CN115725055A - Epoxy resin composition - Google Patents
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- CN115725055A CN115725055A CN202111009390.5A CN202111009390A CN115725055A CN 115725055 A CN115725055 A CN 115725055A CN 202111009390 A CN202111009390 A CN 202111009390A CN 115725055 A CN115725055 A CN 115725055A
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Abstract
The purpose of the present invention is to provide an epoxy resin composition that can achieve a low viscosity, an improved low-temperature curability, a shortened curing time, and a sufficient cured region secured when heat conduction is insufficient. An epoxy resin composition comprising the following component (A), the following component (B) and the following component (C). (A) an epoxy resin; (B) a curing agent; (C) a compound represented by the following formula (1).
Description
Technical Field
The present invention relates to an epoxy resin composition.
Background
Epoxy resins are widely used in a wide range of applications such as insulating materials, sealing materials, adhesives, conductive materials, and matrix resins of fiber-reinforced plastics for electrical and electronic components.
In recent years, demands for electronic equipment and apparatuses have been widely directed to miniaturization, higher functionality, lighter weight, and more functions, and in terms of semiconductor chip mounting technology, further miniaturization, and higher density have been advanced by narrowing the pitch between the electrode pads and the pad pitch. An underfill material that protects the bump connection portion and the circuit surface of the chip is present in the gap between the chip and the substrate, and the underfill material is a thermosetting resin using an epoxy resin as an adhesive.
Fiber-reinforced plastics are manufactured using reinforcing fibers and a matrix resin. Thermosetting resins using epoxy resins are often used as the matrix resin. For example, patent document 1 discloses an epoxy resin composition which contains hydrolyzable chlorine and a component having 2 or more alcoholic hydroxyl groups and can provide sufficient storage stability, curing speed, mechanical strength, and heat resistance. In addition, for example, patent document 2 discloses an epoxy resin composition that can be cured in a short time at a low temperature of 70 ℃ or lower by containing an acid anhydride and a polyol compound having an aromatic ring.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2003-301029
Patent document 2: japanese patent application laid-open No. 2010-163573
Disclosure of Invention
Problems to be solved by the invention
In recent years, the viscosity of the underfill material is required to be low so that the underfill material can penetrate into a narrow gap accompanying a narrow pitch. In addition, in order to improve productivity, there is a strong demand for an underfill material to be reduced in curing temperature and curing time.
However, the epoxy resin compositions described in patent documents 1 and 2 have room for improvement in terms of reduction in viscosity, low-temperature curability, shortening of curing time, and securing of a sufficient cured region in the case of uneven heat conduction.
The present invention has been made in view of the above-described situation. That is, an object of the present invention is to provide an epoxy resin composition which can achieve a low viscosity, an improved low-temperature curability, a shortened curing time, and a sufficient cured region secured when heat conduction is insufficient.
Means for solving the problems
The present inventors have conducted extensive studies and, as a result, have found that the above object can be achieved by the following technical means, thereby completing the present invention.
The component having 2 or more alcoholic hydroxyl groups described in patent document 1 does not have a structure represented by the following formula (1).
The present invention is as follows.
[1]
An epoxy resin composition comprising the following component (A), the following component (B) and the following component (C).
(A) Epoxy resin
(B) Curing agent
(C) A compound represented by the following formula (1)
{ formula (1) { wherein R 1 ～R 9 Each is one selected from the group consisting of hydrogen, an alkyl group, an aromatic group, a substituent containing a hetero atom, and a substituent containing a halogen atom. R is 1 ～R 9 Optionally identical or different from each other. In addition, the compound shown in the formula (1) is optionally selected from R 5 ～R 9 Any of which are fused ring compounds present in the same ring. }
[2]
The epoxy resin composition according to [1], wherein the component (B) contains a solid curing agent.
[3]
According to [1]Or [ 2]]The epoxy resin composition, wherein R is represented by the formula (1) 1 Is a hydroxyl group.
[4]
According to [1]～[3]The epoxy resin composition as described in any one of the above, wherein R of the above formula (1) 2 、R 3 And R 4 Is hydrogen.
[5]
The epoxy resin composition according to any one of [1] to [4], which comprises a compound containing 4 or more active hydrogens as the component (B).
[6]
The epoxy resin composition according to any one of [1] to [4], wherein the component (B) contains an imidazole curing agent.
[7]
The epoxy resin composition according to any one of [1] to [4], wherein the component (B) contains a microcapsule-type curing agent.
[8]
The epoxy resin composition according to any one of [1] to [7], further comprising a curing accelerator as the component (D).
[9]
A method for producing an epoxy resin composition comprising the following component (A), the following component (B) and the following component (C), said method comprising the steps of: the component (C) is added to a compound or a composition having at least one selected from the group consisting of the component (a) and the component (B).
(A) Epoxy resin
(B) Curing agent
(C) A compound represented by the following formula (1)
{ formula (1) { wherein R 1 ～R 9 Each is one selected from the group consisting of hydrogen, an alkyl group, an aromatic group, a substituent containing a hetero atom, and a substituent containing a halogen atom. R 1 ～R 9 Optionally identical or different from each other. In addition, the compound shown in the formula (1) is optionally selected from R 5 ～R 9 Any of which are fused ring compounds present in the same ring. }
[10]
The process according to [9], wherein the epoxy resin composition further comprises the following component (D):
(D) A curing accelerator for curing the cured resin composition,
the production method comprises a step of adding a component (C) to a compound or a composition having at least one selected from the group consisting of the component (A), the component (B), and the component (D).
