Masterbatch type thermosetting resin composition and thermosetting resin composition

Abstract

Masterbatch type thermosetting resin composition and thermosetting resin composition. [Subject] To obtain an epoxy resin composition having good adhesion to various organic substrates, excellent storage stability, and excellent curing properties in a wide temperature range. [Solution] A masterbatch type thermosetting resin composition, which contains (A) an epoxy resin and (B) a curing agent, and the differential scanning calorimetry (DSC) at a heating rate of 10°C / min satisfies the following conditions (1) and (2), condition (1): the total heat release is less than 300 J / g, condition (2): the heat release start temperature is below 80°C and the heat release peak temperature is below 120°C.

Description

Technical Field

[0001] The present invention relates to a masterbatch type thermosetting resin composition and a thermosetting resin composition. Background Art

[0002] Epoxy resins and epoxy resin compositions are used in a wide range of applications, such as insulating materials, sealing materials, adhesives, and conductive materials for electronic devices and electrical and electronic parts.

[0003] In particular, as electronic devices become more functional, smaller, and thinner, there is a demand for smaller integration of semiconductor chips and higher density of circuits, as well as a demand for significant improvement in productivity, portability in mobile uses of electronic devices, and improved reliability.

[0004] As a method for curing an epoxy resin composition, a method is known in which a liquid amine-based curing agent is used as the curing agent in a so-called two-component epoxy resin composition (hereinafter sometimes referred to as a "two-component epoxy resin composition") in which the two components, an epoxy resin and a curing agent, are mixed and cured when used.

[0005] The above two-component epoxy resin composition can be cured well at low temperatures, but the epoxy resin and the curing agent need to be stored separately. In addition, the two need to be measured and then quickly and evenly mixed when used, which has the problem of complicated handling. Furthermore, once the epoxy resin and the curing agent are mixed, the usable time thereafter is limited, so there is a problem that the two cannot be mixed in large quantities in advance.

[0006] In order to solve these problems, a masterbatch type resin composition in which a latent curing agent is preliminarily mixed with an epoxy resin has been proposed to improve the mixing and handling.

[0007] However, the masterbatch type thermosetting resin composition has a problem in that it tends to be difficult to achieve both storage stability and curability (particularly curability at low temperatures).

[0008] In view of this situation, a so-called microcapsule-type curing agent having a highly reactive imidazole as a core and covered with a specific shell (see, for example, Patent Document 1) and a masterbatch-type thermosetting resin composition having an adduct encapsulated therein (see, for example, Patent Documents 2 and 3) have been proposed.

[0009] Patent Documents 1 to 3 all describe masterbatch-type thermosetting resin compositions having improved storage stability and low-temperature curability.

[0010] Prior art literature

[0011] Patent Literature

[0012] Patent Document 1: Japanese Patent Application Publication No. 2011-208098

[0013] Patent Document 2: Japanese Patent Application Publication No. 2013-95876

[0014] Patent Document 3: Japanese Patent Application Publication No. 2014-152236 Summary of the invention

[0015] Problem that the invention aims to solve

[0016] However, the masterbatch type thermosetting resin compositions disclosed in Patent Documents 1 to 3 attempt to improve low-temperature curing properties, but have a problem of being unsuitable for use in organic substrates that have begun to be used in large quantities in electronic components in recent years.

[0017] Therefore, an object of the present invention is to provide a masterbatch type thermosetting resin composition having good adhesion to an organic substrate, excellent storage stability, and excellent curability in a wide temperature range.

[0018] Solutions for solving problems

[0019] The present inventors have conducted intensive studies to solve the above-mentioned problems of the prior art and have found that an epoxy resin composition satisfying prescribed physical properties in differential scanning calorimetry (DSC) can solve the above-mentioned problems, thereby completing the present invention.

[0020] That is, the present invention is as follows.

[0021] [1] A masterbatch type thermosetting resin composition comprising (A) an epoxy resin and (B) a curing agent,

[0022] Differential scanning calorimetry (DSC) at a heating rate of 10°C / min satisfies the following conditions (1) and (2),

[0023] Condition (1): Total heat release is less than 300 J / g,

[0024] Condition (2): The exothermic start temperature is 80°C or lower, and the exothermic peak temperature is 120°C or lower.

[0025] [2] The masterbatch type thermosetting resin composition according to [1], wherein the epoxy resin (A) is present in an amount of 30 to 90 parts by mass based on 100 parts by mass of the total of the epoxy resin (A) and the curing agent (B).

[0026] [3] The masterbatch type thermosetting resin composition according to [1] or [2], wherein the curing agent (B) contains a solid amine curing agent.

[0027] [4] The masterbatch type thermosetting resin composition according to any one of [1] to [3] above, wherein the (B) curing agent contains an adduct type epoxy resin curing agent.

[0028] [5] The masterbatch type thermosetting resin composition according to any one of [1] to [4], wherein the circularity of the curing agent (B) is 0.9 or more.

[0029] [6] The masterbatch type thermosetting resin composition according to any one of [1] to [5], wherein the (B) curing agent is a capsule type curing agent.

[0030] [7] The masterbatch type thermosetting resin composition according to any one of [1] to [6], wherein, in a measurement at a temperature increase rate of 1°C / min using a viscoelasticity device,

[0031] The viscosity at 30°C is defined as P30.

[0032] The viscosity at 45°C is defined as P45.

[0033] The viscosity at 50°C is defined as P50.

[0034] When the viscosity at 65°C is defined as P65,

[0035] Satisfying the following (Formula 1) and (Formula 2),

[0036] (Formula 1) P30 ≥ 3 × P50

[0037] (Formula 2) P65≥3×P45.

[0038] [8] A thermosetting resin composition comprising the masterbatch type thermosetting resin composition according to any one of [1] to [7] above and (C) an epoxy resin.

[0039] [9] The thermosetting resin composition according to [8], further comprising a (D) curing agent other than the (B) curing agent.

[0040]

[10] The thermosetting resin composition according to [8] or [9], further comprising (E) an additive.

[0041] Effects of the Invention

[0042] According to the present invention, an epoxy resin composition can be obtained which has good adhesion to various organic substrates, is excellent in storage stability, and is also excellent in curing properties in a wide temperature range. DETAILED DESCRIPTION

[0043] Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “this embodiment”) will be described in detail.

[0044] The present embodiment is an example for explaining the present invention, and the present invention is not limited to the following contents. The present invention can be implemented with various modifications within the scope of the gist of the present invention.

[0045] [Masterbatch type thermosetting resin composition]

[0046] The masterbatch type thermosetting resin composition according to the present embodiment will be described below.

[0047] The masterbatch type thermosetting resin composition contains a resin and a curing agent component thereof, and is formed by pre-dispersing the curing agent component in the resin. By adopting this method, the mixing time can be saved, and other components can be mixed evenly, etc., which can contribute to the improvement of working efficiency.

[0048] The masterbatch type thermosetting resin composition of the present embodiment contains (A) epoxy resin (hereinafter sometimes referred to as component (A)) and (B) curing agent (hereinafter sometimes referred to as component (B)), and differential scanning calorimetry (DSC) at a heating rate of 10°C / min satisfies the following conditions (1) and (2).

