n-propoxymethyl group, i-propoxyethyl group, s-butoxymethyl group, t A C1-6 alkoxy C1-6 alkyl group such as a butoxyethyl group;
C3-8 cycloalkyl C1-6 alkyl groups such as cyclopropylmethyl group, 2-cyclopropylethyl group, cyclopentylmethyl group, 2-cyclohexylethyl group, 2-cyclooctylethyl group;
A C7-11 aralkyl group such as a benzyl group or a phenethyl group;
A cyano C1-6 alkyl group such as a cyanomethyl group and a cyanoethyl group;
And so on.
Ｘ１及びＸ２における、「Ｃ１～６アルコキシ基」としては、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｎ－ブトキシ基、ｎ－ペンチルオキシ基、ｎ－ヘキシルオキシ基、ｉ－プロポキシ基、ｉ－ブトキシ基、ｓ－ブトキシ基、ｔ－ブトキシ基、ｉ－ヘキシルオキシ基などを挙げることができる。
「Ｃ１～６アルコキシ基」上の置換基としては、ハロゲノ基、Ｃ１～６アルコキシ基、Ｃ３～８シクロアルキル基、又はＣ６～１０アリール基が好ましい。 As the “C1-6 alkoxy group” in X 1 and X 2 , a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, an i-propoxy group, Examples include i-butoxy group, s-butoxy group, t-butoxy group, i-hexyloxy group and the like.
The substituent on the “C1-6 alkoxy group” is preferably a halogeno group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, or a C6-10 aryl group.
「Ｃ１～６アルコキシ基」上の置換基としては、ハロゲノ基、Ｃ１～６アルコキシ基、Ｃ３～８シクロアルキル基、又はＣ６～１０アリール基が好ましい。 As the “C1-6 alkoxy group” in X 1 and X 2 , a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, an i-propoxy group, Examples include i-butoxy group, s-butoxy group, t-butoxy group, i-hexyloxy group and the like.
The substituent on the “C1-6 alkoxy group” is preferably a halogeno group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, or a C6-10 aryl group.
「置換基を有するＣ１～６アルコキシ基」としては、具体的には、クロロメトキシ基、ジクロロメトキシ基、ジフルオロメトキシ基、トリクロロメトキシ基、トリフルオロメトキシ基、１－フルオロエトキシ基、１，１－ジフルオロエトキシ基、２，２，２－トリフルオロエトキシ基、ペンタフルオロエトキシ基などのＣ１～６ハロアルコキシ基などを挙げることができる。
Specific examples of the “substituted C1-6 alkoxy group” include chloromethoxy group, dichloromethoxy group, difluoromethoxy group, trichloromethoxy group, trifluoromethoxy group, 1-fluoroethoxy group, 1,1- Examples thereof include C1-6 haloalkoxy groups such as difluoroethoxy group, 2,2,2-trifluoroethoxy group, and pentafluoroethoxy group.
式（Ｉ）で表されるフルオレン化合物としては、具体的には、９,９－ビス（４－ヒドロキシフェニル）フルオレン<9,9-Bis(4-hydroxyphenyl)fluorene>、９,９－ビス（４－ヒドロキシ－３－メチルフェニル）フルオレン<9,9-Bis(4-hydroxy-3-methylphenyl)fluorene>、２，７－ジブロモ－９，９－ビス（４－ヒドロキシフェニル）フルオレン<2,7-Dibromo-9,9-bis(4-hydroxyphenyl)fluorene>、９,９－ビス（３－アミノ－４－ヒドロキシフェニル）フルオレン<9,9-Bis(3-amino-4-hydroxyphenyl)fluorene>、９,９－ビス（４－ヒドロキシ－３、５－ジメチルフェニル）フルオレン<9,9-Bis(4-hydroxy-3,5-dimethylphenyl)fluorene>、９,９－ビス（４－ヒドロキシ－２，６－ジブロモフェニル）フルオレン<9,9-Bis(4-hydroxy-2,6-dibromophenyl)fluorene>などを挙げることができる。
Specific examples of the fluorene compound represented by the formula (I) include 9,9-bis (4-hydroxyphenyl) fluorene <9,9-Bis (4-hydroxyphenyl) fluorene>, 9,9-bis ( 4-hydroxy-3-methylphenyl) fluorene <9,9-Bis (4-hydroxy-3-methylphenyl) fluorene>, 2,7-dibromo-9,9-bis (4-hydroxyphenyl) fluorene <2,7 -Dibromo-9,9-bis (4-hydroxyphenyl) fluorene>, 9,9-bis (3-amino-4-hydroxyphenyl) fluorene <9,9-Bis (3-amino-4-hydroxyphenyl) fluorene>, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene <9,9-Bis (4-hydroxy-3,5-dimethylphenyl) fluorene>, 9,9-bis (4-hydroxy-2, 6-dibromophenyl) fluorene <9,9-Bis (4-hydroxy-2,6-dibromophenyl) fluorene>.
〔イミダゾール化合物〕
次に、式（II）で表されるイミダゾール化合物について説明する。
〔Ｒ１〕
式（II）中、Ｒ１は、水素原子、無置換若しくは置換基を有するＣ１～６アルキル基、又は無置換若しくは置換基を有するＣ６～１０アリール基を表す。 [Imidazole compound]
Next, the imidazole compound represented by the formula (II) will be described.
[R 1 ]
In formula (II), R 1 represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, or an unsubstituted or substituted C6-10 aryl group.
次に、式（II）で表されるイミダゾール化合物について説明する。
〔Ｒ１〕
式（II）中、Ｒ１は、水素原子、無置換若しくは置換基を有するＣ１～６アルキル基、又は無置換若しくは置換基を有するＣ６～１０アリール基を表す。 [Imidazole compound]
Next, the imidazole compound represented by the formula (II) will be described.
[R 1 ]
In formula (II), R 1 represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, or an unsubstituted or substituted C6-10 aryl group.
Ｒ１における「Ｃ１～６アルキル基」、としては、前記Ｘ１において例示したそれらと同じものを挙げることができる。「Ｃ１～６アルキル基」上の置換基としては、ハロゲノ基、水酸基、Ｃ１～６アルコキシ基、Ｃ３～８シクロアルキル基、Ｃ６～１０アリール基、又はシアノ基が好ましい。
Examples of the “C1-6 alkyl group” for R 1 include the same groups as those exemplified for X 1 above. The substituent on the “C1-6 alkyl group” is preferably a halogeno group, a hydroxyl group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, a C6-10 aryl group, or a cyano group.
Ｒ１における「Ｃ６～１０アリール基」は、単環および多環のいずれであってもよい。多環アリール基は、少なくとも一つの環が芳香環であれば、残りの環が飽和脂環、不飽和脂環または芳香環のいずれであってもよい。
Ｒ１における「Ｃ６～１０アリール基」としては、フェニル基、ナフチル基、アズレニル基、インデニル基、インダニル基、テトラリニル基などを挙げることができる。
「Ｃ６～１０アリール基」上の置換基としては、ハロゲノ基、Ｃ１～６アルキル基、水酸基、Ｃ１～６アルコキシ基、Ｃ１～６ハロアルコキシ基、シアノ基、ニトロ基などを挙げることができる。 The “C6-10 aryl group” in R 1 may be monocyclic or polycyclic. In the polycyclic aryl group, if at least one ring is an aromatic ring, the remaining ring may be a saturated alicyclic ring, an unsaturated alicyclic ring, or an aromatic ring.
Examples of the “C6-10 aryl group” in R 1 include a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group.
Examples of the substituent on the “C6-10 aryl group” include halogeno group, C1-6 alkyl group, hydroxyl group, C1-6 alkoxy group, C1-6 haloalkoxy group, cyano group, nitro group and the like.
Ｒ１における「Ｃ６～１０アリール基」としては、フェニル基、ナフチル基、アズレニル基、インデニル基、インダニル基、テトラリニル基などを挙げることができる。
「Ｃ６～１０アリール基」上の置換基としては、ハロゲノ基、Ｃ１～６アルキル基、水酸基、Ｃ１～６アルコキシ基、Ｃ１～６ハロアルコキシ基、シアノ基、ニトロ基などを挙げることができる。 The “C6-10 aryl group” in R 1 may be monocyclic or polycyclic. In the polycyclic aryl group, if at least one ring is an aromatic ring, the remaining ring may be a saturated alicyclic ring, an unsaturated alicyclic ring, or an aromatic ring.
Examples of the “C6-10 aryl group” in R 1 include a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group.
Examples of the substituent on the “C6-10 aryl group” include halogeno group, C1-6 alkyl group, hydroxyl group, C1-6 alkoxy group, C1-6 haloalkoxy group, cyano group, nitro group and the like.
〔Ｒ２～Ｒ４〕
式（II）中、Ｒ２～Ｒ４は、それぞれ独立に、水素原子、ハロゲノ基、無置換若しくは置換基を有するＣ１～６アルキル基、無置換若しくは置換基を有するＣ６～１０アリール基、ニトロ基、又はシアノ基を表す。 [R 2 to R 4 ]
In the formula (II), R 2 to R 4 each independently represent a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, nitro Represents a group or a cyano group.
式（II）中、Ｒ２～Ｒ４は、それぞれ独立に、水素原子、ハロゲノ基、無置換若しくは置換基を有するＣ１～６アルキル基、無置換若しくは置換基を有するＣ６～１０アリール基、ニトロ基、又はシアノ基を表す。 [R 2 to R 4 ]
In the formula (II), R 2 to R 4 each independently represent a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, nitro Represents a group or a cyano group.
