Masterbatch type thermosetting resin composition and thermosetting resin composition

Abstract

To provide an epoxy resin composition that has excellent adhesion to a variety of organic base materials, excellent storage stability, and excellent curability in a wide temperature range.SOLUTION: A master batch-type thermosetting resin composition contains (A) an epoxy resin and (B) a curing agent. The differential scanning calorimetry (DSC) at a temperature increase rate of 10°C / min satisfies the following conditions (1) and (2). The condition (1): the gross heating value is less than 300 J / g. The condition (2): the heating start temperature is 80°C or lower and the heating peak temperature is 120°C or lower.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Epoxy resins and epoxy resin compositions are used in a wide range of applications, such as insulating materials for electronic devices and electric / electronic components, sealing materials, adhesives, and conductive materials. In particular, as electronic devices become more functional, smaller, and thinner, there is a demand for miniaturized integration of semiconductor chips, higher circuit density, significant improvements in productivity, and improvements in portability and reliability for mobile use of electronic devices.

[0003] 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 two components, an epoxy resin and a curing agent, are mixed and cured at the time of use. The two-part epoxy resin composition can be cured well at low temperatures, but it has problems in that the epoxy resin and the curing agent must be stored separately, and when used, they must be measured and then mixed quickly and uniformly, making handling cumbersome.Furthermore, once the epoxy resin and the curing agent are mixed, the usable time thereafter is limited, so that it is not possible to mix them in large quantities in advance.

[0004] In order to solve these problems, masterbatch-type resin compositions in which a latent curing agent is blended in advance with an epoxy resin have been proposed, and improvements have been made in blending and handling. 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).

[0005] In view of these circumstances, so-called microcapsule-type curing agents in which highly reactive imidazole is used as a core and is coated with a specific shell (see, for example, Patent Document 1), and masterbatch-type thermosetting resin compositions in which an adduct is encapsulated (see, for example, Patent Documents 2 and 3) have been proposed. Patent Documents 1 to 3 all describe masterbatch type thermosetting resin compositions having improved storage stability and low-temperature curing properties. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2011-208098 A [Patent Document 2] JP 2013-95876 A [Patent Document 3] JP 2014-152236 A Summary of the Invention [Problem to be solved by the invention]

[0007] However, the masterbatch type thermosetting resin compositions disclosed in Patent Documents 1 to 3 have the problem that, although attempts have been made to improve low-temperature curing properties, they are not suitable for application to organic base materials, which have recently begun to be widely used in electronic components.

[0008] Therefore, an object of the present invention is to provide a masterbatch type thermosetting resin composition which has good adhesion to organic substrates, excellent storage stability, and excellent curability over a wide temperature range. [Means for solving the problem]

[0009] Means for Solving the Problems of the Prior Art As a result of intensive research conducted by the present inventors, it was found that an epoxy resin composition satisfying predetermined physical properties as measured by differential scanning calorimetry (DSC) can solve the problems described above, and thus the present invention was completed. That is, the present invention is as follows.

[0010] [1] (A) an epoxy resin; and (B) a curing agent, The (B) curing agent is an amine-based curing agent, Differential scanning calorimetry (DSC) at a heating rate of 10°C / min satisfies the following conditions (1) and (2): A masterbatch type thermosetting resin composition. Condition (1): The total heat generated is 250J / g or more Less than 300J / g Condition (2): Heat generation starting temperature Over 55°C The exothermic peak temperature is 80°C or less. Over 95℃ 120℃ or less 〔2〕 (A) an epoxy resin; and (B) a curing agent, the (B) curing agent is a capsule-type amine-based curing agent, Differential scanning calorimetry (DSC) at a heating rate of 10°C / min satisfies the following conditions (1) and (2): A masterbatch type thermosetting resin composition. Condition (1): The total heat generated is 250J / g or more Less than 300J / g Condition (2): Heat generation starting temperature Over 45℃ The exothermic peak temperature is 80°C or less. Over 95℃ 120℃ or less 〔3〕 For a total of 100 parts by mass of the (A) epoxy resin and the (B) curing agent, The (A) epoxy resin is 30 to 90 parts by mass. The above [1] Or [2] 2. The masterbatch type thermosetting resin composition according to claim 1 . 〔4〕 The (B) curing agent includes a solid amine-based curing agent. The above [1] Any one of [3] to [4] 2. The masterbatch type thermosetting resin composition according to claim 1 . 〔5〕 The (B) curing agent contains an adduct type epoxy resin curing agent. The above [1] to 〔4〕 10. The masterbatch type thermosetting resin composition according to claim 9 . 〔6〕 The circularity of the (B) curing agent is 0.9 or more. The above [1] to 〔5〕 10. The masterbatch type thermosetting resin composition according to claim 9 . 〔7〕 The (B) curing agent is a capsule-type curing agent. The above [1] , [3] to [6] 10. The masterbatch type thermosetting resin composition according to claim 9 . 〔8〕 When measured with a viscoelasticity device at a heating rate of 1℃ / min, The viscosity at 30°C is P30. The viscosity at 45°C is P45. The viscosity at 50°C is P50. When the viscosity at 65℃ is P65, Satisfy the following (Formula 1) and (Formula 2), The above [1] to 〔7〕 10. The masterbatch type thermosetting resin composition according to claim 9 . (Formula 1) P30 ≧ 3×P50 (Formula 2) P65 ≧ 3×P45 〔9〕 The above [1] to 〔8〕 The masterbatch type thermosetting resin composition according to any one of the above items, (C) Epoxy resin and Contains Thermosetting resin composition. 〔10〕 The composition further contains a curing agent (D) other than the curing agent (B). 〔9〕 The thermosetting resin composition according to claim 1. 〔11〕 (E) the additive further contains, [9] or

[10] The thermosetting resin composition according to claim 1. Effect of the Invention

[0011] According to the present invention, an epoxy resin composition can be obtained which has good adhesion to various organic substrates, excellent storage stability, and excellent curability over a wide temperature range. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, an embodiment of the present invention (hereinafter, referred to as "the present embodiment") will be described in detail. The present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following contents. The present invention can be implemented in various modifications within the scope of the gist thereof.