[0049] Condition (1): Total heat release is less than 300 J / g

[0050] Condition (2): Exothermic start temperature is 80°C or less, exothermic peak temperature is 120°C or less

[0051] The masterbatch type thermosetting resin composition of the present embodiment has excellent adhesion to various organic substrates. Therefore, the thermosetting resin composition using the masterbatch type thermosetting resin composition of the present embodiment can be suitably used as a one-component thermosetting adhesive for mounting camera components such as mobile phones, smart phones, tablet terminals, driving recorders, and car cameras. In addition, it can also be used as an adhesive or liquid sealant for various electronic components.

[0052] The masterbatch type thermosetting resin composition of the present embodiment contains (A) an epoxy resin and (B) a curing agent.

[0053] ((A) Epoxy resin)

[0054] (A) The epoxy resin is not particularly limited, and various known epoxy resins can be appropriately selected and used.

[0055] (A) Epoxy resins include, but are not limited to, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol AD ​​epoxy resins, tetrabromobisphenol A epoxy resins, biphenyl epoxy resins, tetramethylbiphenyl epoxy resins, tetrabromobiphenyl epoxy resins, diphenyl ether epoxy resins, benzophenone epoxy resins, phenyl benzoate epoxy resins, diphenyl sulfide epoxy resins, diphenyl sulfoxide epoxy resins, diphenyl sulfone epoxy resins, diphenyl disulfide epoxy resins, naphthalene epoxy resins, anthracene epoxy resins, hydroquinone epoxy resins, methylhydroquinone epoxy resins, dibutylhydroquinone epoxy resins, resorcinol epoxy resins, methylresorcinol epoxy resins. Resin, catechol type epoxy resin, N, N-diglycidyl aniline type epoxy resin and other difunctional epoxy resins; N, N-diglycidyl aminobenzene type epoxy resin, o-(N, N-diglycidyl amino) toluene type epoxy resin, triazine type epoxy resin and other trifunctional epoxy resins; tetraglycidyl diaminodiphenylmethane type epoxy resin, diaminobenzene type epoxy resin and other quadrifunctional epoxy resins; 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, brominated phenol novolac type epoxy resin and other multifunctional epoxy resins;2-ethylhexyl glycidyl ether, cyclohexanedimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, hydrogenated bisphenol A type epoxy resin, silicone modified epoxy resin, (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerol Oil diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane type diglycidyl ether, dicyclopentadiene type diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, vinyl (3,4-cyclohexene) dioxide, 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane, tetraglycidyl bis (aminomethyl) cyclohexane and other glycidylamine type epoxy resins, 1,3 -Diglycidyl-5-methyl-5-ethylhydantoin epoxy resin, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane epoxy resin, phenyl glycidyl ether, cresyl glycidyl ether, p-isobutylphenyl glycidyl ether, styrene oxide, p-tert-butylphenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, N-glycidyl phthalimide, n-butyl Aliphatic epoxy resins and alicyclic epoxy resins that can also be used as reactive diluents include 1-vinyl-3,4-epoxycyclohexane, 1,2-epoxy-4-(2-methyl-oxiranyl)-1-methylcyclohexane, 1,3-bis(3-glycidyloxypropyl)-1,1,3,3-tetramethyldisiloxane, and neodecanoic acid glycidyl ester. ;

[0056] These can be used individually by 1 type or in combination of 2 or more types.

[0057] ((B) Curing agent)

[0058] (B) The curing agent is not particularly limited as long as the effects of the present invention can be exhibited, and examples thereof include amine curing agents, amide curing agents, acid anhydride curing agents, phenol curing agents, latent curing agents, and catalyst-type curing agents.

[0059] These can be used individually by 1 type or in combination of 2 or more types.

[0060] (Condition (1))

[0061] The masterbatch type thermosetting resin composition of the present embodiment has a total heat release value of less than 300 J / g as measured by differential scanning calorimetry (DSC) at a temperature increase rate of 10° C. / min.

[0062] The total heat release obtained by DSC measurement is less than 300 J / g, which means that there is no large temperature rise during curing. When the masterbatch type thermosetting resin composition of this embodiment is used for bonding to an organic substrate, the temperature will not exceed the melting point of the organic substrate, which can protect the organic substrate and obtain the effect that the strain energy during curing will not increase.

[0063] The total heat release is preferably less than 290 J / g, more preferably less than 280 J / g.

[0064] Examples of methods for making the total heat release obtained by DSC less than 300 J / g include methods such as reducing the number of functional groups by adducting part of the curing agent, using a resin with a large epoxy equivalent, or modifying part of the epoxy resin with allyl groups or the like.

[0065] The masterbatch type thermosetting resin composition according to the present embodiment has an exothermic start temperature of 80° C. or less in differential scanning calorimetry (DSC) measured at a temperature increase rate of 10° C. / min.

[0066] When the exothermic start temperature is 80° C. or lower, it is possible to obtain an effect that curing can be performed at a sufficiently low temperature for practical use.

[0067] The exothermic onset temperature is preferably 78°C or lower, more preferably 75°C or lower.

[0068] The exothermic start temperature of the masterbatch type thermosetting resin composition under the above conditions can be controlled within the above temperature range by adjusting the type of curing agent, accelerator, stabilizer, their concentrations, and mixing conditions.

[0069] The masterbatch type thermosetting resin composition according to the present embodiment has an exothermic peak temperature of 120° C. or less in differential scanning calorimetry (DSC) measured at a temperature increase rate of 10° C. / min.

[0070] When the exothermic peak temperature is 120° C. or lower, the curing rate at low temperatures is improved.

[0071] The exothermic peak temperature is preferably 115°C or lower, more preferably 110°C or lower.

[0072] The exothermic peak temperature of the masterbatch type thermosetting resin composition under the above conditions can be controlled within the above temperature range by adjusting the type of curing agent, the type of accelerator, the type of stabilizer, their concentrations, and the mixing conditions.

[0073] The adhesive using the masterbatch type thermosetting resin composition of the present embodiment has sufficient adhesion to the organic substrate. Although the mechanism is not intended to be limited to the following, it is considered to be as follows.

[0074] It is believed that since the exothermic start temperature is below 80°C, the reaction can proceed from low temperature, and since the exothermic peak temperature is below 120°C, the curing reaction proceeds even at low temperatures, and the physical properties of the cured product are improved. Since the total heat release in the masterbatch is less than 300 J / g, the strain energy is small and no excess stress is applied to the interface between the cured product and the organic substrate, and the affinity works.

[0075] Therefore, the thermosetting resin composition using the masterbatch type thermosetting resin composition of the present embodiment that satisfies the above-mentioned conditions (1) and (2) can express sufficient adhesion to an organic substrate.

[0076] ((A) Epoxy resin content)

[0077] In the masterbatch type thermosetting resin composition of the present embodiment, the component (A) is preferably contained in an amount of 30 to 90 parts by mass based on 100 parts by mass of the total of the components (A) and (B).

[0078] The amount is more preferably 35 to 75 parts by mass, and still more preferably 40 to 60 parts by mass.