Ｒ２～Ｒ４における、「ハロゲノ基」、「Ｃ１～６アルキル基」、及び「Ｃ６～１０アリール基」としては、前記Ｘ１において例示したそれらと同じものを挙げることができる。
「Ｃ１～６アルキル基」上の置換基としては、ハロゲノ基、水酸基、Ｃ１～６アルコキシ基、Ｃ３～８シクロアルキル基、Ｃ６～１０アリール基、又はシアノ基が好ましい。「Ｃ６～１０アリール基」上の置換基としては、ハロゲノ基、Ｃ１～６アルキル基、水酸基、Ｃ１～６アルコキシ基、Ｃ１～６ハロアルコキシ基、シアノ基、ニトロ基などを挙げることができる。 Examples of the “halogeno group”, “C1-6 alkyl group”, and “C6-10 aryl group” in R 2 to R 4 are the same as those exemplified for X 1 above.
The substituent on the “C1-6 alkyl group” is preferably a halogeno group, a hydroxyl group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, a C6-10 aryl group, or a cyano group. Examples of the substituent on the “C6-10 aryl group” include halogeno group, C1-6 alkyl group, hydroxyl group, C1-6 alkoxy group, C1-6 haloalkoxy group, cyano group, nitro group and the like.
「Ｃ１～６アルキル基」上の置換基としては、ハロゲノ基、水酸基、Ｃ１～６アルコキシ基、Ｃ３～８シクロアルキル基、Ｃ６～１０アリール基、又はシアノ基が好ましい。「Ｃ６～１０アリール基」上の置換基としては、ハロゲノ基、Ｃ１～６アルキル基、水酸基、Ｃ１～６アルコキシ基、Ｃ１～６ハロアルコキシ基、シアノ基、ニトロ基などを挙げることができる。 Examples of the “halogeno group”, “C1-6 alkyl group”, and “C6-10 aryl group” in R 2 to R 4 are the same as those exemplified for X 1 above.
The substituent on the “C1-6 alkyl group” is preferably a halogeno group, a hydroxyl group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, a C6-10 aryl group, or a cyano group. Examples of the substituent on the “C6-10 aryl group” include halogeno group, C1-6 alkyl group, hydroxyl group, C1-6 alkoxy group, C1-6 haloalkoxy group, cyano group, nitro group and the like.
式（II）で表されるイミダゾール化合物としては、具体的には、イミダゾール、２－エチル－４－メチルイミダゾール、１－メチルイミダゾール、２－メチルイミダゾール、４－メチルイミダゾール、１－ベンジル－２－メチルイミダゾール、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、１－ベンジル－２－フェニルイミダゾール、１，２－ジメチルイミダゾール、１－シアノエチル－２－メチルイミダゾール、１－シアノエチル－２－エチル－４－メチルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、２－フェニル－４，５－ジヒドロキシメチルイミダゾールなどを挙げることができる。
Specific examples of the imidazole compound represented by the formula (II) include imidazole, 2-ethyl-4-methylimidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 1-benzyl-2- Methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl Examples include -2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and the like.
〔エポキシ樹脂硬化用触媒〕
本発明のエポキシ樹脂硬化用触媒は、式（Ｉ）で表されるフルオレン化合物と、式（II）で表されるイミダゾール化合物とを主成分とするものである。
本発明のエポキシ樹脂硬化用触媒は、ポリエステル樹脂、エポキシ樹脂、エポキシ・ポリエステル樹脂、ウレタン樹脂等の樹脂硬化剤として使用することができ、特にエポキシ樹脂の硬化剤として好適に使用することができる。 [Catalyst for curing epoxy resin]
The epoxy resin curing catalyst of the present invention comprises a fluorene compound represented by formula (I) and an imidazole compound represented by formula (II) as main components.
The epoxy resin curing catalyst of the present invention can be used as a resin curing agent such as a polyester resin, an epoxy resin, an epoxy-polyester resin, or a urethane resin, and can be particularly preferably used as a curing agent for an epoxy resin.
本発明のエポキシ樹脂硬化用触媒は、式（Ｉ）で表されるフルオレン化合物と、式（II）で表されるイミダゾール化合物とを主成分とするものである。
本発明のエポキシ樹脂硬化用触媒は、ポリエステル樹脂、エポキシ樹脂、エポキシ・ポリエステル樹脂、ウレタン樹脂等の樹脂硬化剤として使用することができ、特にエポキシ樹脂の硬化剤として好適に使用することができる。 [Catalyst for curing epoxy resin]
The epoxy resin curing catalyst of the present invention comprises a fluorene compound represented by formula (I) and an imidazole compound represented by formula (II) as main components.
The epoxy resin curing catalyst of the present invention can be used as a resin curing agent such as a polyester resin, an epoxy resin, an epoxy-polyester resin, or a urethane resin, and can be particularly preferably used as a curing agent for an epoxy resin.
本発明のエポキシ樹脂硬化用触媒における式（Ｉ）で表されるフルオレン化合物及び式（II）で表されるイミダゾール化合物の配合割合としては、式（Ｉ）で表されるフルオレン化合物１モルに対して、式（II）で表されるイミダゾール化合物が、０．０１モル以上であることが好ましい。上限は、特に存在せず、経済的理由を満たす範囲で、０．０１モル以上の比率であればよい。十分な効果が得られる範囲として好ましくは、０．１モル～１０モルである。
The blending ratio of the fluorene compound represented by the formula (I) and the imidazole compound represented by the formula (II) in the epoxy resin curing catalyst of the present invention is 1 mol of the fluorene compound represented by the formula (I). The imidazole compound represented by the formula (II) is preferably 0.01 mol or more. The upper limit is not particularly present and may be a ratio of 0.01 mol or more as long as it satisfies economic reasons. The range for obtaining a sufficient effect is preferably 0.1 to 10 mol.
〔エポキシ硬化樹脂形成用組成物〕
本発明のエポキシ硬化樹脂形成用組成物としては、エポキシ樹脂と、上記本発明の硬化触媒とを含有するものあれば特に制限されるものではなく、上述した通りである。 [Epoxy cured resin forming composition]
The composition for forming an epoxy cured resin of the present invention is not particularly limited as long as it contains an epoxy resin and the curing catalyst of the present invention, and is as described above.
本発明のエポキシ硬化樹脂形成用組成物としては、エポキシ樹脂と、上記本発明の硬化触媒とを含有するものあれば特に制限されるものではなく、上述した通りである。 [Epoxy cured resin forming composition]
The composition for forming an epoxy cured resin of the present invention is not particularly limited as long as it contains an epoxy resin and the curing catalyst of the present invention, and is as described above.
〔エポキシ樹脂〕
エポキシ樹脂としては、従来公知の各種ポリエポキシ化合物が使用でき、例えば、ビス（４－ヒドロキシフェニル）プロパンジグリシジルエーテル、ビス（４－ヒドロキシ－３，５－ジブロモフェニル）プロパンジグリシジルエーテル、ビス（４－ヒドロキシフェニル）エタンジグリシジルエーテル、ビス（４－ヒドロキシフェニル）メタンジグリシジルエーテル、レゾルシノールジグリシジルエーテル、フロログリシノールトリグリシジルエーテル、トリヒドロキシビフェニルトリグリシジルエーテル、テトラグリシジルベンゾフェノン、ビスレゾルシノールテトラグリシジルエーテル、テトラメチルビスフェノールＡジグリシジルエーテル、ビスフェノールＣジグリシジルエーテル、ビスフェノールヘキサフルオロプロパンジグリシジルエーテル、１，３－ビス〔１－（２，３－エポキシ プロパキシ）－１－トリフルオロメチル－２，２，２－トリフルオロエチル〕ベンゼン、１，４－ビス〔１－（２，３－エポキシ プロパキシ）－１－トリフルオロメチル－２，２，２－トリフルオロメチル〕ベンゼン、４，４′－ビス（２，３－エポキシプロポキシ）オクタフルオロビフェニル、フェノールノボラック型ビスエポキシ化合物などの芳香族系グリシジルエーテル化合物；アリサイクリックジエポキシ アセタール、アリサイクリックジエポキシ アジペート、アリサイクリックジエポキシ カルボキシレート、ビニルシクロヘキセンジオキシドなどの脂環式ポリエポキシ化合物；ジグリシジルフタレート、ジグリシジルテトラヒドロフタレート、ジグリシジルヘキサヒドロフタレート、ジメチルグリシジルフタレート、ジメチルグリシジルヘキサヒドロフタレート、ジグリシジル－ｐ－オキシベンゾエート、ジグリシジルシクロペンタン－１，３－ジカルボキシレート、ダイマー酸グリシジルエステルなどのグリシジルエステル化合物；ジグリシジルアニリン、ジグリシジルトルイジン、トリグリシジルアミノフェノール、テトラグリシジルジアミノジフェニルメタン、ジグリシジルトリブロモアニリンなどのグリシジルアミン化合物；ジグリシジルヒダントイン、グリシジルグリシドオキシアルキルヒダントイン、トリグリシジルイソシアヌレートなどの複素環式エポキシ化合物などを挙げることができる。 〔Epoxy resin〕
As the epoxy resin, various conventionally known polyepoxy compounds can be used. For example, bis (4-hydroxyphenyl) propane diglycidyl ether, bis (4-hydroxy-3,5-dibromophenyl) propane diglycidyl ether, bis ( 4-hydroxyphenyl) ethane diglycidyl ether, bis (4-hydroxyphenyl) methane diglycidyl ether, resorcinol diglycidyl ether, phloroglicinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether Tetramethylbisphenol A diglycidyl ether, bisphenol C diglycidyl ether, bisphenol hexafluoropropane diglycidyl Ether, 1,3-bis [1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoroethyl] benzene, 1,4-bis [1- (2,3- Epoxy propoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl] benzene, 4,4'-bis (2,3-epoxypropoxy) octafluorobiphenyl, aromatics such as phenol novolac bisepoxy compounds Alicyclic diepoxy acetals, alicyclic diepoxy adipates, alicyclic diepoxy carboxylates, vinylcyclohexene dioxide, and other alicyclic polyepoxy compounds; diglycidyl phthalate, diglycidyl tetrahydrophthalate, di Glycidyl hexahydrophthale Glycidyl ester compounds, such as diglycidyl phthalate, dimethyl glycidyl phthalate, dimethyl glycidyl hexahydrophthalate, diglycidyl-p-oxybenzoate, diglycidyl cyclopentane-1,3-dicarboxylate, dimer acid glycidyl ester; Glycidylamine compounds such as triglycidylaminophenol, tetraglycidyldiaminodiphenylmethane, diglycidyltribromoaniline; and heterocyclic epoxy compounds such as diglycidylhydantoin, glycidylglycidoxyalkylhydantoin, and triglycidylisocyanurate .