[0013] [Masterbatch type thermosetting resin composition] The masterbatch type thermosetting resin composition of the present embodiment will be described below. A masterbatch type thermosetting resin composition is a composition that contains a resin and its curing agent component, and the curing agent component is dispersed in the resin in advance. By adopting such a form, it is possible to reduce the effort of blending, and it is possible to mix other components uniformly when they are mixed, which contributes to improving work efficiency. The masterbatch type thermosetting resin composition of the present embodiment contains an epoxy resin (A) (hereinafter may be referred to as component (A)) and a curing agent (B) (hereinafter may be referred to as component (B)), and satisfies the following conditions (1) and (2) in differential scanning calorimetry (DSC) at a heating rate of 10°C / min. Condition (1): Total heat generation is less than 300 J / g Condition (2): The heat generation start temperature is 80°C or less, and the heat generation peak temperature is 120°C or less.

[0014] The masterbatch type thermosetting resin composition of the present embodiment has excellent adhesiveness 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 assembling camera modules such as mobile phones, smartphones, tablet terminals, drive recorders, and vehicle-mounted cameras. It can also be used as an adhesive and liquid sealant for various electronic components.

[0015] The masterbatch type thermosetting resin composition of the present embodiment contains (A) an epoxy resin and (B) a curing agent.

[0016] ((A) Epoxy resin) The epoxy resin (A) is not particularly limited, and various known resins can be appropriately selected and used. (A) Epoxy resin is not limited to the following, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD ​​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, phenyl 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, hydroquinone type epoxy resin, methylhydroquinone type epoxy resin, dibutylhydroquinone type epoxy resin, rezo Bifunctional epoxy resins such as rusine type epoxy resins, methylresorcin type epoxy resins, catechol type epoxy resins, and N,N-diglycidylaniline type epoxy resins; trifunctional epoxy resins such as N,N-diglycidylaminobenzene type epoxy resins, o-(N,N-diglycidylamino)toluene type epoxy resins, and triazine type epoxy resins; tetrafunctional epoxy resins such as tetraglycidyldiaminodiphenylmethane type epoxy resins and diaminobenzene type epoxy resins; multifunctional epoxy resins such as phenol novolac type epoxy resins, cresol novolac type epoxy resins, triphenylmethane type epoxy resins, tetraphenylethane type epoxy resins, dicyclopentadiene type epoxy resins, naphthol aralkyl type epoxy resins, and brominated phenol novolac type 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 , glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane type diglycidyl ether, dicyclopentadiene type diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, vinyl(3,4-cyclohexene) dioxide, 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane, glycidylamine type epoxy resins such as tetraglycidyl bis(aminomethyl)cyclohexane, 1,3-diglycidyl-5-methyl- Aliphatic epoxy resins that can also be used as reactive diluents such as 5-ethylhydantoin type epoxy resins, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane type epoxy resins, phenyl glycidyl ether, cresyl glycidyl ether, ps-butylphenyl glycidyl ether, styrene oxide, p-tert-butylphenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, N-glycidyl phthalimide, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, α-pinene oxide, allyl glycidyl ether, 1-vinyl-3,4-epoxycyclohexane, 1,2-epoxy-4-(2-methyloxiranyl)-1-methylcyclohexane, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, and neodecanoic acid glycidyl ester, and alicyclic epoxy resins are mentioned. These may be used alone or in combination of two or more.

[0017] ((B) Hardener) The (B) curing agent is not particularly limited as long as it can produce the effects of the present invention, and examples thereof include amine-based curing agents, amide-based curing agents, acid anhydride-based curing agents, phenol-based curing agents, latent curing agents, and catalyst-type curing agents. These may be used alone or in combination of two or more.

[0018] (Condition (1)) The masterbatch type thermosetting resin composition of this embodiment has a total calorific value of less than 300 J / g as measured by differential scanning calorimetry (DSC) at a heating rate of 10° C. / min. The total heat generation amount measured by DSC being less than 300 J / g means that there is no significant temperature rise during curing, and when the masterbatch type thermosetting resin composition of the present embodiment is used for bonding to an organic substrate, the temperature does not exceed the melting point of the organic substrate, the organic substrate can be protected, and the strain energy during curing does not become large. The total calorific value is preferably less than 290 J / g, more preferably less than 280 J / g. Examples of methods for making the total calorific value by DSC less than 300 J / g include reducing the number of functional groups by converting part of the curing agent into an adduct, using a resin with a large epoxy equivalent, and modifying part of the epoxy resin with an allyl group or the like.

[0019] The masterbatch type thermosetting resin composition of this embodiment has an exothermic start temperature of 80° C. or lower in differential scanning calorimetry (DSC) measured at a temperature rise rate of 10° C. / min. By setting the heat generation starting temperature to 80° C. or less, it is possible to obtain the effect that curing can be performed at a temperature that is sufficiently low for practical use. The heat generation starting temperature is preferably 78° C. or lower, and more preferably 75° C. or lower. The heat generation initiation temperature of the masterbatch type thermosetting resin composition under the above conditions can be controlled within the above temperature range by selecting the type of curing agent, accelerator, and stabilizer, and adjusting their concentrations and mixing conditions.

[0020] The masterbatch type thermosetting resin composition of this embodiment has an exothermic peak temperature of 120° C. or lower in differential scanning calorimetry (DSC) measured at a heating rate of 10° C. / min. By having the exothermic peak temperature of 120°C or less, the curing rate at low temperatures is improved. The exothermic peak temperature is preferably 115°C or less, and more preferably 110°C or less. The exothermic peak temperature of the masterbatch type thermosetting resin composition under the above conditions can be controlled within the above temperature range by selecting the type of curing agent, accelerator, and stabilizer, and adjusting their concentrations and mixing conditions.

[0021] An adhesive using the masterbatch type thermosetting resin composition of the present embodiment has sufficient adhesion to organic substrates, and the mechanism by which this occurs is believed to be as follows, although it is not intended to be limited thereto. Since the heat generation starting temperature is 80°C or less, the reaction is possible even at low temperatures, and since the heat generation peak temperature is 120°C or less, the curing reaction proceeds even at low temperatures, improving the physical properties of the cured material. Since the total heat generation in the master batch form is less than 300 J / g, the strain energy is small, so no extra stress is applied to the interface between the cured material and the organic base material, and it is believed that affinity works. Therefore, a thermosetting resin composition using the masterbatch type thermosetting resin composition of the present embodiment that satisfies the above conditions (1) and (2) can exhibit sufficient adhesion to an organic substrate.