[0079] When the content of the component (A) is 30 parts by mass or more, the curing agent component can be uniformly dispersed, and thus the performance as a masterbatch can be easily exhibited.

[0080] Moreover, since the content of the component (A) is 90 parts by mass or less, a large amount of other epoxy resins can be added, and the practicality is excellent.

[0081] (Solid amine curing agent)

[0082] In the masterbatch type thermosetting resin composition of the present embodiment, it is preferred that the (B) curing agent contains a solid amine-based curing agent.

[0083] The (B) curing agent may be liquid or solid at room temperature, but a solid amine curing agent is preferably used because the stability at room temperature is improved, the reactivity with the (A) epoxy resin is improved, and when used in combination with other curing agents, a curing catalyst can be formed.

[0084] (Adduct type epoxy resin curing agent)

[0085] In the masterbatch type thermosetting resin composition of the present embodiment, it is preferred that the (B) curing agent contains an adduct type epoxy resin curing agent.

[0086] When the curing agent (B) contains an adduct-type epoxy resin curing agent, the dispersion in the epoxy resin becomes good and the curing property improves.

[0087] ((B) Circularity of curing agent)

[0088] From the viewpoints of particle aggregation, moisture resistance, and permeability, the masterbatch type thermosetting resin composition of the present embodiment preferably has a circularity of the curing agent component (B) of 0.9 or more, more preferably 0.92 or more, and even more preferably 0.94 or more.

[0089] When the circularity of the (B) curing agent is within the above range, the solvent resistance and moisture resistance after encapsulation tend to be good.

[0090] Here, the circularity can be measured by the method described in the examples described later, and the closer the circularity is to 1, the closer it is to a true sphere.

[0091] The method for controlling the circularity within the above range is not particularly limited, but surface modification of the (B) curing agent is effective, for example, mechanically rounding the particles or performing a hot air treatment.

[0092] (Capsule type curing agent)

[0093] In the masterbatch type thermosetting resin composition of the present embodiment, it is preferred that the (B) curing agent is an encapsulated capsule type curing agent.

[0094] By encapsulating the (B) curing agent, the curing agent can be physically isolated, thereby improving stability.

[0095] The (B) curing agent to be encapsulated is not limited to the following, and examples thereof include epoxy-based, acrylic-based, latex-based, urethane-based, and silica-based curing agents.

[0096] The method for encapsulating the (B) curing agent is not limited to the following, and examples thereof include the following methods (1) to (3).

[0097] (1): After dissolving and dispersing particles of a capsule component and a curing agent in a solvent as a dispersion medium, the solubility of the capsule component in the dispersion medium is reduced to thereby precipitate capsules on the surface of particles of the curing agent for the epoxy resin.

[0098] (2): A method in which particles of a curing agent are dispersed in a dispersion medium, and the capsule-forming material is added to the dispersion medium to precipitate on the particles of the curing agent.

[0099] (3) A method in which the raw material components for forming capsules are added to a dispersion medium and the surface of the particles of the curing agent is used as a reaction site to generate a shell-forming material there.

[0100] Here, the methods (2) and (3) described above are preferred because they allow the reaction and the covering to proceed simultaneously.

[0101] After forming capsules by the methods of (2) and (3), the method for separating the capsule-type curing agent from the dispersion medium is not particularly limited, but it is preferred to separate / remove the unreacted raw materials and the dispersion medium after the capsules are formed. As such a method, a method of removing the dispersion medium and the unreacted capsule forming material by filtration can be cited.

[0102] After the dispersion medium is removed, the capsule-type curing agent is preferably washed, thereby removing unreacted capsule-forming material adhering to the surface of the capsule-type curing agent.

[0103] The washing method is not particularly limited, and when the residue is separated by filtration, washing can be performed using a dispersion medium or a solvent that does not dissolve the capsule-type curing agent.

[0104] After filtering and washing, the capsule-type curing agent is dried to obtain a powdered microcapsule-type curing agent. The drying method is not particularly limited, but it is preferably dried at a temperature below the melting point or softening point of the curing agent, and examples thereof include reduced pressure drying.

[0105] By making the encapsulated curing agent into powder, it can be easily applied to the mixing operation with epoxy resin. In addition, if epoxy resin is used as a dispersion medium, a liquid resin composition containing epoxy resin and microcapsule type epoxy resin curing agent can be obtained while forming capsules, so it is preferred.

[0106] The capsule forming reaction is usually carried out in a temperature range of -10°C to 150°C, preferably 0°C to 100°C, for a reaction time of 10 minutes to 72 hours, preferably 30 minutes to 24 hours.

[0107] (Viscosity at a predetermined temperature measured at a predetermined heating rate using a viscoelasticity device)

[0108] The masterbatch type thermosetting resin composition of the present embodiment preferably satisfies the following two equations when the viscosity at 30°C is set to P30, the viscosity at 45°C is set to P45, the viscosity at 50°C is set to P50, and the viscosity at 65°C is set to P65 in the measurement of a temperature increase of 1°C / min using a viscoelasticity device.

[0109] (Formula 1) P30 ≥ 3 × P50

[0110] (Formula 2) P65≥3×P45.

[0111] By satisfying the above (Formula 1) and (Formula 2), it is possible to achieve curing inhibition at low temperatures, and to perform curing at an earlier stage, making it less likely to produce a rapid reaction at high temperatures, thereby reducing internal stress. It is also possible to inhibit the dissolution of adherends, such as liquid crystal polymers, due to the heat of curing, thereby helping to improve adhesion.

[0112] In order to satisfy the above (Formula 1) and (Formula 2), the type of curing agent and the method of treating the curing agent, for example, the method of improving circularity or performing encapsulation as described above, are effective.

[0113] [Thermosetting resin composition]

[0114] The thermosetting resin composition of the present embodiment contains the masterbatch type thermosetting resin composition of the present embodiment described above and (C) an epoxy resin.

[0115] The epoxy resin that can be used may be used alone or in combination of two or more epoxy resins similar to the above-mentioned component (A).

[0116] ((D): Curing agent other than the aforementioned (B) curing agent)

[0117] The thermosetting resin composition of the present embodiment may contain a curing agent other than the component (B) as the component (D).

[0118] The component (D) which is a curing agent other than the component (B) is not particularly limited, and various known curing agents can be appropriately selected for use. However, from the viewpoint of the reaction rate during curing, it is preferably at least one selected from the group consisting of thiol compounds, guanidine derivatives, aromatic amine compounds and novolac-type phenolic resins.

[0119] These can be used individually by 1 type or in combination of 2 or more types.

[0120] The thiol compound may contain two or more thiol groups in one molecule, but is not limited to the following, and examples thereof include 3,3'-dithiodipropionic acid, trimethylolpropane tris(thioglycolate), pentaerythritol tetra(thioglycolate), ethylene glycol dithioglycolate, 1,4-bis(3-mercaptobutyryloxy)butane, tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, 1,3,5-tris(3-mercaptopropionyloxy)-ethyl]-isocyanurate, butyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexa(3-mercaptopropionate), 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, 4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, etc.

[0121] These can be used individually by 1 type or in combination of 2 or more types.