[11]
The process for producing an epoxy resin composition according to [9] or [10], wherein the epoxy resin composition further comprises the following component (E):
(E) The filler is filled in the inner cavity of the shell,
the production method comprises a step of adding a component (C) to a compound or a composition having at least one selected from the group consisting of the component (A), the component (B), and the component (E).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, an epoxy resin composition which can realize a low viscosity, an improved low-temperature curability, a shortened curing time, and a sufficient cured region secured when heat conduction is insufficient can be provided.
Detailed Description
The mode for carrying out the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail below. The following embodiments are illustrative of the present invention, and the present invention is not limited to the following embodiments. The present invention can be suitably modified within the scope of the gist thereof.
< epoxy resin composition >
The epoxy resin composition of the present embodiment contains (a) an epoxy resin (hereinafter also referred to as "component (a)"), and (B) a curing agent (hereinafter also referred to as "component (B)"), and (C) a compound represented by the following formula (1) (hereinafter also referred to as "component (C)").
{ formula (1) { wherein R 1 ～R 9 Each is one selected from the group consisting of hydrogen, an alkyl group, an aromatic group, a substituent containing a hetero atom, and a substituent containing a halogen atom. R is 1 ～R 9 Optionally identical or different from each other. In addition, the compound shown in the formula (1) is optionally selected from R 5 ～R 9 Any of which are fused ring compounds present in the same ring. }
The epoxy resin composition of the present embodiment can achieve a low viscosity, an improved low-temperature curability, a shortened curing time, and a sufficient cured region when heat conduction is insufficient, by including the components (a) to (C).
< component (A) epoxy resin >
The epoxy resin as the component (a) is not limited to the following, and examples thereof include 2-functional epoxy resins such as bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, tetrabromobisphenol a type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, tetrabromobiphenyl type epoxy resin, diphenyl ether type epoxy resin, benzophenone type epoxy resin, benzoate type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl sulfoxide type epoxy resin, diphenyl sulfone type epoxy resin, diphenyl disulfide type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, P-phenylene type epoxy resin, methyl-P-phenylene type epoxy resin, dibutyl-P-phenylene type epoxy resin, resorcinol type epoxy resin, methyl resorcinol type epoxy resin, o-phenylene type epoxy resin, N-diglycidylphenylamine type epoxy resin and the like; 3-functional epoxy resins such as N, N-diglycidylaminophenyl epoxy resins, o- (N, N-diglycidylamino) toluene epoxy resins, triazine epoxy resins, and the like; 4-functional epoxy resins such as tetraglycidyl diaminodiphenylmethane epoxy resins and diaminobenzene epoxy resins; polyfunctional epoxy resins such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene type epoxy resin, naphthol aralkyl type epoxy resin, and brominated phenol novolac type epoxy resin; and alicyclic epoxy resins. These may be used alone or in combination of two or more. Further, they may be used in combination with an epoxy resin modified with isocyanate or the like. The epoxy resin composition of the present embodiment preferably contains a bisphenol type epoxy resin from the viewpoint of handling properties and heat resistance.
The content of the (a) epoxy resin is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and further more preferably 20% by mass or more, based on the mass of the entire epoxy resin composition, from the viewpoint of providing a cured product with sufficient strength. The content of the epoxy resin (a) is preferably 98% by mass or less, more preferably 95% by mass or less, and still more preferably 92% by mass or less, based on the mass of the entire epoxy resin composition, from the viewpoint of adding the component (B) and the component (C) to impart sufficient curability.
< ingredient (B) curing agent >
The curing agent of the component (B) contained in the epoxy resin composition of the present embodiment is not limited to the following, and examples thereof include amine-based curing agents, amide-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, latent curing agents, catalyst-type curing agents, and the like. The curing agent is not limited to these.
The amine-based curing agent is not limited to the following, and examples thereof include aliphatic amines and aromatic amines.
The aliphatic amine is not limited to the following, and examples thereof include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, and the like.
Examples of the aromatic amine include, but are not limited to, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis (4-aminobenzoate), poly-1,4-butanediol bis (p-aminobenzoate), KAYAHARD A-a (manufactured by japan chemical products), ETHACURE100 (MITSUI FINE CHEMICALS, INC co., manufactured by ltd).
The amide curing agent is not limited to the following, and examples thereof include dicyandiamide having 4 active hydrogens and guanidine compounds as derivatives thereof, acid anhydrides obtained by adding an amine curing agent, and hydrazide compounds.
Examples of the hydrazide curing agent containing the hydrazide-based compound include, but are not limited to, succinic dihydrazide, adipic dihydrazide, phthalic dihydrazide, isophthalic dihydrazide, terephthalic dihydrazide, p-hydroxybenzoic acid hydrazide, salicylic acid hydrazide, phenylamino propionic acid hydrazide, maleic acid dihydrazide, and the like.
The guanidine-based curing agent containing a guanidine compound is not limited to the following, and examples thereof include dicyandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, and toluylguanidine.
