WO2022009628A1 - Curing agent for epoxy resin - Google Patents

Curing agent for epoxy resin Download PDF

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Publication number
WO2022009628A1
WO2022009628A1 PCT/JP2021/022821 JP2021022821W WO2022009628A1 WO 2022009628 A1 WO2022009628 A1 WO 2022009628A1 JP 2021022821 W JP2021022821 W JP 2021022821W WO 2022009628 A1 WO2022009628 A1 WO 2022009628A1
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WIPO (PCT)
Prior art keywords
epoxy resin
amino groups
curing agent
secondary amino
amino group
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PCT/JP2021/022821
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French (fr)
Japanese (ja)
Inventor
江利子 佐藤
Original Assignee
味の素株式会社
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Priority to JP2022534986A priority Critical patent/JPWO2022009628A1/ja
Publication of WO2022009628A1 publication Critical patent/WO2022009628A1/en

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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
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a curing agent for epoxy resin and the like.
  • the present invention also comprises a resin composition containing an epoxy resin curing agent and an epoxy resin, a cured product of the resin composition and a composite material containing carbon fibers, a method for producing an epoxy resin curing agent, a method for producing a cured product, and the like. Regarding the curing method of epoxy resin.
  • Fiber-reinforced composite materials which consist of reinforced fibers such as carbon fiber and thermosetting materials such as epoxy resin, are lightweight and have excellent physical properties such as high strength, and therefore are used in many fields such as aircraft and automobiles. It is used.
  • diaminodiphenyl sulfone is often used as a curing agent for epoxy resins used in composite materials.
  • a cured product of an epoxy resin composition using diaminodiphenyl sulfone as a curing agent has excellent performance such as high heat resistance and high strength.
  • diaminodiphenyl sulfone has a high melting point of 180 ° C., is sparingly soluble in epoxy resin, and the resin composition tends to have high viscosity, so that it is difficult to quickly impregnate reinforcing fibers such as carbon fibers.
  • Patent Document 1 and Patent Document 2 describe an epoxy resin composition using a curing agent in which diaminodiphenyl sulfone is dissolved in a liquid aromatic polyamine.
  • the epoxy resin composition using this curing agent takes a long time to cure, and the impact strength of the obtained cured product is not satisfactory.
  • One of the problems to be solved by the present invention is to provide a curing agent for an epoxy resin, which provides a resin composition having a low viscosity and a fast curing property and a cured product having a high impact strength.
  • the present inventors have combined (A) a liquid aromatic polyamine and (B) a solid aromatic polyamine containing a secondary amino group to obtain (B) a secondary amino group. If the solid aromatic amine contained does not contain (B1) a solid aromatic amine in which the number of secondary amino groups is greater than the total number of primary and tertiary amino groups, then (C) an aliphatic cyclic polyamine is further combined.
  • B1 a solid aromatic amine in which the number of secondary amino groups is greater than the total number of primary and tertiary amino groups
  • C an aliphatic cyclic polyamine is further combined.
  • a curing agent for an epoxy resin containing (A) a liquid aromatic polyamine and (B) a solid aromatic amine containing a secondary amino group.
  • B) The solid aromatic amine containing a secondary amino group contains or does not contain (B1) a solid aromatic amine in which the number of secondary amino groups is greater than the total number of primary amino groups and tertiary amino groups. If not contained, the epoxy resin curing agent further contains (C) an aliphatic cyclic polyamine.
  • B) The solid aromatic amine containing a secondary amino group contains (B1) a solid aromatic amine in which the number of secondary amino groups is larger than the total number of primary amino groups and tertiary amino groups.
  • (B1) A solid aromatic amine having a larger number of secondary amino groups than the total number of primary amino groups and tertiary amino groups contains only a secondary amino group as the (B1') amino group.
  • the solid aromatic amine containing only a secondary amino group as the (B1') amino group is N-phenyl-1-naphthylamine, octylated diphenylamine, 4,4'-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine.
  • N- (p-tolyl) -1-naphthylamine N-phenyl-3-biphenylamine, bis (3-biphenylyl) amine, 2- (3-biphenylyl) amino-9,9-dimethylfluorene, bis (4- tert-butylphenyl) amine, 4-tert-butylphenylphenylamine, bis- ⁇ -methylbenzylphenothiazine, reaction product of diphenylamine with 2,4,4-trimethylpentene, diphenylamine, N-phenylbenzylamine, 3-methyl Diphenylamine, 3,4-dimethyldiphenylamine, 4,4'-dimethyldiphenylamine, 3-methoxydiphenylamine, 10-methoxy-2,2'-iminostylben, N-benzyl-2-naphthylamine, 1,2'-dinaphthylamine, 1,1'-Dinaphthylamine
  • the solid aromatic amine containing a secondary amino group further contains (B2) a solid aromatic polyamine in which the number of secondary amino groups is equal to or less than the total number of primary amino groups and tertiary amino groups.
  • the curing agent for epoxy resin according to any one of the above [2] to [4].
  • (B2) Solid aromatic polyamines in which the number of secondary amino groups is equal to or less than the total number of primary amino groups and tertiary amino groups are 4-aminodiphenylamine, 2,4-diaminodiphenylamine, and 2-aminodiphenylamine.
  • Solid aromatic polyamines in which the number of secondary amino groups is equal to or less than the total number of primary amino groups and tertiary amino groups are 4-aminodiphenylamine, 2,4-diaminodiphenylamine, and 2-aminodiphenylamine.
  • the liquid aromatic polyamine is selected from the group consisting of dimethylthiotoluenediamine, diethyltoluenediamine and 4,4'-methylenebis [N- (1-methylpropyl) aniline], as described above [18].
  • the curing agent for epoxy resin described in. [20] The curing agent for an epoxy resin according to any one of the above [1] to [19], which is a liquid.
  • a (numerical value) to B (numerical value) means “A or more and B or less”
  • the ratio means a mass ratio.
  • the preferable embodiment and the more preferable embodiment exemplified below can be used in combination with each other as appropriate regardless of the expressions such as “favorable” and “more preferable”.
  • the description of the numerical range is an example, and a range in which the upper limit and the lower limit of each range and the numerical values of the examples are appropriately combined can also be preferably used regardless of expressions such as “preferable” and “more preferable”. ..
  • the present invention is a curing agent for an epoxy resin containing (A) a liquid aromatic polyamine and (B) a solid aromatic amine containing a secondary amino group, and (B) a solid aromatic amine containing a secondary amino group.
  • (B1) contains or does not contain a solid aromatic amine in which the number of secondary amino groups is greater than the total number of primary amino groups and tertiary amino groups
  • the curing agent for epoxy resin is (C).
  • the present invention relates to a curing agent for an epoxy resin, further containing an aliphatic cyclic polyamine.
  • liquid aromatic polyamine in the present invention means an aromatic polyamine having a melting point lower than room temperature (25 ° C.), that is, a liquid state at room temperature (25 ° C.).
  • Liquid aromatic polyamines are aromatic compounds having two or more amino groups.
  • the "amino group” includes a “primary amino group", a “secondary amino group” and a “tertiary amino group”. Since the tertiary amino group promotes the self-polymerization of the epoxy resin and tends to lower the heat resistance of the obtained cured product, from the viewpoint of obtaining a highly heat-resistant cured product, the liquid aromatic polyamine has two or more liquid aromatic polyamines. It preferably contains a primary amino group, two or more secondary amino groups, or one or more primary amino groups and one or more secondary amino groups.
  • the liquid aromatic polyamine preferably has a viscosity of 100 cP or less under heating conditions of 80 ° C. or higher, more preferably 0.001 to 60 cP, still more preferably 0.01. It has a viscosity of ⁇ 20 cP.
  • the viscosity of the liquid aromatic polyamine can be measured using a commercially available viscosity measuring device, for example, RheoStress6000 manufactured by HAAKE.
  • the liquid aromatic polyamine preferably has a boiling point of 140 ° C. or higher, more preferably 150 ° C. to 500 ° C., still more preferably 160 ° C. to 400 ° C., and even more preferably 180 to 350 ° C.
  • the boiling point is 140 ° C. or higher
  • the temperature is sufficiently higher than the temperature at which the reinforcing fiber is impregnated with the resin composition in the manufacturing process of the fiber-reinforced composite material using the epoxy resin as the matrix resin. Volatilization can be suppressed, and as a result, structural defects and a decrease in strength of the fiber-reinforced composite material can be suppressed.
  • Preferred liquid aromatic polyamines include, for example, dimethylthiotoluenediamine, diethyltoluenediamine, 4,4'-methylenebis [N- (1-methylpropyl) aniline] and the like.
  • liquid aromatic polyamines examples include dimethylthiotoluenediamine (“Etacure 300” manufactured by Albemarle, “Heartcure 30” manufactured by Kumiai Chemical Industry Co., Ltd.), diethyltoluenediamine (“Etacure 100 Plus” manufactured by Albemarle), and “Heart Cure 10" manufactured by Kumiai Chemical Industry Co., Ltd.) and the like can be mentioned.
  • the liquid aromatic polyamine may be used alone or in combination of two or more.
  • a liquid aromatic containing two or more primary amino groups with respect to the total mass of the liquid aromatic amine from the viewpoint of increasing the strength and heat resistance of the cured product is preferably contained in a proportion of 50 to 90% by mass, more preferably 60 to 80% by mass.
  • the liquid aromatic polyamine is preferably 40 to 97% by mass, more preferably 50 to 95% by mass, still more preferably 55 to 93, from the viewpoint of obtaining a resin composition having a low viscosity. It is contained in the curing agent in an amount of% by mass.
  • Solid aromatic amine containing a secondary amino group The "solid" aromatic amine in the present invention is an aromatic amine having a melting point higher than room temperature (25 ° C), that is, a solid state at room temperature (25 ° C). Refers to amine.
  • the solid aromatic amine of the present invention contains a secondary amino group. Since the solid aromatic amine contains a secondary amino group, the impact strength of the cured product can be increased.
  • the solid aromatic amine containing a secondary amino group preferably has a melting point of 160 ° C. or lower, for example, 155 ° C. or lower, or 150 ° C. or lower. Further, the solid aromatic amine containing a secondary amino group preferably has a melting point of, for example, 30 ° C. or higher, 40 ° C. or higher, 50 ° C. or higher, 60 ° C. or higher, or 70 ° C. or higher. When the melting point is 160 ° C. or lower, it can be easily dissolved in a liquid aromatic polyamine in a short time.
  • solid aromatic amine containing a secondary amino group having a melting point of 160 ° C. or lower examples include N-phenyl-1-naphthylamine, octylated diphenylamine, 4,4'-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine, and N.
  • the solid aromatic amine containing a secondary amino group preferably has a boiling point of 140 ° C. or higher, more preferably 145 ° C. to 550 ° C., still more preferably 150 ° C. to 500 ° C., still more preferably 160 ° C. to 450 ° C. Particularly preferably, it has a boiling point of 170 to 400 ° C.
  • the boiling point is 140 ° C. or higher, the temperature is sufficiently higher than the temperature at which the reinforcing fiber is impregnated with the resin composition in the manufacturing process of the fiber-reinforced composite material using the epoxy resin as the matrix resin, and therefore contains a secondary amino group. Volatilization of the solid aromatic amine component can be suppressed, and as a result, structural defects and a decrease in strength of the fiber-reinforced composite material can be suppressed.
  • solid aromatic amine containing a secondary amino group having a boiling point of 140 ° C. or higher examples include N-phenyl-1-naphthylamine, octylated diphenylamine, 4,4'-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine, and N.
  • the solid aromatic amine containing a secondary amino group may contain a monoamine having one secondary amino group, and a polyamine having two or more amino groups, of which at least one is a secondary amino group. It may be included. From the viewpoint of improving the curing rate of the resin composition and the mechanical properties of the cured product, the solid aromatic amine containing a secondary amino group has (B1) a number of secondary amino groups of primary amino group and tertiary amino group. It is preferable to contain more solid aromatic amines than the total number of.
  • (B1) As a solid aromatic amine in which the number of secondary amino groups is larger than the total number of primary amino groups and tertiary amino groups, a solid aromatic amine containing only a secondary amino group as a (B1') amino group (B1') It is preferable that the number of secondary amino groups is one, two or three or more, and the total number of primary amino groups and tertiary amino groups is 0).
  • B1 As a solid aromatic amine in which the number of secondary amino groups is larger than the total number of primary amino groups and tertiary amino groups, for example, a solid aromatic monoamine having only one secondary amino group as an amino group (B1).
  • B1' a solid aromatic polyamine having only two or more secondary amino groups as an amino group (corresponding to B1')
  • a solid aromatic polyamine having one primary amino group and two secondary amino groups Solid aromatic polyamines with two secondary amino groups and one tertiary amino group, solid aromatic polyamines with one primary amino group and three or more secondary amino groups, and three or more secondary amino groups. Examples thereof include solid aromatic polyamines having one tertiary amino group.
  • solid aromatic monoamines having only one secondary amino group as an amino group are N-phenyl-1-naphthylamine, octylated diphenylamine, 4,4'-bis ( ⁇ , ⁇ ).
  • Preferred examples of solid aromatic polyamines having only two or more secondary amino groups as amino groups are 4-isopropylaminodiphenylamine, 2,6-bis [(2-hydroxyethyl) amino].
  • Toluene 4- (2-octylamino) diphenylamine, N- (1,3-dimethylbutyl) -N'-phenyl-1,4-phenylenediamine, 2,2,4-trimethyl-1,2-dihydroquinoline weight
  • 1,3-diphenylguanidine p- (p-toluenesulfonylamide) diphenylamine, N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, bis (2-benzamidephenyl) ) Disulfide, N, N'-diphenyl-1,4-phenylenediamine, 1,3-di-o-tolylguanidine,
  • solid aromatic amines in which the number of secondary amino groups is greater than the total number of primary and tertiary amino groups are 1- (o-tolyl) biguanide, 1-phenylguanidine, phenyl.
  • examples thereof include biguanide, a high molecular weight biguanide compound containing a terminal amino group, 4-phenylsemicarbazide, 4-phenyl-3-thiosemicarbazide, 1,2,3-triphenylguanidine and the like.
  • the solid aromatic amine containing a secondary amino group may contain (B2) a solid aromatic polyamine in which the number of secondary amino groups is not more than the total number of primary amino groups and tertiary amino groups.
  • (B) a solid aromatic amine containing a secondary amino group does not contain (B1) a solid aromatic amine in which the number of secondary amino groups is greater than the total number of primary and tertiary amino groups.
  • B2) A solid aromatic polyamine in which the number of secondary amino groups is not more than the total number of primary amino groups and tertiary amino groups may be contained.
  • the curing agent for epoxy resin further contains (C) aliphatic cyclic polyamine described later.
  • (B) a solid aromatic amine containing a secondary amino group (B1) a solid aromatic amine in which the number of secondary amino groups is larger than the total number of primary amino groups and tertiary amino groups, and (B2).
  • a solid aromatic polyamine in which the number of secondary amino groups is not more than the total number of primary amino groups and tertiary amino groups may be used in combination.
  • the curing agent for epoxy resin may or may not further contain (C) the aliphatic cyclic polyamine described later.
  • the solid aromatic polyamine in which the number of secondary amino groups is not more than the total number of primary amino groups and tertiary amino groups is a solid aromatic polyamine containing a primary amino group and a secondary amino group (for example, for example.
  • Solid aromatic polyamines with one primary amino group and one secondary amino group such as solid aromatic polyamines with two primary amino groups and one secondary amino group), secondary amino groups and tertiary aminos.
  • Contains solid aromatic polyamines containing groups eg, solid aromatic polyamines containing one secondary amino group and one tertiary amino group), primary amino groups, secondary amino groups and tertiary amino groups. Examples include solid aromatic polyamines.
  • (B2) Preferred examples of the solid aromatic polyamine in which the number of secondary amino groups is not more than the total number of primary amino groups and tertiary amino groups are 4-aminodiphenylamine, 2,4-diaminodiphenylamine, and 2-amino.
  • the solid aromatic amine containing a secondary amino group may be used alone or in combination of two or more.
  • a solid aromatic polyamine which is not more than the total number of polyamines.
  • a solid aromatic amine in which the number of two or more (B1) secondary amino groups is larger than the total number of the primary amino group and the tertiary amino group is used. It may be used in combination, or a solid aromatic polyamine in which the number of two or more kinds of (B2) secondary amino groups is not more than the total number of primary amino groups and tertiary amino groups may be used in combination.
  • the solid aromatic amine containing a secondary amino group may have a substituent such as halogen in the aromatic ring.
  • a solid aromatic amine containing a (B) secondary amino group having a halogen substituent on the aromatic ring it is possible to improve the viscosity stability of the resin composition.
  • Examples of commercially available solid aromatic polyamines containing a secondary amino group are 1- (o-tolyl) biganide ("Noxeller BG” manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., "Aradur 2844” manufactured by HUNTSMAN, and manufactured by Thomas Swan.
  • Cisamine OTB 4-isopropylaminodiphenylamine
  • Nocrack 810-NA 4-isopropylaminodiphenylamine
  • Antage 3C manufactured by Kawaguchi Kagaku Kogyo Co., Ltd.
  • 4-aminodiphenylamine 4-aminodiphenylamine
  • 4-Amino manufactured by Seiko Kagaku Co., Ltd.
  • Diphenylamine "4-ADPA” manufactured by LANXESS
  • 2,2,4-trimethyl-1,2-dihydroquinoline polymer ("Nocrack 224 (224-S)” manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., Seiko Kagaku Co., Ltd.
  • Non-Flex RD Non-Flex QS
  • N-phenyl-1-naphthylamine Nocrack PA
  • 1,3-diphenylguanidine manufactured by Ouchi Shinko Chemical Industry Co., Ltd. "” Noxeller D “, Sanshin Chemical Industry Co., Ltd.”
  • 4,4'-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine "Nocrack CD "manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., Seiko Kagaku "Non-flex DCD” manufactured by the company) and the like can be mentioned.
  • the solid aromatic polyamine containing a secondary amino group is preferably 1 to 45% by mass, more preferably 2 to 40% by mass, and further, from the viewpoint of increasing the impact strength of the cured product. It is contained in the curing agent in an amount of preferably 3 to 35% by mass.
  • the curing agent of the present invention is optionally a solid aromatic having a melting point of 160 ° C. or lower and containing no secondary amino group but containing a primary amino group. It may contain amines.
  • solid aromatic amines having a melting point of 160 ° C. or lower, which do not contain a secondary amino group but contain a primary amino group are 4,4'-methylenebis (2-ethyl-6-methylaniline) and 2,2'-.
  • the curing agent for epoxy resin of the present invention contains (B) a solid aromatic amine containing a secondary amino group, and (B1) a primary amino group and a tertiary amino group having a secondary amino group number.
  • the solid aromatic amine containing more than the total number of (B) the secondary amino group is not contained (that is, (B2) the number of the secondary amino group is the primary amino group and the tertiary amino group as the solid aromatic amine containing the secondary amino group.
  • (C) further contains aliphatic cyclic polyamines.
  • the number of (B1) secondary amino groups as a solid aromatic amine containing (B) secondary amino groups is larger than the total number of primary amino groups and tertiary amino groups.
  • (C) the aliphatic cyclic polyamine may or may not be further contained.
  • the (C) aliphatic cyclic polyamine in the curing agent has an action of accelerating the curing of the epoxy resin by (A) a liquid aromatic polyamine and (B) a solid aromatic amine containing a secondary amino group. That is, the curing agent of the present invention can accelerate the curing of the resin composition and accelerate the curing rate by containing the aliphatic cyclic polyamine.
  • the aliphatic cyclic polyamine may be an aliphatic hydrocarbon having two or more amino groups as substituents on the ring structure (ie, attached to the ring) and in the ring structure (ie, ring). It may be a heterocyclic amine having two or more amino groups (constituting).
  • it may be a heterocyclic amine having one or more amino groups as a substituent on the ring structure and having one or more amino groups in the ring structure.
  • the amino group as the substituent on the ring structure include a primary amino group and a secondary amino group, and a primary amino group is preferable.
  • a secondary amino group is preferable.
  • the resin composition is higher than that of an aliphatic cyclic polyamine in which a nitrogen atom or an amino group is stabilized by forming a complex or salt structure.
  • the curing speed of the object can be increased.
  • an element (carbon atom or the like) adjacent to the amino group (preferably a secondary amino group) in the ring structure and / or an amino group on the ring structure are bonded to each other.
  • Those in which all the substituents of the element (carbon atom, etc.) adjacent to the element (carbon atom, etc.) are hydrogen atoms are selected.
  • all of the above substituents are hydrogen atoms, there is no steric hindrance in the reaction of the amino group with the epoxy resin as compared with the case where a substituent other than the hydrogen atom (for example, an alkyl group) is bonded.
  • the curing rate of the resin composition can be further increased.
  • At least all the substituents of the two elements adjacent to one amino group in the ring structure may be hydrogen atoms, but all of them in the ring structure. It is preferable that all the substituents of the element adjacent to the amino group are hydrogen atoms.
  • at least if the substituents of the two elements adjacent to the one element to which the amino group is bonded are all hydrogen atoms.
  • all the substituents of the element adjacent to all the elements to which the amino group is bonded are hydrogen atoms.
  • an element (carbon atom or the like) other than the amino group (preferably a secondary amino group) in the ring structure and / or an element other than the element (carbon atom or the like) to which the amino group on the ring structure is bonded carbon atom or the like.
  • Those in which all the substituents of (carbon atom, etc.) are hydrogen atoms are selected.
  • the aliphatic cyclic polyamine preferably has a boiling point of 140 ° C. or higher, and more preferably 145 ° C. to 250 ° C.
  • the temperature is sufficiently higher than the temperature at which the reinforcing fiber is impregnated into the resin composition in the manufacturing process of the fiber-reinforced composite material using the epoxy resin as the matrix resin. Volatilization can be suppressed, and as a result, structural defects and a decrease in strength of the fiber-reinforced composite material can be suppressed.
  • the aliphatic cyclic polyamine preferably has a melting point of 160 ° C. or lower, for example, 150 ° C. or lower, 140 ° C. or lower, 130 ° C. or lower, or 120 ° C. or lower.
  • the melting point is 160 ° C. or lower, it can be easily dissolved in a liquid aromatic polyamine in a short time.
  • the aliphatic cyclic polyamine is preferably a compound having one, two or three ring structures from the viewpoint of lowering the viscosity of the resin composition.
  • the aliphatic cyclic polyamine preferably contains a primary amino group or a secondary amino group from the viewpoint of enhancing the heat resistance of the cured product. From the viewpoint of reactivity, it is more preferable that the amino group in the ring structure contains a secondary amino group, further preferably it contains only a secondary amino group, and the amino group as a substituent is a primary amino group. It is more preferable to include it. As long as it contains a primary amino group or a secondary amino group, it may contain a tertiary amino group as long as it does not adversely affect physical properties such as heat resistance of the cured product.
  • the aliphatic cyclic polyamine containing a secondary amino group preferably has a piperazine skeleton, for example, piperazine, 2-methylpiperazine, homopiperazine, trans-2,5-dimethylpiperazine, cis-2,6-dimethylpiperazine. , (S)-(+)-2-methylpiperazine, N- (2-aminoethyl) piperazine, 1-butylpiperazine, 1-methylpiperazine, 2-piperazinone and the like.
  • the aliphatic cyclic polyamine is more preferably piperazine because it has high reactivity and can shorten the curing time.
  • an aliphatic cyclic polyamine containing a secondary amino group is 1,3-bis (aminomethyl) cyclohexane, dexrazoxane, 3-aminopyrrolidine, 3- (methylamino) pyrrolidine, 3- (ethylamino).
  • the aliphatic cyclic polyamine when the curing agent is 100% by mass, is preferably in an amount of 1 to 15% by mass, more preferably 2 to 12% by mass, still more preferably 3 to 10% by mass. , Included in the curing agent. If the content of the aliphatic cyclic polyamine is 1% by mass or more, the curing rate of the resin composition can be increased, and if it is 15% by mass, the heat resistance of the cured product is not impaired.
  • the curing agent for epoxy resin of the present invention optionally contains additional components such as a borate compound, a titanate compound, a zirconate compound, a silane compound, a carboxylic acid compound, a phenol compound and a halogen compound within a range not impairing the effect of the present invention. But it may be.
  • additional components may be contained in the form of (B) a salt with a solid aromatic amine containing a secondary amino group.
  • the curing agent of the present invention may be in a liquid form in which a solid aromatic amine containing a secondary amino group and an aliphatic cyclic polyamine, if present, are dissolved in a liquid aromatic polyamine.
  • the solid aromatic amine containing a secondary amino group and the aliphatic cyclic polyamine, if present, may be in the form of a suspension existing as a solid in the aromatic polyamine.
  • the curing agent of the present invention is preferably in a liquid form.
  • a solid aromatic amine containing a secondary amino group is dissolved in a liquid aromatic polyamine to dissolve the curing agent for an epoxy resin.
  • B Solid aromatic amines containing secondary amino groups, and (B1) solid aromatic amines having more secondary amino groups than the total number of primary amino groups and tertiary amino groups. If not, it further comprises the step of dissolving (C) the aliphatic cyclic polyamine.
  • the method for producing a curing agent for an epoxy resin in a liquid form is as follows: (B) a solid aromatic amine containing a secondary amino group, and (B1) the total number of secondary amino groups of a primary amino group and a tertiary amino group.
  • (B) a solid aromatic amine containing a secondary amino group and (B1) the total number of secondary amino groups of a primary amino group and a tertiary amino group.
  • A the solid aromatic amine containing a secondary amino group in the liquid aromatic polyamine
  • C dissolving the aliphatic cyclic polyamine. Further steps may be included.
  • the melting means is not particularly limited, and for example, after mixing each raw material, it may be heated and melted using a heating device such as an oven or a heating type tank.
  • Conditions for using the oven include, for example, at a temperature of 80-120 ° C, 90-110 ° C, or 95-105 ° C, for example, 20-90 minutes, 30-60 minutes, or 40-50 minutes. It may be heated.
  • the heating temperature and heating time can be appropriately adjusted according to the heating device used and the scale of the raw material.
  • the epoxy resin contained in the resin composition a conventionally known epoxy resin can be used without particular limitation.
  • the epoxy resin can be appropriately selected depending on the intended use and the desired properties of the cured product. For example, from the viewpoint of the impact strength of the cured product, a bifunctional or higher functional epoxy resin is preferable, and a trifunctional or higher functional epoxy resin is used. It is more preferable to have.
  • the trifunctional or higher functional epoxy resin is preferably a glycidylamine type epoxy resin, for example, a diaminodiphenylmethane type epoxy resin, a diaminodiphenylsulfone type epoxy resin, an aminophenol type epoxy resin, a methaxylene diamine type epoxy resin, 1,3-.
  • a glycidylamine type epoxy resin for example, a diaminodiphenylmethane type epoxy resin, a diaminodiphenylsulfone type epoxy resin, an aminophenol type epoxy resin, a methaxylene diamine type epoxy resin, 1,3-.
  • examples thereof include bisaminomethylcyclohexane type epoxy resin and isocyanurate type epoxy resin.