[0022] ((A) Epoxy resin content) In the masterbatch type thermosetting resin composition of the present embodiment, the amount of the component (A) is preferably in the range of 30 to 90 parts by mass per 100 parts by mass of the total of the components (A) and (B). The amount is more preferably 35 to 75 parts by mass, and further preferably 40 to 60 parts by mass. By setting the content of the component (A) to 30 parts by mass or more, the curing agent component can be uniformly dispersed, making it easier for the masterbatch to exhibit its performance. Furthermore, by keeping the content of the component (A) at 90 parts by mass or less, other epoxy resins can be added in large amounts, making the composition highly practical.

[0023] (Solid amine hardener) In the masterbatch type thermosetting resin composition of the present embodiment, the (B) curing agent preferably contains a solid amine-based curing agent. The (B) curing agent may be liquid or solid at room temperature, but by including a solid amine-based curing agent, the stability at room temperature is improved, the reactivity with the (A) epoxy resin is improved, and further, when another curing agent is used in combination, it can act as a curing catalyst, which is preferable.

[0024] (Adduct type epoxy resin hardener) In the masterbatch type thermosetting resin composition of the present embodiment, the (B) curing agent preferably contains an adduct type epoxy resin curing agent. (B) When the curing agent contains an adduct type epoxy resin curing agent, dispersion in the epoxy resin is improved, and curing properties are improved.

[0025] ((B) Circularity of hardener) In the masterbatch type thermosetting resin composition of the present embodiment, from the viewpoints of particle aggregation, moisture resistance, and permeability, the circularity of the (B) curing agent component is preferably 0.9 or more, more preferably 0.92 or more, and even more preferably 0.94 or more. 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. The degree of circularity here can be measured by the method described in the Examples below, and the closer the degree of circularity is to 1, the closer it is to a perfect sphere. The method for controlling the circularity to the above range is not particularly limited, but it is effective to modify the surface of the (B) curing agent, for example, by mechanically rounding the particles or by subjecting the particles to hot air treatment.

[0026] (Capsule-type hardener) In the masterbatch type thermosetting resin composition of the present embodiment, the (B) curing agent is preferably an encapsulated curing agent. (B) The hardener is encapsulated, which improves stability by physically isolating the hardener. Examples of the encapsulated (B) curing agent include, but are not limited to, epoxy-based, acrylic-based, latex-based, urethane-based, and silica-based. Methods for encapsulating the (B) curing agent include, but are not limited to, the following methods (1) to (3). (1): A method in which the capsule components and hardener particles are dissolved / dispersed in a solvent, which is a dispersion medium, and then the solubility of the capsule components in the dispersion medium is reduced to precipitate the capsules on the surface of the epoxy resin hardener particles. (2) A method in which hardener particles are dispersed in a dispersion medium, and the capsule-forming material is added to the dispersion medium and precipitated on the hardener particles. (3) A method in which capsule-forming raw material components are added to a dispersion medium, and the surface of the hardener particles is used as a reaction site to produce shell-forming materials. Here, the above methods (2) and (3) are preferred because they allow reaction and coating to be carried out simultaneously.

[0027] After forming capsules by the above methods (2) and (3), the method for separating the capsule-shaped curing agent from the dispersion medium is not particularly limited, but it is preferable to separate and remove both the unreacted raw materials and the dispersion medium after the capsules are formed. Such a method includes a method of removing the dispersion medium and the unreacted capsule forming material by filtration.

[0028] After removing the dispersion medium, it is preferable to wash the capsule-type hardener, which can remove unreacted capsule-forming material adhering to the surface of the capsule-type hardener. The washing method is not particularly limited, but washing can be performed using a solvent that does not dissolve the dispersion medium or capsule-type hardener when separating the residue by filtration. After filtering and washing, the capsule-type hardener can be dried to obtain a powdered microcapsule-type hardener. The drying method is not particularly limited, but it is preferable to dry the hardener at a temperature below the melting point or softening point, for example, reduced pressure drying.

[0029] By making the encapsulated curing agent into a powder form, it is possible to easily apply the blending process with the epoxy resin. In addition, when the epoxy resin is used as a dispersion medium, it is preferable because a liquid resin composition consisting of the epoxy resin and the microencapsulated epoxy resin curing agent can be obtained at the same time as the capsules are formed. The capsule formation reaction is usually carried out at 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.

[0030] (Viscosity at a given temperature when measured at a given heating rate using a viscoelasticity device) The masterbatch type thermosetting resin composition of the present embodiment has a viscosity of P30 at 30° C., P45 at 45° C., P50 at 50° C., and P65 at 65° C., as measured with a viscoelasticity device at a temperature rise rate of 1° C. / min. (Formula 1) P30 ≧ 3×P50 (Formula 2) P65 ≧ 3×P45 It is preferable that the following two formulas are satisfied. By satisfying the above (Formula 1) and (Formula 2), curing at low temperatures can be suppressed and curing can proceed at an early stage. This makes it difficult for a sudden reaction to occur at high temperatures, leading to a decrease in internal stress. It also makes it possible to suppress dissolution of the adherend, such as a liquid crystal polymer, due to the amount of heat required for curing, thereby contributing to improved adhesion. In order to satisfy the above formulas (1) and (2), it is effective to use a type of curing agent and a method of treating it, such as increasing the circularity or carrying out encapsulation, as described above.

[0031] [Thermosetting resin composition] The thermosetting resin composition of the present embodiment contains the masterbatch type thermosetting resin composition of the present embodiment described above and an epoxy resin (C). The epoxy resins that can be used are the same as those used for the component (A) described above, and one type may be used alone or two or more types may be used in combination.

[0032] ((D): a curing agent other than the (B) curing agent) The thermosetting resin composition of the present embodiment may contain a curing agent other than the component (B) as the component (D). 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 and used. From the viewpoint of the reaction rate during curing, however, it is preferably at least one selected from the group consisting of thiol compounds, guanidine derivatives, aromatic amine compounds, and novolac-type phenolic resins. These may be used alone or in combination of two or more.