エポキシ樹脂としては、従来公知の各種ポリエポキシ化合物が使用でき、例えば、ビス（４－ヒドロキシフェニル）プロパンジグリシジルエーテル、ビス（４－ヒドロキシ－３，５－ジブロモフェニル）プロパンジグリシジルエーテル、ビス（４－ヒドロキシフェニル）エタンジグリシジルエーテル、ビス（４－ヒドロキシフェニル）メタンジグリシジルエーテル、レゾルシノールジグリシジルエーテル、フロログリシノールトリグリシジルエーテル、トリヒドロキシビフェニルトリグリシジルエーテル、テトラグリシジルベンゾフェノン、ビスレゾルシノールテトラグリシジルエーテル、テトラメチルビスフェノールＡジグリシジルエーテル、ビスフェノールＣジグリシジルエーテル、ビスフェノールヘキサフルオロプロパンジグリシジルエーテル、１，３－ビス〔１－（２，３－エポキシ プロパキシ）－１－トリフルオロメチル－２，２，２－トリフルオロエチル〕ベンゼン、１，４－ビス〔１－（２，３－エポキシ プロパキシ）－１－トリフルオロメチル－２，２，２－トリフルオロメチル〕ベンゼン、４，４′－ビス（２，３－エポキシプロポキシ）オクタフルオロビフェニル、フェノールノボラック型ビスエポキシ化合物などの芳香族系グリシジルエーテル化合物；アリサイクリックジエポキシ アセタール、アリサイクリックジエポキシ アジペート、アリサイクリックジエポキシ カルボキシレート、ビニルシクロヘキセンジオキシドなどの脂環式ポリエポキシ化合物；ジグリシジルフタレート、ジグリシジルテトラヒドロフタレート、ジグリシジルヘキサヒドロフタレート、ジメチルグリシジルフタレート、ジメチルグリシジルヘキサヒドロフタレート、ジグリシジル－ｐ－オキシベンゾエート、ジグリシジルシクロペンタン－１，３－ジカルボキシレート、ダイマー酸グリシジルエステルなどのグリシジルエステル化合物；ジグリシジルアニリン、ジグリシジルトルイジン、トリグリシジルアミノフェノール、テトラグリシジルジアミノジフェニルメタン、ジグリシジルトリブロモアニリンなどのグリシジルアミン化合物；ジグリシジルヒダントイン、グリシジルグリシドオキシアルキルヒダントイン、トリグリシジルイソシアヌレートなどの複素環式エポキシ化合物などを挙げることができる。 〔Epoxy resin〕
As the epoxy resin, various conventionally known polyepoxy compounds can be used. For example, bis (4-hydroxyphenyl) propane diglycidyl ether, bis (4-hydroxy-3,5-dibromophenyl) propane diglycidyl ether, bis ( 4-hydroxyphenyl) ethane diglycidyl ether, bis (4-hydroxyphenyl) methane diglycidyl ether, resorcinol diglycidyl ether, phloroglicinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether Tetramethylbisphenol A diglycidyl ether, bisphenol C diglycidyl ether, bisphenol hexafluoropropane diglycidyl Ether, 1,3-bis [1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoroethyl] benzene, 1,4-bis [1- (2,3- Epoxy propoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl] benzene, 4,4'-bis (2,3-epoxypropoxy) octafluorobiphenyl, aromatics such as phenol novolac bisepoxy compounds Alicyclic diepoxy acetals, alicyclic diepoxy adipates, alicyclic diepoxy carboxylates, vinylcyclohexene dioxide, and other alicyclic polyepoxy compounds; diglycidyl phthalate, diglycidyl tetrahydrophthalate, di Glycidyl hexahydrophthale Glycidyl ester compounds, such as diglycidyl phthalate, dimethyl glycidyl phthalate, dimethyl glycidyl hexahydrophthalate, diglycidyl-p-oxybenzoate, diglycidyl cyclopentane-1,3-dicarboxylate, dimer acid glycidyl ester; Glycidylamine compounds such as triglycidylaminophenol, tetraglycidyldiaminodiphenylmethane, diglycidyltribromoaniline; and heterocyclic epoxy compounds such as diglycidylhydantoin, glycidylglycidoxyalkylhydantoin, and triglycidylisocyanurate .
本発明のエポキシ硬化樹脂形成用組成物におけるエポキシ樹脂及び式（II）で表されるイミダゾール化合物の割合は、エポキシ樹脂のエポキシ環１モルに対して、式（II）で表されるイミダゾール化合物を０．０１～１．０モル含有することが好ましく、０．１～１．０モル含有することがより好ましく、０．３～１．０モル含有することがさらに好ましい。
溶媒としては、水、メタノール、エタノール、イソプロピルアルコール、酢酸エチル、酢酸メチル、ジエチルエーテル、ジメチルエーテル、テトラヒドロフラン、１，４－ジオキサン、アセトン、メチルエチルケトン、アセトニトリル、ベンゼン、トルエン、ヘキサン、クロロホルム、ジクロロメタン、四塩化炭素等を用いることができる。
本発明のエポキシ樹脂硬化用触媒は、式（Ｉ）で表されるフルオレン化合物及び式（II）で表されるイミダゾール化合物を溶媒に添加後、必要に応じて攪拌しながら、加熱処理又は加熱還流処理を行い、再結晶させて析出させることにより得ることができる。また、溶媒への溶解のしやすさを考慮すると、式（Ｉ）で表されるフルオレン化合物及び式（II）で表されるイミダゾール化合物をそれぞれ溶媒に溶解後、溶解液同士を混合することが好ましい。 The ratio of the epoxy resin and the imidazole compound represented by the formula (II) in the epoxy cured resin forming composition of the present invention is the ratio of the imidazole compound represented by the formula (II) to 1 mol of the epoxy ring of the epoxy resin. The content is preferably 0.01 to 1.0 mol, more preferably 0.1 to 1.0 mol, and still more preferably 0.3 to 1.0 mol.
Solvents include water, methanol, ethanol, isopropyl alcohol, ethyl acetate, methyl acetate, diethyl ether, dimethyl ether, tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, acetonitrile, benzene, toluene, hexane, chloroform, dichloromethane, tetrachloride. Carbon or the like can be used.
The epoxy resin curing catalyst of the present invention is a heat treatment or heating reflux with stirring as necessary after adding the fluorene compound represented by formula (I) and the imidazole compound represented by formula (II) to the solvent. It can be obtained by performing treatment, recrystallization and precipitation. In consideration of ease of dissolution in a solvent, the fluorene compound represented by the formula (I) and the imidazole compound represented by the formula (II) may be dissolved in the solvent and then mixed with each other. preferable.
溶媒としては、水、メタノール、エタノール、イソプロピルアルコール、酢酸エチル、酢酸メチル、ジエチルエーテル、ジメチルエーテル、テトラヒドロフラン、１，４－ジオキサン、アセトン、メチルエチルケトン、アセトニトリル、ベンゼン、トルエン、ヘキサン、クロロホルム、ジクロロメタン、四塩化炭素等を用いることができる。
本発明のエポキシ樹脂硬化用触媒は、式（Ｉ）で表されるフルオレン化合物及び式（II）で表されるイミダゾール化合物を溶媒に添加後、必要に応じて攪拌しながら、加熱処理又は加熱還流処理を行い、再結晶させて析出させることにより得ることができる。また、溶媒への溶解のしやすさを考慮すると、式（Ｉ）で表されるフルオレン化合物及び式（II）で表されるイミダゾール化合物をそれぞれ溶媒に溶解後、溶解液同士を混合することが好ましい。 The ratio of the epoxy resin and the imidazole compound represented by the formula (II) in the epoxy cured resin forming composition of the present invention is the ratio of the imidazole compound represented by the formula (II) to 1 mol of the epoxy ring of the epoxy resin. The content is preferably 0.01 to 1.0 mol, more preferably 0.1 to 1.0 mol, and still more preferably 0.3 to 1.0 mol.