[0122] From the viewpoint of impact resistance, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, pentaerythritoltetrakis(3-mercaptopropionate) and pentaerythritoltetrakis(3-mercaptobutyrate) are preferred. From the viewpoint of low-temperature curability, pentaerythritoltetrakis(3-mercaptopropionate) and pentaerythritoltetrakis(3-mercaptobutyrate) are more preferred.

[0123] Examples of guanidine derivatives include, but are not limited to, dicyandiamide, dicyandiamide-aniline adducts, dicyandiamide-methylaniline adducts, dicyandiamide-diaminodiphenylmethane adducts, dicyandiamide-diaminodiphenyl ether adducts and other dicyandiamide derivatives; guanidine salts such as guanidine nitrate, guanidine carbonate, guanidine phosphate, guanidine sulfamate, and aminoguanidine bicarbonate; acetylguanidine, diacetylguanidine, propionylguanidine, dipropionylguanidine, cyanoacetylguanidine, guanidine succinate, diethylcyanoacetylguanidine, guanyl urea, N-oxymethyl-N'-cyanoguanidine, and N,N'-dicarbonylethoxyguanidine.

[0124] Examples of the aromatic amine compound include, but are not limited to, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenylmethane, and 4,4′-diaminodiphenyl ether.

[0125] Examples of the novolac-type phenolic resin include, but are not limited to, phenol novolac, bisphenol A novolac, cresol novolac, and naphthol novolac.

[0126] ((E) Additives)

[0127] The thermosetting resin composition of the present embodiment may further contain (E) an additive.

[0128] The component (E) is not limited to the following, and examples thereof include organic fillers, inorganic fillers, diluents, pigments, dyes, flow regulators, thickeners, reinforcing agents, release agents, wetting agents, flame retardants, surfactants, organic solvents, conductive fine particles, crystalline alcohols, resins, etc., and these may be used alone or in combination of two or more.

[0129] Examples of the organic filler include, but are not limited to, one organic filler selected from the group consisting of thermoplastic resins such as triblock copolymers, thermoplastic elastomers, carbon fibers, cellulose, polyethylene powders, and polypropylene powders.

[0130] Examples of the inorganic filler include, but are not limited to, fused silica, crystalline silica, alumina, talc, silicon nitride, aluminum nitride, coal tar, glass fiber, asbestos fiber, boron fiber, quartz powder, mineral silicate, mica, asbestos powder, and slate powder.

[0131] The diluent is not limited to the following, and for example, a reactive diluent or a non-reactive diluent can be used.

[0132] Examples of the reactive diluent include, but are not limited to, cresol, ethylphenol, propylphenol, p-butylphenol, p-pentylphenol, hexylphenol, octylphenol, nonylphenol, dodecylphenol, octadecylphenol, and terpenephenol.

[0133] The non-reactive diluent is not particularly limited, and examples thereof include dioctyl phthalate, dibutyl phthalate, benzyl alcohol, and the like.

[0134] Examples of the pigment include, but are not limited to, kaolin, alumina trihydrate, aluminum hydroxide, chalk powder, gypsum, calcium carbonate, antimony trioxide, Penton, silica, aerosol, lithopone, barite, and titanium dioxide.

[0135] Examples of the dye include, but are not limited to, plant-derived dyes such as madder root and indigo, mineral-derived dyes such as yellow earth and ochre, natural dyes, synthetic dyes such as alizarin and indigo, and fluorescent dyes.

[0136] Examples of the flow control agent include, but are not limited to, silane coupling agents; organic titanium compounds such as tetraisopropoxytitanium and diisopropoxybis(acetylacetonate)titanium; and organic zirconium compounds such as tetra-n-butoxyzirconium and tetraacetylacetonate zirconium.

[0137] Examples of thickeners include, but are not limited to, animal thickeners such as gelatin; plant thickeners such as polysaccharides and cellulose; and chemically synthesized thickeners such as polyacrylic acid, modified polyacrylic acid, polyether, urethane-modified polyether, and carboxymethyl cellulose.

[0138] Examples of the reinforcing agent include, but are not limited to, polyethylene sulfone powder such as "SUMIKA EXCELPES" manufactured by Sumitomo Chemical Co., Ltd., nano-sized functional group-modified core-shell rubber particles such as "Kane Ace MX" manufactured by Kaneka Corporation, and silicone-based reinforcing agents such as polyorganosiloxane.

[0139] Examples of the release agent include, but are not limited to, fluorine-based release agents, silicone-based release agents, and acrylic release agents containing a copolymer of glycidyl (meth)acrylate and a C16-22 linear alkyl (meth)acrylate.

[0140] Examples of the wetting agent include, but are not limited to, unsaturated polyester copolymer-based wetting agents having an acidic group such as acrylic acid polyphosphate.

[0141] Examples of the flame retardant include, but are not limited to, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, halogen flame retardants such as chlorine compounds and bromine compounds, phosphorus flame retardants such as condensed phosphate esters, antimony flame retardants such as antimony trioxide and antimony pentoxide, and inorganic oxides such as silica fillers.

[0142] Examples of surfactants include, but are not limited to, anionic surfactants such as alkylbenzene sulfonates and alkyl polyoxyethylene sulfates, cationic surfactants such as alkyl dimethyl ammonium salts, amphoteric surfactants such as alkyl dimethyl amine oxides and alkyl carboxy betaines, and nonionic surfactants such as linear alcohols having 25 or more carbon atoms and fatty acid esters.

[0143] Examples of the organic solvent include, but are not limited to, toluene, xylene, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), ethyl acetate, and butyl acetate.

[0144] The conductive fine particles are not limited to the following, and examples thereof include carbon black, graphite, carbon nanotubes, fullerenes, iron oxides, gold, silver, aluminum powder, iron powder, nickel, copper, zinc, chromium, solder, nano-sized metal crystals, and intermetallic compounds.

[0145] Examples of the crystalline alcohol include, but are not limited to, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, pentaerythritol, sorbitol, sucrose, and trimethylolpropane.

[0146] Examples of the resins include, but are not limited to, polyester resins, polyurethane resins, acrylic resins, polyether resins, melamine resins, urethane-modified epoxy resins, rubber-modified epoxy resins, alkyd-modified epoxy resins and other modified epoxy resins.

[0147] The above-mentioned (E) additives may be added in an amount equivalent in function. For example, a pigment and / or a dye may be added in an amount capable of adding a desired color to the epoxy resin composition of the present embodiment.

[0148] (use)

[0149] The thermosetting resin composition of this embodiment and the cured product obtained therefrom can be used for various purposes where epoxy resin is used as a material. In particular, it is particularly useful as a one-component thermosetting adhesive for mounting camera components. In addition, it is also suitable for electronic equipment chassis adhesives, bottom filling glue, semiconductor sealing materials such as molding, conductive adhesives such as anisotropic conductive films (ACF), solder resists, protective films (coverlay films) and other printed wiring substrates, but is not limited to them.

[0150] Example

[0151] The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0152] The methods for measuring the physical properties and characteristics used in Examples and Comparative Examples are shown below.