[0033] The thiol compound may be any compound containing two or more thiol groups in one molecule, and examples thereof include, but are not limited to, 3,3'-dithiodipropionic acid, trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol dithioglycolate, 1,4-bis(3-mercaptobutyryloxy)butane, tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, 1,3,5-tris(3-mercaptobutyloxyethyl)- Examples of the mercaptothiol include 1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexakis(3-mercaptopropionate), 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, 4-butanedithiol, 1,6-hexaneedithiol, and 1,10-decanedithiol. These may be used alone or in combination of two or more. From the viewpoint of impact resistance, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, pentaerythritol tetrakis(3-mercaptopropionate), and pentaerythritol tetrakis(3-mercaptobutyrate) are preferred, and from the viewpoint of low-temperature curing property, pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate) are more preferred.

[0034] Examples of the guanidine derivative include, but are not limited to, dicyandiamide derivatives such as dicyandiamide, dicyandiamide-aniline adduct, dicyandiamide-methylaniline adduct, dicyandiamide-diaminodiphenylmethane adduct, and dicyandiamide-diaminodiphenyl ether adduct; guanidine salts such as guanidine nitrate, guanidine carbonate, guanidine phosphate, guanidine sulfamate, and aminoguanidine bicarbonate; acetyl guanidine, diacetyl guanidine, propionyl guanidine, dipropionyl guanidine, cyanoacetyl guanidine, guanidine succinate, diethylcyanoacetyl guanidine, dicyandiamide, N-oxymethyl-N'-cyanoguanidine, and N,N'-dicarbethoxyguanidine.

[0035] Examples of aromatic amine compounds include, but are not limited to, metaphenylenediamine, paraphenylenediamine, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl methane, and 4,4'-diaminodiphenyl ether.

[0036] Examples of novolac-type phenolic resins include, but are not limited to, phenol novolac, bisphenol A novolac, cresol novolac, naphthol novolac, and the like.

[0037] ((E) Additives) The thermosetting resin composition of the present embodiment may further contain an additive (E). Examples of the component (E) include, but are not limited to, organic fillers, inorganic fillers, diluents, pigments, dyes, flow control agents, thickeners, reinforcing agents, release agents, wetting agents, flame retardants, surfactants, organic solvents, conductive fine particles, crystalline alcohols, and resins. These may be used alone or in combination of two or more.

[0038] The organic filler is not limited to the following, but may be, for example, one type of organic filler selected from the group consisting of thermoplastic resins such as triblock copolymers, thermoplastic elastomers, carbon fibers, cellulose, polyethylene powder, and polypropylene powder.

[0039] Examples of inorganic fillers 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 silicates, mica, asbestos powder, slate powder, and the like.

[0040] The diluent is not limited to the following, but for example, a reactive diluent or a non-reactive diluent can be used. Examples of reactive diluents include, but are not limited to, cresol, ethylphenol, propylphenol, p-butylphenol, p-amylphenol, hexylphenol, octylphenol, nonylphenol, dodecylphenol, octadecylphenol, and terpene phenol. The non-reactive diluent is not particularly limited, but examples thereof include dioctyl phthalate, dibutyl phthalate, and benzyl alcohol.

[0041] Examples of pigments include, but are not limited to, kaolin, aluminum oxide trihydrate, aluminum hydroxide, chalk powder, gypsum, calcium carbonate, antimony trioxide, pentone, silica, aerosol, lithopone, baryte, titanium dioxide, and the like.

[0042] Dyes include, but are not limited to, natural dyes such as dyes derived from plants such as madder and indigo, dyes derived from minerals such as yellow ocher and red clay, synthetic dyes such as alizarin and indigo, and fluorescent dyes.

[0043] Examples of flow control agents include, but are not limited to, silane coupling agents; organic titanium compounds such as titanium tetraisopropoxide and titanium diisopropoxybis(acetylacetonate); and organic zirconium compounds such as zirconium tetra-n-butoxide and zirconium tetraacetylacetonate.

[0044] Examples of thickeners include, but are not limited to, animal thickeners such as gelatin; vegetable thickeners such as polysaccharides and cellulose; and chemically synthesized thickeners such as polyacrylics, modified polyacrylics, polyethers, urethane-modified polyethers, and carboxymethylcellulose.

[0045] Examples of reinforcing agents include, but are not limited to, polyethylene sulfone powder such as "Sumika Excel PES" 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.

[0046] Examples of the release agent include, but are not limited to, fluorine-based release agents, silicone-based release agents, and acrylic-based release agents made of a copolymer of glycidyl (meth)acrylate and linear alkyl (meth)acrylate having 16 to 22 carbon atoms.

[0047] Examples of wetting agents include, but are not limited to, unsaturated polyester copolymer wetting agents having acidic groups, such as acrylic polyphosphate esters.

[0048] Examples of flame retardants include, but are not limited to, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, halogen-based flame retardants such as chlorine compounds and bromine compounds, phosphorus-based flame retardants such as condensed phosphate esters, antimony-based flame retardants such as antimony trioxide and antimony pentoxide, and inorganic oxides such as silica filler.

[0049] Examples of surfactants include, but are not limited to, anionic surfactants such as alkylbenzenesulfonates and alkylpolyoxyethylenesulfates, cationic surfactants such as alkyldimethylammonium salts, amphoteric surfactants such as alkyldimethylamine oxides and alkylcarboxybetaines, and nonionic surfactants such as linear alcohols and fatty acid esters having 25 or more carbon atoms.

[0050] 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.

[0051] Examples of conductive fine particles include, but are not limited to, carbon black, graphite, carbon nanotubes, fullerenes, iron oxide, gold, silver, aluminum powder, iron powder, nickel, copper, zinc, chromium, solder, nano-sized metal crystals, and intermetallic compounds.

[0052] Examples of crystalline alcohols include, but are not limited to, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, pentaerythritol, sorbitol, sucrose, trimethylolpropane, and the like.

[0053] Examples of resins include, but are not limited to, polyester resin, polyurethane resin, acrylic resin, polyether resin, melamine resin, and modified epoxy resins such as urethane-modified epoxy resin, rubber-modified epoxy resin, and alkyd-modified epoxy resin.

[0054] The above-mentioned (E) additives can be added in a functionally equivalent amount. For example, pigments and / or dyes can be added in an amount that can impart a desired color to the epoxy resin composition of the present embodiment.