The acid anhydride curing agent is not limited to the following, and examples thereof include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.
The phenol-based curing agent is not limited to the following, and examples thereof include a phenol novolac resin, a cresol novolac resin, a phenol aralkyl resin, a cresol aralkyl resin, a naphthol aralkyl resin, a biphenyl-modified phenol novolac resin, a biphenyl-modified phenol aralkyl resin, a dicyclopentadiene-modified phenol resin, an aminotriazine-modified phenol resin, a naphthol novolac resin, a naphthol-phenol co-condensed novolac resin, a naphthol-cresol co-condensed novolac resin, and an allyl acrylic novolac resin.
The latent curing agent is not limited to the following, and examples thereof include imidazole compounds, polyamine compounds, amine-epoxy adducts, amine-urea adducts, microcapsule-type curing agents coated with these compounds, and curing agents obtained by adsorbing these compounds to a porous body. Specific examples thereof include, but are not limited to, novacure HX-3721, HX-3722, HX-3613, HX-3921HP, HXA9322HP (manufactured by Asahi Kasei Co., ltd.), ajicure PN-23J, PN-40J, PN-H, MY-24 (Ajinomoto Fine-technique Co., inc.), fujicure FXR-1020, and FXR-1030 (manufactured by Fuji Kasei chemical Co., ltd.). These may be used alone or in combination of two or more.
The curing agent preferably contains an imidazole curing agent, from the viewpoint that the curing agent has good curability at low temperatures, can cure a resin by adding a small amount of the curing agent, and can obtain a cured product having a high glass transition temperature by curing in a short time. The imidazole compound contained in the imidazole-based curing agent is not particularly limited, and examples thereof include 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2,4-diamino-6- [ 2-methylimidazolyl- (1) ] ethyl-s-triazine, 2-phenylimidazoline, 2,3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole. The imidazole curing agent is not particularly limited, and examples thereof include Novacure HX-3721, HX-3722, HX-3613, HX-3921HP, and HXA9322HP (manufactured by Asahi Kasei corporation).
The catalyst-type curing agent is not limited to the following, and examples thereof include cationic thermosetting catalysts and BF 3 Amine complexes and the like.
From the viewpoint of storage stability, the curing agent as the component (B) preferably contains a solid curing agent, i.e., a curing agent which is solid at 25 ℃ and 1013 hPa. The epoxy resin composition can have both reactivity and storage stability by dispersing a solid curing agent in the epoxy resin composition and starting a curing reaction after a predetermined time has elapsed from the start of heating at a predetermined temperature. The solid curing agent is preferably dicyandiamide, a solid imidazole compound, a solid polyamine compound, and a masterbatch-type latent curing agent containing the same, and the masterbatch-type latent curing agent containing the solid imidazole microcapsule curing agent is more preferably one containing Novacure HX-3721, HX-3722, HX-3613, HX-3921HP, and HXA9322HP.
The (B) curing agent preferably contains a microcapsule-type curing agent from the viewpoint of storage stability at room temperature and thickening when the epoxy resin composition is applied to a dispenser for control or the like. As the microcapsule curing agent, novacure HX-3721, HX-3722, HX-3613, HX-3921HP, HXA9322HP can be used.
In addition, from the viewpoint of increasing the crosslinking point, which complicates the crosslinking structure and improves the strength of the cured product, it is preferable to contain a compound containing 4 or more active hydrogens as the component (B), and from the viewpoint of improving the adhesion to the substrate, it is more preferable to contain a compound containing a heteroatom and containing 4 or more active hydrogens. Such a compound is not particularly limited, and dicyandiamide may be mentioned, for example.
These curing agents may be used alone or in combination of two or more.
The content of the component (B) is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more, based on the whole epoxy resin composition. The content of the component (B) is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less, based on the whole epoxy resin composition.
< component (C) the compound represented by the formula (1) >
The epoxy resin composition of the present embodiment contains a compound represented by the following formula (1) (component (C)). The epoxy resin composition of the present embodiment contains the compound represented by the following formula (1) (component (C)), and thus can realize excellent low-temperature curability, a reduction in viscosity, a reduction in curing time, and a sufficient cured region.
In the formula (1), R 1 ～R 9 Each is one selected from the group consisting of hydrogen, an alkyl group (preferably an alkyl group having 1 to 50 carbon atoms), an aromatic group, a substituent containing a hetero atom, and a substituent containing a halogen atom. R is 1 ～R 9 Optionally identical or different from each other. In addition, the compound shown in the formula (1) is optionally selected from R 5 ～R 9 Any of which are fused ring compounds in the same ring. The compound represented by the above formula (1) is contained as the component (C) from the viewpoint of improving curability by combining excellent coordination to the curing agent (B) and compatibility with the epoxy resin (a) obtained by having an aromatic ring.
Further, from the viewpoint of improving the coordination to the curing agent (B) and further improving curability, R in the above formula (1) is preferable 1 Is a hydroxyl group.
In addition, from the viewpoint of not inhibiting the coordination of hydroxyl groups due to steric hindrance, R in the above formula (1) is preferred 2 、R 3 And R 4 Is hydrogen.