[0153] [Masterbatch type thermosetting resin composition, and physical property measurement of thermosetting resin composition]

[0154] ((1) Differential Scanning Calorimetry (DSC Measurement))

[0155] The masterbatch type thermosetting resin composition was heated from 25°C to 250°C at a heating rate of 10°C / min using EXSTER7020 (manufactured by Hitachi High-Tech Science Corporation), and the exothermic start temperature, exothermic peak temperature and total heat release were measured from the observed DSC curve.

[0156] ((2) Rheometer measurement using a viscoelastic device)

[0157] The masterbatch type thermosetting resin composition was heated from 20°C to 100°C at 1°C / min in an oscillation mode of 1 Hz using HAAKE MARS I (manufactured by Thermo Fisher Scientific). From the observed dynamic viscosity curve, the viscosities at 30°C, 45°C, 50°C, and 65°C were determined and designated as P30, P45, P50, and P65, respectively.

[0158] ((3) Circularity)

[0159] The circularity of the curing agent (B) was determined by measuring the dispersion obtained by dispersing various curing agents obtained in the manufacturing process in cyclohexane at 0.5 mass % using a flow particle image analyzer FPIA-3000S (manufactured by Spectris Co., Ltd.). The encapsulated curing agent was regarded as a uniformly encapsulated curing agent, and the circularity of the curing agent was used directly.

[0160] ((4) Measurement of tensile shear bond strength of thermosetting resin composition using liquid crystal polymer as counterpart material)

[0161] The tensile shear adhesive strength of the thermosetting resin compositions of Examples 6 to 17 and Comparative Examples 5 to 12 when cured under the conditions described below was measured in accordance with JIS K6850.

[0162] SUMIKA SUPER E6007LHF (manufactured by Sumitomo Chemical Co., Ltd.) was used as the counterpart material, and the test was carried out with n=5. The average value was calculated and made into the tensile shear bond strength.

[0163] The difference between the maximum and minimum values ​​among the five samples and the average value by more than 1.2 times was considered as a large deviation and was marked as ×; the difference between 1.1 times and less than 1.2 times was considered as △; and the difference between less than 1.1 times was considered as a small deviation and was marked as 0.

[0164] ((5) Stability evaluation)

[0165] The thermosetting resin compositions of Examples 6 to 17 and Comparative Examples 5 to 12 were measured for their initial viscosity using an E-type viscometer and their viscosity after storage at 40° C. for 3 days.

[0166] The viscosity after storage was 2 times or more compared with the initial viscosity, and was marked as ×; the viscosity after storage was 1.5 times or more and less than 2.0 times, and was marked as △; the viscosity after storage was less than 1.5 times, and was marked as ○.

[0167] [Example 1]

[0168] 110 g of 2-ethyl 4-methylimidazole (manufactured by Shikoku Chemical: trade name "2E4MZ") was dissolved in a solution of 100 g of toluene, and after heating to 100°C, 360 g of a 50 mass % toluene solution of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation: trade name "jER828US") was added to carry out a reaction.

[0169] Next, the reaction liquid was heated and decompressed, and toluene was distilled off from the reaction liquid to obtain 273 g of epoxy resin curing agent AD1-1.

[0170] The epoxy resin curing agent AD1-1 obtained was pulverized twice at a pulverizing pressure of 0.5 MPa·s using a jet mill (manufactured by NISSHIN ENGINEERING INC., “CJ25 model”), and then classified using an air classifier (manufactured by NISSHIN ENGINEERING INC., “Turbo classifier”) to remove coarse particles, thereby obtaining an epoxy resin curing agent AD1-2.

[0171] The average particle size of the obtained epoxy resin curing agent AD1-2 was 2.5 μm.

[0172] KRYPTRON ORB manufactured by Earth Technica Co., Ltd. was used as the epoxy resin curing agent AD1-2. The curing agent was heated at a temperature of 10°C and a humidity of 30% at a rotation speed of 13500 rpm, a supply rate of 10 kg / hr, and an air volume of 3 m 3 / minute, and shape correction treatment was performed to obtain epoxy resin curing agent AD1-3.

[0173] Next, 70 g of the obtained epoxy resin curing agent AD1-3 was added to 140 g of methylcyclohexane, and after being dispersed in the methylcyclohexane, 25.2 g of isophorone diisocyanate and 6.0 g of a bisphenol A type epoxy resin (manufactured by Asahi Kasei Corporation, "AER2603", epoxy equivalent 189, total chlorine content 1800 ppm, hydrolyzable chlorine content 50 ppm) were added as an epoxy resin, and the mixture was reacted at 50° C. for 4 hours.

[0174] After the reaction was completed, the mixture was filtered, washed and dried to obtain epoxy resin curing agent A-1.

[0175] For epoxy resin curing agent A-1, the specific surface area value is 2.02m 2 / g, the moisture content was 0.6%, D50 was 2.4 μm, D99 / D50 was 4.5, and the circularity was 0.93.

[0176] 100 g of the epoxy resin curing agent A-1 was dispersed in 100 g of a liquid epoxy resin (manufactured by Asahi Kasei Corporation: product name "AER260") using a stirrer to obtain a masterbatch type thermosetting resin composition B-1.

[0177] The masterbatch type thermosetting resin composition B-1 was subjected to DSC measurement and rheometer measurement. As a result, the exothermic start temperature was 74° C., the exothermic peak temperature was 115° C., and the total heat release was 270 J / g.

[0178] In addition, regarding the viscosity at each temperature in the measurement using the viscoelasticity device, P30 was 560 Pa·s, P50 was 160 Pa·s, P45 was 183 Pa·s, and P65 was 210 Pa·s.

[0179] [Example 2]

[0180] 70 g of diethylenetriamine (manufactured by TOSOH CORPORATION) was dissolved in 100 g of toluene solution, and after heating to 70°C, 360 g of a 50 mass % toluene solution of bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation: trade name "jER828US") was added to carry out a reaction.

[0181] The reaction liquid was then heated and decompressed to distill off toluene and unreacted diethylenetriamine from the reaction liquid, and 60 g of epoxy resin curing agent AD1-1 prepared in Example 1 was added and melt-mixed to obtain 250 g of epoxy resin curing agent AD2-1.

[0182] The epoxy resin curing agent AD2-1 obtained was pulverized twice at a pulverizing pressure of 0.8 MPa·s using an air jet mill (manufactured by NISSHIN ENGINEERING INC., “CJ25 model”), and then classified using an air classifier (manufactured by NISSHIN ENGINEERING INC., “Turbo classifier”) to remove coarse particles, thereby obtaining an epoxy resin curing agent AD2-2.

[0183] The average particle size of the obtained epoxy resin curing agent AD2-2 was 3.0 μm.

[0184] KRYPTRON ORB manufactured by Earth Technica Co., Ltd. was used as the epoxy resin curing agent AD2-2. The temperature was 10°C and the humidity was 30%. The rotation speed was 8000 rpm, the supply speed was 5 kg / hr, and the air volume was 3 m 3 / min, and shape correction treatment was performed to obtain a specific surface area value of 2.55m 2 / g, a moisture content of 0.8%, a D50 of 3.0 μm, a D99 / D50 of 3.6, and a circularity of 0.91.