Solvents include water, methanol, ethanol, isopropyl alcohol, ethyl acetate, methyl acetate, diethyl ether, dimethyl ether, tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, acetonitrile, benzene, toluene, hexane, chloroform, dichloromethane, tetrachloride. Carbon or the like can be used.
The epoxy resin curing catalyst of the present invention is a heat treatment or heating reflux with stirring as necessary after adding the fluorene compound represented by formula (I) and the imidazole compound represented by formula (II) to the solvent. It can be obtained by performing treatment, recrystallization and precipitation. In consideration of ease of dissolution in a solvent, the fluorene compound represented by the formula (I) and the imidazole compound represented by the formula (II) may be dissolved in the solvent and then mixed with each other. preferable.
また、本発明のエポキシ硬化樹脂形成用組成物は、エポキシ樹脂、式（Ｉ）で表される化合物、及び式（II）で表わされる化合物を混合することにより製造することができるが、十分な混合状態が形成されるよう、通常、室温～１００℃程度に加熱して混合する。エポキシ硬化樹脂の製造においては、このときの温度での一液安定性が重要となる。
Moreover, the composition for forming an epoxy cured resin of the present invention can be produced by mixing an epoxy resin, a compound represented by the formula (I), and a compound represented by the formula (II). Usually, the mixture is heated to about room temperature to about 100 ° C. so that a mixed state is formed. In the production of an epoxy cured resin, the stability of one liquid at this temperature is important.
本発明の組成物には、上記の成分以外にも所望の特性を付与する目的で以下の成分を追加することができる。
（１）エポキシ樹脂用硬化触媒
本発明の組成物には、上記の硬化触媒以外に、公知の硬化触媒を併用できる。
例えば、１，５－ジアザビシクロ［４．３．０］ノナ－５－エン、１，８－ジアザビシクロ［５．４．０］ウンデカ－７－エン、５，６－ジブチルアミノ－１，８－ジアザビシクロ［５．４．０］ウンデカ－７－エン等の環状アミジン化合物；無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、無水マレイン酸、無水トリメリット酸等の酸無水物；１，４－ベンゾキノン、２，５－トルキノン、１，４－ナフトキノン、２，３－ジメチルベンゾキノン、２，６－ジメチルベンゾキノン、２，３－ジメトキシ－５－メチル－１，４ベンゾキノン、２，３－ジメトキシ－１，４－ベンゾキノン、フェニル－１，４－ベンゾキノン等のキノン化合物；トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス（ジメチルアミノメチル）フェノール等の第三級アミン化合物；ｏ－フェニレンジアミン、ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン、ｍ－キシレンジアミン等の芳香族アミン化合物；イミダゾール、２－メチルイミダゾール、２－エチル－４－メチルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール等のイミダゾール化合物；トリメチルホスフィン、トリエチルホスフィン、トリフェニルホスフィン、ジフェニル（ｐ－トリル）ホスフィン等の有機ホスフィン化合物；等が挙げられる。 In addition to the above components, the following components can be added to the composition of the present invention for the purpose of imparting desired properties.
(1) Curing Catalyst for Epoxy Resin In addition to the above curing catalyst, a known curing catalyst can be used in combination with the composition of the present invention.
For example, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 5,6-dibutylamino-1,8-diazabicyclo [5.4.0] Cyclic amidine compounds such as undec-7-ene; acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, trimellitic anhydride; 1,4- Benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4benzoquinone, 2,3-dimethoxy-1 Quinone compounds such as 1,4-benzoquinone and phenyl-1,4-benzoquinone; triethylenediamine, benzyldimethylamine, triethanolamine, Tertiary amine compounds such as methylaminoethanol and tris (dimethylaminomethyl) phenol; aromatic amines such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and m-xylenediamine Compounds; imidazole compounds such as imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; And organic phosphine compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenyl (p-tolyl) phosphine.
（１）エポキシ樹脂用硬化触媒
本発明の組成物には、上記の硬化触媒以外に、公知の硬化触媒を併用できる。
例えば、１，５－ジアザビシクロ［４．３．０］ノナ－５－エン、１，８－ジアザビシクロ［５．４．０］ウンデカ－７－エン、５，６－ジブチルアミノ－１，８－ジアザビシクロ［５．４．０］ウンデカ－７－エン等の環状アミジン化合物；無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、無水マレイン酸、無水トリメリット酸等の酸無水物；１，４－ベンゾキノン、２，５－トルキノン、１，４－ナフトキノン、２，３－ジメチルベンゾキノン、２，６－ジメチルベンゾキノン、２，３－ジメトキシ－５－メチル－１，４ベンゾキノン、２，３－ジメトキシ－１，４－ベンゾキノン、フェニル－１，４－ベンゾキノン等のキノン化合物；トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス（ジメチルアミノメチル）フェノール等の第三級アミン化合物；ｏ－フェニレンジアミン、ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン、ｍ－キシレンジアミン等の芳香族アミン化合物；イミダゾール、２－メチルイミダゾール、２－エチル－４－メチルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール等のイミダゾール化合物；トリメチルホスフィン、トリエチルホスフィン、トリフェニルホスフィン、ジフェニル（ｐ－トリル）ホスフィン等の有機ホスフィン化合物；等が挙げられる。 In addition to the above components, the following components can be added to the composition of the present invention for the purpose of imparting desired properties.
(1) Curing Catalyst for Epoxy Resin In addition to the above curing catalyst, a known curing catalyst can be used in combination with the composition of the present invention.
For example, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 5,6-dibutylamino-1,8-diazabicyclo [5.4.0] Cyclic amidine compounds such as undec-7-ene; acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, trimellitic anhydride; 1,4- Benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4benzoquinone, 2,3-dimethoxy-1 Quinone compounds such as 1,4-benzoquinone and phenyl-1,4-benzoquinone; triethylenediamine, benzyldimethylamine, triethanolamine, Tertiary amine compounds such as methylaminoethanol and tris (dimethylaminomethyl) phenol; aromatic amines such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and m-xylenediamine Compounds; imidazole compounds such as imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; And organic phosphine compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenyl (p-tolyl) phosphine.
（２）硬化剤
さらにエポキシ樹脂を硬化させるための公知の硬化剤を使用できる。例えば、レゾルシン、カテコール、ビスフェノールＡ、ビスフェノールＦ等の１分子中に２個のフェノール性水酸基を有する化合物；フェノールノボラック樹脂、クレゾールノボラック樹脂、クレゾールアラルキル樹脂、フェノールアラルキル樹脂、ビフェニルアラルキル樹脂、ジシクロペンタジエン型フェノール樹脂、ナフトールアラルキル樹脂等の多価フェノール樹脂；等が挙げられる。 (2) Curing agent Further known curing agents for curing the epoxy resin can be used. For example, compounds having two phenolic hydroxyl groups in one molecule such as resorcin, catechol, bisphenol A, bisphenol F; phenol novolak resin, cresol novolak resin, cresol aralkyl resin, phenol aralkyl resin, biphenyl aralkyl resin, dicyclopentadiene Polyphenol resin such as a type phenol resin and a naphthol aralkyl resin; and the like.
さらにエポキシ樹脂を硬化させるための公知の硬化剤を使用できる。例えば、レゾルシン、カテコール、ビスフェノールＡ、ビスフェノールＦ等の１分子中に２個のフェノール性水酸基を有する化合物；フェノールノボラック樹脂、クレゾールノボラック樹脂、クレゾールアラルキル樹脂、フェノールアラルキル樹脂、ビフェニルアラルキル樹脂、ジシクロペンタジエン型フェノール樹脂、ナフトールアラルキル樹脂等の多価フェノール樹脂；等が挙げられる。 (2) Curing agent Further known curing agents for curing the epoxy resin can be used. For example, compounds having two phenolic hydroxyl groups in one molecule such as resorcin, catechol, bisphenol A, bisphenol F; phenol novolak resin, cresol novolak resin, cresol aralkyl resin, phenol aralkyl resin, biphenyl aralkyl resin, dicyclopentadiene Polyphenol resin such as a type phenol resin and a naphthol aralkyl resin; and the like.
（３）フィラー
また、粘度や硬化物の物性を制御するためにフィラーを配合してもよい。フィラーとしては、絶縁性無機フィラーやウィスカー、樹脂フィラーを使用できる。絶縁性無機フィラーとしては、例えば、ガラス、シリカ、アルミナ、酸化チタン、カーボンブラック、マイカ、窒化ホウ素等が挙げられる。ウィスカーとしてはホウ酸アルミニウム、チタン酸アルミニウム、酸化亜鉛、珪酸カルシウム、硫酸マグネシウム、窒化ホウ素等が挙げられる。樹脂フィラーとしては、ポリウレタン樹脂、ポリイミド樹脂などを用いることができる。
その他にも、金、銀、銅、ニッケル、ハンダ等の金属粒子、及びカーボン等の導電フィラーも電子部品の接合用接着剤を構成する場合に使用できる。 (3) Filler In addition, a filler may be blended in order to control the viscosity and physical properties of the cured product. As the filler, an insulating inorganic filler, whisker, or resin filler can be used. Examples of the insulating inorganic filler include glass, silica, alumina, titanium oxide, carbon black, mica, and boron nitride. Examples of whiskers include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, and boron nitride. A polyurethane resin, a polyimide resin, or the like can be used as the resin filler.
In addition, metal particles such as gold, silver, copper, nickel, solder, and conductive fillers such as carbon can also be used when constituting an adhesive for joining electronic components.