  • the trifunctional or higher functional epoxy resin may preferably be a glycidyl ether type epoxy resin, for example, a phenol novolac type epoxy resin, an orthocresol novolac type epoxy resin, a trishydroxyphenylmethane type epoxy resin, or a tetraphenylol ethane type epoxy.
  • a resin and a dicyclopentadiene type epoxy resin examples include a resin and a dicyclopentadiene type epoxy resin.
  • Examples of commercially available products of trifunctional or higher glycidylamine type epoxy resin are diaminodiphenylmethane type epoxy resin ("ELM434" manufactured by Sumitomo Chemical Co., Ltd., "jER604" manufactured by Mitsubishi Chemical Co., Ltd., "Araldite” manufactured by Huntsman Advanced Materials Co., Ltd. MY720, “Araldite MY721”, “Araldite MY9512”, “Araldite MY9663”, Toto Kasei Co., Ltd. "Epototo YH-434"), Aminophenol type epoxy resin (Japan Epoxy Resin Co., Ltd. "jER630", Huntsman Co., Ltd.
  • Examples of commercially available products of trifunctional or higher glycidyl ether type epoxy resin are phenol novolac type epoxy resin (“DEN431” and “DEN438” manufactured by Dow Chemical Co., Ltd., “jER152” manufactured by Japan Epoxy Resin Co., Ltd.) and orthocresol novolac type epoxy.
  • the epoxy resin may be bifunctional.
  • glycidyl ether type epoxy resin is preferable, and for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, urethane modified epoxy resin. , Hydant-in type epoxy resin and the like can be mentioned.
  • Examples of commercial products of bifunctional glycidyl ether type epoxy resin are bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd. "jER828”, “jER825", DIC Co., Ltd. "Epicron 850", Toto Kasei Co., Ltd. "Epototo YD-”. 128 ”,“ DER-331 ”,“ DER-332 ”manufactured by Dow Chemical Co., Ltd., bisphenol F type epoxy resin (“jER806”, “jER807”, “jER1750” manufactured by Mitsubishi Chemical Co., Ltd., “Epicron 830” manufactured by DIC Co., Ltd., Toto Kasei Co., Ltd.
  • the epoxy equivalent of the epoxy resin contained in the resin composition is preferably 50 to 500, more preferably 75 to 300, and even more preferably 100 to 200.
  • the epoxy equivalent of the epoxy resin is 50 or more, the viscosity is low, the viscosity is not low, and the viscosity is easy to handle, which is preferable. Further, when the epoxy equivalent of the epoxy resin is 500 or less, the viscosity does not become high and it is suitable in terms of handling.
  • the epoxy equivalent is the mass of the epoxy resin containing one equivalent of the epoxy group, and can be measured according to, for example, JIS K 7236 (2009).
  • the epoxy resin may be used alone or in combination of two or more.
  • the epoxy resin may be liquid or solid. Further, a mixture of a liquid resin and a solid resin may be used.
  • liquid and solid refer to the state of the epoxy resin at room temperature (25 ° C.). From the viewpoint of processability, it is preferable that at least 10% by mass or more of the entire epoxy resin used is a liquid epoxy resin.
  • the content of the epoxy resin in the resin composition is not particularly limited, but is preferably 1 to 99% by mass, more preferably 20 to 95% by mass, and even more preferably 50 to 90% by mass. ..
  • the curing agent for epoxy resin of the present invention is preferably 10 to 75% by mass, more preferably 15 to 65% by mass, still more preferably, from the viewpoint of reducing the viscosity of the resin composition. Is contained in the resin composition in an amount of 20 to 55% by mass.
  • the resin composition of the present invention further comprises a curing agent, a curing accelerator, a thermosetting resin, a thermoplastic resin, an inorganic filler, an organic filler, a thickener, a defoaming agent, a leveling agent, and an adhesion imparting agent. It can contain one or more selected from the group consisting of colorants and organic solvents.
  • the curing agent means a curing agent for epoxy resin other than the curing agent for epoxy resin of the present invention, and for example, an acid anhydride compound, a thiol compound, a guanidine compound, a hydrazide compound, a phenol compound, a naphthol compound, an active ester compound, and the like.
  • an acid anhydride compound for example, an acid anhydride compound, a thiol compound, a guanidine compound, a hydrazide compound, a phenol compound, a naphthol compound, an active ester compound, and the like.
  • examples thereof include benzoxazine compounds, cyanate ester compounds, and carbodiimide compounds.
  • Thiol compounds include trimethylolpropanetris (thioglycolate), pentaerythritol tetrakis (thioglycolate), ethylene glycol dithioglycolate, trimethylolpropanetris (3-mercaptopropionate), and trimethylolpropanetris ( ⁇ -).
  • Thiol compounds obtained by esterification of mercapto organic acids with polyols such as thiopropionate), pentaerythritol tetrakis ( ⁇ -thiopropionate), dipentaerythritol poly ( ⁇ -thiopropionate); 1,4 -Alkyl polythiol compounds such as butanedithiol, 1,6-hexanedithiol, 1,10-decandithiol; terminal thiol group-containing polyether; terminal thiol group-containing polythioether; thiol compounds obtained by the reaction of epoxy compounds with hydrogen sulfide.
  • polyols such as thiopropionate), pentaerythritol tetrakis ( ⁇ -thiopropionate), dipentaerythritol poly ( ⁇ -thiopropionate); 1,4 -Alkyl polythiol compounds such as butanedithiol, 1,6-hexanedithio
  • Examples thereof include thiol compounds having a terminal thiol group obtained by reacting a polythiol compound with an epoxy compound.
  • the acid anhydride compound tetrahydroanhydride phthalic acid, hexahydroanhydride phthalic acid, methyltetrahydroanhydride phthalic acid, methylhexahydroanhydride phthalic acid, methylnadic acid anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride , Tetrapropenyl Anhydrous Succinic Acid (3-Dodecenyl Anhydrous Succinic Acid), Octenyl Succinic Anhydrous, Ethylene Glycol Bisuanhydrotrimeritate, Methylendomethylene Tetrahydro Anhydrous Phthanoic Acid, 3,4-dimethyl-6- (2-Methyl) -1-propenyl) -4-cyclohexene-1,2-dicarboxylic
  • Examples of commercially available acid anhydrides include HN-2200 (methyltetrahydrophthalic anhydride) and HN-5500 (methyltetrahydrophthalic anhydride) manufactured by Hitachi Chemical Co., Ltd.
  • Guanidine compounds include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, dimethylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5.
  • guanidine compound dicyandiamide is particularly preferable.
  • examples of commercially available guanidine compounds include "jER Cure DICY-7" (dicyandiamide) manufactured by Japan Epoxy Resin Co., Ltd.
  • hydrazide compound examples include carbohydrazide, dihydrazide oxalic acid, dihydrazide malonic acid, dihydrazide succinic acid, dihydrazide iminodiacetate, dihydrazide adipic acid, dihydrazide dimeric acid, dihydrazide siberic acid, dihydrazide azelaic acid, and dihydrazide hydrazide.
  • Hexadecane dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartrate dihydrazide, apple acid dihydrazide, citrate trihydrazide and the like can be mentioned.
  • Examples of commercially available hydrazide compounds include Ajinomoto Fine-Techno Co., Ltd.'s Amicure VDH and Amicure UDH.
  • Specific examples of the phenol compound and the naphthol compound include, for example, "MEH-7700", “MEH-7810", “MEH-7851” manufactured by Meiwa Kasei Co., Ltd., and "NHN” manufactured by Nippon Kayaku Co., Ltd.
  • the active ester compound is not particularly limited, but generally contains 2 highly reactive ester groups such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. Compounds having more than one are preferably used.
  • the active ester compound is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound.
  • an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferable.
  • the "dicyclopentadiene-type diphenol structure” represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.
  • Examples of the active ester compound contained include “YLH1026” (manufactured by Mitsubishi Chemical Corporation). Specific examples of the benzoxazine compound include “HFB2006M” manufactured by Showa High Polymer Co., Ltd., “Pd” and “FA” manufactured by Shikoku Chemicals Corporation. Examples of the cyanate ester compound include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylencyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4'-.
  • cyanate ester-based curing agent examples include "PT30” and “PT60” (both are phenol novolac type polyfunctional cyanate ester resins) and “BA230" (part or all of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. Is a prepolymer that has been triadinated into a trimer) and the like.
  • specific examples of the carbodiimide compound include “V-03” and "V-07” manufactured by Nisshinbo Chemical Co., Ltd.
  • the curing accelerator does not contain the aliphatic cyclic polyamine of the present invention, and examples thereof include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, and a guanidine-based curing accelerator.
  • the curing accelerator may be used alone or in combination of two or more.
  • Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl) triphenylphosphonium thiocyanate.
  • Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.
  • the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo.
  • Examples thereof include (5,4,0) -undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.
  • Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and the like.
  • the imidazole-based curing accelerator a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.
  • the guanidine-based curing accelerator the same compound as the guanidine compound as the curing agent can be used, and for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, etc.
  • the content of the curing accelerator in the resin composition is not particularly
  • thermosetting resin means a thermosetting resin other than the above-mentioned epoxy resin, and examples thereof include vinylbenzyl compounds, acrylic compounds, maleimide compounds, and blocked isocyanate compounds.
  • thermoplastic resin examples include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, and polyether. Examples thereof include ether ketone resin and polyester resin, and phenoxy resin is preferable.
  • the thermoplastic resin may be used alone or in combination of two or more.
  • the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and even more preferably in the range of 20,000 to 60,000.
  • the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method.
  • the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K- of Showa Denko Corporation as a column. 804L / K-804L can be calculated by measuring the column temperature at 40 ° C. using chloroform or the like as a mobile phase and using a standard polystyrene calibration curve.
  • phenoxy resin examples include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadienyl skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, and adamantan skeleton.
  • the terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.
  • the phenoxy resin may be used alone or in combination of two or more.
  • Specific examples of the phenoxy resin include “1256" and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” manufactured by Mitsubishi Chemical Corporation.
  • Bisphenol acetophenone skeleton-containing phenoxy resin) and also “FX280” and "FX293” manufactured by Nippon Steel & Sumitomo Metal Corporation, "YL6954BH30", “YX7553”, “YL7769BH30” manufactured by Mitsubishi Chemical Corporation, Examples thereof include “YL6794", "YL7213", “YL7290” and "YL7482".
  • polyvinyl acetal resin examples include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferable.
  • Specific examples of the polyvinyl acetal resin include "Electrified Butyral 4000-2", “Electrified Butyral 5000-A”, “Electrified Butyral 6000-C”, and “Electrified Butyral 6000-EP” manufactured by Denki Kagaku Kogyo Co., Ltd. , Eslek BH series, BX series, KS series, BL series, BM series, etc. manufactured by Sekisui Chemical Industry Co., Ltd. can be mentioned.
  • polyimide resin examples include “Ricacoat SN20” and “Ricacoat PN20” manufactured by NEW JAPAN CHEMICAL CO., LTD.
  • polyamide-imide resin examples include “Vilomax HR11NN” and “Vilomax HR16NN” manufactured by Toyobo Co., Ltd.
  • polyamide-imide resin examples include modified polyamide-imides such as “KS9100” and “KS9300” (polysiloxane skeleton-containing polyamide-imide) manufactured by Hitachi Chemical Industries, Ltd.
  • polyether sulfone resin examples include "PES5003P” manufactured by Sumitomo Chemical Co., Ltd.
  • polysulfone resin examples include polysulfones "P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.
  • the content of the thermoplastic resin in the resin composition is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, and further preferably 1% by mass to 5% by mass. ..
  • the inorganic filler is not particularly limited, and is, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water.
  • silica examples include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, as silica, spherical silica is preferable.
  • the average particle size is not particularly limited, but is preferably 600 nm or less, more preferably 300 nm or less, and further preferably 200 nm or less.
  • the lower limit of the average particle size is not particularly limited, but is preferably 5 nm or more. Examples of commercially available products include "SO-C2", “SO-C1", and "SO-C4" manufactured by Admatex Co., Ltd.
  • the average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory.
  • the conductive filler include solder particles, nickel particles, nano-sized metal crystals, particles having a metal surface coated with another metal, metal particles such as copper and silver gradient particles, and styrene resin, for example. , Urethane resin, melamine resin, epoxy resin, acrylic resin, phenol resin, styrene-butadiene resin and other resin particles coated with a conductive thin film such as gold, nickel, silver, copper and solder.
  • the conductive filler is usually spherical fine particles having a size of about 1 to 20 ⁇ m.
  • the magnetic filler include pure iron powder, Fe—Si alloy powder, Fe—Si—Al alloy powder, Fe—Ni alloy powder, Fe—Ni—Mo alloy powder, and Fe—Ni—.
  • Mo—Cu alloy powder Fe—Co alloy powder, Fe—Ni—Co alloy powder, Fe—Cr alloy powder, Fe—Cr—Si alloy powder, Fe—Ni—Cr alloy powder, or Fe -Fe alloys such as Cr-Al alloy powder, Fe-based amorphous, Amorphous alloys such as Co-based amorphous, Mg-Zn-based ferrite, Mn-Zn-based ferrite, Mn-Mg-based ferrite, Cu-Zn-based ferrite, Spinnel-type ferrites such as Mg-Mn-Sr-based ferrite and Ni-Zn-based ferrite, Ba-Zn-based ferrite, Ba-Mg-based ferrite, Ba-Ni-based ferrite, Ba-Co-based fer
  • the heat conductive filler examples include aluminum nitride, alumina, boron nitride, silicon nitride, graphite powder and silicon carbide.
  • Examples of commercially available aluminum nitride products include “Shapal H” manufactured by Tokuyama Corporation, and examples of commercially available silicon nitride products include “SN-9S” manufactured by Denki Kagaku Kogyo Co., Ltd.
  • Examples of commercially available alumina products include "AHP300” manufactured by Nippon Light Metal Co., Ltd. and “Arnabeads (registered trademark) CB” manufactured by Showa Denko Co., Ltd. (for example, “CB-P05” and “CB-A30S”) Denka Co., Ltd. Examples thereof include “DAW-45", “DAW-05", and "ASFP-20” manufactured by Japan.
  • organic filler examples include silicon powder, nylon powder, fluorine powder, acrylic rubber particles, polyamide fine particles, and silicone particles.
  • acrylic rubber particles include fine particles of a resin such as acrylonitrile butadiene rubber, butadiene rubber, and acrylic rubber that are chemically crosslinked and insoluble and insoluble in an organic solvent. Anything may be used, specifically, XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Staphyroid AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (manufactured by Aika Kogyo Co., Ltd.), Examples thereof include Pararoid EXL2655 and EXL2602 (all manufactured by Kureha Chemical Industry Co., Ltd.).
  • polyamide fine particles include aliphatic polyamides such as nylon, aromatic polyamides such as Kevlar, and any fine particles of a resin having an amide bond such as polyamide-imide of 50 microns or less. Any one may be used, and specific examples thereof include VESTOSINT 2070 (manufactured by Daiselhurus Co., Ltd.) and SP500 (manufactured by Toray Industries, Inc.).
  • thickener examples include Orben, Benton and the like.
  • defoaming agent examples include silicone-based defoaming agents, fluorine-based defoaming agents, and polymer-based defoaming agents.
  • a commercially available surfactant can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, and amphoteric surfactants, which may be used alone. Two or more kinds may be used in combination.
  • the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines.
  • KP manufactured by Shinetsu Chemical Industry Co., Ltd.
  • Polyflow manufactured by Kyoeisha Chemical Co., Ltd.
  • Ftop Mitsubishi Material Denshi Kasei Co., Ltd.
  • Megafuck manufactured by DIC Co., Ltd.
  • Florard manufactured by Sumitomo 3M Co., Ltd.
  • Asahi Guard manufactured by Asahi Glass Co., Ltd.
  • Surfron manufactured by AGC Seimi Chemical Co., Ltd.
  • Solsperse manufactured by Zeneca Co., Ltd.
  • EFKA manufactured by CIBA
  • Azisper manufactured by Ajinomoto Fine Techno Co., Ltd.
  • adhesion-imparting agent examples include imidazole-based, thiazole-based, triazole-based, and silane coupling agents.
  • colorant examples include phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, carbon black and the like.
  • organic solvent examples include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbi such as cellosolve and butyl carbitol.
  • ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone
  • acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate
  • carbi such as cellosolve and butyl carbitol.
  • examples include tolls, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide (DMAc
  • the resin composition is preferably 100 cP or less, more preferably 99 cP or less under heating conditions of 80 ° C. or higher (for example, 90 ° C.). More preferably, it has an initial viscosity of 98 cP or less.
  • the resin composition may have a viscosity of, for example, 10 cP or more, 20 cP or more, 30 cP or more, or 40 cP or more under heating conditions of 80 ° C. or higher (for example, 90 ° C.).
  • the "initial viscosity” means the viscosity measured immediately after mixing the epoxy resin and the curing agent for the epoxy resin.
  • the viscosity can be measured using a commercially available viscosity measuring device, for example, RheoStress6000 manufactured by HAAKE.
  • the "low viscosity" resin composition refers to a resin composition having an initial viscosity of 100 cP or less under heating conditions of 80 ° C. or higher (for example, 90 ° C.).
  • a fast-curing resin composition By using the curing agent of the present invention, a fast-curing resin composition can be obtained.
  • the curing rate of the resin composition is determined by, for example, using a commercially available differential scanning calorimetry device, for example, a differential scanning calorimetry DSC7000X manufactured by Hitachi High-Tech Science Co., Ltd., for the cured product of the resin composition obtained under specific curing conditions. It can be evaluated by measuring the peak. If the uncured resin composition remains, an exothermic peak appears. In the case of a "fast-curing" resin composition, no exothermic peak is observed, or even if it is observed, the calorific value obtained from the area of the exothermic peak is small.
  • the resin composition of the present invention it is possible to provide a two-component kit containing a main agent containing an epoxy resin and a curing agent for an epoxy resin.
  • the resin composition (kit) of the present invention can be used, for example, as an epoxy resin material in various fields such as construction, civil engineering, automobiles, ships, aerospace, industrial machinery, robots, communications, electrical / electronics, semiconductors, and displays. It is particularly suitable as a matrix resin for composite materials used in aircraft and the like.
  • the present invention further relates to a cured product of an epoxy resin composition.
  • the present invention also comprises a method for producing a cured product, which comprises a step of mixing an epoxy resin and a curing agent for an epoxy resin and curing the epoxy resin to obtain a cured product, and an epoxy resin and a curing agent for an epoxy resin.
  • the present invention relates to a method for curing an epoxy resin, which comprises a step of mixing and curing the epoxy resin.
  • mixing means for the epoxy resin and the curing agent for the epoxy resin conventionally known mixing means can be used without particular limitation.
  • a commercially available rotation / revolution type stirring / defoaming machine may be used for stirring and defoaming.
  • heating is preferable, and for example, at a temperature of 120 to 250 ° C., 150 to 220 ° C., or 170 ° C. to 190 ° C., for example, 30 minutes to 4 hours, 1 to 3 hours, or 1.5 to 2.
  • the epoxy resin may be cured by holding it for 5 hours.
  • the cured product of the resin composition of the present invention has excellent mechanical properties such as high impact strength.
  • the mechanical properties of the cured product for example, the elastic modulus, bending strength, elongation, etc. are measured by a three-point bending compression test using a Tencilon universal tester, or the impact strength is measured using a commercially available impact tester. It can be evaluated by this.
  • the cured product of the resin composition of the present invention also has high heat resistance. The heat resistance can be evaluated by the glass transition temperature of the cured product.
  • a composite material containing a cured product of the resin composition of the present invention and reinforcing fibers examples include a composite material used in the resin transfer molding method, a composite material used in the filament winding method, and a prepreg.
  • the reinforcing fiber is not particularly limited, and carbon fiber, glass fiber, aramid fiber and the like that are commonly used as reinforcing fiber can be used. Carbon fiber is particularly preferable from the viewpoint of achieving both weight reduction and strength of the composite material.
  • a fiber-reinforced composite material can be obtained by injecting a resin composition into the reinforcing fibers arranged in a mold and heat-curing the resin composition.
  • the resin composition of the present invention has a low initial viscosity and is fast-curing, it can be suitably used for the resin transfer molding method. Further, since the cured product of the resin composition of the present invention has excellent mechanical properties, the composite material containing the cured product can be applied particularly to fields where high performance is required such as aircraft members.
  • Example 1 The curing agent of Example 1 was prepared by heating and dissolving for 45 minutes.
  • Examples 2 to 24 and Comparative Examples 1 to 1 are the same as in Example 1 except that the types and amounts of liquid aromatic polyamines, solid aromatic polyamines, and aliphatic polyamines are changed as shown in Tables 1 to 7, respectively. Twenty-two hardeners were prepared. Regarding the solubility, the state after heating for 45 minutes was visually observed, and those in which a solid substance could be confirmed were designated as "insoluble", and those without a solid substance were designated as "soluble".
  • Preparation Example 2 of Resin Composition> The resin was changed to 100 parts by mass of a bisphenol A type liquid epoxy resin (jER828, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184 to 194), and the curing agents of Examples 15 to 24 and Comparative Examples 15 to 22 were mixed in the ratios of Tables 5 to 7.
  • a resin composition was obtained in the same manner as in Preparation Example 1 except that the resin composition was added so as to be.
  • the temperature of the aluminum plate is raised from 25 ° C to 180 ° C at a setting of 2 ° C / min, held for 2 hours, and then lowered to room temperature at a setting of 3 ° C / min to remove the cured product from the mold. It was removed to make a resin plate with a thickness of 2 mm or a thickness of 3.5 mm. Regarding the state of the cured product, a resin plate having a thickness of 3.5 mm was visually observed, and those in which 10 or more bubbles were confirmed on the plate were defined as "foaming", and those having 10 or less bubbles were defined as "no bubbles".
  • a resin plate with a thickness of 3.5 mm is cut into a size of 10 mm ⁇ 96 mm, and a 3-point bending compression test is performed under the conditions of 25 ° C. and 5 mm / min using a Tencilon universal testing machine manufactured by TOYO BALDWIN, and the elastic modulus is obtained. The modulus, bending strength, and elongation were calculated.
  • ⁇ Measurement of glass dislocation temperature Tg> A resin plate with a thickness of 2 mm is cut into a size of 7 mm ⁇ 60 mm, and measurement is performed using a dynamic viscoelasticity measuring device EXSTAR6000 manufactured by Hitachi High-Tech Science Co., Ltd. at a temperature rise rate of 5 ° C./min, a frequency of 1 Hz, and a bending method. The intersection point where two tangents were drawn with respect to the bending point of the storage elastic modulus E'was defined as the glass transition temperature Tg.
  • a resin plate having a thickness of 2 mm was cut into a size of 20 mm ⁇ 40 mm for Examples 1 to 14 and Comparative Examples 1 to 14, and 10 mm ⁇ 40 mm for Examples 15 to 24 and Comparative Examples 15 to 22, respectively.
  • the impact strength was measured under the condition of no load using the Izod impact tester CIT-40I manufactured by Orientec.

Abstract

One problem addressed by the present invention is to provide a curing agent for an epoxy resin that yields a resin composition having low viscosity and rapid curing and a cured product having high impact strength. The present invention provides a curing agent for an epoxy resin, etc., in which there are combined (A) a liquid aromatic polyamine and (B) a solid aromatic polyamine including a secondary amino group, and in which (C) an aliphatic cyclic polyamine is furthermore used in combination when the (B) solid aromatic amine including a secondary amino group does not include (B1) a solid aromatic amine in which the number of secondary amino groups is greater than the total number of primary amino groups and tertiary amino groups.

Description

エポキシ樹脂用硬化剤Hardener for epoxy resin
　本発明は、エポキシ樹脂用硬化剤等に関する。本発明はまた、エポキシ樹脂用硬化剤とエポキシ樹脂とを含む樹脂組成物、樹脂組成物の硬化物及び炭素繊維を含む複合材料、エポキシ樹脂用硬化剤の製造方法、硬化物の製造方法、並びにエポキシ樹脂の硬化方法に関する。 The present invention relates to a curing agent for epoxy resin and the like. The present invention also comprises a resin composition containing an epoxy resin curing agent and an epoxy resin, a cured product of the resin composition and a composite material containing carbon fibers, a method for producing an epoxy resin curing agent, a method for producing a cured product, and the like. Regarding the curing method of epoxy resin.
　炭素繊維等の強化繊維と、エポキシ樹脂等の熱硬化性材料とからなる繊維強化複合材料は、軽量で且つ高強度等の優れた物性を有するため、航空機や自動車をはじめとする多くの分野に用いられている。 Fiber-reinforced composite materials, which consist of reinforced fibers such as carbon fiber and thermosetting materials such as epoxy resin, are lightweight and have excellent physical properties such as high strength, and therefore are used in many fields such as aircraft and automobiles. It is used.
　従来、複合材料に用いられるエポキシ樹脂用の硬化剤として、ジアミノジフェニルスルホンが多く用いられている。硬化剤としてジアミノジフェニルスルホンを使用したエポキシ樹脂組成物の硬化物は、高耐熱性、高強度等の優れた性能を有する。しかしながら、ジアミノジフェニルスルホンは、融点が１８０℃と高く、エポキシ樹脂に難溶であるうえ、樹脂組成物が高粘度になりやすく、炭素繊維等の強化繊維に速やかに含浸させることが困難である。一方、エポキシ樹脂用硬化剤として一般的に知られている液状ポリアミンを使用した場合、樹脂組成物を低粘度にすることは可能であるが、硬化に長時間を要し、硬化物の衝撃強度も十分ではない。 Conventionally, diaminodiphenyl sulfone is often used as a curing agent for epoxy resins used in composite materials. A cured product of an epoxy resin composition using diaminodiphenyl sulfone as a curing agent has excellent performance such as high heat resistance and high strength. However, diaminodiphenyl sulfone has a high melting point of 180 ° C., is sparingly soluble in epoxy resin, and the resin composition tends to have high viscosity, so that it is difficult to quickly impregnate reinforcing fibers such as carbon fibers. On the other hand, when a liquid polyamine generally known as a curing agent for an epoxy resin is used, it is possible to reduce the viscosity of the resin composition, but it takes a long time to cure and the impact strength of the cured product is high. Is not enough.
　特許文献１及び特許文献２には、液状芳香族ポリアミンにジアミノジフェニルスルホンを溶解させた硬化剤を使用したエポキシ樹脂組成物が記載されている。しかしながら、この硬化剤を使用したエポキシ樹脂組成物は、硬化に長時間を要し、得られる硬化物の衝撃強度も満足できるものではない。 Patent Document 1 and Patent Document 2 describe an epoxy resin composition using a curing agent in which diaminodiphenyl sulfone is dissolved in a liquid aromatic polyamine. However, the epoxy resin composition using this curing agent takes a long time to cure, and the impact strength of the obtained cured product is not satisfactory.
特許第４３９６２７４号Patent No. 4396274 特許第５２２８８５３号Patent No. 5228853
　本発明が解決しようとする課題の一つは、低粘度かつ速硬化性の樹脂組成物及び高い衝撃強度を有する硬化物をもたらす、エポキシ樹脂用硬化剤を提供することである。 One of the problems to be solved by the present invention is to provide a curing agent for an epoxy resin, which provides a resin composition having a low viscosity and a fast curing property and a cured product having a high impact strength.