[0185] To 120 parts by mass of a liquid epoxy resin (Asahi Kasei Corporation: product name "AER2502"), 80 parts by mass of the epoxy resin curing agent AD2-2 and 5 parts by mass of an encapsulating agent (TOSOH CORPORATION: "MR400") were added, and the mixture was allowed to react for 3 hours at 50°C while stirring to obtain a masterbatch type thermosetting resin composition B-2.

[0186] The masterbatch type thermosetting resin composition B-2 was subjected to DSC measurement and rheometer measurement. As a result, the exothermic start temperature was 65° C., the exothermic peak temperature was 105° C., and the total heat release was 290 J / g.

[0187] In addition, regarding the viscosity at each temperature in the measurement using the viscoelasticity device, P30 was 200 Pa·s, P50 was 60 Pa·s, P45 was 87 Pa·s, and P65 was 310 Pa·s.

[0188] [Example 3]

[0189] 200 g of the epoxy resin curing agent AD2-1 prepared in Example 2 was dissolved at 150° C., and 40 g of triethylenediamine (manufactured by TOSOH CORPORATION: trade name “TEDA”) was added and melt-mixed to obtain 238 g of epoxy resin curing agent AD3-1.

[0190] The epoxy resin curing agent AD3-1 obtained was pulverized twice at a pulverizing pressure of 0.3 MPa·s using an air jet mill (manufactured by NISSHIN ENGINEERING INC., "CJ25 model"), and then classified using an air classifier (manufactured by NISSHIN ENGINEERING INC., "Turbo classifier") to remove coarse particles, thereby obtaining an epoxy resin curing agent AD3-2. The obtained epoxy resin curing agent AD3-2 had an average particle size of 4.5 μm.

[0191] The epoxy resin curing agent AD3-2 was heat treated using Meteorainbow-MR-10 manufactured by Nippon Pneumatic Mfg. Co., Ltd. at a feed rate of 2.0 kg / hr and a treatment temperature of 275° C. A cyclone collector and a bag filter were attached. 0° C. circulating cooling water was circulated on the wall of the powder recovery section to cool the container to below 40° C. Air with a temperature of 25° C. and a humidity of 10% was introduced as cooling air after hot air treatment at 275° C., and a classifier was used to perform classification operation, thereby obtaining a specific surface area value of 1.0 m 2 / g, a moisture content of 0.6%, a D50 of 5.0 μm, a D99 / D50 of 2.5, and a circularity of 0.97.

[0192] 110 g of the aforementioned epoxy resin curing agent AD3-3 and 3 g of an encapsulating agent (TOSOH CORPORATION: "Coronate 1391") were added to 90 g of a liquid epoxy resin (DIC Corporation product name "EXA850CRP"), and the mixture was allowed to react for 3 hours at 50°C while stirring to obtain a masterbatch type thermosetting resin composition B-3.

[0193] The masterbatch type thermosetting resin composition B-3 was subjected to DSC measurement and rheometer measurement. As a result, the exothermic start temperature was 55° C., the exothermic peak temperature was 100° C., and the total heat release was 250 J / g.

[0194] In addition, regarding the viscosity at each temperature in the measurement using the viscoelasticity device, P30 was 382 Pa·s, P50 was 24 Pa·s, P45 was 40 Pa·s, and P65 was 10320 Pa·s.

[0195] [Example 4]

[0196] 100 g of N,N-dimethylaminopropylamine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 100 g of toluene solution, and after heating to 70° C., 300 g of a 50 mass % toluene solution of bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation: trade name “jER1001”) was added to react.

[0197] Next, the reaction liquid was heated and decompressed to distill off toluene and unreacted N,N-dimethylaminopropylamine from the reaction liquid, and 100 g of epoxy resin curing agent AD1-1 prepared in Example 1 was added and melt-mixed to obtain 280 g of epoxy resin curing agent AD4-1.

[0198] The obtained epoxy resin curing agent AD4-1 was pulverized twice at a pulverizing pressure of 0.8 MPa·s using an air jet mill (manufactured by NISSHIN ENGINEERING INC., "CJ25 model"), and then classified by an air classifier (manufactured by NISSHIN ENGINEERING INC., "Turbo classifier") to remove coarse particles, and the obtained finely pulverized product was used as epoxy resin curing agent AD4-2. The average particle size of the obtained epoxy resin curing agent AD4-2 was 3.3 μm.

[0199] KRYPTRON ORB manufactured by Earth Technica Co., Ltd. was used as the epoxy resin curing agent AD4-2. The temperature was 10°C and the humidity was 30%. The rotation speed was 12000 rpm, the supply speed was 8 kg / hr, and the air volume was 3 m 3 / min, and shape correction treatment was performed to obtain a specific surface area value of 2.01m 2 / g, a moisture content of 0.6%, a D50 of 3.2 μm, a D99 / D50 of 3.4, and a circularity of 0.94.

[0200] 210 g of the epoxy resin curing agent AD4-4 was dispersed in 90 g of a liquid epoxy resin (manufactured by Daiso Chemical Co., Ltd.: product name "LX-01") using a disperser to obtain a masterbatch type thermosetting resin composition B-4.

[0201] The masterbatch type thermosetting resin composition B-4 was subjected to DSC measurement and rheometer measurement. As a result, the exothermic start temperature was 45° C., the exothermic peak temperature was 95° C., and the total heat release was 220 J / g.

[0202] In addition, regarding the viscosity at each temperature in the measurement using the viscoelasticity device, P30 was 950 Pa·s, P50 was 320 Pa·s, P45 was 260 Pa·s, and P65 was 8000 Pa·s.

[0203] [Example 5]

[0204] The epoxy resin curing agent AD1-1 obtained in the above-mentioned [Example 1] was pulverized using a turbo mill (manufactured by MATSUBO Corporation, “T400”) to obtain a curing agent AD5-1 for epoxy resin.

[0205] The specific surface area of ​​the epoxy resin curing agent AD5-1 obtained was 0.3 m 2 / g, the moisture content was 0.3%, D50 was 12.1 μm, D99 / D50 was 2.8, and the circularity was 0.82.

[0206] 72 g of the epoxy resin curing agent AD5-1 was dispersed in 28 g of a liquid epoxy resin (manufactured by CVC Thermoset Specialties: product name "GE-22") using an ultrasonic homogenizer to obtain a masterbatch type thermosetting resin composition B-5.

[0207] The masterbatch type thermosetting resin composition B-5 was subjected to DSC measurement and rheometer measurement. As a result, the exothermic start temperature was 50° C., the exothermic peak temperature was 98° C., and the total heat release was 220 J / g.

[0208] In addition, regarding the viscosity at each temperature in the measurement using the viscoelasticity device, P30 was 650 Pa·s, P50 was 220 Pa·s, P45 was 180 Pa·s, and P65 was 1050 Pa·s.

[0209] [Comparative Example 1]

[0210] To 120 g of a liquid epoxy resin (Asahi Kasei Corporation: product name "AER260"), 80 g of the epoxy resin curing agent AD1-2 prepared in Example 1 and 10 g of an encapsulating agent (TOSOH CORPORATION: "Coronate T80") were added, and the mixture was allowed to react for 3 hours at 50°C while stirring to obtain a masterbatch type thermosetting resin composition B-6.