また、粘度や硬化物の物性を制御するためにフィラーを配合してもよい。フィラーとしては、絶縁性無機フィラーやウィスカー、樹脂フィラーを使用できる。絶縁性無機フィラーとしては、例えば、ガラス、シリカ、アルミナ、酸化チタン、カーボンブラック、マイカ、窒化ホウ素等が挙げられる。ウィスカーとしてはホウ酸アルミニウム、チタン酸アルミニウム、酸化亜鉛、珪酸カルシウム、硫酸マグネシウム、窒化ホウ素等が挙げられる。樹脂フィラーとしては、ポリウレタン樹脂、ポリイミド樹脂などを用いることができる。
その他にも、金、銀、銅、ニッケル、ハンダ等の金属粒子、及びカーボン等の導電フィラーも電子部品の接合用接着剤を構成する場合に使用できる。 (3) Filler In addition, a filler may be blended in order to control the viscosity and physical properties of the cured product. As the filler, an insulating inorganic filler, whisker, or resin filler can be used. Examples of the insulating inorganic filler include glass, silica, alumina, titanium oxide, carbon black, mica, and boron nitride. Examples of whiskers include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, and boron nitride. A polyurethane resin, a polyimide resin, or the like can be used as the resin filler.
In addition, metal particles such as gold, silver, copper, nickel, solder, and conductive fillers such as carbon can also be used when constituting an adhesive for joining electronic components.
（４）その他の添加剤
また、本発明の目的とする所望の特性を阻害しない範囲で、離型剤、レベリング剤、シランカップリング剤、難燃剤、酸化防止剤、着色剤、シリコーン系可撓剤、イオントラップ剤等の公知の添加剤を配合できる。 (4) Other additives In addition, the release agent, leveling agent, silane coupling agent, flame retardant, antioxidant, colorant, silicone-based flexibility, as long as the desired properties of the present invention are not impaired. Known additives such as an agent and an ion trapping agent can be blended.
また、本発明の目的とする所望の特性を阻害しない範囲で、離型剤、レベリング剤、シランカップリング剤、難燃剤、酸化防止剤、着色剤、シリコーン系可撓剤、イオントラップ剤等の公知の添加剤を配合できる。 (4) Other additives In addition, the release agent, leveling agent, silane coupling agent, flame retardant, antioxidant, colorant, silicone-based flexibility, as long as the desired properties of the present invention are not impaired. Known additives such as an agent and an ion trapping agent can be blended.
〔エポキシ硬化樹脂〕
本発明のエポキシ硬化樹脂の製造方法としては、上記エポキシ硬化樹脂形成用組成物を加熱処理して硬化させる方法であれば特に制限されるものではなく、通常、加熱処理の加熱温度としては、６０～２５０℃であり、好ましくは、１００～２００℃であり、かかる温度において短時間で硬化することが好ましい。 [Epoxy cured resin]
The method for producing the epoxy curable resin of the present invention is not particularly limited as long as it is a method of curing the epoxy curable resin-forming composition by heat treatment. Usually, the heating temperature of the heat treatment is 60 It is preferably from 250 to 250 ° C., and preferably from 100 to 200 ° C., and it is preferably cured at such temperature for a short time.
本発明のエポキシ硬化樹脂の製造方法としては、上記エポキシ硬化樹脂形成用組成物を加熱処理して硬化させる方法であれば特に制限されるものではなく、通常、加熱処理の加熱温度としては、６０～２５０℃であり、好ましくは、１００～２００℃であり、かかる温度において短時間で硬化することが好ましい。 [Epoxy cured resin]
The method for producing the epoxy curable resin of the present invention is not particularly limited as long as it is a method of curing the epoxy curable resin-forming composition by heat treatment. Usually, the heating temperature of the heat treatment is 60 It is preferably from 250 to 250 ° C., and preferably from 100 to 200 ° C., and it is preferably cured at such temperature for a short time.
〔使用用途〕
本発明のエポキシ硬化樹脂形成用組成物の使用用途としては、特に制限されるものではなく、例えば、アンダーフィル、熱硬化性プリプレグ、注型材料、構造用接着剤、粉体塗料等を挙げることができる。特には、電材関連について、プリント基板用プリプレグ、半導体・電子部品用封止材、電子部品用接着剤、導電性接着剤、レジストインク、絶縁材料等を挙げることができる。 〔Use applications〕
The use of the composition for forming an epoxy curable resin of the present invention is not particularly limited, and examples thereof include underfill, thermosetting prepreg, casting material, structural adhesive, and powder coating. Can do. In particular, regarding electrical materials, printed circuit board prepregs, semiconductor / electronic component sealing materials, electronic component adhesives, conductive adhesives, resist inks, insulating materials, and the like can be given.
本発明のエポキシ硬化樹脂形成用組成物の使用用途としては、特に制限されるものではなく、例えば、アンダーフィル、熱硬化性プリプレグ、注型材料、構造用接着剤、粉体塗料等を挙げることができる。特には、電材関連について、プリント基板用プリプレグ、半導体・電子部品用封止材、電子部品用接着剤、導電性接着剤、レジストインク、絶縁材料等を挙げることができる。 〔Use applications〕
The use of the composition for forming an epoxy curable resin of the present invention is not particularly limited, and examples thereof include underfill, thermosetting prepreg, casting material, structural adhesive, and powder coating. Can do. In particular, regarding electrical materials, printed circuit board prepregs, semiconductor / electronic component sealing materials, electronic component adhesives, conductive adhesives, resist inks, insulating materials, and the like can be given.
〔エポキシ硬化樹脂〕
本発明のエポキシ硬化樹脂の製造方法としては、上記エポキシ硬化樹脂形成用組成物を加熱処理して硬化させる方法であれば特に制限されるものではなく、通常、加熱処理の加熱温度としては、６０～２５０℃であり、好ましくは、１００～２００℃であり、かかる温度において短時間で硬化することが好ましい。 [Epoxy cured resin]
The method for producing the epoxy curable resin of the present invention is not particularly limited as long as it is a method of curing the epoxy curable resin-forming composition by heat treatment. Usually, the heating temperature of the heat treatment is 60 It is preferably from 250 to 250 ° C., and preferably from 100 to 200 ° C., and it is preferably cured at such temperature for a short time.
本発明のエポキシ硬化樹脂の製造方法としては、上記エポキシ硬化樹脂形成用組成物を加熱処理して硬化させる方法であれば特に制限されるものではなく、通常、加熱処理の加熱温度としては、６０～２５０℃であり、好ましくは、１００～２００℃であり、かかる温度において短時間で硬化することが好ましい。 [Epoxy cured resin]
The method for producing the epoxy curable resin of the present invention is not particularly limited as long as it is a method of curing the epoxy curable resin-forming composition by heat treatment. Usually, the heating temperature of the heat treatment is 60 It is preferably from 250 to 250 ° C., and preferably from 100 to 200 ° C., and it is preferably cured at such temperature for a short time.
以下、実施例により本発明をより具体的に説明するが、本発明の技術的範囲はこれらの例示に限定されるものではない。
Hereinafter, the present invention will be described more specifically by way of examples. However, the technical scope of the present invention is not limited to these examples.
［実施例１］
（エポキシ硬化樹脂形成用組成物Ａの調製）
エポキシ樹脂（商品名：エポトート（登録商標）ＹＤ－１２８、東邦化成（株）製）５ｇに対して、硬化触媒として２－エチル－４－メチルイミダゾール（以下、２Ｅ４ＭＺ）を２００ｍｇ（１．８２ｍｍｏｌ）、９,９－ビス（４－ヒドロキシフェニル）フルオレンを６３．０ｍｇ（０．１８１ｍｍｏｌ）をそれぞれ添加した後、２５℃で１０分間混練することで、エポキシ硬化樹脂形成用組成物Ａを得た。 [Example 1]
(Preparation of composition A for epoxy cured resin formation)
200 mg (1.82 mmol) of 2-ethyl-4-methylimidazole (hereinafter, 2E4MZ) as a curing catalyst with respect to 5 g of epoxy resin (trade name: Epototo (registered trademark) YD-128, manufactured by Toho Kasei Co., Ltd.) After adding 63.0 mg (0.181 mmol) of 9,9-bis (4-hydroxyphenyl) fluorene, the mixture was kneaded at 25 ° C. for 10 minutes to obtain an epoxy cured resin forming composition A.
（エポキシ硬化樹脂形成用組成物Ａの調製）
エポキシ樹脂（商品名：エポトート（登録商標）ＹＤ－１２８、東邦化成（株）製）５ｇに対して、硬化触媒として２－エチル－４－メチルイミダゾール（以下、２Ｅ４ＭＺ）を２００ｍｇ（１．８２ｍｍｏｌ）、９,９－ビス（４－ヒドロキシフェニル）フルオレンを６３．０ｍｇ（０．１８１ｍｍｏｌ）をそれぞれ添加した後、２５℃で１０分間混練することで、エポキシ硬化樹脂形成用組成物Ａを得た。 [Example 1]
(Preparation of composition A for epoxy cured resin formation)
200 mg (1.82 mmol) of 2-ethyl-4-methylimidazole (hereinafter, 2E4MZ) as a curing catalyst with respect to 5 g of epoxy resin (trade name: Epototo (registered trademark) YD-128, manufactured by Toho Kasei Co., Ltd.) After adding 63.0 mg (0.181 mmol) of 9,9-bis (4-hydroxyphenyl) fluorene, the mixture was kneaded at 25 ° C. for 10 minutes to obtain an epoxy cured resin forming composition A.