　本発明者らは、上記課題を解決すべく鋭意検討した結果、（Ａ）液状芳香族ポリアミンと（Ｂ）二級アミノ基を含む固形芳香族ポリアミンとを組み合わせ、（Ｂ）二級アミノ基を含む固形芳香族アミンが、（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンを含まない場合、さらに（Ｃ）脂肪族環状ポリアミンを組み合わせることにより、低粘度かつ速硬化性の樹脂組成物及び高い衝撃強度を有する硬化物をもたらすエポキシ樹脂用硬化剤が得られることを見出し、本発明を完成するに至った。
　すなわち、本発明は以下の態様を含むものである。 As a result of diligent studies to solve the above problems, the present inventors have combined (A) a liquid aromatic polyamine and (B) a solid aromatic polyamine containing a secondary amino group to obtain (B) a secondary amino group. If the solid aromatic amine contained does not contain (B1) a solid aromatic amine in which the number of secondary amino groups is greater than the total number of primary and tertiary amino groups, then (C) an aliphatic cyclic polyamine is further combined. As a result, it has been found that a resin composition having a low viscosity and a fast curing property and a curing agent for an epoxy resin which brings about a cured product having a high impact strength can be obtained, and the present invention has been completed.
That is, the present invention includes the following aspects.
〔１〕（Ａ）液状芳香族ポリアミン及び（Ｂ）二級アミノ基を含む固形芳香族アミンを含む、エポキシ樹脂用硬化剤であって、
　（Ｂ）二級アミノ基を含む固形芳香族アミンが、（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンを含むか又は含まず、含まない場合、前記エポキシ樹脂用硬化剤が、（Ｃ）脂肪族環状ポリアミンをさらに含む、エポキシ樹脂用硬化剤。
〔２〕（Ｂ）二級アミノ基を含む固形芳香族アミンが、（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンを含む、前記〔１〕に記載のエポキシ樹脂用硬化剤。
〔３〕（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンが、（Ｂ１’）アミノ基として二級アミノ基のみを含む固形芳香族アミンを含む、前記〔２〕に記載のエポキシ樹脂用硬化剤。
〔４〕（Ｂ１’）アミノ基として二級アミノ基のみを含む固形芳香族アミンが、Ｎ－フェニル－１－ナフチルアミン、オクチル化ジフェニルアミン、４，４’－ビス（α，α－ジメチルベンジル）ジフェニルアミン、Ｎ－（ｐ－トリル）－１－ナフチルアミン、Ｎ－フェニル－３－ビフェニルアミン、ビス（３－ビフェニリル）アミン、２－（３－ビフェニリル）アミノ－９，９－ジメチルフルオレン、ビス（４－ｔｅｒｔ－ブチルフェニル）アミン、４－ｔｅｒｔ－ブチルフェニルフェニルアミン、ビス－α－メチルベンジルフェノチアジン、ジフェニルアミンと２，４，４－トリメチルペンテンとの反応物、ジフェニルアミン、Ｎ－フェニルベンジルアミン、３－メチルジフェニルアミン、３，４－ジメチルジフェニルアミン、４，４’－ジメチルジフェニルアミン、３－メトキシジフェニルアミン、１０－メトキシ－２，２’－イミノスチルベン、Ｎ－ベンジル－２－ナフチルアミン、１，２’－ジナフチルアミン、１，１’－ジナフチルアミン、４－イソプロピルアミノジフェニルアミン、２，６－ビス［（２－ヒドロキシエチル）アミノ］トルエン、４－（２－オクチルアミノ）ジフェニルアミン、Ｎ－（１，３－ジメチルブチル）－Ｎ’－フェニル－１，４－フェニレンジアミン、２，２，４－トリメチル－１，２－ジヒドロキノリン重合体、１，３－ジフェニルグアニジン、ｐ－（ｐ－トルエンスルホニルアミド）ジフェニルアミン、Ｎ－フェニル－Ｎ’－（３－メタクリロイルオキシ－２－ヒドロキシプロピル）－ｐ－フェニレンジアミン、ビス（２－ベンズアミドフェニル）ジスルフィド、Ｎ，Ｎ’－ジフェニル－１，４－フェニレンジアミン、１，３－ジ－ｏ－トリルグアニジン、１，５－ジフェニルカルボノヒドラジド、Ｎ，Ｎ’－ジフェニルエチレンジアミン及び５－（アセトアセトアミド）－２－ベンゾイミダゾリノンからなる群から選択される、前記〔３〕に記載のエポキシ樹脂用硬化剤。
〔５〕（Ｂ）二級アミノ基を含む固形芳香族アミンが、（Ｂ２）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数以下である固形芳香族ポリアミンをさらに含む、前記〔２〕～〔４〕のいずれか１項に記載のエポキシ樹脂用硬化剤。
〔６〕（Ｂ２）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数以下である固形芳香族ポリアミンが、４－アミノジフェニルアミン、２，４－ジアミノジフェニルアミン、２－アミノジフェニルアミン、４－アミノ－４’－メトキシジフェニルアミン、１－フェニルビグアニド、イソフタル酸ジヒドラジド、テレフタル酸ジヒドラジド、２，６－ナフトエ酸ジヒドラジド、４，４’－ビスベンゼンジヒドラジド、１，４－ナフトエ酸ジヒドラジド、ナフタレン－２，６－ジカルボヒドラジド、及び３－ヒドロキシ－２－ナフトエ酸ヒドラジドからなる群から選択される、前記〔５〕に記載のエポキシ樹脂用硬化剤。
〔７〕前記エポキシ樹脂用硬化剤が、（Ｃ）脂肪族環状ポリアミンをさらに含む、前記〔２〕～〔６〕のいずれか１項に記載のエポキシ樹脂用硬化剤。
〔８〕（Ｂ）二級アミノ基を含む固形芳香族アミンが、（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンを含まず、（Ｂ２）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数以下である固形芳香族ポリアミンを含む、前記〔１〕に記載のエポキシ樹脂用硬化剤。
〔９〕（Ｂ２）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数以下である固形芳香族ポリアミンが、４－アミノジフェニルアミン、２，４－ジアミノジフェニルアミン、２－アミノジフェニルアミン、４－アミノ－４’－メトキシジフェニルアミン、１－フェニルビグアニド、イソフタル酸ジヒドラジド、テレフタル酸ジヒドラジド、２，６－ナフトエ酸ジヒドラジド、４，４’－ビスベンゼンジヒドラジド、１，４－ナフトエ酸ジヒドラジド、ナフタレン－２，６－ジカルボヒドラジド、及び３－ヒドロキシ－２－ナフトエ酸ヒドラジドからなる群から選択される、前記〔８〕に記載のエポキシ樹脂用硬化剤。
〔１０〕（Ｃ）脂肪族環状ポリアミンの沸点が、１４０℃以上である、前記〔７〕～〔９〕のいずれか１項に記載のエポキシ樹脂用硬化剤。
〔１１〕（Ｃ）脂肪族環状ポリアミンが、一級アミノ基又は二級アミノ基を含む、前記〔７〕～〔１０〕のいずれか１項に記載のエポキシ樹脂用硬化剤。
〔１２〕（Ｃ）脂肪族環状ポリアミンが、環構造中のアミノ基として二級アミノ基のみを含む、前記〔７〕～〔１１〕のいずれか１項に記載のエポキシ樹脂用硬化剤。
〔１３〕（Ｃ）脂肪族環状ポリアミンが、錯体又は塩構造を形成していない、前記〔７〕～〔１２〕のいずれか１項に記載のエポキシ樹脂用硬化剤。
〔１４〕（Ｃ）脂肪族環状ポリアミンにおいて、環構造中のアミノ基に隣接する元素及び／又は環構造上のアミノ基が結合している元素に隣接する元素の置換基が全て水素原子である、前記〔７〕～〔１３〕のいずれか１項に記載のエポキシ樹脂用硬化剤。
〔１５〕（Ｃ）脂肪族環状ポリアミンが、ピペラジン骨格を有する、前記〔７〕～〔１４〕のいずれか１項に記載のエポキシ樹脂用硬化剤。
〔１６〕（Ｃ）脂肪族環状ポリアミンが、ピペラジンである、前記〔７〕～〔１５〕のいずれか１項に記載のエポキシ樹脂用硬化剤。
〔１７〕（Ｂ）二級アミノ基を含む固形芳香族アミンの融点が、１６０℃以下である、前記〔１〕～〔１６〕のいずれか１項に記載のエポキシ樹脂用硬化剤。
〔１８〕（Ａ）液状芳香族ポリアミンが、２つ以上の一級アミノ基、２つ以上の二級アミノ基、又は１つ以上の一級アミノ基と１つ以上の二級アミノ基とを含む、前記〔１〕～〔１７〕のいずれか１項に記載のエポキシ樹脂用硬化剤。
〔１９〕（Ａ）液状芳香族ポリアミンが、ジメチルチオトルエンジアミン、ジエチルトルエンジアミン及び４，４’－メチレンビス［Ｎ－（１－メチルプロピル）アニリン］からなる群から選択される、前記〔１８〕に記載のエポキシ樹脂用硬化剤。
〔２０〕液状である、前記〔１〕～〔１９〕のいずれか１項に記載のエポキシ樹脂用硬化剤。
〔２１〕前記〔１〕～〔２０〕のいずれか１項に記載のエポキシ樹脂用硬化剤と、エポキシ樹脂とを含む、樹脂組成物。
〔２２〕前記〔２１〕に記載の樹脂組成物の硬化物。
〔２３〕前記〔２２〕に記載の硬化物及び炭素繊維を含む、複合材料。 [1] A curing agent for an epoxy resin containing (A) a liquid aromatic polyamine and (B) a solid aromatic amine containing a secondary amino group.
(B) The solid aromatic amine containing a secondary amino group contains or does not contain (B1) a solid aromatic amine in which the number of secondary amino groups is greater than the total number of primary amino groups and tertiary amino groups. If not contained, the epoxy resin curing agent further contains (C) an aliphatic cyclic polyamine.
[2] (B) The solid aromatic amine containing a secondary amino group contains (B1) a solid aromatic amine in which the number of secondary amino groups is larger than the total number of primary amino groups and tertiary amino groups. The curing agent for epoxy resin according to [1].
[3] (B1) A solid aromatic amine having a larger number of secondary amino groups than the total number of primary amino groups and tertiary amino groups contains only a secondary amino group as the (B1') amino group. The curing agent for an epoxy resin according to the above [2], which contains an amine.
[4] The solid aromatic amine containing only a secondary amino group as the (B1') amino group is N-phenyl-1-naphthylamine, octylated diphenylamine, 4,4'-bis (α, α-dimethylbenzyl) diphenylamine. , N- (p-tolyl) -1-naphthylamine, N-phenyl-3-biphenylamine, bis (3-biphenylyl) amine, 2- (3-biphenylyl) amino-9,9-dimethylfluorene, bis (4- tert-butylphenyl) amine, 4-tert-butylphenylphenylamine, bis-α-methylbenzylphenothiazine, reaction product of diphenylamine with 2,4,4-trimethylpentene, diphenylamine, N-phenylbenzylamine, 3-methyl Diphenylamine, 3,4-dimethyldiphenylamine, 4,4'-dimethyldiphenylamine, 3-methoxydiphenylamine, 10-methoxy-2,2'-iminostylben, N-benzyl-2-naphthylamine, 1,2'-dinaphthylamine, 1,1'-Dinaphthylamine, 4-isopropylaminodiphenylamine, 2,6-bis [(2-hydroxyethyl) amino] toluene, 4- (2-octylamino) diphenylamine, N- (1,3-dimethylbutyl) -N'-Phenyl-1,4-phenylenediamine, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 1,3-diphenylguanidine, p- (p-toluenesulfonylamide) diphenylamine, N- Phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, bis (2-benzamidephenyl) disulfide, N, N'-diphenyl-1,4-phenylenediamine, 1,3-di The above-mentioned [3], which is selected from the group consisting of -o-tolylguanidine, 1,5-diphenylcarbonohydrazide, N, N'-diphenylethylenediamine and 5- (acetoacetamide) -2-benzoimidazolinone. Hardener for epoxy resin.
[5] (B) The solid aromatic amine containing a secondary amino group further contains (B2) a solid aromatic polyamine in which the number of secondary amino groups is equal to or less than the total number of primary amino groups and tertiary amino groups. , The curing agent for epoxy resin according to any one of the above [2] to [4].
[6] (B2) Solid aromatic polyamines in which the number of secondary amino groups is equal to or less than the total number of primary amino groups and tertiary amino groups are 4-aminodiphenylamine, 2,4-diaminodiphenylamine, and 2-aminodiphenylamine. , 4-Amino-4'-methoxydiphenylamine, 1-phenylbiguanide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 4,4'-bisbenzenedihydrazide, 1,4-naphthoic acid dihydrazide, naphthalene The curing agent for an epoxy resin according to the above [5], which is selected from the group consisting of -2,6-dicarbohydrazide and 3-hydroxy-2-naphthoic acid hydrazide.
[7] The epoxy resin curing agent according to any one of [2] to [6] above, wherein the epoxy resin curing agent further contains (C) an aliphatic cyclic polyamine.
[8] (B) The solid aromatic amine containing a secondary amino group does not contain (B1) a solid aromatic amine in which the number of secondary amino groups is larger than the total number of primary amino groups and tertiary amino groups. (B2) The curing agent for an epoxy resin according to the above [1], which comprises a solid aromatic polyamine in which the number of secondary amino groups is not more than the total number of primary amino groups and tertiary amino groups.
[9] (B2) Solid aromatic polyamines in which the number of secondary amino groups is equal to or less than the total number of primary amino groups and tertiary amino groups are 4-aminodiphenylamine, 2,4-diaminodiphenylamine, and 2-aminodiphenylamine. , 4-Amino-4'-methoxydiphenylamine, 1-phenylbiguanide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 4,4'-bisbenzenedihydrazide, 1,4-naphthoic acid dihydrazide, naphthalene The curing agent for an epoxy resin according to the above [8], which is selected from the group consisting of -2,6-dicarbohydrazide and 3-hydroxy-2-naphthoic acid hydrazide.
[10] The curing agent for epoxy resin according to any one of [7] to [9] above, wherein the (C) aliphatic cyclic polyamine has a boiling point of 140 ° C. or higher.
[11] The curing agent for an epoxy resin according to any one of [7] to [10] above, wherein the (C) aliphatic cyclic polyamine contains a primary amino group or a secondary amino group.
[12] The curing agent for epoxy resin according to any one of [7] to [11] above, wherein the (C) aliphatic cyclic polyamine contains only a secondary amino group as an amino group in the ring structure.
[13] The curing agent for an epoxy resin according to any one of [7] to [12] above, wherein the (C) aliphatic cyclic polyamine does not form a complex or a salt structure.
[14] In the aliphatic cyclic polyamine, all the substituents of the element adjacent to the amino group in the ring structure and / or the element adjacent to the element to which the amino group on the ring structure is bonded are hydrogen atoms. , The curing agent for an epoxy resin according to any one of the above [7] to [13].
[15] The curing agent for an epoxy resin according to any one of [7] to [14] above, wherein the (C) aliphatic cyclic polyamine has a piperazine skeleton.
[16] The curing agent for an epoxy resin according to any one of [7] to [15] above, wherein the (C) aliphatic cyclic polyamine is piperazine.
[17] (B) The curing agent for an epoxy resin according to any one of [1] to [16] above, wherein the solid aromatic amine containing a secondary amino group has a melting point of 160 ° C. or lower.
[18] (A) The liquid aromatic polyamine contains two or more primary amino groups, two or more secondary amino groups, or one or more primary amino groups and one or more secondary amino groups. The curing agent for an epoxy resin according to any one of the above [1] to [17].
[19] (A) The liquid aromatic polyamine is selected from the group consisting of dimethylthiotoluenediamine, diethyltoluenediamine and 4,4'-methylenebis [N- (1-methylpropyl) aniline], as described above [18]. The curing agent for epoxy resin described in.
[20] The curing agent for an epoxy resin according to any one of the above [1] to [19], which is a liquid.
[21] A resin composition containing the epoxy resin curing agent according to any one of the above [1] to [20] and an epoxy resin.
[22] A cured product of the resin composition according to the above [21].
[23] A composite material containing the cured product and carbon fiber according to the above [22].
　本発明により、低粘度かつ速硬化性の樹脂組成物及び高い衝撃強度を有する硬化物をもたらす、エポキシ樹脂用硬化剤を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a curing agent for an epoxy resin, which provides a resin composition having a low viscosity and a fast curing property and a cured product having a high impact strength.
　以下、本発明の実施形態について詳細に説明する。なお、本発明は以下の実施形態に限定されない。また、本明細書において、特に断らない限り、「Ａ（数値）～Ｂ（数値）」は「Ａ以上Ｂ以下」を意味し、割合は質量割合を意味する。なお、以下で例示する好ましい態様やより好ましい態様等は、「好ましい」や「より好ましい」等の表現にかかわらず適宜相互に組み合わせて使用することができる。また、数値範囲の記載は例示であって、「好ましい」や「より好ましい」等の表現にかかわらず各範囲の上限と下限並びに実施例の数値とを適宜組み合わせた範囲も好ましく使用することができる。さらに、「含有する」又は「含む」等の用語は、適宜「本質的になる」や「のみからなる」と読み替えてもよい。
　本発明は、（Ａ）液状芳香族ポリアミン及び（Ｂ）二級アミノ基を含む固形芳香族アミンを含む、エポキシ樹脂用硬化剤であって、（Ｂ）二級アミノ基を含む固形芳香族アミンが、（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンを含むか又は含まず、含まない場合、前記エポキシ樹脂用硬化剤が（Ｃ）脂肪族環状ポリアミンをさらに含む、エポキシ樹脂用硬化剤に関する。 Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments. Further, in the present specification, unless otherwise specified, "A (numerical value) to B (numerical value)" means "A or more and B or less", and the ratio means a mass ratio. In addition, the preferable embodiment and the more preferable embodiment exemplified below can be used in combination with each other as appropriate regardless of the expressions such as "favorable" and "more preferable". Further, the description of the numerical range is an example, and a range in which the upper limit and the lower limit of each range and the numerical values of the examples are appropriately combined can also be preferably used regardless of expressions such as "preferable" and "more preferable". .. Further, terms such as "contains" or "contains" may be appropriately read as "essentially" or "consisting of only".
The present invention is a curing agent for an epoxy resin containing (A) a liquid aromatic polyamine and (B) a solid aromatic amine containing a secondary amino group, and (B) a solid aromatic amine containing a secondary amino group. However, if (B1) contains or does not contain a solid aromatic amine in which the number of secondary amino groups is greater than the total number of primary amino groups and tertiary amino groups, the curing agent for epoxy resin is (C). ) The present invention relates to a curing agent for an epoxy resin, further containing an aliphatic cyclic polyamine.
（Ａ）液状芳香族ポリアミン
　本発明における「液状」芳香族ポリアミンとは、融点が室温（２５℃）よりも低い、すなわち、室温（２５℃）において液体状態である芳香族ポリアミンをいう。 (A) Liquid Aromatic Polyamine The "liquid" aromatic polyamine in the present invention means an aromatic polyamine having a melting point lower than room temperature (25 ° C.), that is, a liquid state at room temperature (25 ° C.).
　液状芳香族ポリアミンは、２つ以上のアミノ基を有する、芳香族化合物である。本明細書において、特に断らない限り、「アミノ基」は、「一級アミノ基」、「二級アミノ基」及び「三級アミノ基」を含む。三級アミノ基はエポキシ樹脂の自己重合を促進し、得られる硬化物の耐熱性を低くする傾向があるため、高耐熱性の硬化物を得る観点から、液状芳香族ポリアミンは、２つ以上の一級アミノ基を含むか、２つ以上の二級アミノ基を含むか、あるいは、１つ以上の一級アミノ基と１つ以上の二級アミノ基とを含むことが好ましい。 Liquid aromatic polyamines are aromatic compounds having two or more amino groups. In the present specification, unless otherwise specified, the "amino group" includes a "primary amino group", a "secondary amino group" and a "tertiary amino group". Since the tertiary amino group promotes the self-polymerization of the epoxy resin and tends to lower the heat resistance of the obtained cured product, from the viewpoint of obtaining a highly heat-resistant cured product, the liquid aromatic polyamine has two or more liquid aromatic polyamines. It preferably contains a primary amino group, two or more secondary amino groups, or one or more primary amino groups and one or more secondary amino groups.
　液状芳香族ポリアミンは、樹脂組成物の粘度を低くする観点から、粘度が８０℃以上の加熱条件下で１００ｃＰ以下であることが好ましく、より好ましくは０．００１～６０ｃＰ、更に好ましくは０．０１～２０ｃＰの粘度を有する。液状芳香族ポリアミンの粘度は、市販の粘度測定装置、例えば、ＨＡＡＫＥ社製ＲｈｅｏＳｔｒｅｓｓ６０００を用いて測定することができる。 From the viewpoint of lowering the viscosity of the resin composition, the liquid aromatic polyamine preferably has a viscosity of 100 cP or less under heating conditions of 80 ° C. or higher, more preferably 0.001 to 60 cP, still more preferably 0.01. It has a viscosity of ~ 20 cP. The viscosity of the liquid aromatic polyamine can be measured using a commercially available viscosity measuring device, for example, RheoStress6000 manufactured by HAAKE.
　液状芳香族ポリアミンは、沸点が１４０℃以上であることが好ましく、より好ましくは１５０℃～５００℃、更に好ましくは１６０℃～４００℃、更により好ましくは１８０～３５０℃の沸点を有する。沸点が１４０℃以上であれば、エポキシ樹脂をマトリックス樹脂とする繊維強化複合材料の製造過程において、樹脂組成物を強化繊維に含浸させる際の温度よりも十分に高いため、液状芳香族ポリアミン成分の揮発を抑制することができ、その結果、繊維強化複合材料の構造欠陥及び強度低下を抑制することができる。 The liquid aromatic polyamine preferably has a boiling point of 140 ° C. or higher, more preferably 150 ° C. to 500 ° C., still more preferably 160 ° C. to 400 ° C., and even more preferably 180 to 350 ° C. When the boiling point is 140 ° C. or higher, the temperature is sufficiently higher than the temperature at which the reinforcing fiber is impregnated with the resin composition in the manufacturing process of the fiber-reinforced composite material using the epoxy resin as the matrix resin. Volatilization can be suppressed, and as a result, structural defects and a decrease in strength of the fiber-reinforced composite material can be suppressed.
　好ましい液状芳香族ポリアミンとしては、例えば、ジメチルチオトルエンジアミン、ジエチルトルエンジアミン、４，４’－メチレンビス［Ｎ－（１－メチルプロピル）アニリン］等が挙げられる。 Preferred liquid aromatic polyamines include, for example, dimethylthiotoluenediamine, diethyltoluenediamine, 4,4'-methylenebis [N- (1-methylpropyl) aniline] and the like.
　液状芳香族ポリアミンの市販品の例としては、ジメチルチオトルエンジアミン（アルベマール社製「エタキュア３００」、クミアイ化学工業社製「ハートキュア３０」）、ジエチルトルエンジアミン（アルベマール社製「エタキュア１００プラス」、クミアイ化学工業社製「ハートキュア１０」）等が挙げられる。 Examples of commercially available liquid aromatic polyamines include dimethylthiotoluenediamine ("Etacure 300" manufactured by Albemarle, "Heartcure 30" manufactured by Kumiai Chemical Industry Co., Ltd.), diethyltoluenediamine ("Etacure 100 Plus" manufactured by Albemarle), and "Heart Cure 10") manufactured by Kumiai Chemical Industry Co., Ltd.) and the like can be mentioned.
　液状芳香族ポリアミンは、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。二種以上の液状芳香族ポリアミンを組み合わせて用いる場合には、硬化物の強度及び耐熱性を高める観点から、液状芳香族アミンの総質量に対して、２つ以上の一級アミノ基を含む液状芳香族ポリアミンが５０～９０質量％の割合で含まれることが好ましく、６０～８０質量％の割合で含まれることがより好ましい。 The liquid aromatic polyamine may be used alone or in combination of two or more. When two or more liquid aromatic polyamines are used in combination, a liquid aromatic containing two or more primary amino groups with respect to the total mass of the liquid aromatic amine from the viewpoint of increasing the strength and heat resistance of the cured product. The group polyamine is preferably contained in a proportion of 50 to 90% by mass, more preferably 60 to 80% by mass.
　硬化剤を１００質量％とした場合、液状芳香族ポリアミンは、低粘度の樹脂組成物を得る観点から、好ましくは４０～９７質量％、より好ましくは５０～９５質量％、更に好ましくは５５～９３質量％の量で、硬化剤に含まれる。 When the curing agent is 100% by mass, the liquid aromatic polyamine is preferably 40 to 97% by mass, more preferably 50 to 95% by mass, still more preferably 55 to 93, from the viewpoint of obtaining a resin composition having a low viscosity. It is contained in the curing agent in an amount of% by mass.
（Ｂ）二級アミノ基を含む固形芳香族アミン
　本発明における「固形」芳香族アミンとは、融点が室温（２５℃）よりも高い、すなわち、室温（２５℃）において固体状態である芳香族アミンをいう。 (B) Solid aromatic amine containing a secondary amino group The "solid" aromatic amine in the present invention is an aromatic amine having a melting point higher than room temperature (25 ° C), that is, a solid state at room temperature (25 ° C). Refers to amine.
　本発明の固形芳香族アミンは、二級アミノ基を含む。固形芳香族アミンが二級アミノ基を含むことにより、硬化物の衝撃強度を高くすることができる。 The solid aromatic amine of the present invention contains a secondary amino group. Since the solid aromatic amine contains a secondary amino group, the impact strength of the cured product can be increased.
　二級アミノ基を含む固形芳香族アミンは、融点が１６０℃以下であることが好ましく、例えば、１５５℃以下、又は１５０℃以下であることが好ましい。また、二級アミノ基を含む固形芳香族アミンは、融点が、例えば、３０℃以上、４０℃以上、５０℃以上、６０℃以上、又は７０℃以上であることが好ましい。融点が１６０℃以下であれば、液状芳香族ポリアミンに短時間で容易に溶解させることができる。 The solid aromatic amine containing a secondary amino group preferably has a melting point of 160 ° C. or lower, for example, 155 ° C. or lower, or 150 ° C. or lower. Further, the solid aromatic amine containing a secondary amino group preferably has a melting point of, for example, 30 ° C. or higher, 40 ° C. or higher, 50 ° C. or higher, 60 ° C. or higher, or 70 ° C. or higher. When the melting point is 160 ° C. or lower, it can be easily dissolved in a liquid aromatic polyamine in a short time.