[0211] The masterbatch type thermosetting resin composition B-6 was subjected to DSC measurement and rheometer measurement. As a result, the exothermic start temperature was 75° C., the exothermic peak temperature was 114° C., and the total heat release was 330 J / g.

[0212] In addition, regarding the viscosity at each temperature in the measurement using the viscoelasticity device, P30 was 127 Pa·s, P50 was 100 Pa·s, P45 was 69 Pa·s, and P65 was 1044 Pa·s.

[0213] [Comparative Example 2]

[0214] To 140 g of a liquid epoxy resin (Asahi Kasei Corporation: product name "AER260"), 60 g of the epoxy resin curing agent AD1-3 prepared in Example 1 and 3 g of an encapsulating agent (TOSOH CORPORATION: "Coronate 1391") were added, and the mixture was allowed to react for 3 hours at 50°C while stirring to obtain a masterbatch type thermosetting resin composition B-7.

[0215] The masterbatch type thermosetting resin composition B-7 was subjected to DSC measurement and rheometer measurement. As a result, the exothermic start temperature was 72° C., the exothermic peak temperature was 110° C., and the total heat release was 360 J / g.

[0216] In addition, regarding the viscosity at each temperature in the measurement using the viscoelasticity device, P30 was 10 Pa·s, P50 was 20 Pa·s, P45 was 22 Pa·s, and P65 was 2.3 Pa·s.

[0217] [Comparative Example 3]

[0218] With reference to Example 2 of Japanese Patent Application Laid-Open No. 2014-152236, a masterbatch type thermosetting resin composition B-8 was prepared.

[0219] 146 g of triethylenetetramine (molecular weight 146) as an amine compound was dissolved in a mixed solution of 100 g of xylene and 100 g of isopropyl alcohol to obtain a solution. Then, 189 g of bisphenol A epoxy resin (Asahi Kasei Corporation, "AER2603", epoxy equivalent 189, total chlorine content 1800 ppm, hydrolyzable chlorine content 50 ppm) was added to the obtained solution at 60 to 100° C. and reacted to obtain a reaction solution.

[0220] Next, the reaction liquid was heated and decompressed to distill off xylene and isopropyl alcohol from the reaction liquid, and unreacted diethylenetriamine was also distilled off from the reaction liquid, thereby obtaining epoxy resin curing agent AD6-1.

[0221] Furthermore, 220 g of 2-ethyl-4-methylimidazole as an amine compound was added to 408 g of a solution prepared by mixing 1-butanol and toluene at a ratio of 1 / 1 (mass ratio), and the mixture was heated to 80° C. in an oil bath while stirring to dissolve 2-ethyl-4-methylimidazole, thereby preparing a 2-ethyl-4-methylimidazole solution.

[0222] Next, 378 g of a bisphenol A epoxy resin (manufactured by Asahi Kasei Corporation, "AER2603", epoxy equivalent 189, total chlorine content 1800 ppm, hydrolyzable chlorine content 50 ppm) as an epoxy resin was dissolved in 250 g of a solution obtained by mixing 1-butanol and toluene at a ratio of 1 / 1 (mass ratio) to prepare a bisphenol A epoxy resin solution.

[0223] In a reaction container, a bisphenol A type epoxy resin solution was added dropwise to a 2-ethyl-4-methylimidazole solution using an isobaric dropping funnel over 180 minutes. After the addition was completed, the obtained reaction solution was heated at 80° C. for 5 hours to react. Then, the reaction solution was further heated to 180° C., and the solvent was distilled off from the reaction solution. Then, the temperature of the reaction solution was maintained at 180° C., and the pressure in the reaction container was reduced to less than 10 mmHg, thereby distilling off the residual solvent from the reaction solution and distilling off the unreacted 2-ethyl-4-methylimidazole, to obtain an epoxy resin curing agent AD6-2.

[0224] 80 g of the obtained epoxy resin curing agent AD6-1, 70 g of epoxy resin curing agent AD6-2, and 10 g of 1-azabicyclo[2.2.2]octane-3-ol (molecular weight 127, number of tertiary amino groups 1, molecular weight per tertiary amino group 127, melting point 222° C.) as a low molecular amine compound were put into a flask, and stirred and mixed while heating at 180° C. until uniform, and then recovered and cooled to obtain a solid epoxy resin curing agent AD6-3 at room temperature.

[0225] The obtained solid epoxy resin curing agent AD6-3 was roughly pulverized into an average particle size of about 0.1 to 2 mm using a pulverizer "ROTOPLEX" (manufactured by Hosokawa Micron Corporation) to obtain a coarse powder.

[0226] The obtained coarse powder was subjected to repeated pulverization at a pulverizing pressure of 0.6 MPa·s twice using an air jet mill (manufactured by NISSHIN ENGINEERING INC., "CJ25 model") to obtain a pulverized product. The obtained pulverized product was then classified using an air classifier (manufactured by NISSHIN ENGINEERING INC., "Turbo classifier") to remove coarse particles, thereby obtaining an epoxy resin curing agent AD6-4.

[0227] The specific surface area of ​​the epoxy resin curing agent AD6-4 obtained was 2.9 m 2 / g, the moisture content was 0.5%, D50 was 2.7 μm, D99 / D50 was 4.8, and the circularity was 0.89.

[0228] 70 g of finely pulverized epoxy resin curing agent AD6-4 was added to 150 g of n-hexane, and dispersed in n-hexane. Then, 1.0 g of water, 5.5 g of hexamethylene diisocyanate, and 3.0 g of bisphenol A epoxy resin (Asahi Kasei Corporation, "AER2603", epoxy equivalent 189, total chlorine content 1800 ppm, hydrolyzable chlorine content 50 ppm) were added as epoxy resin, and reacted at 40° C. for 2 hours. After the reaction was completed, the mixture was filtered, washed, and dried to obtain a microcapsule-type amine curing agent (A-2).

[0229] Using 50 g of the microcapsule-type amine curing agent (A-2) obtained above and 100 g of bisphenol F-type epoxy resin (epoxy equivalent 175, total chlorine content 1500 ppm, hydrolyzable chlorine content 300 ppm, viscosity 3500 mPa·s) as a liquid epoxy resin, a masterbatch-type thermosetting resin composition B-8 was obtained.

[0230] The masterbatch type curable resin composition B-8 was subjected to DSC measurement and rheometer measurement. As a result, the exothermic start temperature was 50° C., the exothermic peak temperature was 98° C., and the total heat release was 320 J / g.

[0231] In addition, regarding the viscosity at each temperature in the measurement using the viscoelasticity device, P30 was 250 Pa·s, P50 was 220 Pa·s, P45 was 60 Pa·s, and P65 was 1050 Pa·s.

[0232] [Comparative Example 4]

[0233] Dicyandiamide (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used. KRYPTRON ORB manufactured by Earth Technica Co., Ltd. was used under an environment of temperature 10°C and humidity 30% at a rotation speed of 20,000 rpm, a supply speed of 12 kg / hr, and an air volume of 3 m3 / min, and shape correction treatment was performed to obtain a specific surface area value of 2.67m 2 / g, a moisture content of 0.9%, a D50 of 3.7 μm, a D99 / D50 of 3.5, and a circularity of 0.95.