[0055] (Application) The thermosetting resin composition of the present embodiment and the cured product obtained therefrom can be used in various applications in which epoxy resins are used as materials. In particular, it is particularly useful as a one-part thermosetting adhesive for assembling camera modules. It can also be suitably used for electronic device housing adhesives, semiconductor encapsulants such as underfills and moldings, conductive adhesives such as anisotropic conductive films (ACFs), printed wiring boards such as solder resists and coverlay films, etc., but is not limited thereto. EXAMPLES

[0056] The present invention will be explained more specifically with reference to examples and comparative examples, but the present invention is not limited to these in any way. The methods for measuring physical properties and characteristics used in the examples and comparative examples are shown below.

[0057] [Measurement of physical properties of masterbatch type thermosetting resin composition and thermosetting resin composition] ((1) Differential scanning calorimetry (DSC) Using an EXSTER7020 (Hitachi High-Tech Science Corporation), the masterbatch type thermosetting resin composition was heated from 25°C to 250°C at a heating rate of 10°C / min, and the heat generation start temperature, heat generation peak temperature, and total heat generation amount were measured from the observed DSC curve.

[0058] ((2) Rheometer measurement using a viscoelastic device) Using HAAKE MARS I (manufactured by Thermo Fisher), 1Hz oscillation In the dynamic viscosity mode, the masterbatch type thermosetting resin composition was heated from 20°C to 100°C at a rate of 1°C / min, and the viscosities at 30°C, 45°C, 50°C, and 65°C were determined from the observed dynamic viscosity curve, and designated as P30, P45, P50, and P65, respectively.

[0059] ((3) Circularity) Using a flow type particle image analyzer FPIA-3000S (Spectris Co., Ltd.), the circularity of the curing agent (B) was obtained by measuring a dispersion in which various curing agents obtained during the manufacturing process were dispersed in cyclohexane at 0.5 mass%. The encapsulated ones were considered to be uniformly encapsulated, and the circularity of the curing agent was used as it was.

[0060] (4) Measurement of tensile shear adhesive strength of thermosetting resin composition when liquid crystal polymer is used as a mating material The thermosetting resin compositions of Examples 6 to 17 and Comparative Examples 5 to 12 were cured under the conditions described below, and the tensile shear adhesive strength was measured in accordance with JIS K6850. Sumika Super E6007LHF (manufactured by Sumitomo Chemical Co., Ltd.) was used as the mating material, and tests were performed with n=5. The average value was calculated and this was taken as the tensile shear adhesive strength. Of the five, if the difference between the maximum and minimum values ​​was 1.2 times or more compared to the average value, it was deemed that the variation was large and marked with an ×, if it was between 1.1 and less than 1.2, it was deemed that the variation was small and marked with a 〇, and if it was less than 1.1 times, it was deemed that the variation was small and marked with a 〇.

[0061] ((5) Stability evaluation) 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. Viscosity after storage that was more than twice the initial value was rated as x, viscosity that was 1.5 to less than 2.0 times was rated as △, and viscosity that was less than 1.5 times was rated as ◯.

[0062] Example 1 110 g of 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei: product name "2E4MZ") was dissolved in 100 g of toluene solution and heated to 100°C. Then, 360 g of a 50 mass % toluene solution of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical: product name "jER828US") was added and reacted. Next, the reaction liquid was heated under reduced pressure, and the toluene was distilled off from the reaction liquid, yielding 273 g of an epoxy resin curing agent AD1-1. The obtained epoxy resin curing agent AD1-1 was pulverized twice using a jet mill (Nisshin Engineering, "CJ25 type") at a pulverization pressure of 0.5 MPa·s, and then classified using an air classifier (Nisshin Engineering, "Turbo Classifier") to remove coarse particles, thereby obtaining epoxy resin curing agent AD1-2. The average particle size of the obtained epoxy resin curing agent core AD1-2 was 2.5 μm. Epoxy resin hardener AD1-2 was used in a Cryptron Orb manufactured by EarthTechnica Corporation, at a temperature of 10°C, humidity of 30%, rotation speed of 13,500 rpm, supply speed of 10 kg / hr, and air volume of 3 m 3 / min, shape correction treatment was performed to obtain epoxy resin hardener AD1-3. Then, 70 g of the obtained epoxy resin curing agent AD1-3 was added to 140 g of methylcyclohexane and dispersed in the methylcyclohexane, and then 25.2 g of isophorone diisocyanate and 6.0 g of 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. After the reaction was completed, the mixture was filtered, washed and dried to obtain epoxy resin curing agent A-1. The epoxy resin curing agent A-1 had a specific surface area of ​​2.02 m 2 / g, moisture content was 0.6%, D50 was 2.4 μm, D99 / D50 was 4.5, and circularity was 0.93. 100 g of the epoxy resin curing agent A-1 was dispersed in 100 g of liquid epoxy resin (manufactured by Asahi Kasei Corporation: product name "AER260") using a stirrer to obtain a masterbatch type thermosetting resin composition B-1. Masterbatch type thermosetting resin composition B-1 was subjected to DSC measurement and rheometer measurement, and the heat generation start temperature was 74° C., the heat generation peak temperature was 115° C., and the total heat generation amount was 270 J / g. In addition, the viscosity at each temperature measured using a viscoelasticity device was 560 Pa·s for P30, 160 Pa·s for P50, 183 Pa·s for P45, and 210 Pa·s for P65.