（エポキシ硬化樹脂形成用組成物ＡのＤＳＣ測定）
ＤＳＣ測定装置（ＤＳＣ１、メトラー・トレド社製）を用い、アルミ容器内に９．４ｍｇのエポキシ硬化樹脂形成用組成物Ａを量りとり、窒素パージ下（窒素の流速：５０ｍＬ／ｍｉｎ）、３０℃から２５０℃まで昇温（昇温速度：１０ｋ／ｍｉｎ）を行い、エポキシ硬化樹脂形成用組成物Ａの硬化反応に基づく発熱を測定した。横軸に時間及び温度を採った測定結果を図１に示す。 (DSC measurement of composition A for epoxy cured resin formation)
Using a DSC measuring apparatus (DSC1, manufactured by METTLER TOLEDO), 9.4 mg of the epoxy cured resin forming composition A was weighed in an aluminum container, and purged with nitrogen (flow rate of nitrogen: 50 mL / min) at 30 ° C. To 250 ° C. (temperature increase rate: 10 k / min), and heat generation based on the curing reaction of the epoxy cured resin forming composition A was measured. The measurement results with time and temperature on the horizontal axis are shown in FIG.
ＤＳＣ測定装置（ＤＳＣ１、メトラー・トレド社製）を用い、アルミ容器内に９．４ｍｇのエポキシ硬化樹脂形成用組成物Ａを量りとり、窒素パージ下（窒素の流速：５０ｍＬ／ｍｉｎ）、３０℃から２５０℃まで昇温（昇温速度：１０ｋ／ｍｉｎ）を行い、エポキシ硬化樹脂形成用組成物Ａの硬化反応に基づく発熱を測定した。横軸に時間及び温度を採った測定結果を図１に示す。 (DSC measurement of composition A for epoxy cured resin formation)
Using a DSC measuring apparatus (DSC1, manufactured by METTLER TOLEDO), 9.4 mg of the epoxy cured resin forming composition A was weighed in an aluminum container, and purged with nitrogen (flow rate of nitrogen: 50 mL / min) at 30 ° C. To 250 ° C. (temperature increase rate: 10 k / min), and heat generation based on the curing reaction of the epoxy cured resin forming composition A was measured. The measurement results with time and temperature on the horizontal axis are shown in FIG.
［実施例２］
（エポキシ硬化樹脂形成用組成物Ｂの調製）
実施例１のエポキシ硬化樹脂形成用組成物Ａの調製において、硬化触媒として２Ｅ４ＭＺを２００ｍｇ（１．８２ｍｍｏｌ）、９,９－ビス（４－ヒドロキシフェニル）フルオレンを１５８．０ｍｇ（０．４５３ｍｍｏｌ）をそれぞれ添加する以外は同様に調製してエポキシ硬化樹脂形成用組成物Ｂを得た。 [Example 2]
(Preparation of composition B for forming epoxy cured resin)
In the preparation of the epoxy cured resin-forming composition A of Example 1, 2 mg of E2MZ as a curing catalyst (200 mg, 1.82 mmol) and 9,9-bis (4-hydroxyphenyl) fluorene as 158.0 mg (0.453 mmol) were used. An epoxy cured resin forming composition B was obtained in the same manner except that each was added.
（エポキシ硬化樹脂形成用組成物Ｂの調製）
実施例１のエポキシ硬化樹脂形成用組成物Ａの調製において、硬化触媒として２Ｅ４ＭＺを２００ｍｇ（１．８２ｍｍｏｌ）、９,９－ビス（４－ヒドロキシフェニル）フルオレンを１５８．０ｍｇ（０．４５３ｍｍｏｌ）をそれぞれ添加する以外は同様に調製してエポキシ硬化樹脂形成用組成物Ｂを得た。 [Example 2]
(Preparation of composition B for forming epoxy cured resin)
In the preparation of the epoxy cured resin-forming composition A of Example 1, 2 mg of E2MZ as a curing catalyst (200 mg, 1.82 mmol) and 9,9-bis (4-hydroxyphenyl) fluorene as 158.0 mg (0.453 mmol) were used. An epoxy cured resin forming composition B was obtained in the same manner except that each was added.
（エポキシ硬化樹脂形成用組成物ＢのＤＳＣ測定）
実施例１のエポキシ硬化樹脂形成用組成物ＡのＤＳＣ測定において、エポキシ硬化樹脂形成用組成物Ａを８．７ｍｇのエポキシ硬化樹脂形成用組成物Ｂへと変更した以外は同様にして測定した。測定結果を図２に示す。 (DSC measurement of composition B for epoxy cured resin formation)
In the DSC measurement of the epoxy cured resin forming composition A of Example 1, the measurement was performed in the same manner except that the epoxy cured resin forming composition A was changed to 8.7 mg of the epoxy cured resin forming composition B. The measurement results are shown in FIG.
実施例１のエポキシ硬化樹脂形成用組成物ＡのＤＳＣ測定において、エポキシ硬化樹脂形成用組成物Ａを８．７ｍｇのエポキシ硬化樹脂形成用組成物Ｂへと変更した以外は同様にして測定した。測定結果を図２に示す。 (DSC measurement of composition B for epoxy cured resin formation)
In the DSC measurement of the epoxy cured resin forming composition A of Example 1, the measurement was performed in the same manner except that the epoxy cured resin forming composition A was changed to 8.7 mg of the epoxy cured resin forming composition B. The measurement results are shown in FIG.
［実施例３］
（エポキシ硬化樹脂形成用組成物Ｃの調製）
実施例１のエポキシ硬化樹脂形成用組成物Ａの調製において、９,９－ビス（４－ヒドロキシフェニル）フルオレンの添加量を３１８．０ｍｇ（０．９０７ｍｍｏｌ）へと変更する以外は同様に調製してエポキシ硬化樹脂形成用組成物Ｃを得た。 [Example 3]
(Preparation of epoxy cured resin forming composition C)
In the preparation of the epoxy cured resin forming composition A of Example 1, the same preparation was carried out except that the amount of 9,9-bis (4-hydroxyphenyl) fluorene was changed to 318.0 mg (0.907 mmol). Thus, an epoxy cured resin forming composition C was obtained.
（エポキシ硬化樹脂形成用組成物Ｃの調製）
実施例１のエポキシ硬化樹脂形成用組成物Ａの調製において、９,９－ビス（４－ヒドロキシフェニル）フルオレンの添加量を３１８．０ｍｇ（０．９０７ｍｍｏｌ）へと変更する以外は同様に調製してエポキシ硬化樹脂形成用組成物Ｃを得た。 [Example 3]
(Preparation of epoxy cured resin forming composition C)
In the preparation of the epoxy cured resin forming composition A of Example 1, the same preparation was carried out except that the amount of 9,9-bis (4-hydroxyphenyl) fluorene was changed to 318.0 mg (0.907 mmol). Thus, an epoxy cured resin forming composition C was obtained.
（エポキシ硬化樹脂形成用組成物ＣのＤＳＣ測定）
実施例１のエポキシ硬化樹脂形成用組成物ＡのＤＳＣ測定において、エポキシ硬化樹脂形成用組成物Ａを９．０ｍｇのエポキシ硬化樹脂形成用組成物Ｃへと変更した以外は同様に測定した。測定結果を図３に示す。 (DSC measurement of epoxy cured resin forming composition C)
In the DSC measurement of the epoxy cured resin forming composition A of Example 1, the same measurement was performed except that the epoxy cured resin forming composition A was changed to 9.0 mg of the epoxy cured resin forming composition C. The measurement results are shown in FIG.
実施例１のエポキシ硬化樹脂形成用組成物ＡのＤＳＣ測定において、エポキシ硬化樹脂形成用組成物Ａを９．０ｍｇのエポキシ硬化樹脂形成用組成物Ｃへと変更した以外は同様に測定した。測定結果を図３に示す。 (DSC measurement of epoxy cured resin forming composition C)
In the DSC measurement of the epoxy cured resin forming composition A of Example 1, the same measurement was performed except that the epoxy cured resin forming composition A was changed to 9.0 mg of the epoxy cured resin forming composition C. The measurement results are shown in FIG.
［実施例４］
（エポキシ硬化樹脂形成用組成物Ｄの調製）
実施例１のエポキシ硬化樹脂形成用組成物Ａの調製において、９,９－ビス（４－ヒドロキシフェニル）フルオレンの添加量を６３５．０ｍｇ（１．８１５ｍｍｏｌ）へと変更する以外は同様に調製してエポキシ硬化樹脂形成用組成物Ｄを得た。 [Example 4]
(Preparation of composition D for epoxy cured resin formation)
In the preparation of the epoxy cured resin forming composition A of Example 1, the same preparation was carried out except that the amount of 9,9-bis (4-hydroxyphenyl) fluorene was changed to 635.0 mg (1.815 mmol). Thus, an epoxy cured resin forming composition D was obtained.
（エポキシ硬化樹脂形成用組成物Ｄの調製）
実施例１のエポキシ硬化樹脂形成用組成物Ａの調製において、９,９－ビス（４－ヒドロキシフェニル）フルオレンの添加量を６３５．０ｍｇ（１．８１５ｍｍｏｌ）へと変更する以外は同様に調製してエポキシ硬化樹脂形成用組成物Ｄを得た。 [Example 4]
(Preparation of composition D for epoxy cured resin formation)
In the preparation of the epoxy cured resin forming composition A of Example 1, the same preparation was carried out except that the amount of 9,9-bis (4-hydroxyphenyl) fluorene was changed to 635.0 mg (1.815 mmol). Thus, an epoxy cured resin forming composition D was obtained.