The compound represented by the above formula (1) is not particularly limited, and examples thereof include: 3-phenoxy-1-propanol, 3-phenoxy-1,2-propanediol, 3-phenoxy-1,3-propanediol, cresyl glycerol ether (3- (2-methylphenoxy) -1,2-propanediol), guaiacol glycerol ether (3- (2-methoxyphenoxy) propane-1,2-diol), bisphenol A (3-hydroxypropyl) glycidyl ether, bisphenol A (2,3-hydroxypropyl) glycidyl ether,
A compound represented by the following formula (1-1) (hereinafter also referred to as "compound 1")
A compound represented by the following formula (1-2) (hereinafter also referred to as "compound 2")
A compound represented by the following formula (1-3) (hereinafter also referred to as "compound 3")
A compound having a 1-propanol structure produced by ring-opening of terminal epoxy groups of a bisphenol F-type epoxy resin, a compound having a 1,2-propanediol structure produced by ring-opening of terminal epoxy groups of a bisphenol F-type epoxy resin (for example, bisphenol F glycidyl 2,3-dihydroxypropyl ether), a compound having a 1-propanol structure produced by ring-opening of terminal epoxy groups of a naphthalene-type epoxy resin, a compound having a 1,2-propanediol structure produced by ring-opening of terminal epoxy groups of a naphthalene-type epoxy resin, a compound having a 1-propanol structure produced by ring-opening of terminal epoxy groups of a phenol novolac-type epoxy resin, a compound having a 1,2-propanediol structure produced by ring-opening of terminal epoxy groups of a phenol novolac-type epoxy resin, a compound having a 1-propanol structure produced by ring-opening of terminal epoxy groups of a cresol novolac-type epoxy resin, a compound having a 1,2-propanediol structure produced by ring-opening of terminal epoxy groups of a cresol novolac-type epoxy resin, and the like. Among them, 3-phenoxy-1-propanol, 3-phenoxy-1,2-propanediol, bisphenol a (3-hydroxypropyl) glycidyl ether, bisphenol a (2,3-hydroxypropyl) glycidyl ether, compound 1, compound 2, and compound 3 are preferable from the viewpoint of having a high effect of lowering the thickening initiation temperature of the epoxy resin composition and obtaining a uniform epoxy resin composition because of good compatibility with the epoxy resin (a). These compounds represented by the formula (1) as the component (C) may be used singly or in combination of two or more.
The content of the component (C) is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and further preferably 0.001% by mass or more, based on the whole epoxy resin composition. The content of the component (C) is preferably less than 20% by mass, more preferably less than 15% by mass, even more preferably less than 10% by mass, even more preferably less than 8% by mass, even more preferably less than 7% by mass, very preferably less than 6% by mass, even very preferably less than 5% by mass, even very preferably less than 3% by mass, and particularly very preferably less than 2% by mass, based on the whole epoxy resin composition. The epoxy resin composition of the present embodiment contains the component (C) in an amount of 0.00001 mass% or more, and thus can further achieve a reduction in the thickening initiation temperature, a reduction in viscosity, a reduction in the curing time, and sufficient curing in the cured region. From the viewpoint of storage stability, the content of the component (C) is preferably less than 20% by mass based on the entire epoxy resin composition.
The mechanism by which the component (C) exhibits effects in reducing the viscosity, improving the low-temperature curability, shortening the curing time, and improving the cured region is considered to be as follows, but is not limited thereto. The aromatic group and the hydroxyl group of the component (C) act on the interaction between the epoxy resins (a), thereby eliminating the interaction between the epoxy resins (a). This facilitates the molecular movement of the entire epoxy resin composition, thereby reducing the viscosity. Further, the compatibility of the (B) curing agent with the (a) epoxy resin is improved by forming a coordinate bond between the hydroxyl group of the component (C) and the (B) curing agent, and the diffusibility of the (B) curing agent in the epoxy resin composition is improved, whereby the sufficient diffusion of the (B) curing agent in the (a) epoxy resin component at a lower temperature and the curing reaction accompanied therewith can be realized. From the viewpoint of improving the coordinatability with the curing agent (B), the component (C) is more preferably a 1,2-diol structure. The improvement in compatibility and diffusion of the curing agent (B) to the epoxy resin (a) after the component (C) is coordinated thereto contributes to shortening of the curing time and improvement of the cured region. The effects on interaction, coordination, and compatibility are greatly influenced by the molecular structure. Accordingly, the component (C) of the epoxy resin composition of the present embodiment contains the compound represented by the above formula (1).
As an index of compatibility, there is an sp value (δ), and it is known that when the difference between sp values of compounds is small, good compatibility is exhibited. From the viewpoint of excellent compatibility between the component (C) and the epoxy resin as the component (a), and excellent compatibility with the component (a) after the component (C) is coordinated to the curing agent as the component (B), and further exhibiting the effects of lowering viscosity, improving low-temperature curability, shortening curing time, and improving cured region, it is preferable that the sp value of the component (C) has a value close to that of the epoxy resin as the component (a). The sp value of each compound at 25 ℃ was determined by the Fedors calculation method (formula (i)) using the value described in Robert F.FEDORS, POLYMER ENGINEERING AND SCIENCE, FEBRUARY,1974,Vol.14,No.2.
δ＝(∑⊿e/∑⊿v) 1/2 Question-math (i)
Δ e represents the inner energy of each substituent, and Δ v represents the molar volume.