[0063] Example 2 70 g of diethylenetriamine (manufactured by Tosoh Corporation) was dissolved in 100 g of toluene solution and heated to 70° C., after which 360 g of a 50% by mass toluene solution of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation: product name “jER828US”) was added and reacted. Next, the reaction liquid was heated and decompressed to distill off toluene and unreacted diethylenetriamine from the reaction liquid, and 60 g of the 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. The obtained epoxy resin curing agent AD2-1 was pulverized twice using an air jet mill (manufactured by Nisshin Engineering, "CJ25 type") at a pulverization pressure of 0.8 MPa·s, and then classified using an air classifier (manufactured by Nisshin Engineering, "Turbo Classifier") to remove coarse particles, thereby obtaining epoxy resin curing agent AD2-2. The average particle size of the obtained epoxy resin curing agent AD2-2 was 3.0 μm. Epoxy resin hardener AD2-2 was used in a Cryptron Orb manufactured by EarthTechnica Corporation, at a temperature of 10°C, humidity of 30%, rotation speed of 8000 rpm, supply rate of 5 kg / hr, and air volume of 3 m 3 / min, shape correction was performed, and the specific surface area was 2.55 m 2 Thus, an epoxy resin curing agent AD2-2 having a particle size of 0.7 / g, a water content of 0.8%, a D50 of 3.0 μm, a D99 / D50 of 3.6, and a circularity of 0.91 was obtained. To 120 parts by mass of a liquid epoxy resin (manufactured by 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 (manufactured by Tosoh Corporation: "MR400") were added, and the reaction was continued for 3 hours with stirring at 50°C to obtain a masterbatch type thermosetting resin composition B-2. Masterbatch type thermosetting resin composition B-2 was subjected to DSC measurement and rheometer measurement, and the heat generation start temperature was 65° C., the heat generation peak temperature was 105° C., and the total heat generation amount was 290 J / g. In addition, the viscosity at each temperature measured using a viscoelasticity device was 200 Pa·s for P30, 60 Pa·s for P50, 87 Pa·s for P45, and 310 Pa·s for P65.

[0064] Example 3 200 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: product name “TEDA”) was added and melt-mixed to obtain 238 g of epoxy resin curing agent AD3-1. The obtained epoxy resin curing agent AD3-1 was crushed twice using an air jet mill (manufactured by Nisshin Engineering, "CJ25 type") at a crushing pressure of 0.3 MPa·s, and then classified using an air classifier (manufactured by Nisshin Engineering, "Turbo Classifier") to remove coarse particles, yielding epoxy resin curing agent AD3-2. The average particle size of the obtained epoxy resin curing agent AD3-2 was 4.5 μm. The epoxy resin hardener AD3-2 was heat-treated using Japan Pneumatic Co., Ltd.'s "Meteor Rainbow MR-10" at a hardener particle feed rate of 2.0 kg / hr and a treatment temperature of 275°C. A cyclone collector and a bag filter were attached, and 0°C circulating cooling water was passed through the powder recovery section wall to cool the container's internal temperature to 40°C or less. Air controlled to a temperature of 25°C and a humidity of 10% was introduced as cooling air after the 275°C hot air treatment, and classification was performed using a classifier to obtain a specific surface area of ​​1.0 m. 2 The epoxy resin curing agent AD3-3 having a molecular weight of 1.001 g / g, a water content of 0.6%, a D50 of 5.0 μm, a D99 / D50 of 2.5, and a circularity of 0.97 was obtained. 110 g of the epoxy resin curing agent AD3-3 and 3 g of an encapsulating agent (Tosoh Corporation: "Coronate 1391") were added to 90 g of liquid epoxy resin (DIC Corporation: product name "EXA850CRP"), and the reaction was continued for 3 hours with stirring at 50°C to obtain a masterbatch type thermosetting resin composition B-3. Masterbatch type thermosetting resin composition B-3 was subjected to DSC measurement and rheometer measurement, and the heat generation start temperature was 55° C., the heat generation peak temperature was 100° C., and the total heat generation amount was 250 J / g. In addition, the viscosity at each temperature measured using a viscoelasticity device was 382 Pa·s for P30, 24 Pa·s for P50, 40 Pa·s for P45, and 10,320 Pa·s for P65.

[0065] [ Reference example 4) In a 100 g toluene solution, N,N-dimethylaminopropylamine (Tokyo Chemical Industry Co., Ltd., Reagent) 100g was dissolved, heated to 70℃, and then bisphenol A type epoxy resin (Mitsubishi Chemical 300 g of a 50% by weight toluene solution of 1,2-dichlorophenyl ether (manufactured by Caltech Co., Ltd., product name "jER1001") was added to the reaction vessel. He responded. Next, the reaction mixture was heated and decompressed to remove toluene and unreacted N,N-dimethylaminopropane. The diethylamine was distilled off from the reaction solution, and the epoxy resin curing agent A prepared in Example 1 was added. Add 100g of D1-1 and melt mix to make 28% of epoxy resin hardener AD4-1. I got 0g. The obtained epoxy resin hardener AD4-1 was mixed with an air jet mill (Nisshin Engineering The crushing was repeated twice at a crushing pressure of 0.8 MPa·s using a grinding machine (CJ25 type, manufactured by AG). Then, using an air classifier (Nisshin Engineering, "Turbo Classifier") The coarse particles are removed by classification, and the resulting finely ground material is used as epoxy resin hardener AD4-2. The average particle size of the obtained epoxy resin curing agent AD4-2 was 3.3 μm. Epoxy resin hardener AD4-2 was used with the Cryptron Orb manufactured by EarthTechnica Corporation. The temperature was 10℃, the humidity was 30%, the rotation speed was 12000rpm, and the supply speed was 8k. g / hr, air volume 3m 3 / min, shape correction was performed, and the specific surface area was 2.01 m 2 / g, Moisture content is 0.6%, D50 is 3.2μm, D99 / D50 is 3.4, circularity is 0.94 As a result, epoxy resin curing agent AD4-4 was obtained. Add 90 g of liquid epoxy resin (manufactured by Daiso Chemical Co., Ltd.: product name "LX-01") to the Disperse 210g of epoxy resin hardener AD4-4 in a disperser and mix it into a masterbatch type thermosetting resin. A curable resin composition B-4 was obtained. Masterbatch type thermosetting resin composition B-4 was subjected to DSC and rheometer measurements. The heat generation start temperature was 45°C, the heat generation peak temperature was 95°C, and the total heat generation was 220 J. / g. In addition, the viscosity at each temperature measured by a viscoelasticity device was 950 Pa s for P30, 950 Pa s for P P50 was 320 Pa·s, P45 was 260 Pa·s, and P65 was 8000 Pa·s.