（エポキシ硬化樹脂形成用組成物ＤのＤＳＣ測定）
実施例１のエポキシ硬化樹脂形成用組成物ＡのＤＳＣ測定において、エポキシ硬化樹脂形成用組成物Ａを９．６ｍｇのエポキシ硬化樹脂形成用組成物Ｄへと変更した以外は同様に測定した。測定結果を図４に示す。 (DSC measurement of epoxy cured resin forming composition D)
In the DSC measurement of the epoxy cured resin forming composition A of Example 1, the measurement was performed in the same manner except that the epoxy cured resin forming composition A was changed to 9.6 mg of the epoxy cured resin forming composition D. The measurement results are shown in FIG.
実施例１のエポキシ硬化樹脂形成用組成物ＡのＤＳＣ測定において、エポキシ硬化樹脂形成用組成物Ａを９．６ｍｇのエポキシ硬化樹脂形成用組成物Ｄへと変更した以外は同様に測定した。測定結果を図４に示す。 (DSC measurement of epoxy cured resin forming composition D)
In the DSC measurement of the epoxy cured resin forming composition A of Example 1, the measurement was performed in the same manner except that the epoxy cured resin forming composition A was changed to 9.6 mg of the epoxy cured resin forming composition D. The measurement results are shown in FIG.
［実施例５］
（エポキシ硬化樹脂形成用組成物Ｅの調製）
実施例１のエポキシ硬化樹脂形成用組成物Ａの調製において、９,９－ビス（４－ヒドロキシフェニル）フルオレンの添加量を１．２７ｇ（３．６３ｍｍｏｌ）へと変更する以外は同様に調製してエポキシ硬化樹脂形成用組成物Ｅを得た。 [Example 5]
(Preparation of composition E for epoxy cured resin formation)
In the preparation of the epoxy cured resin forming composition A of Example 1, the same preparation was performed except that the amount of 9,9-bis (4-hydroxyphenyl) fluorene added was changed to 1.27 g (3.63 mmol). Thus, an epoxy cured resin forming composition E was obtained.
（エポキシ硬化樹脂形成用組成物Ｅの調製）
実施例１のエポキシ硬化樹脂形成用組成物Ａの調製において、９,９－ビス（４－ヒドロキシフェニル）フルオレンの添加量を１．２７ｇ（３．６３ｍｍｏｌ）へと変更する以外は同様に調製してエポキシ硬化樹脂形成用組成物Ｅを得た。 [Example 5]
(Preparation of composition E for epoxy cured resin formation)
In the preparation of the epoxy cured resin forming composition A of Example 1, the same preparation was performed except that the amount of 9,9-bis (4-hydroxyphenyl) fluorene added was changed to 1.27 g (3.63 mmol). Thus, an epoxy cured resin forming composition E was obtained.
（エポキシ硬化樹脂形成用組成物ＥのＤＳＣ測定）
実施例１のエポキシ硬化樹脂形成用組成物ＡのＤＳＣ測定において、エポキシ硬化樹脂形成用組成物Ａを８．９ｍｇのエポキシ硬化樹脂形成用組成物Ｅへと変更した以外は同様に測定した。測定結果を図５に示す。 (DSC measurement of composition E for epoxy cured resin formation)
In the DSC measurement of the epoxy cured resin forming composition A of Example 1, the measurement was performed in the same manner except that the epoxy cured resin forming composition A was changed to 8.9 mg of the epoxy cured resin forming composition E. The measurement results are shown in FIG.
実施例１のエポキシ硬化樹脂形成用組成物ＡのＤＳＣ測定において、エポキシ硬化樹脂形成用組成物Ａを８．９ｍｇのエポキシ硬化樹脂形成用組成物Ｅへと変更した以外は同様に測定した。測定結果を図５に示す。 (DSC measurement of composition E for epoxy cured resin formation)
In the DSC measurement of the epoxy cured resin forming composition A of Example 1, the measurement was performed in the same manner except that the epoxy cured resin forming composition A was changed to 8.9 mg of the epoxy cured resin forming composition E. The measurement results are shown in FIG.
［実施例６］
（エポキシ硬化樹脂形成用組成物Ｆの調製）
実施例１のエポキシ硬化樹脂形成用組成物Ａの調製において、９,９－ビス（４－ヒドロキシフェニル）フルオレンの添加量を３．１７ｇ（９．０８ｍｍｏｌ）へと変更する以外は同様に調製してエポキシ硬化樹脂形成用組成物Ｆを得た。 [Example 6]
(Preparation of composition F for forming an epoxy cured resin)
In the preparation of the epoxy cured resin forming composition A of Example 1, the same preparation was carried out except that the amount of 9,9-bis (4-hydroxyphenyl) fluorene was changed to 3.17 g (9.08 mmol). Thus, a composition F for forming an epoxy cured resin was obtained.
（エポキシ硬化樹脂形成用組成物Ｆの調製）
実施例１のエポキシ硬化樹脂形成用組成物Ａの調製において、９,９－ビス（４－ヒドロキシフェニル）フルオレンの添加量を３．１７ｇ（９．０８ｍｍｏｌ）へと変更する以外は同様に調製してエポキシ硬化樹脂形成用組成物Ｆを得た。 [Example 6]
(Preparation of composition F for forming an epoxy cured resin)
In the preparation of the epoxy cured resin forming composition A of Example 1, the same preparation was carried out except that the amount of 9,9-bis (4-hydroxyphenyl) fluorene was changed to 3.17 g (9.08 mmol). Thus, a composition F for forming an epoxy cured resin was obtained.
（エポキシ硬化樹脂形成用組成物ＦのＤＳＣ測定）
実施例１のエポキシ硬化樹脂形成用組成物ＡのＤＳＣ測定において、エポキシ硬化樹脂形成用組成物Ａを７．８ｍｇのエポキシ硬化樹脂形成用組成物Ｆへと変更した以外は同様に測定した。測定結果を図６に示す。 (DSC measurement of epoxy cured resin forming composition F)
In the DSC measurement of the epoxy cured resin forming composition A of Example 1, the measurement was performed in the same manner except that the epoxy cured resin forming composition A was changed to 7.8 mg of the epoxy cured resin forming composition F. The measurement results are shown in FIG.
実施例１のエポキシ硬化樹脂形成用組成物ＡのＤＳＣ測定において、エポキシ硬化樹脂形成用組成物Ａを７．８ｍｇのエポキシ硬化樹脂形成用組成物Ｆへと変更した以外は同様に測定した。測定結果を図６に示す。 (DSC measurement of epoxy cured resin forming composition F)
In the DSC measurement of the epoxy cured resin forming composition A of Example 1, the measurement was performed in the same manner except that the epoxy cured resin forming composition A was changed to 7.8 mg of the epoxy cured resin forming composition F. The measurement results are shown in FIG.
［比較例１］
（エポキシ硬化樹脂形成用組成物Ｇの調製）
実施例１のエポキシ硬化樹脂形成用組成物Ａの調製において、硬化触媒として２Ｅ４ＭＺのみを２００ｍｇ（１．８２ｍｍｏｌ）添加する以外は同様に調製して、エポキシ硬化樹脂形成用組成物Ｇを得た。 [Comparative Example 1]
(Preparation of epoxy cured resin forming composition G)
In the preparation of the epoxy cured resin forming composition A of Example 1, an epoxy cured resin forming composition G was obtained in the same manner except that 200 mg (1.82 mmol) of 2E4MZ alone was added as a curing catalyst.
（エポキシ硬化樹脂形成用組成物Ｇの調製）
実施例１のエポキシ硬化樹脂形成用組成物Ａの調製において、硬化触媒として２Ｅ４ＭＺのみを２００ｍｇ（１．８２ｍｍｏｌ）添加する以外は同様に調製して、エポキシ硬化樹脂形成用組成物Ｇを得た。 [Comparative Example 1]
(Preparation of epoxy cured resin forming composition G)
In the preparation of the epoxy cured resin forming composition A of Example 1, an epoxy cured resin forming composition G was obtained in the same manner except that 200 mg (1.82 mmol) of 2E4MZ alone was added as a curing catalyst.
（エポキシ硬化樹脂形成用組成物ＧのＤＳＣ測定）
実施例１のエポキシ硬化樹脂形成用組成物ＡのＤＳＣ測定において、エポキシ硬化樹脂形成用組成物Ａを７．８ｍｇのエポキシ硬化樹脂形成用組成物Ｇへと変更した以外は同様に測定した。測定結果を図１～６にそれぞれ実施例１～６に対比して示す。 (DSC measurement of composition G for epoxy cured resin formation)
In the DSC measurement of the epoxy cured resin forming composition A of Example 1, the measurement was performed in the same manner except that the epoxy cured resin forming composition A was changed to 7.8 mg of the epoxy cured resin forming composition G. The measurement results are shown in FIGS. 1 to 6 in comparison with Examples 1 to 6, respectively.
実施例１のエポキシ硬化樹脂形成用組成物ＡのＤＳＣ測定において、エポキシ硬化樹脂形成用組成物Ａを７．８ｍｇのエポキシ硬化樹脂形成用組成物Ｇへと変更した以外は同様に測定した。測定結果を図１～６にそれぞれ実施例１～６に対比して示す。 (DSC measurement of composition G for epoxy cured resin formation)
In the DSC measurement of the epoxy cured resin forming composition A of Example 1, the measurement was performed in the same manner except that the epoxy cured resin forming composition A was changed to 7.8 mg of the epoxy cured resin forming composition G. The measurement results are shown in FIGS. 1 to 6 in comparison with Examples 1 to 6, respectively.