[ component (A) ]
Bisphenol a type epoxy resin (n = 0) · δ =10.9 (cal/cm) 3 ) 1/2
Bisphenol F epoxy resin (n = 0) · δ =12.1 (cal/cm) 3 ) 1/2
Epoxy cresol novolac · δ =11.0 (cal/cm) 3 ) 1/2
Tetraglycidyl diaminodiphenylmethane · δ =11.9 (cal/cm) 3 ) 1/2
[ component (B) ]
Dicyandiamide · δ =17.8 (cal/cm) 3 ) 1/2
[ component (C) ]
3-phenoxy-1-propanol · δ =12.0 (cal/cm) 3 ) 1/2
3-phenoxy-1,2-propanediol····δ＝14.3(cal/cm 3 ) 1/2
Bisphenol A (3-hydroxypropyl) glycidyl ether. Cndot. Delta. =11.6 (cal/cm) 3 ) 1/2
Bisphenol A (2,3-hydroxypropyl) glycidyl ether. Delta. Cndot. Cndot. =12.9 (cal/cm) 3 ) 1/2
Compound 1 · δ =12.0 (cal/cm) 3 ) 1/2
Compound 2 · δ =12.0 (cal/cm) 3 ) 1/2
Compound 3 · δ =12.6 (cal/cm) 3 ) 1/2
[ other Components ]
Glycerol · δ =20.0 (cal/cm) 3 ) 1/2
From the viewpoint of further exhibiting the effects of lowering viscosity, improving low-temperature curability, shortening curing time, and improving cured region by bringing the sp value of the component (C) and the sp value of the component (A) close to each other, the component (A) contains a compound having an sp value of 10 to 13 (cal/cm) 3 ) 1/2 In the case of the epoxy resin of (4), the lower limit of sp value of the component (C) is preferably 7 (cal/cm) 3 ) 1/2 Above, more preferably 8 (cal/cm) 3 ) 1/2 Above, more preferably 9 (cal/cm) 3 ) 1/2 Above, more preferably 10 (cal/cm) 3 ) 1/2 Above, more preferably 11 (cal/cm) 3 ) 1/2 The upper limit of the sp value of the component (C) is preferably less than 20 (cal/cm) 3 ) 1/2 More preferably 18 (cal/cm) 3 ) 1/2 Hereinafter, more preferably 16 (cal/cm) 3 ) 1/2 The following.
The component (C) may be added when mixed with other components, may be produced in the system after mixing, or may be produced in the system when producing the other components (a) and (B), and the components (D) and (E) described later.
< component (D) curing accelerator >
The epoxy resin composition of the present embodiment may further contain (D) a curing accelerator (hereinafter also referred to as "component (D)") for the purpose of accelerating the curing reaction. The curing accelerator (D) is not particularly limited, and examples thereof include amine compounds, imidazole compounds, boron salts of onium compounds, phosphorus compounds, lewis acids, urea derivatives, and the like. The urea derivative is not particularly limited, and examples thereof include 3- (3,4-dichlorophenyl) -1,1-dimethylurea (also known as DCMU and diuron), and 3- (4-chlorophenyl) -1,1-dimethylurea. These may be used alone or in combination of two or more.
The imidazole compound as the curing agent of the component (B) corresponds to the curing accelerator of the component (D) depending on the combination when the other curing agent of the component (B) is contained. In the present specification, the imidazole compound is used as the component (D) as the curing accelerator in the following cases.
The component (B) contains at least 1 of a guanidine compound, a hydrazide compound, an acid anhydride compound, a phenol resin, a polythiol compound, an aromatic amine, a benzoxazine and a cyanate ester, and when an imidazole compound is added, the curing effect such as shortening of the curing time, lowering of the curing temperature, and improvement of the strength of the cured product is exhibited, the imidazole compound is the component (D) curing accelerator.
When the component (B) contains 2 or more imidazole compounds, the imidazole compound which has a small contribution to the curability improvement effect such as shortening of the curing time, lowering of the curing temperature, and improvement of the strength of the cured product is used as the component (D) curing accelerator on average per portion.
As specific examples of the curing agent of the component (B) described above when an imidazole compound is used as the curing accelerator of the component (D), the compounds described in the paragraph of the above [ curing agent of the component (B) ] and the like can be used.
The imidazole compound which is combined to form the curing accelerator as the component (D) is not particularly limited, and examples thereof include 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2,4-diamino-6- [ 2-methylimidazolyl- (1) ] ethyl-s-triazine, 2-phenylimidazoline, 2,3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, novacure HX-3721, HX-3722, HX-3613, HX-3921HP, HXA9322HP (manufactured by Asahi Kasei), AER Hardner D1207, and D1301 (manufactured by Asahi Kasei).
The content of the component (D) in the epoxy resin composition is preferably 2% by mass or more, more preferably 3% by mass or more, and further preferably 4% by mass or more, from the viewpoint of exhibiting sufficient curability. From the viewpoint of exhibiting sufficient storage stability, the content of the component (D) in the epoxy resin composition is preferably 20% by mass or less, more preferably 17% by mass or less, and still more preferably 14% by mass or less.
< ingredient (E) Filler >
The epoxy resin composition of the present embodiment may contain (E) an organic filler and/or an inorganic filler (hereinafter also referred to as "component (E)") as necessary.