　融点が１６０℃以下の二級アミノ基を含む固形芳香族アミンとしては、例えば、Ｎ－フェニル－１－ナフチルアミン、オクチル化ジフェニルアミン、４，４’－ビス（α，α－ジメチルベンジル）ジフェニルアミン、Ｎ－（ｐ－トリル）－１－ナフチルアミン、Ｎ－フェニル－３－ビフェニルアミン、ビス（３－ビフェニリル）アミン、２－（３－ビフェニリル）アミノ－９，９－ジメチルフルオレン、ビス（４－ｔｅｒｔ－ブチルフェニル）アミン、４－ｔｅｒｔ－ブチルフェニルフェニルアミン、ビス－α－メチルベンジルフェノチアジン、ジフェニルアミンと２，４，４－トリメチルペンテンとの反応物、ジフェニルアミン、Ｎ－フェニルベンジルアミン、３－メチルジフェニルアミン、３，４－ジメチルジフェニルアミン、４，４’－ジメチルジフェニルアミン、３－メトキシジフェニルアミン、１０－メトキシ－２，２’－イミノスチルベン、Ｎ－ベンジル－２－ナフチルアミン、１，２’－ジナフチルアミン、１，１’－ジナフチルアミン、４－イソプロピルアミノジフェニルアミン、２，６－ビス［（２－ヒドロキシエチル）アミノ］トルエン、４－（２－オクチルアミノ）ジフェニルアミン、Ｎ－（１，３－ジメチルブチル）－Ｎ’－フェニル－１，４－フェニレンジアミン、２，２，４－トリメチル－１，２－ジヒドロキノリン重合体、１，３－ジフェニルグアニジン、ｐ－（ｐ－トルエンスルホニルアミド）ジフェニルアミン、Ｎ－フェニル－Ｎ’－（３－メタクリロイルオキシ－２－ヒドロキシプロピル）－ｐ－フェニレンジアミン、ビス（２－ベンズアミドフェニル）ジスルフィド、Ｎ，Ｎ’－ジフェニル－１，４－フェニレンジアミン、Ｎ，Ｎ’－ジフェニルエチレンジアミン、５－（アセトアセトアミド）－２－ベンゾイミダゾリノン、１－（ｏ－トリル）ビグアニド、フェニルビグアニド、末端アミノ基を含む高分子ビグアニド化合物、４－フェニルセミカルバジド、４－フェニル－３－チオセミカルバジド、１，２，３－トリフェニルグアニジン等が挙げられる。 Examples of the solid aromatic amine containing a secondary amino group having a melting point of 160 ° C. or lower include N-phenyl-1-naphthylamine, octylated diphenylamine, 4,4'-bis (α, α-dimethylbenzyl) diphenylamine, and N. -(P-Trill) -1-naphthylamine, N-phenyl-3-biphenylamine, bis (3-biphenylyl) amine, 2- (3-biphenylyl) amino-9,9-dimethylfluorene, bis (4-tert- Butylphenyl) amine, 4-tert-butylphenylphenylamine, bis-α-methylbenzylphenothiazine, reactants of diphenylamine with 2,4,4-trimethylpentene, diphenylamine, N-phenylbenzylamine, 3-methyldiphenylamine, 3,4-dimethyldiphenylamine, 4,4'-dimethyldiphenylamine, 3-methoxydiphenylamine, 10-methoxy-2,2'-iminostylben, N-benzyl-2-naphthylamine, 1,2'-dinaphthylamine, 1, 1'-Dinaphthylamine, 4-isopropylaminodiphenylamine, 2,6-bis [(2-hydroxyethyl) amino] toluene, 4- (2-octylamino) diphenylamine, N- (1,3-dimethylbutyl) -N '-Phenyl-1,4-phenylenediamine, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 1,3-diphenylguanidine, p- (p-toluenesulfonylamide) diphenylamine, N-phenyl- N'-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, bis (2-benzamidephenyl) disulfide, N, N'-diphenyl-1,4-phenylenediamine, N, N'-diphenylethylenediamine , 5- (Acetoacetamide) -2-benzoimidazolinone, 1- (o-tolyl) biguanide, phenylbiguanide, high molecular weight biguanide compound containing terminal amino group, 4-phenylsemicarbazide, 4-phenyl-3-thiosemicarbazide, 1,2,3-triphenylguanidine and the like can be mentioned.
　二級アミノ基を含む固形芳香族アミンは、沸点が１４０℃以上であることが好ましく、より好ましくは１４５℃～５５０℃、更に好ましくは１５０℃～５００℃、更により好ましくは１６０℃～４５０℃、特に好ましくは１７０～４００℃の沸点を有する。沸点が１４０℃以上であれば、エポキシ樹脂をマトリックス樹脂とする繊維強化複合材料の製造過程において、樹脂組成物を強化繊維に含浸させる際の温度よりも十分に高いため、二級アミノ基を含む固形芳香族アミン成分の揮発を抑制することができ、その結果、繊維強化複合材料の構造欠陥及び強度低下を抑制することができる。 The solid aromatic amine containing a secondary amino group preferably has a boiling point of 140 ° C. or higher, more preferably 145 ° C. to 550 ° C., still more preferably 150 ° C. to 500 ° C., still more preferably 160 ° C. to 450 ° C. Particularly preferably, it has a boiling point of 170 to 400 ° C. When the boiling point is 140 ° C. or higher, the temperature is sufficiently higher than the temperature at which the reinforcing fiber is impregnated with the resin composition in the manufacturing process of the fiber-reinforced composite material using the epoxy resin as the matrix resin, and therefore contains a secondary amino group. Volatilization of the solid aromatic amine component can be suppressed, and as a result, structural defects and a decrease in strength of the fiber-reinforced composite material can be suppressed.
　沸点が１４０℃以上の二級アミノ基を含む固形芳香族アミンとしては、例えば、Ｎ－フェニル－１－ナフチルアミン、オクチル化ジフェニルアミン、４，４’－ビス（α，α－ジメチルベンジル）ジフェニルアミン、Ｎ－（ｐ－トリル）－１－ナフチルアミン、Ｎ－フェニル－３－ビフェニルアミン、ビス（３－ビフェニリル）アミン、２－（３－ビフェニリル）アミノ－９，９－ジメチルフルオレン、ビス（４－ｔｅｒｔ－ブチルフェニル）アミン、４－ｔｅｒｔ－ブチルフェニルフェニルアミン、ビス－α－メチルベンジルフェノチアジン、ジフェニルアミンと２，４，４－トリメチルペンテンとの反応物、ジフェニルアミン、Ｎ－フェニルベンジルアミン、３－メチルジフェニルアミン、３，４－ジメチルジフェニルアミン、４，４’－ジメチルジフェニルアミン、３－メトキシジフェニルアミン、１０－メトキシ－２，２’－イミノスチルベン、Ｎ－ベンジル－２－ナフチルアミン、１，２’－ジナフチルアミン、１，１’－ジナフチルアミン、４－イソプロピルアミノジフェニルアミン、２，６－ビス［（２－ヒドロキシエチル）アミノ］トルエン、４－（２－オクチルアミノ）ジフェニルアミン、Ｎ－（１，３－ジメチルブチル）－Ｎ’－フェニル－１，４－フェニレンジアミン、２，２，４－トリメチル－１，２－ジヒドロキノリン重合体、１，３－ジフェニルグアニジン、ｐ－（ｐ－トルエンスルホニルアミド）ジフェニルアミン、Ｎ－フェニル－Ｎ’－（３－メタクリロイルオキシ－２－ヒドロキシプロピル）－ｐ－フェニレンジアミン、ビス（２－ベンズアミドフェニル）ジスルフィド、Ｎ，Ｎ’－ジフェニル－１，４－フェニレンジアミン、１，３－ジ－ｏ－トリルグアニジン、１，５－ジフェニルカルボノヒドラジド、Ｎ，Ｎ’－ジフェニルエチレンジアミン、５－（アセトアセトアミド）－２－ベンゾイミダゾリノン、１－（ｏ－トリル）ビグアニド、１－フェニルグアニジン、フェニルビグアニド、末端アミノ基を含む高分子ビグアニド化合物、４－フェニルセミカルバジド、４－フェニル－３－チオセミカルバジド、１，２，３－トリフェニルグアニジン等が挙げられる。 Examples of the solid aromatic amine containing a secondary amino group having a boiling point of 140 ° C. or higher include N-phenyl-1-naphthylamine, octylated diphenylamine, 4,4'-bis (α, α-dimethylbenzyl) diphenylamine, and N. -(P-Trill) -1-naphthylamine, N-phenyl-3-biphenylamine, bis (3-biphenylyl) amine, 2- (3-biphenylyl) amino-9,9-dimethylfluorene, bis (4-tert- Butylphenyl) amine, 4-tert-butylphenylphenylamine, bis-α-methylbenzylphenothiazine, reactants of diphenylamine with 2,4,4-trimethylpentene, diphenylamine, N-phenylbenzylamine, 3-methyldiphenylamine, 3,4-dimethyldiphenylamine, 4,4'-dimethyldiphenylamine, 3-methoxydiphenylamine, 10-methoxy-2,2'-iminostylben, N-benzyl-2-naphthylamine, 1,2'-dinaphthylamine, 1, 1'-Dinaphthylamine, 4-isopropylaminodiphenylamine, 2,6-bis [(2-hydroxyethyl) amino] toluene, 4- (2-octylamino) diphenylamine, N- (1,3-dimethylbutyl) -N '-Phenyl-1,4-phenylenediamine, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 1,3-diphenylguanidine, p- (p-toluenesulfonylamide) diphenylamine, N-phenyl- N'-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, bis (2-benzamidephenyl) disulfide, N, N'-diphenyl-1,4-phenylenediamine, 1,3-di-o -Trilguanidine, 1,5-diphenylcarbonohydrazide, N, N'-diphenylethylenediamine, 5- (acetoacetamide) -2-benzoimidazolinone, 1- (o-tolyl) biguanide, 1-phenylguanidine, phenylbiguanide , High molecular weight biguanide compounds containing a terminal amino group, 4-phenylsemicarbazide, 4-phenyl-3-thiosemicarbazide, 1,2,3-triphenylguanidine and the like.
　二級アミノ基を含む固形芳香族アミンとしては、１つの二級アミノ基を有するモノアミンを含んでもよく、２つ以上のアミノ基を有し、そのうちの少なくとも１つが二級アミノ基であるポリアミンを含んでもよい。樹脂組成物の硬化速度や硬化物の機械的性質を向上させる観点から、二級アミノ基を含む固形芳香族アミンは、（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンを含むことが好ましい。（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンとしては、（Ｂ１’）アミノ基として二級アミノ基のみを含む固形芳香族アミン（二級アミノ基の数が１つ、２つ又は３つ以上、一級アミノ基と三級アミノ基との合計数が０）を含むことが好ましい。 The solid aromatic amine containing a secondary amino group may contain a monoamine having one secondary amino group, and a polyamine having two or more amino groups, of which at least one is a secondary amino group. It may be included. From the viewpoint of improving the curing rate of the resin composition and the mechanical properties of the cured product, the solid aromatic amine containing a secondary amino group has (B1) a number of secondary amino groups of primary amino group and tertiary amino group. It is preferable to contain more solid aromatic amines than the total number of. (B1) As a solid aromatic amine in which the number of secondary amino groups is larger than the total number of primary amino groups and tertiary amino groups, a solid aromatic amine containing only a secondary amino group as a (B1') amino group (B1') It is preferable that the number of secondary amino groups is one, two or three or more, and the total number of primary amino groups and tertiary amino groups is 0).
　（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンとしては、例えば、アミノ基として１つの二級アミノ基のみを有する固形芳香族モノアミン（Ｂ１’に相当）、アミノ基として２つ以上の二級アミノ基のみを有する固形芳香族ポリアミン（Ｂ１’に相当）、１つの一級アミノ基と２つの二級アミノ基を有する固形芳香族ポリアミン、２つの二級アミノ基と１つの三級アミノ基を有する固形芳香族ポリアミン、１つの一級アミノ基と３つ以上の二級アミノ基を有する固形芳香族ポリアミン、３つ以上の二級アミノ基と１つの三級アミノ基を有する固形芳香族ポリアミン等が挙げられる。 (B1) As a solid aromatic amine in which the number of secondary amino groups is larger than the total number of primary amino groups and tertiary amino groups, for example, a solid aromatic monoamine having only one secondary amino group as an amino group (B1). B1'), a solid aromatic polyamine having only two or more secondary amino groups as an amino group (corresponding to B1'), a solid aromatic polyamine having one primary amino group and two secondary amino groups, Solid aromatic polyamines with two secondary amino groups and one tertiary amino group, solid aromatic polyamines with one primary amino group and three or more secondary amino groups, and three or more secondary amino groups. Examples thereof include solid aromatic polyamines having one tertiary amino group.
　アミノ基として１つの二級アミノ基のみを有する固形芳香族モノアミン（Ｂ１’に相当）の好ましい例としては、Ｎ－フェニル－１－ナフチルアミン、オクチル化ジフェニルアミン、４，４’－ビス（α，α－ジメチルベンジル）ジフェニルアミン、Ｎ－（ｐ－トリル）－１－ナフチルアミン、Ｎ－フェニル－３－ビフェニルアミン、ビス（３－ビフェニリル）アミン、２－（３－ビフェニリル）アミノ－９，９－ジメチルフルオレン、ビス（４－ｔｅｒｔ－ブチルフェニル）アミン、４－ｔｅｒｔ－ブチルフェニルフェニルアミン、ビス－α－メチルベンジルフェノチアジン、ジフェニルアミンと２，４，４－トリメチルペンテンとの反応物、ジフェニルアミン、Ｎ－フェニルベンジルアミン、３－メチルジフェニルアミン、３，４－ジメチルジフェニルアミン、４，４’－ジメチルジフェニルアミン、３－メトキシジフェニルアミン、１０－メトキシ－２，２’－イミノスチルベン、Ｎ－ベンジル－２－ナフチルアミン、１，２’－ジナフチルアミン、１，１’－ジナフチルアミン等が挙げられる。 Preferred examples of solid aromatic monoamines (corresponding to B1') having only one secondary amino group as an amino group are N-phenyl-1-naphthylamine, octylated diphenylamine, 4,4'-bis (α, α). -Didimethylbenzyl) diphenylamine, N- (p-tolyl) -1-naphthylamine, N-phenyl-3-biphenylamine, bis (3-biphenylyl) amine, 2- (3-biphenylyl) amino-9,9-dimethylfluorene , Bis (4-tert-butylphenyl) amine, 4-tert-butylphenylphenylamine, bis-α-methylbenzylphenothiazine, reaction product of diphenylamine with 2,4,4-trimethylpentene, diphenylamine, N-phenylbenzyl Amine, 3-methyldiphenylamine, 3,4-dimethyldiphenylamine, 4,4'-dimethyldiphenylamine, 3-methoxydiphenylamine, 10-methoxy-2,2'-iminostylben, N-benzyl-2-naphthylamine, 1,2 '-Dinaphthylamine, 1,1'-dinaphthylamine and the like can be mentioned.
　アミノ基として２つ以上の二級アミノ基のみを有する固形芳香族ポリアミン（Ｂ１’に相当）の好ましい例としては、４－イソプロピルアミノジフェニルアミン、２，６－ビス［（２－ヒドロキシエチル）アミノ］トルエン、４－（２－オクチルアミノ）ジフェニルアミン、Ｎ－（１，３－ジメチルブチル）－Ｎ’－フェニル－１，４－フェニレンジアミン、２，２，４－トリメチル－１，２－ジヒドロキノリン重合体、１，３－ジフェニルグアニジン、ｐ－（ｐ－トルエンスルホニルアミド）ジフェニルアミン、Ｎ－フェニル－Ｎ’－（３－メタクリロイルオキシ－２－ヒドロキシプロピル）－ｐ－フェニレンジアミン、ビス（２－ベンズアミドフェニル）ジスルフィド、Ｎ，Ｎ’－ジフェニル－１，４－フェニレンジアミン、１，３－ジ－ｏ－トリルグアニジン、１，５－ジフェニルカルボノヒドラジド、Ｎ，Ｎ’－ジフェニルエチレンジアミン、５－（アセトアセトアミド）－２－ベンゾイミダゾリノン等が挙げられる。 Preferred examples of solid aromatic polyamines (corresponding to B1') having only two or more secondary amino groups as amino groups are 4-isopropylaminodiphenylamine, 2,6-bis [(2-hydroxyethyl) amino]. Toluene, 4- (2-octylamino) diphenylamine, N- (1,3-dimethylbutyl) -N'-phenyl-1,4-phenylenediamine, 2,2,4-trimethyl-1,2-dihydroquinoline weight Combined, 1,3-diphenylguanidine, p- (p-toluenesulfonylamide) diphenylamine, N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, bis (2-benzamidephenyl) ) Disulfide, N, N'-diphenyl-1,4-phenylenediamine, 1,3-di-o-tolylguanidine, 1,5-diphenylcarbonohydrazide, N, N'-diphenylethylenediamine, 5- (acetoacetamide) )-2-Benzomemidazolinone and the like.
　（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンのその他の例としては、１－（ｏ－トリル）ビグアニド、１－フェニルグアニジン、フェニルビグアニド、末端アミノ基を含む高分子ビグアニド化合物、４－フェニルセミカルバジド、４－フェニル－３－チオセミカルバジド、１，２，３－トリフェニルグアニジン等が挙げられる。 (B1) Other examples of solid aromatic amines in which the number of secondary amino groups is greater than the total number of primary and tertiary amino groups are 1- (o-tolyl) biguanide, 1-phenylguanidine, phenyl. Examples thereof include biguanide, a high molecular weight biguanide compound containing a terminal amino group, 4-phenylsemicarbazide, 4-phenyl-3-thiosemicarbazide, 1,2,3-triphenylguanidine and the like.
　二級アミノ基を含む固形芳香族アミンは、（Ｂ２）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数以下である固形芳香族ポリアミンを含んでもよい。例えば、（Ｂ）二級アミノ基を含む固形芳香族アミンが、（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンを含まず、（Ｂ２）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数以下である固形芳香族ポリアミンを含んでもよい。この場合、エポキシ樹脂用硬化剤は、後述する（Ｃ）脂肪族環状ポリアミンをさらに含む。あるいは、（Ｂ）二級アミノ基を含む固形芳香族アミンとして、（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンと、（Ｂ２）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数以下である固形芳香族ポリアミンとを併用してもよい。この場合、エポキシ樹脂用硬化剤は、後述する（Ｃ）脂肪族環状ポリアミンをさらに含んでもよく、含まなくてもよい。 The solid aromatic amine containing a secondary amino group may contain (B2) a solid aromatic polyamine in which the number of secondary amino groups is not more than the total number of primary amino groups and tertiary amino groups. For example, (B) a solid aromatic amine containing a secondary amino group does not contain (B1) a solid aromatic amine in which the number of secondary amino groups is greater than the total number of primary and tertiary amino groups. B2) A solid aromatic polyamine in which the number of secondary amino groups is not more than the total number of primary amino groups and tertiary amino groups may be contained. In this case, the curing agent for epoxy resin further contains (C) aliphatic cyclic polyamine described later. Alternatively, as (B) a solid aromatic amine containing a secondary amino group, (B1) a solid aromatic amine in which the number of secondary amino groups is larger than the total number of primary amino groups and tertiary amino groups, and (B2). A solid aromatic polyamine in which the number of secondary amino groups is not more than the total number of primary amino groups and tertiary amino groups may be used in combination. In this case, the curing agent for epoxy resin may or may not further contain (C) the aliphatic cyclic polyamine described later.
　（Ｂ２）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数以下である固形芳香族ポリアミンとしては、一級アミノ基と二級アミノ基とを含む固形芳香族ポリアミン（例えば、１つの一級アミノ基と１つの二級アミノ基とを有する固形芳香族ポリアミン、２つの一級アミノ基と１つの二級アミノ基とを有する固形芳香族ポリアミン等）、二級アミノ基と三級アミノ基とを含む固形芳香族ポリアミン（例えば、１つの二級アミノ基と１つの三級アミノ基とを含む固形芳香族ポリアミン等）、一級アミノ基と二級アミノ基と三級アミノ基とを含む固形芳香族ポリアミンが挙げられる。 (B2) The solid aromatic polyamine in which the number of secondary amino groups is not more than the total number of primary amino groups and tertiary amino groups is a solid aromatic polyamine containing a primary amino group and a secondary amino group (for example, for example. Solid aromatic polyamines with one primary amino group and one secondary amino group, such as solid aromatic polyamines with two primary amino groups and one secondary amino group), secondary amino groups and tertiary aminos. Contains solid aromatic polyamines containing groups (eg, solid aromatic polyamines containing one secondary amino group and one tertiary amino group), primary amino groups, secondary amino groups and tertiary amino groups. Examples include solid aromatic polyamines.
　（Ｂ２）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数以下である固形芳香族ポリアミンの好ましい例としては、４－アミノジフェニルアミン、２，４－ジアミノジフェニルアミン、２－アミノジフェニルアミン、４－アミノ－４’－メトキシジフェニルアミン、１－フェニルビグアニド、イソフタル酸ジヒドラジド、テレフタル酸ジヒドラジド、２，６－ナフトエ酸ジヒドラジド、４，４’－ビスベンゼンジヒドラジド、１，４－ナフトエ酸ジヒドラジド、ナフタレン－２，６－ジカルボヒドラジド、３－ヒドロキシ－２－ナフトエ酸ヒドラジド等が挙げられる。 (B2) Preferred examples of the solid aromatic polyamine in which the number of secondary amino groups is not more than the total number of primary amino groups and tertiary amino groups are 4-aminodiphenylamine, 2,4-diaminodiphenylamine, and 2-amino. Diphenylamine, 4-amino-4'-methoxydiphenylamine, 1-phenylbiguanide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 4,4'-bisbenzenedihydrazide, 1,4-naphthoic acid dihydrazide, Examples thereof include naphthalene-2,6-dicarbohydrazide and 3-hydroxy-2-naphthoic acid hydrazide.
　（Ｂ）二級アミノ基を含む固形芳香族アミンは、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。例えば、（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンと、（Ｂ２）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数以下である固形芳香族ポリアミンとを併用してもよい。あるいは、（Ｂ）二級アミノ基を含む固形芳香族アミンとして、２種以上の（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンを組み合わせて使用してもよく、２種以上の（Ｂ２）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数以下である固形芳香族ポリアミンを組み合わせて使用してもよい。 (B) The solid aromatic amine containing a secondary amino group may be used alone or in combination of two or more. For example, (B1) solid aromatic amines having more secondary amino groups than the total number of primary amino groups and tertiary amino groups, and (B2) primary amino groups and tertiary amino groups having more secondary amino groups. It may be used in combination with a solid aromatic polyamine which is not more than the total number of polyamines. Alternatively, as the (B) solid aromatic amine containing a secondary amino group, a solid aromatic amine in which the number of two or more (B1) secondary amino groups is larger than the total number of the primary amino group and the tertiary amino group is used. It may be used in combination, or a solid aromatic polyamine in which the number of two or more kinds of (B2) secondary amino groups is not more than the total number of primary amino groups and tertiary amino groups may be used in combination.
　（Ｂ）二級アミノ基を含む固形芳香族アミンは、芳香環にハロゲン等の置換基を有していてもよい。芳香環にハロゲン置換基を有する（Ｂ）二級アミノ基を含む固形芳香族アミンを使用することにより、樹脂組成物の粘度安定性を改善することが可能である。 (B) The solid aromatic amine containing a secondary amino group may have a substituent such as halogen in the aromatic ring. By using a solid aromatic amine containing a (B) secondary amino group having a halogen substituent on the aromatic ring, it is possible to improve the viscosity stability of the resin composition.
　二級アミノ基を含む固形芳香族ポリアミンの市販品の例としては、１－（ｏ－トリル）ビグアニド（大内新興化学工業社製「ノクセラーＢＧ」、ＨＵＮＴＳＭＡＮ社製「Ａｒａｄｕｒ２８４４」、Ｔｈｏｍａｓ　Ｓｗａｎ社製「Ｃａｓａｍｉｎｅ　ＯＴＢ」）、４－イソプロピルアミノジフェニルアミン（大内新興化学工業社製「ノクラック８１０－ＮＡ」、川口化学工業社製「アンテージ３Ｃ」）、４－アミノジフェニルアミン（精工化学社製「４－アミノジフェニルアミン」、ＬＡＮＸＥＳＳ社製「４－ＡＤＰＡ」）、２，２，４－トリメチル－１，２－ジヒドロキノリン重合体（大内新興化学工業社製「ノクラック２２４（２２４－Ｓ）」、精工化学社製「ノンフレックスＲＤ」、「ノンフレックスＱＳ」）、Ｎ－フェニル－１－ナフチルアミン（大内新興化学工業社製「ノクラックＰＡ」）、１，３－ジフェニルグアニジン（大内新興化学工業社製「ノクセラーＤ」、三新化学工業社制「サンセラーＤ，Ｄ－Ｇ」）、４，４’－ビス（α，α－ジメチルベンジル）ジフェニルアミン（大内新興化学工業社製「ノクラックＣＤ」、精工化学社製「ノンフレックスＤＣＤ」）等が挙げられる。 Examples of commercially available solid aromatic polyamines containing a secondary amino group are 1- (o-tolyl) biganide ("Noxeller BG" manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., "Aradur 2844" manufactured by HUNTSMAN, and manufactured by Thomas Swan. "Casamine OTB"), 4-isopropylaminodiphenylamine ("Nocrack 810-NA" manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., "Antage 3C" manufactured by Kawaguchi Kagaku Kogyo Co., Ltd.), 4-aminodiphenylamine ("4-Amino" manufactured by Seiko Kagaku Co., Ltd.) "Diphenylamine", "4-ADPA" manufactured by LANXESS), 2,2,4-trimethyl-1,2-dihydroquinoline polymer ("Nocrack 224 (224-S)" manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., Seiko Kagaku Co., Ltd. "Non-Flex RD", "Non-Flex QS"), N-phenyl-1-naphthylamine ("Nocrack PA" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), 1,3-diphenylguanidine (manufactured by Ouchi Shinko Chemical Industry Co., Ltd. "" Noxeller D ", Sanshin Chemical Industry Co., Ltd." Sun Cellar D, DG "), 4,4'-bis (α, α-dimethylbenzyl) diphenylamine ("Nocrack CD "manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., Seiko Kagaku "Non-flex DCD" manufactured by the company) and the like can be mentioned.
　硬化剤を１００質量％とした場合、二級アミノ基を含む固形芳香族ポリアミンは、硬化物の衝撃強度を高める観点から、好ましくは１～４５質量％、より好ましくは２～４０質量％、更に好ましくは３～３５質量％の量で、硬化剤に含まれる。 When the curing agent is 100% by mass, the solid aromatic polyamine containing a secondary amino group is preferably 1 to 45% by mass, more preferably 2 to 40% by mass, and further, from the viewpoint of increasing the impact strength of the cured product. It is contained in the curing agent in an amount of preferably 3 to 35% by mass.