（速硬化性の判断）
図１から図６に示したＤＳＣ測定での発熱ピークを基にそれぞれのエポキシ硬化樹脂形成用組成物の硬化時間を算出し、表１に示した。硬化時間は、発熱ピークがベースラインより離れる時間を硬化開始時間、戻る時間を硬化終了時間とし、硬化終了時間から硬化開始時間を引くことで求めた。
表１より、ビスフェノールフルオレン化合物を添加したいずれの場合でも硬化時間が短縮し、ビスフェノールフルオレン化合物がエポキシ樹脂の速硬化に大きく寄与することが明らかとなった。 (Judgment of fast curability)
The curing time of each composition for forming an epoxy cured resin was calculated based on the exothermic peak in the DSC measurement shown in FIG. 1 to FIG. The curing time was determined by subtracting the curing start time from the curing end time, with the time at which the exothermic peak separated from the baseline as the curing start time and the return time as the curing end time.
From Table 1, it became clear that in any case where the bisphenol fluorene compound was added, the curing time was shortened, and the bisphenol fluorene compound greatly contributed to the rapid curing of the epoxy resin.
図１から図６に示したＤＳＣ測定での発熱ピークを基にそれぞれのエポキシ硬化樹脂形成用組成物の硬化時間を算出し、表１に示した。硬化時間は、発熱ピークがベースラインより離れる時間を硬化開始時間、戻る時間を硬化終了時間とし、硬化終了時間から硬化開始時間を引くことで求めた。
表１より、ビスフェノールフルオレン化合物を添加したいずれの場合でも硬化時間が短縮し、ビスフェノールフルオレン化合物がエポキシ樹脂の速硬化に大きく寄与することが明らかとなった。 (Judgment of fast curability)
The curing time of each composition for forming an epoxy cured resin was calculated based on the exothermic peak in the DSC measurement shown in FIG. 1 to FIG. The curing time was determined by subtracting the curing start time from the curing end time, with the time at which the exothermic peak separated from the baseline as the curing start time and the return time as the curing end time.
From Table 1, it became clear that in any case where the bisphenol fluorene compound was added, the curing time was shortened, and the bisphenol fluorene compound greatly contributed to the rapid curing of the epoxy resin.
Claims (9)
- 式（Ｉ）
ｍは０～４のいずれかの整数を表し、ｎは０～４のいずれかの整数を表す。
Ｘ２は、それぞれ独立に、ハロゲノ基、無置換若しくは置換基を有するＣ１～６アルキル基、水酸基、無置換若しくは置換基を有するＣ１～６アルコキシ基、アミノ基、ニトロ基、又はシアノ基を表す。
ｐは０～４のいずれかの整数を表し、ｑは０～４のいずれかの整数を表す。）で表されるフルオレン化合物と、
式（II）
Ｒ２～Ｒ４は、それぞれ独立に、水素原子、ハロゲノ基、無置換若しくは置換基を有するＣ１～６アルキル基、無置換若しくは置換基を有するＣ６～１０アリール基、ニトロ基、又はシアノ基を表す。）で表されるイミダゾール化合物を含有するエポキシ樹脂用硬化触媒。 Formula (I)
m represents any integer from 0 to 4, and n represents any integer from 0 to 4.
X 2 each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or a cyano group. .
p represents any integer from 0 to 4, and q represents any integer from 0 to 4. Fluorene compound represented by
Formula (II)
R 2 to R 4 each independently represents a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, a nitro group, or a cyano group. To express. The curing catalyst for epoxy resins containing the imidazole compound represented by this. - 式（Ｉ）で表されるフルオレン化合物が、９,９－ビス（４－ヒドロキシフェニル）フルオレンである請求項１に記載のエポキシ樹脂用硬化触媒。 The curing catalyst for epoxy resins according to claim 1, wherein the fluorene compound represented by the formula (I) is 9,9-bis (4-hydroxyphenyl) fluorene.
- 式（II）で表されるイミダゾール化合物１モルに対して、式（Ｉ）で表されるフルオレン化合物を０．０１モル以上含有する請求項１又は２に記載のエポキシ樹脂用硬化触媒。 The curing catalyst for epoxy resins according to claim 1 or 2, comprising 0.01 mol or more of the fluorene compound represented by the formula (I) with respect to 1 mol of the imidazole compound represented by the formula (II).
- 下記（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分を含有するエポキシ硬化樹脂形成用組成物。
（Ａ）エポキシ樹脂；
（Ｂ）式（Ｉ）
ｍは０～４のいずれかの整数を表し、ｎは０～４のいずれかの整数を表す。
Ｘ２は、それぞれ独立に、ハロゲノ基、無置換若しくは置換基を有するＣ１～６アルキル基、水酸基、無置換若しくは置換基を有するＣ１～６アルコキシ基、アミノ基、ニトロ基、又はシアノ基を表す。
ｐは０～４のいずれかの整数を表し、ｑは０～４のいずれかの整数を表す。）で表されるフルオレン化合物；
（Ｃ）式（II）
Ｒ２～Ｒ４は、それぞれ独立に、水素原子、ハロゲノ基、無置換若しくは置換基を有するＣ１～６アルキル基、無置換若しくは置換基を有するＣ６～１０アリール基、ニトロ基、又はシアノ基を表す。）で表されるイミダゾール化合物。 The composition for epoxy cured resin formation containing the following (A) component, (B) component, and (C) component.
(A) epoxy resin;
(B) Formula (I)
m represents any integer from 0 to 4, and n represents any integer from 0 to 4.
X 2 each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amino group, a nitro group, or a cyano group. .
p represents any integer from 0 to 4, and q represents any integer from 0 to 4. Fluorene compound represented by:
(C) Formula (II)
R 2 to R 4 each independently represents a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, a nitro group, or a cyano group. To express. The imidazole compound represented by this. - （Ｃ）成分である式（II）で表されるイミダゾール化合物１モルに対して、（Ｂ）成分である式（Ｉ）で表されるフルオレン化合物を０．０１モル以上含有する請求項４に記載のエポキシ硬化樹脂形成用組成物。 The amount of the fluorene compound represented by the formula (I) as the component (B) is 0.01 mol or more with respect to 1 mol of the imidazole compound represented by the formula (II) as the component (C). The composition for epoxy cured resin formation of description.
- （Ａ）成分であるエポキシ樹脂のエポキシ環１モルに対して、（Ｃ）成分である式（II）で表されるイミダゾール化合物を０．０１～１．０モル含有する請求項４又は５に記載のエポキシ硬化樹脂形成用組成物。 The component (A) contains 0.01 to 1.0 mol of an imidazole compound represented by the formula (II) as a component (C) with respect to 1 mol of an epoxy ring of the epoxy resin as a component. The composition for epoxy cured resin formation of description.
- （Ｂ）成分である式（Ｉ）で表されるフルオレン化合物が、９,９－ビス（４－ヒドロキシフェニル）フルオレンである請求項４～６のいずれか記載のエポキシ硬化樹脂形成用組成物。 The composition for forming an epoxy cured resin according to any one of claims 4 to 6, wherein the fluorene compound represented by the formula (I) as the component (B) is 9,9-bis (4-hydroxyphenyl) fluorene.
- 請求項４～７のいずれか記載のエポキシ硬化樹脂形成用組成物を加熱処理して硬化して、エポキシ硬化樹脂を製造する方法。 A method for producing an epoxy cured resin by heat-treating and curing the composition for forming an epoxy cured resin according to any one of claims 4 to 7.
- 請求項４～７のいずれか記載のエポキシ硬化樹脂形成用組成物を加熱処理して硬化して得られたエポキシ硬化樹脂。 An epoxy curable resin obtained by curing the composition for forming an epoxy curable resin according to any one of claims 4 to 7 by heat treatment.
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|---|---|---|---|---|
| KR102414361B1 (en) * | 2017-07-27 | 2022-06-30 | 도쿄 오카 고교 가부시키가이샤 | An aromatic amine compound, a curing agent for an epoxy compound, a curable composition, a cured product, a method for producing a cured product, and a method for producing an aromatic amine compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004059836A (en) * | 2002-07-31 | 2004-02-26 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg and laminated sheet |
| JP2008255309A (en) * | 2007-03-13 | 2008-10-23 | Osaka Gas Co Ltd | Epoxy resin composition and cured product thereof |
| JP2011157445A (en) * | 2010-01-29 | 2011-08-18 | Hitachi Chem Co Ltd | Thermosetting resin composition, prepreg using the same, and laminated board |
-
2016
- 2016-09-05 WO PCT/JP2016/004038 patent/WO2017047036A1/en active Application Filing
- 2016-09-13 TW TW105129750A patent/TW201714910A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004059836A (en) * | 2002-07-31 | 2004-02-26 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg and laminated sheet |
| JP2008255309A (en) * | 2007-03-13 | 2008-10-23 | Osaka Gas Co Ltd | Epoxy resin composition and cured product thereof |
| JP2011157445A (en) * | 2010-01-29 | 2011-08-18 | Hitachi Chem Co Ltd | Thermosetting resin composition, prepreg using the same, and laminated board |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201714910A (en) | 2017-05-01 |
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