The organic filler is not limited to the following, and examples thereof include thermoplastic resins such as triblock copolymers, thermoplastic elastomers, carbon fibers, cellulose, polyethylene powder, and polypropylene powder. These organic fillers may be used singly or in combination of two or more.
The inorganic filler is not limited to the following, and examples thereof include fused silica, crystalline silica, alumina, talc, silicon nitride, aluminum nitride, zinc oxide (ZnO), coal tar, glass fiber, asbestos fiber, boron fiber, quartz powder, mineral silicate, mica, asbestos powder, slate powder, and the like. These inorganic fillers may be used singly or in combination of two or more.
These organic fillers and inorganic fillers have functions of modifying the viscoelasticity of the epoxy resin composition and optimizing the viscosity, storage modulus, and thixotropy, and tend to improve the fracture toughness of a cured product of the epoxy resin composition and reduce the decrease in curing shrinkage.
The content of the component (E) in the epoxy resin composition is preferably 10 mass% or more, more preferably 20 mass% or more, and still more preferably 25 mass% or more, from the viewpoint of sufficiently optimizing the thixotropy and improving fracture toughness. The content of the component (E) in the epoxy resin composition is preferably 85 mass% or less, more preferably 80 mass% or less, and still more preferably 75 mass% or less, from the viewpoint of sufficiently low viscosity and excellent handling properties.
The epoxy resin composition of the present embodiment may contain, as additives, a diluent, a reactive diluent, a pigment, a dye, a flow control agent, a thickener, a reinforcing agent, a mold release agent, a wetting agent, a flame retardant, a surfactant, resins, and the like, in addition to the above components, as required.
< method for producing epoxy resin composition >
The epoxy resin composition of the present embodiment can be obtained by mixing the component (a), the component (B), and the component (C). The method of mixing the components is not particularly limited, and conventional mixing equipment and processing conditions can be applied. The method is not particularly limited, and specific examples thereof include the following methods: the components (a) to (C), the components (D) and (E) used as needed, and other additive components are thoroughly mixed until uniform with a mixing roll such as a 3-roll mill, a dissolver, a planetary mixer, a kneader, an extruder, or the like to obtain an epoxy resin composition.
In the method for producing an epoxy resin composition according to the present embodiment, it is preferable to include a step of adding the component (C) to a compound or a composition having at least one selected from the group consisting of the component (a) and the component (B) when mixing the respective components, from the viewpoint of obtaining a uniform epoxy resin composition by improving the dispersibility of the component (C) and from the viewpoint of improving productivity by suppressing a curing reaction in the production process.
In the method for producing an epoxy resin composition according to the present embodiment, when the epoxy resin composition further contains the component (D), it is preferable to include a step of adding the component (C) to a compound or a composition having at least one selected from the group consisting of the component (a), the component (B), and the component (D) when mixing the respective components, from the viewpoint of obtaining a uniform epoxy resin composition by improving the dispersibility of the component (C) and from the viewpoint of improving productivity by suppressing a curing reaction in the production process.
In the method for producing an epoxy resin composition according to the present embodiment, when the epoxy resin composition further contains the component (E), it is preferable to include a step of adding the component (C) to a compound or a composition having at least one selected from the group consisting of the component (a), the component (B), and the component (E) when mixing the respective components, from the viewpoint of obtaining a uniform epoxy resin composition by improving the dispersibility of the component (C) and from the viewpoint of improving the productivity by suppressing the curing reaction in the production process.
Examples
The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples. The following "parts" and "%" are by mass unless otherwise specified.
(preparation of epoxy resin composition)
The components (a) to (C) and other components described later were weighed in the compounding ratios shown in table 1 below, and then stirred for 2 minutes and defoamed for 3 minutes by a non-bubbling kneader, followed by mixing to prepare an epoxy resin composition. The blending amounts of the respective components in table 1 are shown in parts by mass when the total amount of the component (a) is 100 parts by mass.
(measurement of thickening onset temperature)
A dynamic viscosity eta' -temperature curve was obtained by a rheometer (HAAKE MARS, manufactured by Thermo scientific) when the epoxy resin composition was heated from 25 ℃ to 200 ℃ in a shaking mode (f =1 Hz) at a heating rate of 5 ℃/min. In the obtained dynamic viscosity-temperature curve, the temperature T0 ℃ at which the dynamic viscosity η ' monotonically increases in the range of T0 ℃ To T0+5 ℃ and the dynamic viscosity η ' (T0 +5 ℃) at T0+5 ℃ satisfies the formula (1) as compared with the dynamic viscosity η ' (To ℃) at T0 ℃ is set as the thickening start temperature.
Eta '(T0 +5 deg.C) -eta' (T0 deg.C) is not less than 500 (mPa. S). The math figure (1)
(measurement of initial viscosity of epoxy resin composition)
The viscosity (initial viscosity) of the epoxy resin composition immediately after the preparation was measured at room temperature (25 ℃ C.) using an E-type viscometer (TVE-35H, manufactured by Toyobo industries Co., ltd.).