　本発明の硬化剤は、硬化物の伸びや曲げ強度等の機械的性質を向上させる観点から、任意に、融点１６０℃以下の、二級アミノ基を含まないが一級アミノ基を含む固形芳香族アミンを含んでもよい。融点１６０℃以下の二級アミノ基を含まないが一級アミノ基を含む固形芳香族アミンの好ましい例としては、４，４’－メチレンビス（２－エチル－６－メチルアニリン）、２，２’－ジイソプロピル－６，６’－ジメチル－４，４’-メチレンジアニリン、２，２’，６，６’－テトライソプロピル－４，４’－メチレンジアニリン、４，４’－メチレンビス（２，６－ジエチルアニリン）、４，４’－メチレンビス（３－クロロ－２,６－ジエチルアニリン）、１，３－フェニレンジアミン、２，４－ジアミノトルエン、２，６－ジアミノトルエン、２，４，６－トリメチル－１,３－フェニレンジアミン、３－アミノビフェニル、３－アミノ－４－メトキシビフェニル、２－アミノフルオレン、２－アミノ－９－フルオレノン、２，７－ジアミノフルオレン、３－アミノベンゾフェノン、３，４’－ジアミノジフェニルメタン、３，３’－ジアミノジフェニルメタン、３，４－ジアミノベンゾフェノン、３，３’－ジアミノベンゾフェノン等が挙げられる。 From the viewpoint of improving mechanical properties such as elongation and bending strength of the cured product, the curing agent of the present invention is optionally a solid aromatic having a melting point of 160 ° C. or lower and containing no secondary amino group but containing a primary amino group. It may contain amines. Preferred examples of solid aromatic amines having a melting point of 160 ° C. or lower, which do not contain a secondary amino group but contain a primary amino group, are 4,4'-methylenebis (2-ethyl-6-methylaniline) and 2,2'-. Diisopropyl-6,6'-dimethyl-4,4'-methylenedianiline, 2,2', 6,6'-tetraisopropyl-4,4'-methylenedianiline, 4,4'-methylenebis (2,6) -Diethylaniline), 4,4'-methylenebis (3-chloro-2,6-diethylaniline), 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 2,4,6 -Trimethyl-1,3-phenylenediamine, 3-aminobiphenyl, 3-amino-4-methoxybiphenyl, 2-aminofluorene, 2-amino-9-fluorenone, 2,7-diaminofluorene, 3-aminobenzophenone, 3 , 4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4-diaminobenzophenone, 3,3'-diaminobenzophenone and the like.
（Ｃ）脂肪族環状ポリアミン
　本発明のエポキシ樹脂用硬化剤は、（Ｂ）二級アミノ基を含む固形芳香族アミンが、（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンを含まない場合（すなわち、（Ｂ）二級アミノ基を含む固形芳香族アミンとして、（Ｂ２）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数以下である固形芳香族ポリアミンのみを含む場合）、（Ｃ）脂肪族環状ポリアミンをさらに含む。また、本発明のエポキシ樹脂用硬化剤は、（Ｂ）二級アミノ基を含む固形芳香族アミンとして（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンを含む場合に、（Ｃ）脂肪族環状ポリアミンをさらに含んでもよく、含まなくてもよい。 (C) aliphatic cyclic polyamine The curing agent for epoxy resin of the present invention contains (B) a solid aromatic amine containing a secondary amino group, and (B1) a primary amino group and a tertiary amino group having a secondary amino group number. When the solid aromatic amine containing more than the total number of (B) the secondary amino group is not contained (that is, (B2) the number of the secondary amino group is the primary amino group and the tertiary amino group as the solid aromatic amine containing the secondary amino group. (When containing only solid aromatic polyamines which are not more than or equal to the total number of polyamines), (C) further contains aliphatic cyclic polyamines. Further, in the curing agent for epoxy resin of the present invention, the number of (B1) secondary amino groups as a solid aromatic amine containing (B) secondary amino groups is larger than the total number of primary amino groups and tertiary amino groups. When the solid aromatic amine is contained, (C) the aliphatic cyclic polyamine may or may not be further contained.
　硬化剤における（Ｃ）脂肪族環状ポリアミンは、（Ａ）液状芳香族ポリアミンと（Ｂ）二級アミノ基を含む固形芳香族アミンによるエポキシ樹脂の硬化を促進する作用を有する。すなわち、本発明の硬化剤は、脂肪族環状ポリアミンを含むことにより、樹脂組成物の硬化を促進し、硬化速度を速めることができる。脂肪族環状ポリアミンは、環構造上に（すなわち、環に結合している）置換基として２つ以上のアミノ基を有する脂肪族炭化水素であってもよく、環構造中に（すなわち、環を構成している）２つ以上のアミノ基を有する複素環式アミンであってもよい。また環構造上に置換基として１つ以上のアミノ基を有し、かつ環構造中に１つ以上のアミノ基を有する複素環式アミンであってもよい。環構造上の置換基としてのアミノ基としては、一級アミノ基又は二級アミノ基が挙げられ、一級アミノ基が好ましい。複素環式アミンの環構造中のアミノ基としては、二級アミノ基が好ましい。 The (C) aliphatic cyclic polyamine in the curing agent has an action of accelerating the curing of the epoxy resin by (A) a liquid aromatic polyamine and (B) a solid aromatic amine containing a secondary amino group. That is, the curing agent of the present invention can accelerate the curing of the resin composition and accelerate the curing rate by containing the aliphatic cyclic polyamine. The aliphatic cyclic polyamine may be an aliphatic hydrocarbon having two or more amino groups as substituents on the ring structure (ie, attached to the ring) and in the ring structure (ie, ring). It may be a heterocyclic amine having two or more amino groups (constituting). Further, it may be a heterocyclic amine having one or more amino groups as a substituent on the ring structure and having one or more amino groups in the ring structure. Examples of the amino group as the substituent on the ring structure include a primary amino group and a secondary amino group, and a primary amino group is preferable. As the amino group in the ring structure of the heterocyclic amine, a secondary amino group is preferable.
　本発明における脂肪族環状ポリアミンにおいては、好ましくは、窒素原子やアミノ基が錯体又は塩構造を形成していないものが選択される。錯体又は塩構造を形成していないフリーのアミノ基を有する脂肪族環状ポリアミンの場合、窒素原子やアミノ基が錯体又は塩構造を形成して安定化されている脂肪族環状ポリアミンに比べ、樹脂組成物の硬化速度をより速めることができる。 In the aliphatic cyclic polyamine of the present invention, those in which nitrogen atoms and amino groups do not form a complex or salt structure are preferably selected. In the case of an aliphatic cyclic polyamine having a free amino group that does not form a complex or salt structure, the resin composition is higher than that of an aliphatic cyclic polyamine in which a nitrogen atom or an amino group is stabilized by forming a complex or salt structure. The curing speed of the object can be increased.
　本発明における脂肪族環状ポリアミンの環構造において、好ましくは、環構造中のアミノ基（好ましくは二級アミノ基）に隣接する元素（炭素原子等）及び／又は環構造上のアミノ基が結合している元素（炭素原子等）に隣接する元素（炭素原子等）の置換基が全て水素原子であるものが選択される。上記置換基が全て水素原子である場合、水素原子以外の置換基（例えば、アルキル基等）が結合している場合に比べ、アミノ基がエポキシ樹脂と反応するうえでの立体障害がないため、樹脂組成物の硬化速度をより速めることができる。環構造中にアミノ基が２つ以上ある場合には、少なくとも、環構造中の１つのアミノ基に隣接する２つの元素の置換基が全て水素原子であればよいが、環構造中の全てのアミノ基に隣接する元素の置換基が全て水素原子であることが好ましい。環構造上に置換基としてのアミノ基が２つ以上結合している場合には、少なくとも、アミノ基が結合している１つの元素に隣接する２つの元素の置換基が全て水素原子であればよいが、アミノ基が結合している全ての元素に隣接する元素の置換基が全て水素原子であることが好ましい。より好ましくは、環構造中のアミノ基（好ましくは二級アミノ基）以外の元素（炭素原子等）及び／又は環構造上のアミノ基が結合している元素（炭素原子等）以外の元素（炭素原子等）の置換基が全て水素原子であるものが選択される。 In the ring structure of the aliphatic cyclic polyamine in the present invention, an element (carbon atom or the like) adjacent to the amino group (preferably a secondary amino group) in the ring structure and / or an amino group on the ring structure are bonded to each other. Those in which all the substituents of the element (carbon atom, etc.) adjacent to the element (carbon atom, etc.) are hydrogen atoms are selected. When all of the above substituents are hydrogen atoms, there is no steric hindrance in the reaction of the amino group with the epoxy resin as compared with the case where a substituent other than the hydrogen atom (for example, an alkyl group) is bonded. The curing rate of the resin composition can be further increased. When there are two or more amino groups in the ring structure, at least all the substituents of the two elements adjacent to one amino group in the ring structure may be hydrogen atoms, but all of them in the ring structure. It is preferable that all the substituents of the element adjacent to the amino group are hydrogen atoms. When two or more amino groups as substituents are bonded on the ring structure, at least if the substituents of the two elements adjacent to the one element to which the amino group is bonded are all hydrogen atoms. However, it is preferable that all the substituents of the element adjacent to all the elements to which the amino group is bonded are hydrogen atoms. More preferably, an element (carbon atom or the like) other than the amino group (preferably a secondary amino group) in the ring structure and / or an element other than the element (carbon atom or the like) to which the amino group on the ring structure is bonded (carbon atom or the like). Those in which all the substituents of (carbon atom, etc.) are hydrogen atoms are selected.
　脂肪族環状ポリアミンは、沸点が１４０℃以上であることが好ましく、１４５℃～２５０℃であることがより好ましい。沸点が１４０℃以上であれば、エポキシ樹脂をマトリックス樹脂とする繊維強化複合材料の製造過程において、強化繊維を樹脂組成物に含浸させる際の温度よりも十分に高いため、脂肪族環状ポリアミン成分の揮発を抑制することができ、その結果、繊維強化複合材料の構造欠陥及び強度低下を抑制することができる。 The aliphatic cyclic polyamine preferably has a boiling point of 140 ° C. or higher, and more preferably 145 ° C. to 250 ° C. When the boiling point is 140 ° C. or higher, the temperature is sufficiently higher than the temperature at which the reinforcing fiber is impregnated into the resin composition in the manufacturing process of the fiber-reinforced composite material using the epoxy resin as the matrix resin. Volatilization can be suppressed, and as a result, structural defects and a decrease in strength of the fiber-reinforced composite material can be suppressed.
　脂肪族環状ポリアミンは、融点が１６０℃以下であることが好ましく、例えば、１５０℃以下、１４０℃以下、１３０℃以下、又は１２０℃以下であることが好ましい。融点が１６０℃以下であれば、液状芳香族ポリアミンに短時間で容易に溶解させることができる。 The aliphatic cyclic polyamine preferably has a melting point of 160 ° C. or lower, for example, 150 ° C. or lower, 140 ° C. or lower, 130 ° C. or lower, or 120 ° C. or lower. When the melting point is 160 ° C. or lower, it can be easily dissolved in a liquid aromatic polyamine in a short time.
　脂肪族環状ポリアミンは、樹脂組成物の粘度を低くする観点から、１個、２個又は３個の環構造を持つ化合物であることが好ましい。 The aliphatic cyclic polyamine is preferably a compound having one, two or three ring structures from the viewpoint of lowering the viscosity of the resin composition.
　脂肪族環状ポリアミンは、硬化物の耐熱性を高める観点から、一級アミノ基又は二級アミノ基を含むことが好ましい。反応性の観点から、環構造中のアミノ基としては二級アミノ基を含むことがより好ましく、二級アミノ基のみを含むことが更により好ましく、置換基としてのアミノ基としては一級アミノ基を含むことがより好ましい。一級アミノ基又は二級アミノ基が含まれていれば、硬化物の耐熱性等の物性に悪影響を与えない範囲で三級アミノ基が含まれていてもよい。 The aliphatic cyclic polyamine preferably contains a primary amino group or a secondary amino group from the viewpoint of enhancing the heat resistance of the cured product. From the viewpoint of reactivity, it is more preferable that the amino group in the ring structure contains a secondary amino group, further preferably it contains only a secondary amino group, and the amino group as a substituent is a primary amino group. It is more preferable to include it. As long as it contains a primary amino group or a secondary amino group, it may contain a tertiary amino group as long as it does not adversely affect physical properties such as heat resistance of the cured product.
　二級アミノ基を含む脂肪族環状ポリアミンとしては、ピペラジン骨格を有するものが好ましく、例えば、ピペラジン、２－メチルピペラジン、ホモピペラジン、ｔｒａｎｓ－２,５－ジメチルピペラジン、ｃｉｓ－２,６－ジメチルピペラジン、（Ｓ）－（＋）－２－メチルピペラジン、Ｎ－（２－アミノエチル）ピペラジン、１－ブチルピペラジン、１－メチルピペラジン、２－ピペラジノン等が挙げられる。なかでも、反応性が高く、硬化時間を短縮できることから、脂肪族環状ポリアミンはピペラジンであることがより好ましい。 The aliphatic cyclic polyamine containing a secondary amino group preferably has a piperazine skeleton, for example, piperazine, 2-methylpiperazine, homopiperazine, trans-2,5-dimethylpiperazine, cis-2,6-dimethylpiperazine. , (S)-(+)-2-methylpiperazine, N- (2-aminoethyl) piperazine, 1-butylpiperazine, 1-methylpiperazine, 2-piperazinone and the like. Among them, the aliphatic cyclic polyamine is more preferably piperazine because it has high reactivity and can shorten the curing time.
　二級アミノ基を含む脂肪族環状ポリアミンの別の好ましい例としては、１，３－ビス（アミノメチル）シクロヘキサン、デキスラゾキサン、３－アミノピロリジン、３－（メチルアミノ）ピロリジン、３－（エチルアミノ）ピロリジン、（１Ｓ，６Ｓ）－２,８－ジアザビシクロ［４．３．０］ノナン、３－アセトアミドピロリジン、４－アミノピペリジン、３－アミノ－２－ピペリドン、３－（アミノメチル）ピペリジン、２－ピペリジンカルボキサミド、３－アセトアミドピペリジン、４－アミノ－２,２,６,６－テトラメチルピペリジン、４，４’－ビピペリジン、ＤＬ－α－アミノ－ε－カプロラクタム、１，２，３，４－シクロブタンテトラカルボン酸ジイミド、ｔｒａｎｓ－Ｎ,Ｎ’－ジメチルシクロヘキサン－１,２－ジアミン、（１Ｓ，２Ｓ）－（＋）－Ｎ,Ｎ’－ジメチルシクロヘキサン－１,２－ジアミン、（１Ｒ，２Ｒ）－（－）－Ｎ,Ｎ’－ジメチルシクロヘキサン－１,２－ジアミン、Ｎ－（３－アミノプロピル）シクロヘキシルアミン、Ｎ－（１－アダマンチル）エチレンジアミン、ｔｒａｎｓ－Ｎ,Ｎ’－ジアセチルシクロヘキサン－１,２－ジアミン、１－アダマンチルチオ尿素、（１Ｓ，２Ｒ）－Ｎ１－（ｔｅｒｔ－ブトキシカルボニル）－１,２－シクロヘキサンジアミン、（１Ｒ，２Ｓ）－Ｎ１－（ｔｅｒｔ－ブトキシカルボニル）－１,２－シクロヘキサンジアミン、（１Ｓ，２Ｓ）－Ｎ１－（ｔｅｒｔ－ブトキシカルボニル）－１,２－シクロヘキサンジアミン、（１Ｒ，２Ｒ）－Ｎ１－（ｔｅｒｔ－ブトキシカルボニル）－１,２－シクロヘキサンジアミン、１，３－ジシクロヘキシル尿素、１，３－ジシクロヘキシルチオ尿素、１－シクロヘキシルグアニジン、１－シクロヘキシルビグアニド等が挙げられる。 Another preferred example of an aliphatic cyclic polyamine containing a secondary amino group is 1,3-bis (aminomethyl) cyclohexane, dexrazoxane, 3-aminopyrrolidine, 3- (methylamino) pyrrolidine, 3- (ethylamino). Pyrrolidine, (1S, 6S) -2,8-diazabicyclo [4.3.0] nonane, 3-acetamidopyrrolidine, 4-aminopiperidin, 3-amino-2-piperidone, 3- (aminomethyl) piperidin, 2- Piperidine carboxamide, 3-acetamide piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4,4'-bipiperidine, DL-α-amino-ε-caprolactam, 1,2,3,4-cyclobutane Diimide tetracarboxylic acid, trans-N, N'-dimethylcyclohexane-1,2-diamine, (1S, 2S)-(+)-N, N'-dimethylcyclohexane-1,2-diamine, (1R, 2R) -(-)-N, N'-dimethylcyclohexane-1,2-diamine, N- (3-aminopropyl) cyclohexylamine, N- (1-adamantyl) ethylenediamine, trans-N, N'-diacetylcyclohexane-1 , 2-Diamine, 1-adamantylthiourea, (1S, 2R) -N1- (tert-butoxycarbonyl) -1,2-cyclohexanediamine, (1R, 2S) -N1- (tert-butoxycarbonyl) -1, 2-Cyclohexanediamine, (1S, 2S) -N1- (tert-butoxycarbonyl) -1,2-cyclohexanediamine, (1R, 2R) -N1- (tert-butoxycarbonyl) -1,2-cyclohexanediamine, 1 , 3-Dicyclohexylurea, 1,3-dicyclohexylthiourea, 1-cyclohexylguanidine, 1-cyclohexylbiguanide and the like.
　硬化剤を１００質量％とした場合、脂肪族環状ポリアミンは、存在する場合には、好ましくは１～１５質量％、より好ましくは２～１２質量％、更に好ましくは３～１０質量％の量で、硬化剤に含まれる。脂肪族環状ポリアミンが１質量％以上であれば、樹脂組成物の硬化速度を速めることができ、１５質量％であれば、硬化物の耐熱性を損なうことがない。 When the curing agent is 100% by mass, the aliphatic cyclic polyamine, if present, is preferably in an amount of 1 to 15% by mass, more preferably 2 to 12% by mass, still more preferably 3 to 10% by mass. , Included in the curing agent. If the content of the aliphatic cyclic polyamine is 1% by mass or more, the curing rate of the resin composition can be increased, and if it is 15% by mass, the heat resistance of the cured product is not impaired.
　本発明のエポキシ樹脂用硬化剤は、本発明の効果を損なわない範囲内で、ボレート化合物、チタネート化合物、ジルコネート化合物、シラン化合物、カルボン酸化合物、フェノール化合物、ハロゲン化合物等の追加成分を任意に含んでもよい。これらの追加成分は、（Ｂ）二級アミノ基を含む固形芳香族アミンとの塩形態で含まれていてもよい。 The curing agent for epoxy resin of the present invention optionally contains additional components such as a borate compound, a titanate compound, a zirconate compound, a silane compound, a carboxylic acid compound, a phenol compound and a halogen compound within a range not impairing the effect of the present invention. But it may be. These additional components may be contained in the form of (B) a salt with a solid aromatic amine containing a secondary amino group.
　本発明の硬化剤は、液状芳香族ポリアミンに、二級アミノ基を含む固形芳香族アミンと、存在する場合には脂肪族環状ポリアミンとを溶解させてなる液状の形態であってもよく、液状芳香族ポリアミン中に、二級アミノ基を含む固形芳香族アミンと、存在する場合には脂肪族環状ポリアミンとが、固体として存在している懸濁物の形態であってもよい。本発明の硬化剤は、好ましくは液状の形態である。液状芳香族ポリアミンに他の成分を溶解させて硬化剤を液体状態にすることにより、エポキシ樹脂をマトリックス樹脂とする繊維強化複合材料の製造過程において、樹脂組成物を繊維に速やかに含浸させることができる。 The curing agent of the present invention may be in a liquid form in which a solid aromatic amine containing a secondary amino group and an aliphatic cyclic polyamine, if present, are dissolved in a liquid aromatic polyamine. The solid aromatic amine containing a secondary amino group and the aliphatic cyclic polyamine, if present, may be in the form of a suspension existing as a solid in the aromatic polyamine. The curing agent of the present invention is preferably in a liquid form. By dissolving other components in liquid aromatic polyamine to make the curing agent into a liquid state, the fiber can be rapidly impregnated with the resin composition in the process of manufacturing a fiber-reinforced composite material using an epoxy resin as a matrix resin. can.
　本発明のエポキシ樹脂用硬化剤の製造方法は、例えば、液状の形態の硬化剤の場合、液状芳香族ポリアミンに、二級アミノ基を含む固形芳香族アミンを溶解させて、エポキシ樹脂用硬化剤を得る工程を含み、（Ｂ）二級アミノ基を含む固形芳香族アミンが、（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンを含まない場合、（Ｃ）脂肪族環状ポリアミンを溶解させる工程をさらに含む。液状の形態のエポキシ樹脂用硬化剤の製造方法は、（Ｂ）二級アミノ基を含む固形芳香族アミンが、（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンを含む場合に、（Ａ）液状芳香族ポリアミンに（Ｂ）二級アミノ基を含む固形芳香族アミンを溶解させる工程に加え、（Ｃ）脂肪族環状ポリアミンを溶解させる工程をさらに含んでもよい。溶解手段には特に制限は無く、例えば、各原料を混合した後、オーブンや加熱式タンク等の加熱装置を使用して加熱溶解してもよい。オーブンを使用する際の条件として、例えば、８０～１２０℃、９０～１１０℃、又は９５～１０５℃の温度で、例えば、２０～９０分、３０～６０分、又は４０～５０分の時間、加熱してもよい。加熱温度及び加熱時間は、使用する加熱装置や原料のスケールに応じて適宜調節できる。 In the method for producing a curing agent for an epoxy resin of the present invention, for example, in the case of a curing agent in a liquid form, a solid aromatic amine containing a secondary amino group is dissolved in a liquid aromatic polyamine to dissolve the curing agent for an epoxy resin. (B) Solid aromatic amines containing secondary amino groups, and (B1) solid aromatic amines having more secondary amino groups than the total number of primary amino groups and tertiary amino groups. If not, it further comprises the step of dissolving (C) the aliphatic cyclic polyamine. The method for producing a curing agent for an epoxy resin in a liquid form is as follows: (B) a solid aromatic amine containing a secondary amino group, and (B1) the total number of secondary amino groups of a primary amino group and a tertiary amino group. When more than a large number of solid aromatic amines are contained, in addition to the step of dissolving (A) the solid aromatic amine containing a secondary amino group in the liquid aromatic polyamine, (C) dissolving the aliphatic cyclic polyamine. Further steps may be included. The melting means is not particularly limited, and for example, after mixing each raw material, it may be heated and melted using a heating device such as an oven or a heating type tank. Conditions for using the oven include, for example, at a temperature of 80-120 ° C, 90-110 ° C, or 95-105 ° C, for example, 20-90 minutes, 30-60 minutes, or 40-50 minutes. It may be heated. The heating temperature and heating time can be appropriately adjusted according to the heating device used and the scale of the raw material.
　本発明の一態様として、エポキシ樹脂用硬化剤とエポキシ樹脂とを含む、樹脂組成物を提供することができる。 As one aspect of the present invention, it is possible to provide a resin composition containing a curing agent for an epoxy resin and an epoxy resin.
　樹脂組成物に含有されるエポキシ樹脂としては、従来公知のエポキシ樹脂を特に制限なく使用できる。エポキシ樹脂は、用途や硬化物の所望の性質に応じて適宜選択でき、例えば、硬化物の衝撃強度の観点からは、２官能以上のエポキシ樹脂であることが好ましく、３官能以上のエポキシ樹脂であることがより好ましい。 As the epoxy resin contained in the resin composition, a conventionally known epoxy resin can be used without particular limitation. The epoxy resin can be appropriately selected depending on the intended use and the desired properties of the cured product. For example, from the viewpoint of the impact strength of the cured product, a bifunctional or higher functional epoxy resin is preferable, and a trifunctional or higher functional epoxy resin is used. It is more preferable to have.
　３官能以上のエポキシ樹脂は、好ましくはグリシジルアミン型エポキシ樹脂であり、例えば、ジアミノジフェニルメタン型エポキシ樹脂、ジアミノジフェニルスルホン型エポキシ樹脂、アミノフェノール型エポキシ樹脂、メタキシレンジアミン型エポキシ樹脂、１，３－ビスアミノメチルシクロヘキサン型エポキシ樹脂、イソシアヌレート型エポキシ樹脂等が挙げられる。３官能以上のエポキシ樹脂は、好ましくはグリシジルエーテル型エポキシ樹脂であってもよく、例えば、フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂、トリスヒドロキシフェニルメタン型エポキシ樹脂、テトラフェニロールエタン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂等が挙げられる。 The trifunctional or higher functional epoxy resin is preferably a glycidylamine type epoxy resin, for example, a diaminodiphenylmethane type epoxy resin, a diaminodiphenylsulfone type epoxy resin, an aminophenol type epoxy resin, a methaxylene diamine type epoxy resin, 1,3-. Examples thereof include bisaminomethylcyclohexane type epoxy resin and isocyanurate type epoxy resin. The trifunctional or higher functional epoxy resin may preferably be a glycidyl ether type epoxy resin, for example, a phenol novolac type epoxy resin, an orthocresol novolac type epoxy resin, a trishydroxyphenylmethane type epoxy resin, or a tetraphenylol ethane type epoxy. Examples thereof include a resin and a dicyclopentadiene type epoxy resin.
　３官能以上のグリシジルアミン型エポキシ樹脂の市販品の例としては、ジアミノジフェニルメタン型エポキシ樹脂（住友化学社製「ＥＬＭ４３４」、三菱化学社製「ｊＥＲ６０４」、ハンツマン・アドバンスト・マテリアルズ社製、「アラルダイトＭＹ７２０」、「アラルダイトＭＹ７２１」、「アラルダイトＭＹ９５１２」、「アラルダイトＭＹ９６６３」、東都化成社製「エポトートＹＨ－４３４」）、アミノフェノール型エポキシ樹脂（ジャパンエポキシレジン社製「ｊＥＲ６３０」、ハンツマン社製「アラルダイトＭＹ０５１０」、「アラルダイトＭＹ０６００」、「アラルダイトＭＹ０６１０」）、メタキシレンジアミン型エポキシ樹脂（三菱ガス化学社製「ＴＥＴＲＡＤ－Ｘ」）、１，３－ビスアミノメチルシクロヘキサン型エポキシ樹脂（三菱ガス化学社製「ＴＥＴＲＡＤ－Ｃ」）、イソシアヌレート型エポキシ樹脂（日産化学工業社製「ＴＥＰＩＣ－Ｐ」）等が挙げられる。 Examples of commercially available products of trifunctional or higher glycidylamine type epoxy resin are diaminodiphenylmethane type epoxy resin ("ELM434" manufactured by Sumitomo Chemical Co., Ltd., "jER604" manufactured by Mitsubishi Chemical Co., Ltd., "Araldite" manufactured by Huntsman Advanced Materials Co., Ltd. MY720, "Araldite MY721", "Araldite MY9512", "Araldite MY9663", Toto Kasei Co., Ltd. "Epototo YH-434"), Aminophenol type epoxy resin (Japan Epoxy Resin Co., Ltd. "jER630", Huntsman Co., Ltd. "Araldite" MY0510 ”,“ Araldite MY0600 ”,“ Araldite MY0610 ”), Metaxylene diamine type epoxy resin (“TETRAD-X” manufactured by Mitsubishi Gas Chemicals), 1,3-bisaminomethylcyclohexane type epoxy resin (manufactured by Mitsubishi Gas Chemicals) "TETRAD-C"), isocyanurate type epoxy resin ("TEPIC-P" manufactured by Nissan Chemical Industry Co., Ltd.) and the like.