[0234] 100 g of the epoxy resin curing agent A-3 was dispersed in 100 g of a liquid epoxy resin (manufactured by Asahi Kasei Corporation: product name "AER260") using a disperser to obtain a masterbatch type thermosetting resin composition B-9.

[0235] The masterbatch type thermosetting resin composition B-9 was subjected to DSC measurement and rheometer measurement. As a result, the exothermic start temperature was 110° C., the exothermic peak temperature was 160° C., and the total heat release was 220 J / g.

[0236] In addition, regarding the viscosity at each temperature in the measurement using the viscoelasticity device, P30 was 50 Pa·s, P50 was 15 Pa·s, P45 was 18 Pa·s, and P65 was 12 Pa·s.

[0237] [Examples 6 to 10, Comparative Examples 5 to 8]

[0238] Using the masterbatch type thermosetting resin compositions (B-1) to (B-9) prepared as described above, thermosetting resin compositions were prepared according to the blending shown in Table 1 below.

[0239] It should be noted that the materials used are as follows.

[0240] YL980: High-purity bisphenol A epoxy resin manufactured by Mitsubishi Chemical Corporation

[0241] YL983U: High-purity bisphenol F epoxy resin manufactured by Mitsubishi Chemical Corporation

[0242] PEMP: SC Organic Chemical Co., Ltd. Pentaerythritol tetrakis(3-mercaptopropionate)

[0243] Based on the above, ((6) stability evaluation) and ((5) measurement of tensile shear adhesive strength when a liquid crystal polymer is used as a counterpart material) were performed.

[0244] It should be noted that the curing conditions in (5) were 80° C.×30 minutes.

[0245] The evaluation results are shown in Table 1 below.

[0246] [Table 1]

[0247]

[0248] [Examples 11 to 15, Comparative Examples 9 and 10]

[0249] Using the masterbatch type thermosetting resin compositions (B-1) to (B-7) prepared as described above, thermosetting resin compositions were prepared according to the blending shown in Table 2 below.

[0250] Based on the above, ((6) stability evaluation) and ((5) measurement of tensile shear adhesive strength when a liquid crystal polymer is used as a counterpart material) were performed.

[0251] It should be noted that the curing conditions in (5) were 70° C.×30 minutes.

[0252] The evaluation results are shown in Table 2 below.

[0253] [Table 2]

[0254]

[0255] [Examples 16, 17, Comparative Examples 11, 12]

[0256] The masterbatch type thermosetting resin compositions (B-1), (B-3), (B-6), and (B-8) prepared in the above manner were used to prepare thermosetting resin compositions according to the blending shown in Table 3 below.

[0257] Based on the above, ((6) stability evaluation) and ((5) measurement of tensile shear adhesive strength when a liquid crystal polymer is used as a counterpart material) were performed.

[0258] It should be noted that the curing conditions in (5) were 130° C.×10 minutes.

[0259] The evaluation results are shown in Table 3 below.

[0260] In Example 17, in ((5) Measurement of tensile shear adhesive strength when liquid crystal polymer is used as the counterpart material), the substrate was broken, so the strength value was recorded as ">12 MPa".

[0261] [Table 3]

[0262]

[0263] Industrial Applicability

[0264] The thermosetting resin composition containing the masterbatch type thermosetting resin composition of the present invention has industrial applicability as a one-component thermosetting adhesive for mounting camera modules such as mobile phones, smart phones, tablet terminals, drive recorders, and car cameras, and as an adhesive or liquid sealant for various electronic components.

Claims

1. A masterbatch type thermosetting resin composition comprising (A) an epoxy resin and (B) a curing agent, Differential scanning calorimetry (DSC) at a heating rate of 10°C / min satisfies the following conditions (1) and (2), Condition (1): Total heat release is less than 300 J / g, Condition (2): The exothermic start temperature is 80°C or less, and the exothermic peak temperature is 120°C or less. The (B) curing agent is an amine curing agent, The epoxy resin (A) is present in an amount of 35 to 75 parts by mass relative to 100 parts by mass of the total of the epoxy resin (A) and the curing agent (B). The masterbatch type thermosetting resin composition satisfies the following (Formula 1) and (Formula 2) when the viscosity at 30°C is set to P30, the viscosity at 45°C is set to P45, the viscosity at 50°C is set to P50, and the viscosity at 65°C is set to P65 in a measurement at a temperature increase rate of 1°C / min using a viscoelasticity device. (Formula 1) P30≥3×P50, (Formula 2) P65≥3×P45.

2. The masterbatch type thermosetting resin composition according to claim 1, wherein Differential scanning calorimetry (DSC) at a heating rate of 10°C / min satisfies the following conditions (1) and (2), Condition (1): Total heat release is less than 290 J / g, Condition (2): The exothermic start temperature is 78°C or lower, and the exothermic peak temperature is 115°C or lower.

3. The masterbatch type thermosetting resin composition according to claim 1, wherein: Differential scanning calorimetry (DSC) at a heating rate of 10°C / min satisfies the following conditions (1) and (2), Condition (1): Total heat release is less than 280 J / g, Condition (2): The exothermic start temperature is 75°C or lower, and the exothermic peak temperature is 110°C or lower.

4. The masterbatch type thermosetting resin composition according to claim 1, wherein: The (A) epoxy resin is contained in an amount of 40 to 60 parts by mass based on 100 parts by mass of the total of the (A) epoxy resin and the (B) curing agent.

5. The masterbatch type thermosetting resin composition according to claim 1, wherein: The (A) epoxy resin is at least one selected from the group consisting of bifunctional epoxy resins, trifunctional epoxy resins, tetrafunctional epoxy resins and other multifunctional epoxy resins.

6. The masterbatch type thermosetting resin composition according to claim 1, wherein: The (A) epoxy resin includes an aliphatic epoxy resin and / or an alicyclic epoxy resin used as a reactive diluent.

7. The masterbatch type thermosetting resin composition according to claim 1, wherein: The (B) curing agent contains a solid amine curing agent.

8. The masterbatch type thermosetting resin composition according to claim 1, wherein: The (B) curing agent contains an adduct-type epoxy resin curing agent.

9. The masterbatch type thermosetting resin composition according to claim 1, wherein: The (B) curing agent has a circularity of 0.9 or more.

10. The masterbatch type thermosetting resin composition according to claim 1, wherein: The (B) curing agent is a capsule type curing agent.

11. The masterbatch type thermosetting resin composition according to claim 10, wherein: The capsule type curing agent is a curing agent encapsulated using epoxy, acrylic, latex, urethane, or silica. 12 . A thermosetting resin composition comprising the masterbatch type thermosetting resin composition according to claim 1 and (C) an epoxy resin. 13 . The thermosetting resin composition according to claim 12 , further comprising a (D) curing agent other than the (B) curing agent.

14. The thermosetting resin composition according to claim 13, wherein The (D) curing agent is at least one selected from the group consisting of thiol compounds, guanidine derivatives, aromatic amine compounds, and novolac-type phenolic resins. 15 . The thermosetting resin composition according to claim 12 , further comprising (E) an additive.

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