(gel time measurement)
The gel time of the epoxy resin composition was measured at a set temperature of 80 ℃ using a curelastometer (curelastometer V, manufactured by テイエスエンジニアリング), and a torque-vulcanization time chart was obtained. With respect to the graph obtained in the present embodiment, a point of 1N · m and a point of 0.5N · m are obtained, and the time when a straight line passing through the two points intersects with the vulcanization time axis is defined as the gel time.
(storage stability Rate)
The initial viscosity of the epoxy resin composition immediately after the preparation and the aged viscosity of the epoxy resin composition after the standing at 40 ℃ for 7 days were measured at room temperature (25 ℃) using an E-type viscometer, and the storage stability ratio was calculated by the following numerical formula (2).
Storage stability factor = aged viscosity/initial viscosity after standing at 40 ℃ for 7 days · equation (2)
The storage stability magnification is preferably 2 or less, more preferably 1.5 or less, further preferably 1.2 or less, further more preferably 1.1 or less, and particularly preferably 1.
(cured region)
The epoxy resin composition was sufficiently poured into a Teflon (registered trademark) mold having a length of 550mm, a width of 350mm and a thickness of 2mm until reaching the opening, and heated at a set temperature of 100 ℃ for 90 minutes in a heating furnace. After the heating, the volume of the cured product taken out of the mold made of teflon (registered trademark) was Vc, and the volume of the epoxy resin composition poured therein was V0, and the cured region was calculated by the following equation (3).
Curing zone (%) =100 xVc/V0. Math (3)
The following judgment was made based on the ratio (%) of the cured region.
[ Table I ]
| Cured area: 100 percent |
| Good cured area: more than 80 percent and less than 100 percent |
| Δ cured area: more than 50 percent and less than 80 percent |
| X cured area: less than 50 percent |
The larger the cured region when the epoxy resin composition is cured, the more excellent the property of ensuring a sufficient cured region when the heat conduction in the cured region is insufficient.
The components shown in table 1 are as follows.
[ (A) epoxy resin ]
Component A-1: bisphenol A type epoxy resin (Mitsubishi chemical corporation, ltd.) (epoxy equivalent 182 g/eq.)
[ (B) curing agent ]
Component B-1: dicyandiamide (Heguang pure chemical industry Co., ltd.)
Component B-2: novacure HXA9322HP (manufactured by Asahi Kasei Kabushiki Kaisha)
Component B-3: solid amine compound of Ajicure PN-H (Ajinomoto Fine-technique Co., manufactured by Inc.)
[ (C) Compound represented by the formula (1) ]
Component C-1: 3-phenoxy-1,2-propanediol (manufactured by Tokyo Kasei Kogyo Co., ltd.)
Component C-2: 3-phenoxy-1-propanol (Tokyo chemical industry Co., ltd.)
[ (D) curing Accelerator ]
Component D-1: AER Hardner D1301 (manufactured by Asahi Kasei corporation)
Component D-2:3- (3,4-dichlorophenyl) -1,1-dimethylurea (also known as DCMU or diuron) (manufactured by Tokyo Kasei Kogyo Co., ltd.)
[ other Components ]
Other components-1: glycerol (manufactured by Tokyo Kasei Kogyo)
Examples 1 to 8 and comparative examples 1 to 5
Epoxy resin compositions were prepared by the above-mentioned method by mixing the respective components in the proportions shown in tables 1-1 to 1-6. The properties of the epoxy resin composition thus prepared were measured by the methods described above. The results of measuring the thickening initiation temperature of each epoxy resin composition and the initial viscosity of each epoxy resin composition in the rheometer measurement are shown in tables 1-1 to 1-6.
[ tables 1-1]
[ tables 1-2]
[ tables 1 to 3]
[ tables 1 to 4]
[ tables 1 to 5]
[ tables 1 to 6]
When examples 1 to 3 and comparative example 1 were compared, in which the components (A) and (B) were in the same ratio, it was found that the epoxy resin compositions of examples 1 to 3 had a lower thickening onset temperature, a lower initial viscosity, a lower viscosity and improved low-temperature curability, as compared with comparative example 1 containing no component (C) (component C-1).
Further, by comparing example 4 and comparative example 2 in which the proportions of the components (A), (B) and (D) are the same, it is understood that the epoxy resin composition of example 4 has a lower thickening onset temperature, a lower initial viscosity, a lower viscosity and an improved low-temperature curability as compared with comparative example 2 containing no component (C) (component C-1).
Further, by comparing example 5 and comparative example 3 in which the proportions of the components (A) and (B) are the same, it is understood that the epoxy resin composition of example 5 has a lower thickening onset temperature, a lower initial viscosity, a lower viscosity and an improved low-temperature curability, as compared with comparative example 3 containing no component (C) (component C-1).
Further, by comparing examples 6 to 8 and comparative example 4 in which the proportions of the components (A) and (B) were the same, it was found that the epoxy resin compositions of examples 6 to 8 had a lower thickening onset temperature, a lower initial viscosity, a lower viscosity and an improved low-temperature curability, as compared with comparative example 4 containing no component (C) (component C-1 or component C-2). As another component, a "another component-1: glycerin "the initial viscosity of the epoxy resin composition of comparative example 5 in place of the component (C) was the same as the initial viscosity (13 Pa · s) of comparative example 4 which was the same except that glycerin was not contained, and it was found that there was no effect of reducing the viscosity.