[0066] [ Reference example 5) The epoxy resin curing agent AD1-1 obtained in Example 1 was used in a commercial refrigeration system using Turbo Mill Co., Ltd. The epoxy resin hardener AD5-1 was used for grinding. obtained. The obtained epoxy resin curing agent AD5-1 has a specific surface area of ​​0.3 m 2 / g, moisture content 0.3%, D50 was 12.1μm, D99 / D50 was 2.8, and circularity was 0.82. Ta. Liquid epoxy resin (manufactured by CVC Thermoset Specialties: product name "GE-22") 28g of epoxy resin hardener AD5-1 was added to 72g of the mixture and dispersed using an ultrasonic homogenizer. This resulted in a masterbatch type thermosetting resin composition B-5. Masterbatch type thermosetting resin composition B-5 was subjected to DSC and rheometer measurements. The heat generation start temperature was 50°C, the heat generation peak temperature was 98°C, and the total heat generation was 220 J. / g. In addition, the viscosity at each temperature measured by a viscoelasticity device was 650 Pa s for P30, 650 Pa s for P P50 was 220 Pa·s, P45 was 180 Pa·s, and P65 was 1050 Pa·s.

[0067] Comparative Example 1 To 120 g of liquid epoxy resin (manufactured by 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 (manufactured by Tosoh Corporation: "Coronate T80") were added, and the reaction was continued for 3 hours with stirring at 50°C to obtain a masterbatch type thermosetting resin composition B-6. Masterbatch type thermosetting resin composition B-6 was subjected to DSC measurement and rheometer measurement, and the heat generation start temperature was 75° C., the heat generation peak temperature was 114° C., and the total heat generation amount was 330 J / g. In addition, the viscosity at each temperature measured using a viscoelasticity device was 127 Pa·s for P30, 100 Pa·s for P50, 69 Pa·s for P45, and 1044 Pa·s for P65.

[0068] Comparative Example 2 To 140 g of liquid epoxy resin (manufactured by 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 (manufactured by Tosoh Corporation: "Coronate 1391") were added, and the reaction was continued for 3 hours with stirring at 50°C to obtain a masterbatch type thermosetting resin composition B-7. The masterbatch type thermosetting resin composition B-7 was subjected to DSC measurement and rheometer measurement, and the heat generation start temperature was 72° C., the heat generation peak temperature was 110° C., and the total heat generation amount was 360 J / g. In addition, the viscosity at each temperature measured using a viscoelasticity device was 10 Pa·s for P30, 20 Pa·s for P50, 22 Pa·s for P45, and 2.3 Pa·s for P65.

[0069] Comparative Example 3 Masterbatch type thermosetting resin composition B-8 was prepared with reference to Example 2 of JP 2014-152236 A. A solution was obtained by dissolving 146 g of triethylenetetramine (molecular weight 146) as an amine compound in a mixed solution of 100 g of xylene and 100 g of isopropyl alcohol. Then, 189 g of bisphenol A type epoxy resin (manufactured by Asahi Kasei Corporation, "AER2603", epoxy equivalent 189, total chlorine amount 1800 ppm, hydrolyzable chlorine 50 ppm) was added to the obtained solution at 60 to 100°C, and a reaction was carried out to obtain a reaction liquid. Next, the reaction liquid was heated and decompressed to distill off xylene and isopropyl alcohol from the reaction liquid, and also distill off unreacted diethylenetriamine from the reaction liquid, thereby obtaining an epoxy resin curing agent AD6-1. Furthermore, 220 g of 2-ethyl-4-methylimidazole as an amine compound was added to 408 g of a solution obtained by mixing 1-butanol and toluene in a 1 / 1 (mass ratio) ratio, and the mixture was heated to 80°C in an oil bath with stirring to dissolve the 2-ethyl-4-methylimidazole, thereby preparing a 2-ethyl-4-methylimidazole solution. Next, 378 g of bisphenol A type epoxy resin (Asahi Kasei Corporation, "AER2603", epoxy equivalent 189, total chlorine content 1800 ppm, hydrolyzable chlorine content 50 ppm) was dissolved as an epoxy resin in 250 g of a solution obtained by mixing 1-butanol and toluene in a 1 / 1 (mass ratio) ratio to prepare a bisphenol A type epoxy resin solution. In the reaction vessel, the bisphenol A type epoxy resin solution was dropped into the 2-ethyl-4-methylimidazole solution using a pressure equalizing dropping funnel over 180 minutes. After the dropwise addition was completed, the resulting reaction solution was heated at 80°C for 5 hours to carry out the reaction. Thereafter, the reaction solution was further heated to 180°C to distill off the solvent from the reaction solution. Thereafter, the temperature of the reaction solution was kept at 180°C, and the pressure in the reaction vessel was reduced to 10 mmHg or less, whereby the unreacted 2-ethyl-4-methylimidazole together with the residual solvent was distilled off from the reaction solution, and the epoxy resin curing agent AD6-2 was obtained. 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]octan-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 weight amine compound were charged into a flask, and the mixture was stirred and mixed while heating at 180°C until it became uniform, and then the mixture was recovered and cooled to obtain epoxy resin curing agent AD6-3 which is solid at room temperature. The obtained solid epoxy resin curing agent AD6-3 was roughly crushed to an average particle size of about 0.1 to 2 mm using a crusher "Rotoplex" (manufactured by Hosokawa Micron Corporation) to obtain a coarse powder. The obtained coarse powder was fed to an air jet mill (Nisshin Engineering, "CJ25 type") and crushed twice at a crushing pressure of 0.6 MPa·s to obtain a crushed product. The crushed product was then classified using an air classifier (Nisshin Engineering, "Turbo Classifier") to remove coarse particles, yielding epoxy resin curing agent AD6-4. The epoxy resin curing agent AD6-4 obtained had a specific surface area of ​​2.9 m 2 / g, moisture content was 0.5%, D50 was 2.7 μm, D99 / D50 was 4.8, and circularity was 0.89. 70g of finely ground epoxy resin curing agent AD6-4 was added to 150g of n-hexane and dispersed in n-hexane, after which 1.0g of water, 5.5g of hexamethylene diisocyanate, and 3.0g of bisphenol A type epoxy resin (Asahi Kasei Corporation, "AER2603", epoxy equivalent 189, total chlorine content 1800ppm, hydrolyzable chlorine content 50ppm) were added as epoxy resin, and the mixture was 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-based curing agent (A-2). A masterbatch type thermosetting resin composition B-8 was obtained using 50 g of the microcapsule type amine-based 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. Masterbatch type curable resin composition B-8 was subjected to DSC measurement and rheometer measurement, and the heat generation start temperature was 50° C., the heat generation peak temperature was 98° C., and the total heat generation amount was 320 J / g. In addition, the viscosity at each temperature measured using a viscoelasticity device was 250 Pa·s for P30, 220 Pa·s for P50, 60 Pa·s for P45, and 1050 Pa·s for P65.