　３官能以上のグリシジルエーテル型エポキシ樹脂の市販品の例としては、フェノールノボラック型エポキシ樹脂（ダウケミカル社製「ＤＥＮ４３１」、「ＤＥＮ４３８」、ジャパンエポキシレジン社製「ｊＥＲ１５２」）、オルソクレゾールノボラック型エポキシ樹脂（日本化薬社製「ＥＯＣＮ－１０２０」、ＤＩＣ社製「エピクロンＮ－６６０」）、トリスヒドロキシフェニルメタン型エポキシ樹脂（ハンツマン・アドバンスト・マテリアルズ社製「Ｔａｃｔｉ×７４２」）、テトラフェニロールエタン型エポキシ樹脂（ジャパンエポキシレジン社製「ｊＥＲ１０３１Ｓ」）、ジシクロペンタジエン型エポキシ樹脂（ＤＩＣ社製「エピクロンＨＰ７２００」）等が挙げられる。 Examples of commercially available products of trifunctional or higher glycidyl ether type epoxy resin are phenol novolac type epoxy resin (“DEN431” and “DEN438” manufactured by Dow Chemical Co., Ltd., “jER152” manufactured by Japan Epoxy Resin Co., Ltd.) and orthocresol novolac type epoxy. Resin (“EOCN-1020” manufactured by Nippon Kayaku Co., Ltd., “Epicron N-660” manufactured by DIC Co., Ltd.), Trishydroxyphenylmethane type epoxy resin (“Tacti × 742” manufactured by Huntsman Advanced Materials Co., Ltd.), Tetraphenylol Examples thereof include an ethane type epoxy resin (“jER1031S” manufactured by Japan Epoxy Resin Co., Ltd.) and a dicyclopentadiene type epoxy resin (“Epiclon HP7200” manufactured by DIC Co., Ltd.).
　エポキシ樹脂は２官能のものであってもよい。２官能のエポキシ樹脂としては、グリシジルエーテル型エポキシ樹脂が好ましく、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ウレタン変性エポキシ樹脂、ヒダントイン型エポキシ樹脂等を挙げることができる。 The epoxy resin may be bifunctional. As the bifunctional epoxy resin, glycidyl ether type epoxy resin is preferable, and for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, urethane modified epoxy resin. , Hydant-in type epoxy resin and the like can be mentioned.
　２官能のグリシジルエーテル型エポキシ樹脂の市販品の例としては、ビスフェノールＡ型エポキシ樹脂（三菱化学社製「ｊＥＲ８２８」、「ｊＥＲ８２５」、ＤＩＣ社製「エピクロン８５０」、東都化成社製「エポトートＹＤ－１２８」、ダウケミカル社製「ＤＥＲ－３３１」、「ＤＥＲ－３３２」）、ビスフェノールＦ型エポキシ樹脂（三菱化学社製「ｊＥＲ８０６」、「ｊＥＲ８０７」、「ｊＥＲ１７５０」、ＤＩＣ社製「エピクロン８３０」、東都化成社製「エポトートＹＤ－１７０」）、ビフェニル型エポキシ樹脂（日本化薬社製「ＮＣ－３０００」）、ウレタン変性エポキシ樹脂（旭化成エポキシ社製「ＡＥＲ４１５２」）、ヒダントイン型エポキシ樹脂（ハンツマン・アドバンスト・マテリアルズ社製「ＡＹ２３８」）等が挙げられる。 Examples of commercial products of bifunctional glycidyl ether type epoxy resin are bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd. "jER828", "jER825", DIC Co., Ltd. "Epicron 850", Toto Kasei Co., Ltd. "Epototo YD-". 128 ”,“ DER-331 ”,“ DER-332 ”manufactured by Dow Chemical Co., Ltd., bisphenol F type epoxy resin (“jER806”, “jER807”, “jER1750” manufactured by Mitsubishi Chemical Co., Ltd., “Epicron 830” manufactured by DIC Co., Ltd., Toto Kasei Co., Ltd. "Epototo YD-170"), biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC-3000"), urethane modified epoxy resin (Asahi Kasei Epoxy Co., Ltd. "AER4152"), hidden in type epoxy resin (Huntsman "AY238" manufactured by Advanced Materials Co., Ltd.) and the like can be mentioned.
　樹脂組成物に含有されるエポキシ樹脂のエポキシ当量は、５０～５００が好ましく、７５～３００がより好ましく、さらに好ましくは、１００～２００である。エポキシ樹脂のエポキシ当量が５０以上であれば、揮発性が少なく、低粘度とならず、取り扱い易い粘度となるので好適である。また、エポキシ樹脂のエポキシ当量が５００以下であれば、高粘度とならず、取り扱いの面で好適である。ここで、エポキシ当量とは、１当量のエポキシ基を含むエポキシ樹脂の質量であり、例えば、ＪＩＳ　Ｋ　７２３６（２００９）に準拠して測定することができる。 The epoxy equivalent of the epoxy resin contained in the resin composition is preferably 50 to 500, more preferably 75 to 300, and even more preferably 100 to 200. When the epoxy equivalent of the epoxy resin is 50 or more, the viscosity is low, the viscosity is not low, and the viscosity is easy to handle, which is preferable. Further, when the epoxy equivalent of the epoxy resin is 500 or less, the viscosity does not become high and it is suitable in terms of handling. Here, the epoxy equivalent is the mass of the epoxy resin containing one equivalent of the epoxy group, and can be measured according to, for example, JIS K 7236 (2009).
　エポキシ樹脂は１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。エポキシ樹脂は液状であってもよく、固形状であってもよい。また液状樹脂と固形状樹脂の混合物を用いてもよい。ここで、「液状」および「固形状」とは、常温（２５℃）でのエポキシ樹脂の状態を指す。加工性の観点から、使用するエポキシ樹脂全体の少なくとも１０質量％以上が液状エポキシ樹脂であることが好ましい。 The epoxy resin may be used alone or in combination of two or more. The epoxy resin may be liquid or solid. Further, a mixture of a liquid resin and a solid resin may be used. Here, "liquid" and "solid" refer to the state of the epoxy resin at room temperature (25 ° C.). From the viewpoint of processability, it is preferable that at least 10% by mass or more of the entire epoxy resin used is a liquid epoxy resin.
　樹脂組成物中のエポキシ樹脂の含有量は特に制限されないが、１～９９質量％であるのが好ましく、２０～９５質量％であるのがより好ましく、５０～９０質量％であるのが更に好ましい。 The content of the epoxy resin in the resin composition is not particularly limited, but is preferably 1 to 99% by mass, more preferably 20 to 95% by mass, and even more preferably 50 to 90% by mass. ..
　エポキシ樹脂を１００質量％とした場合、本発明のエポキシ樹脂用硬化剤は、樹脂組成物の粘度を低下させる観点から、好ましくは１０～７５質量％、より好ましくは１５～６５質量％、更に好ましくは２０～５５質量％の量で、樹脂組成物に含まれる。 When the epoxy resin is 100% by mass, the curing agent for epoxy resin of the present invention is preferably 10 to 75% by mass, more preferably 15 to 65% by mass, still more preferably, from the viewpoint of reducing the viscosity of the resin composition. Is contained in the resin composition in an amount of 20 to 55% by mass.
　本発明の樹脂組成物は、さらに、硬化剤、硬化促進剤、熱硬化性樹脂、熱可塑性樹脂、無機充填材、有機充填材、増粘剤、消泡剤、レベリング剤、密着性付与剤、着色剤、および有機溶剤からなる群から選択される１以上を含有することができる。 The resin composition of the present invention further comprises a curing agent, a curing accelerator, a thermosetting resin, a thermoplastic resin, an inorganic filler, an organic filler, a thickener, a defoaming agent, a leveling agent, and an adhesion imparting agent. It can contain one or more selected from the group consisting of colorants and organic solvents.
　硬化剤としては、本発明のエポキシ樹脂用硬化剤以外のエポキシ樹脂用硬化剤を意味し、例えば、酸無水物化合物、チオール化合物、グアニジン化合物、ヒドラジド化合物、フェノール化合物、ナフトール化合物、活性エステル化合物、ベンゾオキサジン化合物、シアネートエステル化合物、及びカルボジイミド化合物などが挙げられる。 The curing agent means a curing agent for epoxy resin other than the curing agent for epoxy resin of the present invention, and for example, an acid anhydride compound, a thiol compound, a guanidine compound, a hydrazide compound, a phenol compound, a naphthol compound, an active ester compound, and the like. Examples thereof include benzoxazine compounds, cyanate ester compounds, and carbodiimide compounds.
　チオール化合物としては、トリメチロールプロパン トリス（チオグリコレート）、ペンタエリスリトール テトラキス（チオグリコレート）、エチレングリコール ジチオグリコレート、トリメチロールプロパントリス（３－メルカプトプロピオネート）、トリメチロールプロパン トリス（β－チオプロピオネート）、ペンタエリスリトール テトラキス（β－チオプロピオネート）、ジペンタエリスリトール ポリ（β－チオプロピオネート）等のポリオールとメルカプト有機酸のエステル化反応によって得られるチオール化合物；１，４－ブタンジチオール、１，６－ヘキサンジチオール、１，１０－デカンジチオール等のアルキルポリチオール化合物；末端チオール基含有ポリエーテル；末端チオール基含有ポリチオエーテル；エポキシ化合物と硫化水素との反応によって得られるチオール化合物；ポリチオール化合物とエポキシ化合物との反応によって得られる末端チオール基を有するチオール化合物等を挙げることができる。
　酸無水物化合物としてはテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、無水メチルナジック酸、メチルビシクロ[2.2.1]ヘプタン-2,3-ジカルボン酸無水物、テトラプロペニル無水コハク酸（3-ドデセニル無水コハク酸）、オクテニルコハク酸無水物、エチレングリコール ビスアンヒドロトリメリテート、メチルエンドメチレンテトラヒドロ無水フタル酸、３，４－ジメチル－６－（２－メチル－１－プロペニル）－４－シクロヘキセン－１，２－ジカルボン酸無水物または上記化合物と１－イソプロピル－４－メチルビシクロ［２．２．２］オクタ－５－エン－２，３－ジカルボン酸無水物の混合物などが挙げられる。市販されている酸無水物としては、日立化成社製のＨＮ－２２００（メチルテトラヒドロ無水フタル酸）、ＨＮ－５５００（メチルテトラヒドロ無水フタル酸）などが挙げられる。
　グアニジン化合物としてはジシアンジアミド、１－メチルグアニジン、１－エチルグアニジン、ジメチルグアニジン、トリメチルグアニジン、テトラメチルグアニジン、ペンタメチルグアニジン、１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン、７－メチル－１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン、１－メチルビグアニド、１－エチルビグアニド、１－ｎ－ブチルビグアニド、１－ｎ－オクタデシルビグアニド、１，１－ジメチルビグアニド、１，１－ジエチルビグアニド、１－アリルビグアニド、等が挙げられる。グアニジン化合物としては、特にジシアンジアミドが好ましい。市販されているグアニジン化合物としては、ジャパンエポキシレジン（株）製「ｊＥＲキュアＤＩＣＹ－７」（ジシアンジアミド）などが挙げられる。
　ヒドラジド化合物としては、例えば、カルボヒドラジド、シュウ酸ジヒドラジド、マロン酸ジヒドラジド、コハク酸ジヒドラジド、イミノジ酢酸ジヒドラジド、アジピン酸ジヒドラジド、ピメリン酸ジヒドラジド、スベリン酸ジヒドラジド、アゼライン酸ジヒドラジド、セバシン酸ジヒドラジド、ドデカンジオヒドラジド、ヘキサデカンジヒドラジド、マレイン酸ジヒドラジド、フマル酸ジヒドラジド、ジグリコール酸ジヒドラジド、酒石酸ジヒドラジド、リンゴ酸ジヒドラジド、クエン酸トリヒドラジド等が挙げられる。また、ヒドラジド化合物の市販品としては、例えば、味の素ファインテクノ株式会社製のアミキュアＶＤＨ、アミキュアＵＤＨ等が挙げられる。
　フェノール化合物及びナフトール化合物の具体例としては、例えば、明和化成（株）製の「ＭＥＨ－７７００」、「ＭＥＨ－７８１０」、「ＭＥＨ－７８５１」、日本化薬（株）製の「ＮＨＮ」、「ＣＢＮ」、「ＧＰＨ」、新日鉄住金（株）製の「ＳＮ１７０」、「ＳＮ１８０」、「ＳＮ１９０」、「ＳＮ４７５」、「ＳＮ４８５」、「ＳＮ４９５」、「ＳＮ３７５」、「ＳＮ３９５」、ＤＩＣ（株）製の「ＬＡ７０５２」、「ＬＡ７０５４」、「ＬＡ３０１８」、「ＥＸＢ－９５００」、「ＴＤ２０９０」等が挙げられる。
　活性エステル化合物としては、特に制限はないが、一般にフェノールエステル類、チオフェノールエステル類、Ｎ－ヒドロキシアミンエステル類、複素環ヒドロキシ化合物のエステル類等の反応活性の高いエステル基を１分子中に２個以上有する化合物が好ましく用いられる。当該活性エステル化合物は、カルボン酸化合物及び／又はチオカルボン酸化合物とヒドロキシ化合物及び／又はチオール化合物との縮合反応によって得られるものが好ましい。具体的には、ジシクロペンタジエン型ジフェノール構造を含む活性エステル化合物、ナフタレン構造を含む活性エステル化合物、フェノールノボラックのアセチル化物を含む活性エステル化合物、フェノールノボラックのベンゾイル化物を含む活性エステル化合物が好ましい。「ジシクロペンタジエン型ジフェノール構造」とは、フェニレン－ジシクロペンチレン－フェニレンからなる２価の構造単位を表す。活性エステル化合物の市販品としては、ジシクロペンタジエン型ジフェノール構造を含む活性エステル化合物として、「ＥＸＢ９４５１」、「ＥＸＢ９４６０」、「ＥＸＢ９４６０Ｓ」、「ＨＰＣ－８０００－６５Ｔ」（ＤＩＣ（株）製）、ナフタレン構造を含む活性エステル化合物として「ＥＸＢ９４１６－７０ＢＫ」（ＤＩＣ（株）製）、フェノールノボラックのアセチル化物を含む活性エステル化合物として「ＤＣ８０８」（三菱化学（株）製）、フェノールノボラックのベンゾイル化物を含む活性エステル化合物として「ＹＬＨ１０２６」（三菱化学（株）製）などが挙げられる。
　ベンゾオキサジン化合物の具体例としては、昭和高分子（株）製の「ＨＦＢ２００６Ｍ」、四国化成工業（株）製の「Ｐ－ｄ」、「Ｆ－ａ」が挙げられる。
　シアネートエステル化合物としては、例えば、ビスフェノールＡジシアネート、ポリフェノールシアネート、オリゴ（３－メチレン－１，５－フェニレンシアネート）、４，４’－メチレンビス（２，６－ジメチルフェニルシアネート）、４，４’－エチリデンジフェニルジシアネート、ヘキサフルオロビスフェノールＡジシアネート、２，２－ビス（４－シアネート）フェニルプロパン、１，１－ビス（４－シアネートフェニルメタン）、ビス（４－シアネート－３，５－ジメチルフェニル）メタン、１，３－ビス（４－シアネートフェニル－１－（メチルエチリデン））ベンゼン、ビス（４－シアネートフェニル）チオエーテル、及びビス（４－シアネートフェニル）エーテル等の２官能シアネート樹脂、フェノールノボラック及びクレゾールノボラック等から誘導される多官能シアネート樹脂、これらシアネート樹脂が一部トリアジン化したプレポリマーなどが挙げられる。シアネートエステル系硬化剤の具体例としては、ロンザジャパン（株）製の「ＰＴ３０」及び「ＰＴ６０」（いずれもフェノールノボラック型多官能シアネートエステル樹脂）、「ＢＡ２３０」（ビスフェノールＡジシアネートの一部又は全部がトリアジン化され三量体となったプレポリマー）等が挙げられる。
　カルボジイミド化合物の具体例としては、日清紡ケミカル（株）製の「Ｖ－０３」、「Ｖ－０７」等が挙げられる。 Thiol compounds include trimethylolpropanetris (thioglycolate), pentaerythritol tetrakis (thioglycolate), ethylene glycol dithioglycolate, trimethylolpropanetris (3-mercaptopropionate), and trimethylolpropanetris (β-). Thiol compounds obtained by esterification of mercapto organic acids with polyols such as thiopropionate), pentaerythritol tetrakis (β-thiopropionate), dipentaerythritol poly (β-thiopropionate); 1,4 -Alkyl polythiol compounds such as butanedithiol, 1,6-hexanedithiol, 1,10-decandithiol; terminal thiol group-containing polyether; terminal thiol group-containing polythioether; thiol compounds obtained by the reaction of epoxy compounds with hydrogen sulfide. Examples thereof include thiol compounds having a terminal thiol group obtained by reacting a polythiol compound with an epoxy compound.
As the acid anhydride compound, tetrahydroanhydride phthalic acid, hexahydroanhydride phthalic acid, methyltetrahydroanhydride phthalic acid, methylhexahydroanhydride phthalic acid, methylnadic acid anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride , Tetrapropenyl Anhydrous Succinic Acid (3-Dodecenyl Anhydrous Succinic Acid), Octenyl Succinic Anhydrous, Ethylene Glycol Bisuanhydrotrimeritate, Methylendomethylene Tetrahydro Anhydrous Phthanoic Acid, 3,4-dimethyl-6- (2-Methyl) -1-propenyl) -4-cyclohexene-1,2-dicarboxylic acid anhydride or the above compound and 1-isopropyl-4-methylbicyclo [2.2.2] octa-5-ene-2,3-dicarboxylic acid anhydride Examples include a mixture of substances. Examples of commercially available acid anhydrides include HN-2200 (methyltetrahydrophthalic anhydride) and HN-5500 (methyltetrahydrophthalic anhydride) manufactured by Hitachi Chemical Co., Ltd.
Guanidine compounds include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, dimethylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5. En, 7-methyl-1,5,7-triazabicyclo [4.4.0] deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecyl Biguanides, 1,1-dimethylbiguanides, 1,1-diethylbiguanides, 1-allylbiguanides, and the like can be mentioned. As the guanidine compound, dicyandiamide is particularly preferable. Examples of commercially available guanidine compounds include "jER Cure DICY-7" (dicyandiamide) manufactured by Japan Epoxy Resin Co., Ltd.
Examples of the hydrazide compound include carbohydrazide, dihydrazide oxalic acid, dihydrazide malonic acid, dihydrazide succinic acid, dihydrazide iminodiacetate, dihydrazide adipic acid, dihydrazide dimeric acid, dihydrazide siberic acid, dihydrazide azelaic acid, and dihydrazide hydrazide. Hexadecane dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartrate dihydrazide, apple acid dihydrazide, citrate trihydrazide and the like can be mentioned. Examples of commercially available hydrazide compounds include Ajinomoto Fine-Techno Co., Ltd.'s Amicure VDH and Amicure UDH.
Specific examples of the phenol compound and the naphthol compound include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN" manufactured by Nippon Kayaku Co., Ltd. "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395", DIC (stock) manufactured by Nippon Steel & Sumitomo Metal Corporation ), "LA7052", "LA7054", "LA3018", "EXB-9500", "TD2090" and the like.
The active ester compound is not particularly limited, but generally contains 2 highly reactive ester groups such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. Compounds having more than one are preferably used. The active ester compound is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene. Commercially available products of the active ester compound include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" (manufactured by DIC Co., Ltd.) as active ester compounds containing a dicyclopentadiene type diphenol structure. "EXB9416-70BK" (manufactured by DIC Co., Ltd.) as an active ester compound containing a naphthalene structure, "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac, and a benzoylated product of phenol novolac. Examples of the active ester compound contained include "YLH1026" (manufactured by Mitsubishi Chemical Corporation).
Specific examples of the benzoxazine compound include "HFB2006M" manufactured by Showa High Polymer Co., Ltd., "Pd" and "FA" manufactured by Shikoku Chemicals Corporation.
Examples of the cyanate ester compound include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylencyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4'-. Echilidendiphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-dimethylphenyl) Bifunctional cyanate resins such as methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol novolac and Examples thereof include polyfunctional cyanate resins derived from cresol novolak and the like, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (both are phenol novolac type polyfunctional cyanate ester resins) and "BA230" (part or all of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. Is a prepolymer that has been triadinated into a trimer) and the like.
Specific examples of the carbodiimide compound include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.
　硬化促進剤としては、本発明の脂肪族環状ポリアミンは含まれておらず、例えば、リン系硬化促進剤、アミン系硬化促進剤、イミダゾール系硬化促進剤、グアニジン系硬化促進剤等が挙げられる。硬化促進剤は、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　リン系硬化促進剤としては、例えば、トリフェニルホスフィン、ホスホニウムボレート化合物、テトラフェニルホスホニウムテトラフェニルボレート、ｎ－ブチルホスホニウムテトラフェニルボレート、テトラブチルホスホニウムデカン酸塩、（４－メチルフェニル）トリフェニルホスホニウムチオシアネート、テトラフェニルホスホニウムチオシアネート、ブチルトリフェニルホスホニウムチオシアネート等が挙げられ、トリフェニルホスフィン、テトラブチルホスホニウムデカン酸塩が好ましい。
　アミン系硬化促進剤としては、例えば、トリエチルアミン、トリブチルアミン等のトリアルキルアミン、４－ジメチルアミノピリジン、ベンジルジメチルアミン、２，４，６，－トリス（ジメチルアミノメチル）フェノール、１，８－ジアザビシクロ（５，４，０）－ウンデセン等が挙げられ、４－ジメチルアミノピリジン、１，８－ジアザビシクロ（５，４，０）－ウンデセンが好ましい。
　イミダゾール系硬化促進剤としては、例えば、２－メチルイミダゾール、２－ウンデシルイミダゾール、２－ヘプタデシルイミダゾール、１，２－ジメチルイミダゾール、２－エチル－４－メチルイミダゾール、１，２－ジ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、１－ベンジル－２－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－シアノエチル－２－メチルイミダゾール、１－シアノエチル－２－ウンデシルイミダゾール、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、１－シアノエチル－２－ウンデシルイミダゾリウムトリメリテイト、１－シアノエチル－２－フェニルイミダゾリウムトリメリテイト、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２’－ウンデシルイミダゾリル－（１’）］－エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２’－エチル－４’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）]－エチル－ｓ－トリアジンイソシアヌル酸付加物、２－フェニルイミダゾールイソシアヌル酸付加物、２－フェニル－４，５－ジヒドロキシ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、２，３－ジヒドロ－１Ｈ－ピロロ［１，２－ａ］ベンズイミダゾール、１－ドデシル－２－メチル－３－ベンジルイミダゾリウムクロライド、２－メチルイミダゾリン、２－フェニルイミダゾリン等のイミダゾール化合物及びイミダゾール化合物とエポキシ樹脂とのアダクト体が挙げられ、２－エチル－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が好ましい。
　イミダゾール系硬化促進剤としては、市販品を用いてもよく、例えば、三菱化学（株）製の「Ｐ２００－Ｈ５０」等が挙げられる。
　グアニジン系硬化促進剤としては、上記硬化剤としてのグアニジン化合物と同様の化合物を使用することができ、例えば、ジシアンジアミド、１－メチルグアニジン、１－エチルグアニジン、１－シクロヘキシルグアニジン、１－フェニルグアニジン、１－（ｏ－トリル）グアニジン、ジメチルグアニジン、ジフェニルグアニジン、トリメチルグアニジン、テトラメチルグアニジン、ペンタメチルグアニジン、１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン、７－メチル－１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン、１－メチルビグアニド、１－エチルビグアニド、１－ｎ－ブチルビグアニド、１－ｎ－オクタデシルビグアニド、１，１－ジメチルビグアニド、１，１－ジエチルビグアニド、１－シクロヘキシルビグアニド、１－アリルビグアニド、１－フェニルビグアニド、１－（ｏ－トリル）ビグアニド等が挙げられ、ジシアンジアミド、１，５，７－トリアザビシクロ［４．４．０］デカ－５－エンが好ましい。
　樹脂組成物中の硬化促進剤の含有量は特に限定されないが、０．０５質量％～３質量％の範囲で使用することが好ましい。 The curing accelerator does not contain the aliphatic cyclic polyamine of the present invention, and examples thereof include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, and a guanidine-based curing accelerator. The curing accelerator may be used alone or in combination of two or more.
Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.
Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo. Examples thereof include (5,4,0) -undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.
Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and the like. 2-Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5 hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazolin, Examples thereof include an imidazole compound such as 2-phenylimidazolin and an adduct of the imidazole compound and an epoxy resin, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.
As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.
As the guanidine-based curing accelerator, the same compound as the guanidine compound as the curing agent can be used, and for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, etc. 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7- Methyl-1,5,7-triazabicyclo [4.4.0] deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1, Examples thereof include 1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, and dicyandiamide, 1,5,7-triaza. Bicyclo [4.4.0] deca-5-ene is preferred.
The content of the curing accelerator in the resin composition is not particularly limited, but it is preferably used in the range of 0.05% by mass to 3% by mass.
　熱硬化性樹脂としては、先述のエポキシ樹脂以外の熱硬化性樹脂を意味し、例えば、ビニルベンジル化合物、アクリル化合物、マレイミド化合物、ブロックイソシアネート化合物などが挙げられる。 The thermosetting resin means a thermosetting resin other than the above-mentioned epoxy resin, and examples thereof include vinylbenzyl compounds, acrylic compounds, maleimide compounds, and blocked isocyanate compounds.