Further, by comparing example 9 and comparative example 6 in which the proportions of the components (A) and (B) are the same, it is understood that the epoxy resin composition of example 9 has a lower thickening onset temperature, a lower initial viscosity, a lower viscosity and an improved low-temperature curability as compared with comparative example 6 containing no component (C) (component C-1).
Further, by comparing examples 10 and 11 and comparative example 7 in which the proportions of the components (A), (B) and (D) were the same, it was found that the epoxy resin compositions of examples 10 and 11 had a lower thickening onset temperature, a lower initial viscosity, a lower viscosity and an improved low-temperature curability, as compared with comparative example 7 containing no component (C) (component C-1).
The results of measuring the gel time of the epoxy resin compositions of example 6 and comparative example 4 are shown in table 2. It is found that the gel time (curing time) is significantly reduced in the epoxy resin composition of example 6 in which the component (C) (component C-1) is added to the epoxy resin composition of comparative example 4.
[ Table 2]
| Example 6 | Comparative example 4 | |
| Gel time | 32 minutes | Over 90 minutes |
The results of measuring the storage stability ratios of the epoxy resin compositions of examples 1 to 3 and 6 to 8 and comparative example 5 are shown in table 3.
[ Table 3]
| Example 1 | Example 2 | Example 3 | Example 6 | Example 7 | Example 8 | Comparative example 5 | |
| Storage stability ratio | 1 | 1.1 | 1.6 | 1 | More than 2 times | 1 | 1.2 |
The cured area evaluation results of the epoxy resin compositions of examples 5 and 6 and comparative examples 3 and 4 are shown in table 4. The epoxy resin compositions of examples 5 and 6 showed 100% cured areas, while the epoxy resin compositions of comparative examples 3 and 4, which did not contain component (C) (component C-1), did not show sufficient cured areas.
[ Table 4]
| Example 5 | Example 6 | Comparative example 3 | Comparative example 4 | |
| Determination of the curing zone | ◎ | ◎ | × | △ |
The present embodiment has been described above, but the present invention is not limited to this, and can be modified as appropriate within a range not departing from the gist of the invention.
Industrial applicability
According to the present invention, an epoxy resin composition which can realize a low viscosity, an improved low-temperature curability, a shortened curing time, and a sufficient cured region secured when heat conduction is insufficient can be provided.
Claims (11)
1. An epoxy resin composition comprising the following component (A), the following component (B) and the following component (C),
(A) An epoxy resin, and a curing agent,
(B) A curing agent for curing the epoxy resin composition,
(C) A compound represented by the following formula (1),
in the formula (1), R 1 ～R 9 Each is one selected from the group consisting of hydrogen, alkyl, an aromatic group, a substituent containing a hetero atom and a substituent containing a halogen atom, R 1 ～R 9 Are optionally the same or different from each other, and the compound represented by the formula (1) is optionally selected from R 5 ～R 9 Any of which are fused ring compounds in the same ring.
2. The epoxy resin composition of claim 1, wherein the ingredient (B) comprises a solid curing agent.
3. The epoxy resin composition according to claim 1 or 2,wherein R of the formula (1) 1 Is a hydroxyl group.
4. The epoxy resin composition according to any one of claims 1 to 3, wherein R of the formula (1) 2 、R 3 And R 4 Is hydrogen.
5. The epoxy resin composition according to any one of claims 1 to 4, wherein a compound containing 4 or more active hydrogens is contained as the component (B).
6. The epoxy resin composition according to any one of claims 1 to 4, wherein the component (B) contains an imidazole-based curing agent.
7. The epoxy resin composition according to any one of claims 1 to 4, wherein the component (B) comprises a microcapsule-type curing agent.
8. The epoxy resin composition according to any one of claims 1 to 7, further comprising a curing accelerator as the component (D).
9. A method for producing an epoxy resin composition comprising the following component (A), the following component (B) and the following component (C), said method comprising the steps of: adding component (C) to a compound or composition having at least one member selected from the group consisting of component (A) and component (B),
(A) An epoxy resin, and a curing agent,
(B) A curing agent for curing the epoxy resin composition,
(C) A compound represented by the following formula (1),
in the formula (1), R 1 ～R 9 Are respectively selected from hydrogen, alkyl, aromatic group and substituent containing hetero atomAnd a substituent group containing a halogen atom, R 1 ～R 9 Are optionally the same or different from each other, and the compound represented by the formula (1) is optionally selected from R 5 ～R 9 Any of which are fused ring compounds present in the same ring.
10. The method for producing an epoxy resin composition according to claim 9, wherein the epoxy resin composition further comprises the following component (D):
(D) A curing accelerator for curing the cured resin composition,
the production method comprises a step of adding a component (C) to a compound or a composition having at least one selected from the group consisting of the component (A), the component (B), and the component (D).
11. The method for producing an epoxy resin composition according to claim 9 or 10, wherein the epoxy resin composition further comprises the following component (E):
(E) A filler, wherein the filler is selected from the group consisting of,
the production method comprises a step of adding a component (C) to a compound or a composition having at least one selected from the group consisting of the component (A), the component (B), and the component (E).
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| CN202111009390.5A CN115725055A (en) | 2021-08-31 | 2021-08-31 | Epoxy resin composition |
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