[0070] Comparative Example 4 Dicyandiamide (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was used in a Krypton Orb manufactured by EarthTechnica Corporation under conditions of temperature 10°C, humidity 30%, rotation speed 20,000 rpm, supply speed 12 kg / hr, and air volume 3 m 3 / min, shape correction was performed, and the specific surface area was 2.67 m 2 Thus, an epoxy resin curing agent A-3 having a particle size of 0.7 μm, a water content of 0.9%, a D50 of 3.7 μm, a D99 / D50 of 3.5, and a circularity of 0.95 was obtained. 100 g of the epoxy resin curing agent A-3 was dispersed in 100 g of liquid epoxy resin (manufactured by Asahi Kasei Corporation: product name "AER260") using a disperser to obtain a masterbatch type thermosetting resin composition B-9. Masterbatch type thermosetting resin composition B-9 was subjected to DSC measurement and rheometer measurement, and the heat generation start temperature was 110° C., the heat generation peak temperature was 160° C., and the total heat generation amount was 220 J / g. In addition, the viscosity at each temperature measured using a viscoelasticity device was 50 Pa·s for P30, 15 Pa·s for P50, 18 Pa·s for P45, and 12 Pa·s for P65.

[0071] [Example 6- 8. Reference Examples 9-10, Examples 10, Comparative Examples 5 to 8 Using the masterbatch type thermosetting resin compositions (B-1) to (B-9) prepared as above, A thermosetting resin composition was prepared according to the formulation shown in Table 1 below. The materials used are shown below. YL980: High-purity bisphenol A epoxy resin manufactured by Mitsubishi Chemical Corporation YL983U: High purity bisphenol F type epoxy resin manufactured by Mitsubishi Chemical Corporation PEMP: SC Organic Chemical Co., Ltd. Pentaerythritol tetrakis(3-mercapto) Propionate) According to the above, ((6) Stability evaluation) and ((5) When liquid crystal polymer is used as the counter material, Tensile shear adhesive strength was measured. The curing conditions in (5) were 80°C x 30 minutes. The evaluation results are shown in Table 1 below.

[0072] [Table 1]

[0073] [Examples 11 to 13, Reference example 14~ 15, Comparative Examples 9 and 10] Using the masterbatch type thermosetting resin compositions (B-1) to (B-7) prepared as above, A thermosetting resin composition was prepared according to the formulation shown in Table 2 below. According to the above, ((6) Stability evaluation) and ((5) When liquid crystal polymer is used as the counter material, Tensile shear adhesive strength was measured. The curing conditions in (5) were 70°C x 30 minutes. The evaluation results are shown in Table 2 below.

[0074] [Table 2]

[0075] [Examples 16 and 17, Comparative Examples 11 and 12] Using the masterbatch type thermosetting resin compositions (B-1), (B-3), (B-6), and (B-8) prepared above, thermosetting resin compositions were prepared according to the formulations shown in Table 3 below. According to the above, ((6) Evaluation of stability) and ((5) Measurement of tensile shear adhesive strength when a liquid crystal polymer was used as the mating material) were carried out. The curing conditions in (5) were 130°C x 10 minutes. The evaluation results are shown in Table 3 below. In Example 17, in (5) Measurement of tensile shear adhesive strength when liquid crystal polymer is used as the mating material, the substrate was broken, so the strength value was expressed as ">12 MPa."

[0076] [Table 3] [Industrial Applicability]

[0077] 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 assembling camera modules such as mobile phones, smartphones, tablet terminals, drive recorders, and in-vehicle cameras, as well as an adhesive and liquid sealant for various electronic components.

Claims

1. (A) an epoxy resin; and (B) a curing agent, The (B) curing agent is an amine-based curing agent, Differential scanning calorimetry (DSC) at a heating rate of 10° C. / min satisfies the following conditions (1) and (2): A masterbatch type thermosetting resin composition. Condition (1): Total heat generation amount is 250 J / g or more and less than 300 J / g Condition (2): Heat generation start temperature is 55° C. or more and 80° C. or less, and heat generation peak temperature is 95° C. or more and 120° C. or less.

2. (A) an epoxy resin; and (B) a curing agent, The (B) curing agent is a capsule-type amine-based curing agent, Differential scanning calorimetry (DSC) at a heating rate of 10° C. / min satisfies the following conditions (1) and (2): A masterbatch type thermosetting resin composition. Condition (1): Total heat generation amount is 250 J / g or more and less than 300 J / g Condition (2): Heat generation start temperature is 45° C. or more and 80° C. or less, and heat generation peak temperature is 95° C. or more and 120° C. or less.

3. For a total of 100 parts by mass of the epoxy resin (A) and the curing agent (B), The (A) epoxy resin is 30 to 90 parts by mass, The masterbatch type thermosetting resin composition according to claim 1 or 2.

4. The (B) curing agent includes a solid amine-based curing agent. The masterbatch type thermosetting resin composition according to any one of claims 1 to 3.

5. The (B) curing agent contains an adduct type epoxy resin curing agent. The masterbatch type thermosetting resin composition according to any one of claims 1 to 4.

6. The circularity of the (B) curing agent is 0.9 or more. The masterbatch type thermosetting resin composition according to any one of claims 1 to 5.

7. The (B) curing agent is a capsule-type curing agent. The masterbatch type thermosetting resin composition according to any one of claims 1 and 3 to 6.

8. When measured using a viscoelasticity device at a temperature rise rate of 1°C / min, The viscosity at 30°C is P30, The viscosity at 45°C is P45. The viscosity at 50°C is P50, When the viscosity at 65°C is P65, Satisfying the following (Formula 1) and (Formula 2), The masterbatch type thermosetting resin composition according to any one of claims 1 to 7. (Formula 1) P30 ≧ 3×P50 (Formula 2) P65 ≧ 3×P45

9. The masterbatch type thermosetting resin composition according to any one of claims 1 to 8, (C) an epoxy resin; Contains Thermosetting resin composition.

10. The thermosetting resin composition according to claim 9 , further comprising a curing agent (D) other than the curing agent (B).

11. The thermosetting resin composition according to claim 9 or 10, further comprising an additive (E).

Images