　熱可塑性樹脂としては、例えば、フェノキシ樹脂、ポリビニルアセタール樹脂、ポリオレフィン樹脂、ポリブタジエン樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリエーテルイミド樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレンエーテル樹脂、ポリカーボネート樹脂、ポリエーテルエーテルケトン樹脂、ポリエステル樹脂が挙げられ、フェノキシ樹脂が好ましい。熱可塑性樹脂は、１種単独で用いてもよく、又は２種以上を組み合わせて用いてもよい。
　熱可塑性樹脂のポリスチレン換算の重量平均分子量は８，０００～７０，０００の範囲が好ましく、１０，０００～６０，０００の範囲がより好ましく、２０，０００～６０，０００の範囲がさらに好ましい。熱可塑性樹脂のポリスチレン換算の重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法で測定される。具体的には、熱可塑性樹脂のポリスチレン換算の重量平均分子量は、測定装置として（株）島津製作所製ＬＣ－９Ａ／ＲＩＤ－６Ａを、カラムとして昭和電工（株）製Ｓｈｏｄｅｘ　Ｋ－８００Ｐ／Ｋ－８０４Ｌ／Ｋ－８０４Ｌを、移動相としてクロロホルム等を用いて、カラム温度を４０℃にて測定し、標準ポリスチレンの検量線を用いて算出することができる。
　フェノキシ樹脂としては、例えば、ビスフェノールＡ骨格、ビスフェノールＦ骨格、ビスフェノールＳ骨格、ビスフェノールアセトフェノン骨格、ノボラック骨格、ビフェニル骨格、フルオレン骨格、ジシクロペンタジエニル骨格、ノルボルネン骨格、ナフタレン骨格、アントラセン骨格、アダマンタン骨格、テルペン骨格、及びトリメチルシクロヘキサン骨格からなる群から選択される１種以上の骨格を有するフェノキシ樹脂が挙げられる。
　フェノキシ樹脂の末端は、フェノール性水酸基、エポキシ基等のいずれの官能基でもよい。フェノキシ樹脂は１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。フェノキシ樹脂の具体例としては、三菱化学（株）製の「１２５６」及び「４２５０」（いずれもビスフェノールＡ骨格含有フェノキシ樹脂）、「ＹＸ８１００」（ビスフェノールＳ骨格含有フェノキシ樹脂）、及び「ＹＸ６９５４」（ビスフェノールアセトフェノン骨格含有フェノキシ樹脂）が挙げられ、その他にも、新日鉄住金化学（株）製の「ＦＸ２８０」及び「ＦＸ２９３」、三菱化学（株）製の「ＹＬ６９５４ＢＨ３０」、「ＹＸ７５５３」、「ＹＬ７７６９ＢＨ３０」、「ＹＬ６７９４」、「ＹＬ７２１３」、「ＹＬ７２９０」及び「ＹＬ７４８２」等が挙げられる。
　ポリビニルアセタール樹脂としては、例えば、ポリビニルホルマール樹脂、ポリビニルブチラール樹脂が挙げられ、ポリビニルブチラール樹脂が好ましい。ポリビニルアセタール樹脂の具体例としては、例えば、電気化学工業（株）製の「電化ブチラール４０００－２」、「電化ブチラール５０００－Ａ」、「電化ブチラール６０００－Ｃ」、「電化ブチラール６０００－ＥＰ」、積水化学工業（株）製のエスレックＢＨシリーズ、ＢＸシリーズ、ＫＳシリーズ、ＢＬシリーズ、ＢＭシリーズ等が挙げられる。
　ポリイミド樹脂の具体例としては、新日本理化（株）製の「リカコートＳＮ２０」及び「リカコートＰＮ２０」が挙げられる。
　ポリアミドイミド樹脂の具体例としては、東洋紡績（株）製の「バイロマックスＨＲ１１ＮＮ」及び「バイロマックスＨＲ１６ＮＮ」が挙げられる。ポリアミドイミド樹脂の具体例としてはまた、日立化成工業（株）製の「ＫＳ９１００」、「ＫＳ９３００」（ポリシロキサン骨格含有ポリアミドイミド）等の変性ポリアミドイミドが挙げられる。
　ポリエーテルスルホン樹脂の具体例としては、住友化学（株）製の「ＰＥＳ５００３Ｐ」等が挙げられる。
　ポリスルホン樹脂の具体例としては、ソルベイアドバンストポリマーズ（株）製のポリスルホン「Ｐ１７００」、「Ｐ３５００」等が挙げられる。
　樹脂組成物中の熱可塑性樹脂の含有量は、好ましくは０．１質量％～２０質量％、より好ましくは０．５質量％～１０質量％、さらに好ましくは１質量％～５質量％である。 Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, and polyether. Examples thereof include ether ketone resin and polyester resin, and phenoxy resin is preferable. The thermoplastic resin may be used alone or in combination of two or more.
The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and even more preferably in the range of 20,000 to 60,000. The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K- of Showa Denko Corporation as a column. 804L / K-804L can be calculated by measuring the column temperature at 40 ° C. using chloroform or the like as a mobile phase and using a standard polystyrene calibration curve.
Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadienyl skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, and adamantan skeleton. , A phenoxy resin having one or more skeletons selected from the group consisting of a terpene skeleton and a trimethylcyclohexane skeleton.
The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resin), "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" manufactured by Mitsubishi Chemical Corporation. Bisphenol acetophenone skeleton-containing phenoxy resin), and also "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Corporation, "YL6954BH30", "YX7553", "YL7769BH30" manufactured by Mitsubishi Chemical Corporation, Examples thereof include "YL6794", "YL7213", "YL7290" and "YL7482".
Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include "Electrified Butyral 4000-2", "Electrified Butyral 5000-A", "Electrified Butyral 6000-C", and "Electrified Butyral 6000-EP" manufactured by Denki Kagaku Kogyo Co., Ltd. , Eslek BH series, BX series, KS series, BL series, BM series, etc. manufactured by Sekisui Chemical Industry Co., Ltd. can be mentioned.
Specific examples of the polyimide resin include "Ricacoat SN20" and "Ricacoat PN20" manufactured by NEW JAPAN CHEMICAL CO., LTD.
Specific examples of the polyamide-imide resin include "Vilomax HR11NN" and "Vilomax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamide-imide resin include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imide) manufactured by Hitachi Chemical Industries, Ltd.
Specific examples of the polyether sulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.
Specific examples of the polysulfone resin include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd.
The content of the thermoplastic resin in the resin composition is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, and further preferably 1% by mass to 5% by mass. ..
　無機充填材としては、特に限定されないが、例えば、シリカ、アルミナ、ガラス、コーディエライト、ケイ素酸化物、硫酸バリウム、炭酸バリウム、タルク、クレー、雲母粉、酸化亜鉛、ハイドロタルサイト、ベーマイト、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、酸化マグネシウム、窒化ホウ素、窒化アルミニウム、窒化マンガン、ホウ酸アルミニウム、炭酸ストロンチウム、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸マグネシウム、チタン酸ビスマス、酸化チタン、酸化ジルコニウム、チタン酸バリウム、チタン酸ジルコン酸バリウム、ジルコン酸バリウム、ジルコン酸カルシウム、リン酸ジルコニウム、及びリン酸タングステン酸ジルコニウム、鉄、酸化鉄、フェライト、合金、その他の導電フィラー、磁性フィラー、熱伝導フィラー、等が挙げられる。本発明の一態様として、シリカ、導電フィラー、磁性フィラー、熱伝導フィラーからなる群から選択される１以上を含有するエポキシ樹脂組成物が好ましい。 The inorganic filler is not particularly limited, and is, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconate Oxide, Barium Titanium, Barium Zirconate Titate, Barium Zirconate, Calcium Zirconate, Zirconate Titrate, Zirconate Titstate Phosphate, Iron, Iron Oxide, Ferrite, Alloys, Other Conductive Fillers, Magnetic Fillers, Examples include heat conductive fillers. As one aspect of the present invention, an epoxy resin composition containing one or more selected from the group consisting of silica, a conductive filler, a magnetic filler, and a heat conductive filler is preferable.
　シリカとしては、具体的には、無定形シリカ、溶融シリカ、結晶シリカ、合成シリカ、中空シリカ等が挙げられる。またシリカとしては球形シリカが好ましい。平均粒径は特に限定されないが、好ましくは６００ｎｍ以下、より好ましくは３００ｎｍ以下、さらに好ましくは２００ｎｍ以下である。該平均粒径の下限は、特に限定されないが、５ｎｍ以上が好ましい。市販品としては、例えば、（株）アドマテックス製「ＳＯ－Ｃ２」、「ＳＯ－Ｃ１」、「ＳＯ－Ｃ４」等が挙げられる。無機充填材の平均粒径はミー（Ｍｉｅ）散乱理論に基づくレーザー回折・散乱法により測定することができる。 Specific examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, as silica, spherical silica is preferable. The average particle size is not particularly limited, but is preferably 600 nm or less, more preferably 300 nm or less, and further preferably 200 nm or less. The lower limit of the average particle size is not particularly limited, but is preferably 5 nm or more. Examples of commercially available products include "SO-C2", "SO-C1", and "SO-C4" manufactured by Admatex Co., Ltd. The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory.
　導電フィラーとしては、具体的には、半田粒子、ニッケル粒子、ナノサイズの金属結晶、金属の表面を他の金属で被覆した粒子、銅と銀の傾斜粒子等の金属粒子や、例えば、スチレン樹脂、ウレタン樹脂、メラミン樹脂、エポキシ樹脂、アクリル樹脂、フェノール樹脂、スチレン－ブタジエン樹脂等の樹脂粒子に金、ニッケル、銀、銅、半田等の導電性薄膜で被覆を施した粒子等が挙げられる。導電フィラーは、通常、１～２０μｍ程度の球形の微粒子である。 Specific examples of the conductive filler include solder particles, nickel particles, nano-sized metal crystals, particles having a metal surface coated with another metal, metal particles such as copper and silver gradient particles, and styrene resin, for example. , Urethane resin, melamine resin, epoxy resin, acrylic resin, phenol resin, styrene-butadiene resin and other resin particles coated with a conductive thin film such as gold, nickel, silver, copper and solder. The conductive filler is usually spherical fine particles having a size of about 1 to 20 μm.
　磁性フィラーとしては、具体的には、純鉄粉末、Ｆｅ－Ｓｉ系合金粉末、Ｆｅ－Ｓｉ－Ａｌ系合金粉末、Ｆｅ－Ｎｉ系合金粉末、Ｆｅ－Ｎｉ－Ｍｏ系合金粉末、Ｆｅ－Ｎｉ－Ｍｏ－Ｃｕ系合金粉末、Ｆｅ－Ｃｏ系合金粉末、Ｆｅ－Ｎｉ－Ｃｏ系合金粉末、Ｆｅ－Ｃｒ系合金粉末、Ｆｅ－Ｃｒ－Ｓｉ系合金粉末、Ｆｅ－Ｎｉ－Ｃｒ系合金粉末、あるいはＦｅ－Ｃｒ－Ａｌ系合金粉末などのＦｅ合金類、Ｆｅ基アモルファス、Ｃｏ基アモルファスなどのアモルファス合金類、Ｍｇ－Ｚｎ系フェライト、Ｍｎ－Ｚｎ系フェライト、Ｍｎ－Ｍｇ系フェライト、Ｃｕ－Ｚｎ系フェライト、Ｍｇ－Ｍｎ－Ｓｒ系フェライト、Ｎｉ－Ｚｎ系フェライトなどのスピネル型フェライト類、Ｂａ－Ｚｎ系フェライト、Ｂａ－Ｍｇ系フェライト、Ｂａ－Ｎｉ系フェライト、Ｂａ－Ｃｏ系フェライト、Ｂａ－Ｎｉ－Ｃｏ系フェライトなどの六方晶型フェライト類、Ｙ系フェライトなどのガーネット型フェライト類が挙げられる。 Specific examples of the magnetic filler include pure iron powder, Fe—Si alloy powder, Fe—Si—Al alloy powder, Fe—Ni alloy powder, Fe—Ni—Mo alloy powder, and Fe—Ni—. Mo—Cu alloy powder, Fe—Co alloy powder, Fe—Ni—Co alloy powder, Fe—Cr alloy powder, Fe—Cr—Si alloy powder, Fe—Ni—Cr alloy powder, or Fe -Fe alloys such as Cr-Al alloy powder, Fe-based amorphous, Amorphous alloys such as Co-based amorphous, Mg-Zn-based ferrite, Mn-Zn-based ferrite, Mn-Mg-based ferrite, Cu-Zn-based ferrite, Spinnel-type ferrites such as Mg-Mn-Sr-based ferrite and Ni-Zn-based ferrite, Ba-Zn-based ferrite, Ba-Mg-based ferrite, Ba-Ni-based ferrite, Ba-Co-based ferrite, and Ba-Ni-Co-based Hexagonal ferrites such as ferrite and garnet-type ferrites such as Y-based ferrite can be mentioned.
　熱伝導フィラーとしては、具体的には、窒化アルミニウム、アルミナ、窒化ホウ素、窒化ケイ素、グラファイト粉末及び炭化ケイ素が挙げられる。窒化アルミニウムの市販品としては、例えば、（株）トクヤマ製「シェイパルＨ」が挙げられ、窒化ケイ素の市販品としては、例えば、電気化学工業（株）製「ＳＮ－９Ｓ」が挙げられる。アルミナの市販品としては、例えば、日本軽金属（株）製「ＡＨＰ３００」、昭和電工（株）製「アルナビーズ（登録商標）ＣＢ」（例えば、「ＣＢ－Ｐ０５」、「ＣＢ－Ａ３０Ｓ」）デンカ社製「ＤＡＷ－４５」、「ＤＡＷ－０５」、「ＡＳＦＰ－２０」等が挙げられる。 Specific examples of the heat conductive filler include aluminum nitride, alumina, boron nitride, silicon nitride, graphite powder and silicon carbide. Examples of commercially available aluminum nitride products include "Shapal H" manufactured by Tokuyama Corporation, and examples of commercially available silicon nitride products include "SN-9S" manufactured by Denki Kagaku Kogyo Co., Ltd. Examples of commercially available alumina products include "AHP300" manufactured by Nippon Light Metal Co., Ltd. and "Arnabeads (registered trademark) CB" manufactured by Showa Denko Co., Ltd. (for example, "CB-P05" and "CB-A30S") Denka Co., Ltd. Examples thereof include "DAW-45", "DAW-05", and "ASFP-20" manufactured by Japan.
　有機充填材としては、シリコンパウダー、ナイロンパウダー、フッ素パウダー、アクリルゴム粒子、ポリアミド微粒子、シリコーン粒子などが挙げられる。アクリルゴム粒子の具体例としては、アクリロニトリルブタジエンゴム、ブタジエンゴム、アクリルゴムなどのゴム弾性を示す樹脂に化学的架橋処理を施し、有機溶剤に不溶かつ不融とした樹脂の微粒子体であるものならばどのようなものでも良く、具体的には、ＸＥＲ－９１（日本合成ゴム（株）製）、スタフィロイドＡＣ３３５５、ＡＣ３８１６、ＡＣ３８３２、ＡＣ４０３０、ＡＣ３３６４、ＩＭ１０１（以上、アイカ工業（株）製）、パラロイドＥＸＬ２６５５、ＥＸＬ２６０２（以上、呉羽化学工業（株）製）などが挙げられる。ポリアミド微粒子の具体例としてはとしては、ナイロンのような脂肪族ポリアミドやケブラーのような芳香族ポリアミド、さらには、ポリアミドイミドなど、アミド結合を有する樹脂の５０ミクロン以下の微粒子であればどのようなものでも良く、具体的には、ＶＥＳＴＯＳＩＮＴ ２０７０（ダイセルヒュルス（株）製）や、ＳＰ５００（東レ（株）製）などが挙げられる。 Examples of the organic filler include silicon powder, nylon powder, fluorine powder, acrylic rubber particles, polyamide fine particles, and silicone particles. Specific examples of the acrylic rubber particles include fine particles of a resin such as acrylonitrile butadiene rubber, butadiene rubber, and acrylic rubber that are chemically crosslinked and insoluble and insoluble in an organic solvent. Anything may be used, specifically, XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Staphyroid AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (manufactured by Aika Kogyo Co., Ltd.), Examples thereof include Pararoid EXL2655 and EXL2602 (all manufactured by Kureha Chemical Industry Co., Ltd.). Specific examples of the polyamide fine particles include aliphatic polyamides such as nylon, aromatic polyamides such as Kevlar, and any fine particles of a resin having an amide bond such as polyamide-imide of 50 microns or less. Any one may be used, and specific examples thereof include VESTOSINT 2070 (manufactured by Daiselhurus Co., Ltd.) and SP500 (manufactured by Toray Industries, Inc.).
　増粘剤としては、オルベン、ベントン等が挙げられる。 Examples of the thickener include Orben, Benton and the like.
　消泡剤としては、例えば、シリコーン系消泡剤、フッ素系消泡剤、高分子系消泡剤等が挙げられる。 Examples of the defoaming agent include silicone-based defoaming agents, fluorine-based defoaming agents, and polymer-based defoaming agents.
　レベリング剤としては、市販の界面活性剤を用いることができ、例えば、シリコーン系、フッ素系、エステル系、カチオン系、アニオン系、ノニオン系、両性などの界面活性剤などが挙げられ、それぞれ単独でも２種以上を組み合わせて用いてもよい。前記の界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ポリエチレングリコールジエステル類、ソルビタン脂肪酸エステル類、脂肪酸変性ポリエステル類、３級アミン変性ポリウレタン類、ポリエチレンイミン類などのほか、商品名でＫＰ（信越化学工業（株）製）、ポリフロー（共栄社化学（株）製）、エフトップ（三菱マテリアル電子化成（株））、メガファック（ＤＩＣ（株）製）、フロラード（住友スリーエム（株）製）、アサヒガード（旭硝子（株）製）、サーフロン（ＡＧＣセイミケミカル（株）製）、ソルスパース（ゼネカ（株）製）、ＥＦＫＡ（ＣＩＢＡ社製）、アジスパー（味の素ファインテクノ（株）製）などが挙げられる。 As the leveling agent, a commercially available surfactant can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, and amphoteric surfactants, which may be used alone. Two or more kinds may be used in combination. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. In addition, KP (manufactured by Shinetsu Chemical Industry Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ftop (Mitsubishi Material Denshi Kasei Co., Ltd.), Megafuck (manufactured by DIC Co., Ltd.), etc. Florard (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard (manufactured by Asahi Glass Co., Ltd.), Surfron (manufactured by AGC Seimi Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA), Azisper (manufactured by Ajinomoto) Fine Techno Co., Ltd.) and the like.
　密着性付与剤としては、例えば、イミダゾール系、チアゾール系、トリアゾール系、シランカップリング剤等が挙げられる。具体的には、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２－メトキシエトキシ）シラン、Ｎ－（２－アミノエチル）－３－アミノ プロピルメチルジメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－グリシ ドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラ ン、３－クロロプロピルメチルジメトキシシラン、３－クロロプロピルトリメトキシシラン、３－メタクリロイロキシプロピルトリメトキシシラン、３－メルカ プトプロピルトリメトキシシランなどが挙げられる。 Examples of the adhesion-imparting agent include imidazole-based, thiazole-based, triazole-based, and silane coupling agents. Specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)- 3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycydoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysila , 3-Chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.
　着色剤としては、例えば、フタロシアニン・ブルー、フタロシアニン・グリーン、アイオジン・グリーン、ジスアゾイエロー、カーボンブラック等が挙げられる。 Examples of the colorant include phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, carbon black and the like.
　有機溶剤としては、アセトン、メチルエチルケトン（ＭＥＫ）及びシクロヘキサノン等のケトン類、酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート及びカルビトールアセテート等の酢酸エステル類、セロソルブ及びブチルカルビトール等のカルビトール類、トルエン及びキシレン等の芳香族炭化水素類、ジメチルホルムアミド、ジメチルアセトアミド（ＤＭＡｃ）及びＮ－メチルピロリドン等のアミド系溶媒等を挙げることができる。有機溶剤は１種単独で使用してもよく、２種以上を組み合わせて使用してもよい。 Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbi such as cellosolve and butyl carbitol. Examples include tolls, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.
　樹脂組成物は、繊維強化複合材料の製造における強化繊維の含浸の際の作業性の観点から、好ましくは、８０℃以上の加熱条件下（例えば９０℃）で、１００ｃＰ以下、より好ましくは９９ｃＰ以下、更に好ましくは９８ｃＰ以下の初期粘度を有する。樹脂組成物は、例えば、８０℃以上の加熱条件下（例えば９０℃）で、１０ｃＰ以上、２０ｃＰ以上、３０ｃＰ以上、又は４０ｃＰ以上の粘度を有していてもよい。「初期粘度」とは、エポキシ樹脂とエポキシ樹脂用硬化剤とを混合した直後に測定される粘度をいう。粘度は、市販の粘度測定装置、例えば、ＨＡＡＫＥ社製ＲｈｅｏＳｔｒｅｓｓ６０００を用いて測定することができる。「低粘度」の樹脂組成物とは、８０℃以上の加熱条件下（例えば９０℃）で、１００ｃＰ以下の初期粘度を有する樹脂組成物をいう。 From the viewpoint of workability when impregnating the reinforcing fibers in the production of the fiber-reinforced composite material, the resin composition is preferably 100 cP or less, more preferably 99 cP or less under heating conditions of 80 ° C. or higher (for example, 90 ° C.). More preferably, it has an initial viscosity of 98 cP or less. The resin composition may have a viscosity of, for example, 10 cP or more, 20 cP or more, 30 cP or more, or 40 cP or more under heating conditions of 80 ° C. or higher (for example, 90 ° C.). The "initial viscosity" means the viscosity measured immediately after mixing the epoxy resin and the curing agent for the epoxy resin. The viscosity can be measured using a commercially available viscosity measuring device, for example, RheoStress6000 manufactured by HAAKE. The "low viscosity" resin composition refers to a resin composition having an initial viscosity of 100 cP or less under heating conditions of 80 ° C. or higher (for example, 90 ° C.).
　本発明の硬化剤を使用することで、速硬化性の樹脂組成物を得ることができる。樹脂組成物の硬化速度は、例えば、特定の硬化条件で得られる樹脂組成物の硬化物について、市販の示差走査熱量測定装置、例えば、日立ハイテクサイエンス社製示差走査熱量測定ＤＳＣ７０００Ｘを用いて、発熱ピークを測定することにより評価することができる。未硬化の樹脂組成物が残存している場合には、発熱ピークが現れる。「速硬化性」の樹脂組成物であれば、発熱ピークが観察されないか、観察されたとしても発熱ピークの面積から求められる発熱量が小さい。 By using the curing agent of the present invention, a fast-curing resin composition can be obtained. The curing rate of the resin composition is determined by, for example, using a commercially available differential scanning calorimetry device, for example, a differential scanning calorimetry DSC7000X manufactured by Hitachi High-Tech Science Co., Ltd., for the cured product of the resin composition obtained under specific curing conditions. It can be evaluated by measuring the peak. If the uncured resin composition remains, an exothermic peak appears. In the case of a "fast-curing" resin composition, no exothermic peak is observed, or even if it is observed, the calorific value obtained from the area of the exothermic peak is small.
　本発明の樹脂組成物の別の一態様として、エポキシ樹脂を含む主剤と、エポキシ樹脂用硬化剤とを含む、２液型のキットを提供することができる。 As another aspect of the resin composition of the present invention, it is possible to provide a two-component kit containing a main agent containing an epoxy resin and a curing agent for an epoxy resin.
　本発明の樹脂組成物（キット）は、例えば、建築、土木、自動車、船舶、宇宙航空、産業機械、ロボット、通信、電気電子、半導体、ディスプレイ等の各分野におけるエポキシ樹脂材料等として用いることができ、特に、航空機等に用いる複合材料のマトリックス樹脂として適している。 The resin composition (kit) of the present invention can be used, for example, as an epoxy resin material in various fields such as construction, civil engineering, automobiles, ships, aerospace, industrial machinery, robots, communications, electrical / electronics, semiconductors, and displays. It is particularly suitable as a matrix resin for composite materials used in aircraft and the like.
　本発明はさらに、エポキシ樹脂組成物の硬化物に関する。本発明はまた、エポキシ樹脂とエポキシ樹脂用硬化剤とを混合し、エポキシ樹脂を硬化させて硬化物を得る工程を含む、硬化物の製造方法、及び、エポキシ樹脂とエポキシ樹脂用硬化剤とを混合して、エポキシ樹脂を硬化させる工程を含む、エポキシ樹脂の硬化方法に関する。 The present invention further relates to a cured product of an epoxy resin composition. The present invention also comprises a method for producing a cured product, which comprises a step of mixing an epoxy resin and a curing agent for an epoxy resin and curing the epoxy resin to obtain a cured product, and an epoxy resin and a curing agent for an epoxy resin. The present invention relates to a method for curing an epoxy resin, which comprises a step of mixing and curing the epoxy resin.
　エポキシ樹脂とエポキシ樹脂用硬化剤との混合手段には、従来公知の混合手段を特に制限なく使用することができる。例えば、市販の自転公転式撹拌脱泡機を用いて撹拌及び脱泡してもよい。硬化手段としては加熱が好ましく、例えば、１２０～２５０℃、１５０～２２０℃、又は１７０℃～１９０℃の温度で、例えば、３０分～４時間、１～３時間、又は１．５～２．５時間保持してエポキシ樹脂を硬化させてもよい。 As the mixing means for the epoxy resin and the curing agent for the epoxy resin, conventionally known mixing means can be used without particular limitation. For example, a commercially available rotation / revolution type stirring / defoaming machine may be used for stirring and defoaming. As the curing means, heating is preferable, and for example, at a temperature of 120 to 250 ° C., 150 to 220 ° C., or 170 ° C. to 190 ° C., for example, 30 minutes to 4 hours, 1 to 3 hours, or 1.5 to 2. The epoxy resin may be cured by holding it for 5 hours.
　本発明の樹脂組成物の硬化物は、高い衝撃強度等の優れた機械的特性を有する。硬化物の機械的特性は、例えば、テンシロン万能試験機を用いる３点曲げ圧縮試験により、弾性率、曲げ強度、伸び等を測定することや、市販の衝撃試験機を用いて衝撃強度を測定することにより評価することができる。本発明の樹脂組成物の硬化物はまた、高い耐熱性を有する。耐熱性は、硬化物のガラス転移温度により評価することができる。 The cured product of the resin composition of the present invention has excellent mechanical properties such as high impact strength. For the mechanical properties of the cured product, for example, the elastic modulus, bending strength, elongation, etc. are measured by a three-point bending compression test using a Tencilon universal tester, or the impact strength is measured using a commercially available impact tester. It can be evaluated by this. The cured product of the resin composition of the present invention also has high heat resistance. The heat resistance can be evaluated by the glass transition temperature of the cured product.
　本発明のさらなる一態様として、本発明の樹脂組成物の硬化物と強化繊維を含む、複合材料を提供することができる。複合材料としては、例えばレジントランスファーモールディング法に用いられる複合材料、フィラメントワインディング法に用いられる複合材料、プリプレグ等が挙げられる。強化繊維は特に限定されず、炭素繊維、ガラス繊維、アラミド繊維等の、強化繊維として常用されているものを用いることができる。複合材料の軽量化と強度の両立の観点から、炭素繊維が特に好ましい。例えば、レジントランスファーモールディング法の場合、型内に配置した強化繊維に樹脂組成物を注入し、加熱硬化することにより繊維強化複合材料が得られる。 As a further aspect of the present invention, it is possible to provide a composite material containing a cured product of the resin composition of the present invention and reinforcing fibers. Examples of the composite material include a composite material used in the resin transfer molding method, a composite material used in the filament winding method, and a prepreg. The reinforcing fiber is not particularly limited, and carbon fiber, glass fiber, aramid fiber and the like that are commonly used as reinforcing fiber can be used. Carbon fiber is particularly preferable from the viewpoint of achieving both weight reduction and strength of the composite material. For example, in the case of the resin transfer molding method, a fiber-reinforced composite material can be obtained by injecting a resin composition into the reinforcing fibers arranged in a mold and heat-curing the resin composition.
　本発明の樹脂組成物は、初期粘度が低く、速硬化性であるため、レジントランスファーモールディング法に好適に用いることができる。また、本発明の樹脂組成物の硬化物は優れた機械的特性を有するため、硬化物を含む複合材料は、特に、航空機部材等の高い性能が要求される分野にも適用することができる。 Since the resin composition of the present invention has a low initial viscosity and is fast-curing, it can be suitably used for the resin transfer molding method. Further, since the cured product of the resin composition of the present invention has excellent mechanical properties, the composite material containing the cured product can be applied particularly to fields where high performance is required such as aircraft members.
　以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.
　＜硬化剤の調製例＞
　１９．８ｇのジメチルチオトルエンジアミン（粘度３ｃＰ（９０℃、７０ｒｐｍ））、１６．４ｇのジエチルトルエンジアミン（粘度１ｃＰ（９０℃、７０ｒｐｍ））及び１０ｇの４，４－メチレンビス［Ｎ－（１－メチルプロピル）アニリン］（粘度７ｃＰ（９０℃、７０ｒｐｍ））の液状混合物に２．０ｇの１－（ｏ－トリル）ビグアニド（固体）及び２．０ｇの無水ピペラジンを添加し、１００℃のオーブンで４５分間加熱溶解して、実施例１の硬化剤を調製した。液状芳香族ポリアミン、固形芳香族ポリアミン、脂肪族ポリアミンの種類及び量をそれぞれ表１～７に示されるとおりに変更した以外は実施例１と同様にして、実施例２～２４及び比較例１～２２の硬化剤を調製した。溶解性について、４５分間加熱後の状態を目視で観察し、固体状の物質が確認できるものを「不溶」、固体状の物質の無いものを「可溶」とした。 <Preparation example of curing agent>
19.8 g of dimethylthiotoluenediamine (viscosity 3 cP (90 ° C., 70 rpm)), 16.4 g of diethyltoluenediamine (viscosity 1 cP (90 ° C., 70 rpm)) and 10 g of 4,4-methylenebis [N- (1- (1-) Methylpropyl) aniline] (viscosity 7 cP (90 ° C, 70 rpm)) to which 2.0 g of 1- (o-tolyl) biguanide (solid) and 2.0 g of anhydrous piperazine are added and in an oven at 100 ° C. The curing agent of Example 1 was prepared by heating and dissolving for 45 minutes. Examples 2 to 24 and Comparative Examples 1 to 1 are the same as in Example 1 except that the types and amounts of liquid aromatic polyamines, solid aromatic polyamines, and aliphatic polyamines are changed as shown in Tables 1 to 7, respectively. Twenty-two hardeners were prepared. Regarding the solubility, the state after heating for 45 minutes was visually observed, and those in which a solid substance could be confirmed were designated as "insoluble", and those without a solid substance were designated as "soluble".
＜樹脂組成物の調製例１＞
　テトラグリシジルジアミノジフェニルメタン型エポキシ樹脂（ｊＥＲ６０４、三菱化学社製、エポキシ当量１１０～１３０）７０質量部に、トリグリシジル－ｐ－ アミノフェノール（アラルダイトＭＹ０５１０、エポキシ当量１０１）３０質量部を添加し、実施例１～１４及び比較例１～１４の硬化剤を表１～４の比率となるように添加し、自転公転式攪拌脱泡機（株式会社シンキー製ＡＲＥ－３００「あわとり錬太郎」）にて２０００ｒｐｍの条件下で２分間撹拌した後、自転公転式攪拌脱泡機（共立精機株式会社製ハイマージャＨＭ－２００ＷＶ）にて１０００ｒｐｍの条件下で６分間真空脱泡を行い、樹脂組成物を得た。 <Preparation Example 1 of Resin Composition>
Example by adding 30 parts by mass of triglycidyl-p-aminophenol (Araldite MY0510, epoxy equivalent 101) to 70 parts by mass of a tetraglycidyl diaminodiphenylmethane type epoxy resin (jER604, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 110 to 130). Add the curing agents 1 to 14 and Comparative Examples 1 to 14 in the ratios shown in Tables 1 to 4, and use a rotating and revolving stirring defoaming machine (ARE-300 "Awatori Rentaro" manufactured by Shinky Co., Ltd.). After stirring for 2 minutes under the condition of 2000 rpm, vacuum defoaming was performed for 6 minutes under the condition of 1000 rpm with a rotating and revolving stirring defoaming machine (Epoxy HM-200WV manufactured by Kyoritsu Seiki Co., Ltd.) to obtain a resin composition. rice field.
＜樹脂組成物の調製例２＞
　樹脂をビスフェノールＡ型液状エポキシ樹脂（ｊＥＲ８２８、三菱化学社製、エポキシ当量１８４～１９４）１００質量部に変更し、実施例１５～２４及び比較例１５～２２の硬化剤を表５～７の比率となるように添加した以外は調製例１と同様にして、樹脂組成物を得た。 <Preparation Example 2 of Resin Composition>
The resin was changed to 100 parts by mass of a bisphenol A type liquid epoxy resin (jER828, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184 to 194), and the curing agents of Examples 15 to 24 and Comparative Examples 15 to 22 were mixed in the ratios of Tables 5 to 7. A resin composition was obtained in the same manner as in Preparation Example 1 except that the resin composition was added so as to be.
＜硬化物の作製＞
　７５ｃｍ×１２０ｃｍのアルミ板の外周３辺に厚さ２ｍｍ×幅１０ｍｍまたは厚さ３．５ｍｍ×幅７ｍｍの外枠スペーサーを挟んでクリップで固定して型枠を作成し、樹脂組成物をオーブンで１００℃５分間加熱後、シリンジを用いて注入して型枠の淵まで流し込み、立てた状態でオーブンに投入した。２５℃からアルミ板表面温度が１８０℃に到達するまで２℃/分の設定で昇温し、そのまま２時間保持した後、室温まで３℃/分の設定で降温し、硬化物を型枠から取り外して、厚さ２ｍｍまたは厚さ３．５ｍｍの樹脂板を作製した。硬化物の状態について、厚さ３．５ｍｍの樹脂板を目視で観察し、板に気泡が１０個以上確認されるものを「発泡」、１０個以下のものを「泡なし」とした。硬化剤調製後の溶解性の評価の結果が「不溶」であった比較例１～５、８及び１７～２０の硬化剤を使用したものについては、溶解していない固形成分が樹脂組成物の下方に偏り、均一な硬化物が得られなかったため、比較例１についてのみ、硬化物の状態を評価した。硬化物の状態の評価の結果が「泡なし」であったものについて、以下の物性を評価した。 <Preparation of cured product>
An outer frame spacer with a thickness of 2 mm x width of 10 mm or a thickness of 3.5 mm x width of 7 mm is sandwiched between three outer circumferences of a 75 cm x 120 cm aluminum plate and fixed with clips to create a formwork, and the resin composition is placed in an oven. After heating at 100 ° C. for 5 minutes, it was poured using a syringe, poured to the edge of the mold, and put into the oven in an upright state. The temperature of the aluminum plate is raised from 25 ° C to 180 ° C at a setting of 2 ° C / min, held for 2 hours, and then lowered to room temperature at a setting of 3 ° C / min to remove the cured product from the mold. It was removed to make a resin plate with a thickness of 2 mm or a thickness of 3.5 mm. Regarding the state of the cured product, a resin plate having a thickness of 3.5 mm was visually observed, and those in which 10 or more bubbles were confirmed on the plate were defined as "foaming", and those having 10 or less bubbles were defined as "no bubbles". In the case of using the curing agents of Comparative Examples 1 to 5, 8 and 17 to 20 in which the result of the evaluation of the solubility after preparing the curing agent was "insoluble", the undissolved solid component was the resin composition. Since the cured product was biased downward and a uniform cured product could not be obtained, the state of the cured product was evaluated only for Comparative Example 1. The following physical properties were evaluated for those in which the result of evaluation of the state of the cured product was "no bubbles".
＜初期粘度測定＞
　調製直後の各樹脂組成物について、回転式レオメーター（ＨＡＡＫＥ社製ＲｈｅｏＳｔｒｅｓｓ６０００）を用いて、直径２０ｍｍのパラレルプレート、ギャップ０５ｍｍ、サンプル量０．２ｍｌ、９０℃、２０ｒｐｍの条件下で測定し、初期粘度を求めた。 <Initial viscosity measurement>
Each resin composition immediately after preparation was measured using a rotary rheometer (RheoStress6000 manufactured by HAAKE) under the conditions of a parallel plate having a diameter of 20 mm, a gap of 05 mm, a sample volume of 0.2 ml, 90 ° C., and 20 rpm. The viscosity was determined.
＜弾性率、曲げ強度、伸びの測定＞
　厚さ３．５ｍｍの樹脂板を１０ｍｍ×９６ｍｍの大きさに切断し、ＴＯＹＯ ＢＡＬＤＷＩＮ社製、テンシロン万能試験機を用いて２５℃、５ｍｍ／分の条件下で３点曲げ圧縮試験を行い、弾性率、曲げ強度、伸びを求めた。 <Measurement of elastic modulus, bending strength, and elongation>
A resin plate with a thickness of 3.5 mm is cut into a size of 10 mm × 96 mm, and a 3-point bending compression test is performed under the conditions of 25 ° C. and 5 mm / min using a Tencilon universal testing machine manufactured by TOYO BALDWIN, and the elastic modulus is obtained. The modulus, bending strength, and elongation were calculated.
＜ガラス転位温度Ｔｇの測定＞
　厚さ２ｍｍの樹脂板を７ｍｍ×６０ｍｍの大きさに切断し、日立ハイテクサイエンス社製動的粘弾性測定装置ＥＸＳＴＡＲ６０００を用いて昇温速度５℃／分、周波数１Ｈｚ、曲げ方式で測定を行い、貯蔵弾性率Ｅ’の変曲点に対し、２本の接線を引いた交点をガラス転移温度Ｔｇとした。 <Measurement of glass dislocation temperature Tg>
A resin plate with a thickness of 2 mm is cut into a size of 7 mm × 60 mm, and measurement is performed using a dynamic viscoelasticity measuring device EXSTAR6000 manufactured by Hitachi High-Tech Science Co., Ltd. at a temperature rise rate of 5 ° C./min, a frequency of 1 Hz, and a bending method. The intersection point where two tangents were drawn with respect to the bending point of the storage elastic modulus E'was defined as the glass transition temperature Tg.
＜衝撃強度の測定＞
　厚さ２ｍｍの樹脂板を、実施例１～１４及び比較例１～１４については２０ｍｍ×４０ｍｍ、実施例１５～２４及び比較例１５～２２については１０ｍｍ×４０ｍｍの大きさにそれぞれ切断し、株式会社オリエンテック社製アイゾット衝撃試験機ＣＩＴ－４０Ｉを用いて荷重無しの条件で衝撃強度の測定を行った。 <Measurement of impact strength>
A resin plate having a thickness of 2 mm was cut into a size of 20 mm × 40 mm for Examples 1 to 14 and Comparative Examples 1 to 14, and 10 mm × 40 mm for Examples 15 to 24 and Comparative Examples 15 to 22, respectively. The impact strength was measured under the condition of no load using the Izod impact tester CIT-40I manufactured by Orientec.
＜硬化度の測定＞
　厚さ２ｍｍの樹脂板をペンチで切り取って５ｍｇをサンプルパンに量り取り、日立ハイテクサイエンス社製示差走査熱量測定ＤＳＣ７０００Ｘを用いて５℃／分の条件下で３０～３００℃に昇温して測定し、発熱ピークが見られるものについては、その面積から発熱量を求めた。発熱ピークが見られず、硬化残りの無いものを「◎」（最良）、発熱量が１０ｍJ／ｍｇより低いものを「〇」（良）、発熱量が１０ｍJ／ｍｇ以上、２０ｍJ／ｍｇ以下であるものを「△」（可）、発熱量が２０ｍJ／ｍｇより高いものを「×」（不可）とした。 <Measurement of curing degree>
Cut a 2 mm thick resin plate with pliers, weigh 5 mg into a sample pan, and measure by heating to 30 to 300 ° C under the condition of 5 ° C / min using the differential scanning calorimetry DSC7000X manufactured by Hitachi High-Tech Science. However, for those with an exothermic peak, the calorific value was calculated from the area. Those with no exothermic peak and no curing residue are "◎" (best), those with a calorific value lower than 10 mJ / mg are "○" (good), and those with a calorific value of 10 mJ / mg or more and 20 mJ / mg or less. Some were marked with "Δ" (possible), and those with a calorific value higher than 20 mJ / mg were designated as "x" (not possible).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007

Claims (23)

  1. 　（Ａ）液状芳香族ポリアミン及び（Ｂ）二級アミノ基を含む固形芳香族アミンを含む、エポキシ樹脂用硬化剤であって、
    　（Ｂ）二級アミノ基を含む固形芳香族アミンが、（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンを含むか又は含まず、含まない場合、前記エポキシ樹脂用硬化剤が、（Ｃ）脂肪族環状ポリアミンをさらに含む、エポキシ樹脂用硬化剤。     A curing agent for epoxy resins containing (A) a liquid aromatic polyamine and (B) a solid aromatic amine containing a secondary amino group.
    (B) The solid aromatic amine containing a secondary amino group contains or does not contain (B1) a solid aromatic amine in which the number of secondary amino groups is greater than the total number of primary amino groups and tertiary amino groups. If not contained, the epoxy resin curing agent further contains (C) an aliphatic cyclic polyamine.
  2. 　（Ｂ）二級アミノ基を含む固形芳香族アミンが、（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンを含む、請求項１に記載のエポキシ樹脂用硬化剤。 The first aspect of the present invention comprises (B) a solid aromatic amine containing a secondary amino group, and (B1) a solid aromatic amine in which the number of secondary amino groups is greater than the total number of primary amino groups and tertiary amino groups. The curing agent for epoxy resin described.
  3. 　（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンが、（Ｂ１’）アミノ基として二級アミノ基のみを含む固形芳香族アミンを含む、請求項２に記載のエポキシ樹脂用硬化剤。 (B1) Solid aromatic amines having more secondary amino groups than the total number of primary amino groups and tertiary amino groups include (B1') solid aromatic amines containing only secondary amino groups as amino groups. , The curing agent for an epoxy resin according to claim 2.
  4. 　（Ｂ１’）アミノ基として二級アミノ基のみを含む固形芳香族アミンが、Ｎ－フェニル－１－ナフチルアミン、オクチル化ジフェニルアミン、４，４’－ビス（α，α－ジメチルベンジル）ジフェニルアミン、Ｎ－（ｐ－トリル）－１－ナフチルアミン、Ｎ－フェニル－３－ビフェニルアミン、ビス（３－ビフェニリル）アミン、２－（３－ビフェニリル）アミノ－９，９－ジメチルフルオレン、ビス（４－ｔｅｒｔ－ブチルフェニル）アミン、４－ｔｅｒｔ－ブチルフェニルフェニルアミン、ビス－α－メチルベンジルフェノチアジン、ジフェニルアミンと２，４，４－トリメチルペンテンとの反応物、ジフェニルアミン、Ｎ－フェニルベンジルアミン、３－メチルジフェニルアミン、３，４－ジメチルジフェニルアミン、４，４’－ジメチルジフェニルアミン、３－メトキシジフェニルアミン、１０－メトキシ－２，２’－イミノスチルベン、Ｎ－ベンジル－２－ナフチルアミン、１，２’－ジナフチルアミン、１，１’－ジナフチルアミン、４－イソプロピルアミノジフェニルアミン、２，６－ビス［（２－ヒドロキシエチル）アミノ］トルエン、４－（２－オクチルアミノ）ジフェニルアミン、Ｎ－（１，３－ジメチルブチル）－Ｎ’－フェニル－１，４－フェニレンジアミン、２，２，４－トリメチル－１，２－ジヒドロキノリン重合体、１，３－ジフェニルグアニジン、ｐ－（ｐ－トルエンスルホニルアミド）ジフェニルアミン、Ｎ－フェニル－Ｎ’－（３－メタクリロイルオキシ－２－ヒドロキシプロピル）－ｐ－フェニレンジアミン、ビス（２－ベンズアミドフェニル）ジスルフィド、Ｎ，Ｎ’－ジフェニル－１，４－フェニレンジアミン、１，３－ジ－ｏ－トリルグアニジン、１，５－ジフェニルカルボノヒドラジド、Ｎ，Ｎ’－ジフェニルエチレンジアミン及び５－（アセトアセトアミド）－２－ベンゾイミダゾリノンからなる群から選択される、請求項３に記載のエポキシ樹脂用硬化剤。 Solid aromatic amines containing only a secondary amino group as the (B1') amino group are N-phenyl-1-naphthylamine, octylated diphenylamine, 4,4'-bis (α, α-dimethylbenzyl) diphenylamine, N- (P-Trill) -1-naphthylamine, N-phenyl-3-biphenylamine, bis (3-biphenylyl) amine, 2- (3-biphenylyl) amino-9,9-dimethylfluorene, bis (4-tert-butyl) Phenyl) amine, 4-tert-butylphenylphenylamine, bis-α-methylbenzylphenothiazine, reaction product of diphenylamine with 2,4,4-trimethylpentene, diphenylamine, N-phenylbenzylamine, 3-methyldiphenylamine, 3 , 4-dimethyldiphenylamine, 4,4'-dimethyldiphenylamine, 3-methoxydiphenylamine, 10-methoxy-2,2'-iminostylben, N-benzyl-2-naphthylamine, 1,2'-dinaphthylamine, 1,1 '-Dinaphthylamine, 4-isopropylaminodiphenylamine, 2,6-bis [(2-hydroxyethyl) amino] toluene, 4- (2-octylamino) diphenylamine, N- (1,3-dimethylbutyl) -N' -Phenyl-1,4-phenylenediamine, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 1,3-diphenylguanidine, p- (p-toluenesulfonylamide) diphenylamine, N-phenyl-N '-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, bis (2-benzamidephenyl) disulfide, N, N'-diphenyl-1,4-phenylenediamine, 1,3-di-o- The curing for epoxy resin according to claim 3, which is selected from the group consisting of trilyguanidine, 1,5-diphenylcarbonohydrazide, N, N'-diphenylethylenediamine and 5- (acetoacetamide) -2-benzoimidazolinone. Agent.
  5. 　（Ｂ）二級アミノ基を含む固形芳香族アミンが、（Ｂ２）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数以下である固形芳香族ポリアミンをさらに含む、請求項２～４のいずれか１項に記載のエポキシ樹脂用硬化剤。 Claimed that (B) a solid aromatic amine containing a secondary amino group further comprises (B2) a solid aromatic polyamine in which the number of secondary amino groups is less than or equal to the total number of primary amino groups and tertiary amino groups. The curing agent for epoxy resin according to any one of 2 to 4.
  6. 　（Ｂ２）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数以下である固形芳香族ポリアミンが、４－アミノジフェニルアミン、２，４－ジアミノジフェニルアミン、２－アミノジフェニルアミン、４－アミノ－４’－メトキシジフェニルアミン、１－フェニルビグアニド、イソフタル酸ジヒドラジド、テレフタル酸ジヒドラジド、２，６－ナフトエ酸ジヒドラジド、４，４’－ビスベンゼンジヒドラジド、１，４－ナフトエ酸ジヒドラジド、ナフタレン－２，６－ジカルボヒドラジド、及び３－ヒドロキシ－２－ナフトエ酸ヒドラジドからなる群から選択される、請求項５に記載のエポキシ樹脂用硬化剤。 (B2) Solid aromatic polyamines in which the number of secondary amino groups is equal to or less than the total number of primary amino groups and tertiary amino groups are 4-aminodiphenylamine, 2,4-diaminodiphenylamine, 2-aminodiphenylamine, 4-. Amino-4'-methoxydiphenylamine, 1-phenylbiguanide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 4,4'-bisbenzenedihydrazide, 1,4-naphthoic acid dihydrazide, naphthalene-2, The curing agent for an epoxy resin according to claim 5, which is selected from the group consisting of 6-dicarbohydrazide and 3-hydroxy-2-naphthoic acid hydrazide.
  7. 　前記エポキシ樹脂用硬化剤が、（Ｃ）脂肪族環状ポリアミンをさらに含む、請求項２～６のいずれか１項に記載のエポキシ樹脂用硬化剤。 The epoxy resin curing agent according to any one of claims 2 to 6, wherein the epoxy resin curing agent further contains (C) an aliphatic cyclic polyamine.
  8. 　（Ｂ）二級アミノ基を含む固形芳香族アミンが、（Ｂ１）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数より多い固形芳香族アミンを含まず、（Ｂ２）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数以下である固形芳香族ポリアミンを含む、請求項１に記載のエポキシ樹脂用硬化剤。 (B) The solid aromatic amine containing a secondary amino group does not contain (B1) a solid aromatic amine in which the number of secondary amino groups is greater than the total number of primary amino groups and tertiary amino groups, and (B2). The curing agent for an epoxy resin according to claim 1, which comprises a solid aromatic polyamine in which the number of secondary amino groups is equal to or less than the total number of primary amino groups and tertiary amino groups.
  9. 　（Ｂ２）二級アミノ基の数が一級アミノ基と三級アミノ基との合計数以下である固形芳香族ポリアミンが、４－アミノジフェニルアミン、２，４－ジアミノジフェニルアミン、２－アミノジフェニルアミン、４－アミノ－４’－メトキシジフェニルアミン、１－フェニルビグアニド、イソフタル酸ジヒドラジド、テレフタル酸ジヒドラジド、２，６－ナフトエ酸ジヒドラジド、４，４’－ビスベンゼンジヒドラジド、１，４－ナフトエ酸ジヒドラジド、ナフタレン－２，６－ジカルボヒドラジド、及び３－ヒドロキシ－２－ナフトエ酸ヒドラジドからなる群から選択される、請求項８に記載のエポキシ樹脂用硬化剤。 (B2) Solid aromatic polyamines in which the number of secondary amino groups is equal to or less than the total number of primary amino groups and tertiary amino groups are 4-aminodiphenylamine, 2,4-diaminodiphenylamine, 2-aminodiphenylamine, 4-. Amino-4'-methoxydiphenylamine, 1-phenylbiguanide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 4,4'-bisbenzenedihydrazide, 1,4-naphthoic acid dihydrazide, naphthalene-2, The curing agent for an epoxy resin according to claim 8, which is selected from the group consisting of 6-dicarbohydrazide and 3-hydroxy-2-naphthoic acid hydrazide.
  10. 　（Ｃ）脂肪族環状ポリアミンの沸点が、１４０℃以上である、請求項７～９のいずれか１項に記載のエポキシ樹脂用硬化剤。 (C) The curing agent for an epoxy resin according to any one of claims 7 to 9, wherein the aliphatic cyclic polyamine has a boiling point of 140 ° C. or higher.
  11. 　（Ｃ）脂肪族環状ポリアミンが、一級アミノ基又は二級アミノ基を含む、請求項７～１０のいずれか１項に記載のエポキシ樹脂用硬化剤。 (C) The curing agent for an epoxy resin according to any one of claims 7 to 10, wherein the aliphatic cyclic polyamine contains a primary amino group or a secondary amino group.
  12. 　（Ｃ）脂肪族環状ポリアミンが、環構造中のアミノ基として二級アミノ基のみを含む、請求項７～１１のいずれか１項に記載のエポキシ樹脂用硬化剤。 (C) The curing agent for epoxy resin according to any one of claims 7 to 11, wherein the aliphatic cyclic polyamine contains only a secondary amino group as an amino group in the ring structure.
  13. 　（Ｃ）脂肪族環状ポリアミンが、錯体又は塩構造を形成していない、請求項７～１２のいずれか１項に記載のエポキシ樹脂用硬化剤。 (C) The curing agent for an epoxy resin according to any one of claims 7 to 12, wherein the aliphatic cyclic polyamine does not form a complex or a salt structure.
  14. 　（Ｃ）脂肪族環状ポリアミンにおいて、環構造中のアミノ基に隣接する元素及び／又は環構造上のアミノ基が結合している元素に隣接する元素の置換基が全て水素原子である、請求項７～１３のいずれか１項に記載のエポキシ樹脂用硬化剤。 (C) The claim that in the aliphatic cyclic polyamine, all the substituents of the element adjacent to the amino group in the ring structure and / or the element adjacent to the element to which the amino group on the ring structure is bonded are hydrogen atoms. The curing agent for an epoxy resin according to any one of 7 to 13.
  15. 　（Ｃ）脂肪族環状ポリアミンが、ピペラジン骨格を有する、請求項７～１４のいずれか１項に記載のエポキシ樹脂用硬化剤。 (C) The curing agent for an epoxy resin according to any one of claims 7 to 14, wherein the aliphatic cyclic polyamine has a piperazine skeleton.
  16. 　（Ｃ）脂肪族環状ポリアミンが、ピペラジンである、請求項７～１５のいずれか１項に記載のエポキシ樹脂用硬化剤。 (C) The curing agent for an epoxy resin according to any one of claims 7 to 15, wherein the aliphatic cyclic polyamine is piperazine.
  17. 　（Ｂ）二級アミノ基を含む固形芳香族アミンの融点が、１６０℃以下である、請求項１～１６のいずれか１項に記載のエポキシ樹脂用硬化剤。 (B) The curing agent for an epoxy resin according to any one of claims 1 to 16, wherein the solid aromatic amine containing a secondary amino group has a melting point of 160 ° C. or lower.
  18. 　（Ａ）液状芳香族ポリアミンが、２つ以上の一級アミノ基、２つ以上の二級アミノ基、又は１つ以上の一級アミノ基と１つ以上の二級アミノ基とを含む、請求項１～１７のいずれか１項に記載のエポキシ樹脂用硬化剤。 (A) Claim 1 that the liquid aromatic polyamine contains two or more primary amino groups, two or more secondary amino groups, or one or more primary amino groups and one or more secondary amino groups. The curing agent for an epoxy resin according to any one of 17 to 17.
  19. 　（Ａ）液状芳香族ポリアミンが、ジメチルチオトルエンジアミン、ジエチルトルエンジアミン及び４，４’－メチレンビス［Ｎ－（１－メチルプロピル）アニリン］からなる群から選択される、請求項１８に記載のエポキシ樹脂用硬化剤。 (A) The epoxy according to claim 18, wherein the liquid aromatic polyamine is selected from the group consisting of dimethylthiotoluenediamine, diethyltoluenediamine and 4,4'-methylenebis [N- (1-methylpropyl) aniline]. Hardener for resin.
  20. 　液状である、請求項１～１９のいずれか１項に記載のエポキシ樹脂用硬化剤。 The curing agent for epoxy resin according to any one of claims 1 to 19, which is a liquid.
  21. 　請求項１～２０のいずれか１項に記載のエポキシ樹脂用硬化剤と、エポキシ樹脂とを含む、樹脂組成物。 A resin composition containing the epoxy resin curing agent according to any one of claims 1 to 20 and the epoxy resin.
  22. 　請求項２１に記載の樹脂組成物の硬化物。 The cured product of the resin composition according to claim 21.
  23. 　請求項２２に記載の硬化物及び炭素繊維を含む、複合材料。 A composite material containing the cured product and carbon fiber according to claim 22.
PCT/JP2021/022821 2020-07-08 2021-06-16 Curing agent for epoxy resin WO2022009628A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008508113A (en) * 2004-07-27 2008-03-21 ヘクセル コンポジッツ ゲーエムベーハー Continuous pultrusion process for producing high performance structural features
JP2008111106A (en) * 2006-10-06 2008-05-15 Hitachi Chem Co Ltd Liquid resin composition for sealing electronic parts and electronic component device using the same
JP2017008316A (en) * 2015-06-25 2017-01-12 東レ株式会社 Epoxy resin composition, fiber reinforced composite material, molded article and pressure container

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008508113A (en) * 2004-07-27 2008-03-21 ヘクセル コンポジッツ ゲーエムベーハー Continuous pultrusion process for producing high performance structural features
JP2008111106A (en) * 2006-10-06 2008-05-15 Hitachi Chem Co Ltd Liquid resin composition for sealing electronic parts and electronic component device using the same
JP2017008316A (en) * 2015-06-25 2017-01-12 東レ株式会社 Epoxy resin composition, fiber reinforced composite material, molded article and pressure container

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