JPWO2020189711A1 - Resin compositions for molding materials, molded bodies and structures - Google Patents

Abstract

A resin composition for a molding material containing (A) an epoxy resin, (B) a curing agent, and (C) a curing accelerator, which is used for a molding material at 25 to 200 ° C. at 5 ° C./min. Provided is a resin composition for a molding material, which has a heat generation start temperature of 70 ° C. or higher and 90 ° C. or lower and a maximum heat generation temperature of 90 ° C. or higher and lower than 130 ° C. when the differential scanning calorimetry of the resin composition is performed.

Description

The present invention relates to resin compositions for molding materials, molded bodies and structures.

As a technique for accelerating the curing of the epoxy resin, there is one described in Patent Document 1. According to the same document, by using a specific phosphonium compound, the curing of epoxy resin can be promoted, the fluidity during molding is excellent, the curing strength is high, and the curing catalyst can be cured even in a short curing time. It is said that the problem of providing a compound can be solved.

Japanese Unexamined Patent Publication No. 2016-084342

However, when the present inventor examined the technique described in the above-mentioned patent document, it became clear that there is still room for improvement in terms of low temperature curability.

According to the present invention
(A) Epoxy resin and
(B) Hardener and
(C) Curing accelerator and
A resin composition for a molding material containing
When the differential scanning calorimetry of the resin composition for molding material was performed at 25 to 200 ° C. under the condition of 5 ° C./min.
The heat generation start temperature is 70 ° C or higher and 90 ° C or lower.
A resin composition for a molding material having a maximum exothermic temperature of 90 ° C. or higher and lower than 130 ° C. is provided.

According to the present invention, there is provided a molded product made of a cured product of the resin composition for a molding material according to the present invention.

Further, according to the present invention, there is provided a structure having the molded body according to the present invention.

According to the present invention, it is possible to provide a resin composition for a molding material having excellent low temperature curability.

It is sectional drawing which shows typically the structure of the stirring apparatus in embodiment. It is sectional drawing which shows typically the structure of the stirring apparatus in embodiment. It is sectional drawing which shows an example of the structure structure in Embodiment.

Hereinafter, embodiments of the present invention will be described with reference to specific examples of each component. In addition, in this embodiment, the composition may contain each component individually or in combination of two or more kinds. Further, in all the drawings, similar components are designated by a common reference numeral, and the description thereof will be omitted as appropriate. Further, the figure is a schematic view and does not necessarily match the actual dimensional ratio. Further, "X to Y" in the numerical range represents "X or more and Y or less" unless otherwise specified.

In the present embodiment, the resin composition for molding material (hereinafter, also simply referred to as “resin composition”) contains the following components (A) to (C).
(A) Epoxy resin (B) Curing agent (C) Curing accelerator When the differential scanning calorimetry of the resin composition was performed at 25 to 200 ° C. under the condition of 5 ° C./min, the heat generation start temperature was 70 ° C. or higher. It is 90 ° C. or lower, and the maximum heat generation temperature is 90 ° C. or higher and lower than 130 ° C.

The present inventor has studied to improve the low temperature curability of the resin composition used for the molding material. As a result, the resin composition contains the above-mentioned components (A) to (C), and the heat generation start temperature and the maximum heat generation temperature in the differential scanning calorimetry (DSC) are each in a specific range. As a result, they have found that the low temperature curability is effectively improved, and have completed the present invention.

In the present embodiment, it is possible to obtain a resin composition for a molding material that can obtain good curing characteristics even under low temperature conditions of, for example, 100 ° C. or lower.
Hereinafter, each configuration of the resin composition for a molding material will be described in more detail.

(Ingredient (A))
The component (A) is an epoxy resin. As the component (A), an epoxy resin known in the field of epoxy resin compositions for molding materials can be used. As the epoxy resin, a monomer, an oligomer, or a polymer having two or more epoxy groups in one molecule can be used in general, and the molecular weight and molecular structure thereof are not limited.

Specific examples of the component (A) include crystalline epoxy resins such as biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, stillben type epoxy resin, and hydroquinone type epoxy resin; cresol novolac type epoxy resin, phenol. Novolak type epoxy resin such as novolac type epoxy resin, naphthol novolac type epoxy resin; phenol aralkyl type epoxy resin containing phenylene skeleton, phenol aralkyl type epoxy resin containing biphenylene skeleton, phenol aralkyl type epoxy resin such as phenylene skeleton containing naphthol aralkyl type epoxy resin Trifunctional epoxy resin such as triphenol methane type epoxy resin and alkyl modified triphenol methane type epoxy resin; Modified phenol type epoxy resin such as dicyclopentadiene modified phenol type epoxy resin and terpen modified phenol type epoxy resin; Examples thereof include a heterocycle-containing epoxy resin such as an epoxy resin.
From the viewpoint of improving the low temperature curability of the resin composition, the component (A) is preferably selected from the group consisting of orthocresol novolac type epoxy resin, triphenol methane type epoxy resin and biphenylene skeleton-containing phenol aralkyl type epoxy resin. Includes one or more.

The content of the component (A) in the resin composition is preferably 8% by mass or more with respect to the total solid content of the resin composition from the viewpoint of improving the fluidity of the resin composition and improving the moldability. Yes, more preferably 10% by mass or more, still more preferably 12% by mass or more. Further, from the viewpoint of improving moisture resistance reliability, reflow resistance, and temperature cycle resistance of a molded product made of a cured product of the resin composition, a semiconductor device including the molded product, and other structures, the component (A) The content of the resin composition is preferably 35% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, based on the total solid content of the resin composition.

In the present embodiment, the total solid content of the resin composition refers to the non-volatile content in the resin composition, and refers to the balance excluding volatile components such as water and solvent. Moreover, in this embodiment, the content with respect to the whole resin composition means the content with respect to the whole solid content excluding the solvent in the resin composition when a solvent is contained.

(Component (B))
The component (B) is a curing agent. The component (B) is not limited as long as it reacts with the epoxy resin of the component (A) to cure the epoxy resin, and for example, a curing agent known in the field of epoxy resin compositions for molding materials may be used. Can be done.

Specific examples of the component (B) include an amine-based curing agent, that is, a curing agent having an amino group, a phenol-based curing agent, and the like.

Examples of the amine-based curing agent include linear aliphatic diamines having 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, and hexamethylenediamine, metaphenylenediamine, paraphenylenediamine, paraxylenediamine, and 4,4'. -Diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodicyclohexane, bis (4-aminophenyl) phenylmethane, 1 , 5-Diaminonaphthalene, metaxylene diamine, paraxylene diamine, 1,1-bis (4-aminophenyl) cyclohexane, dicyanodiamide and the like.

Examples of the phenol-based curing agent include resole-type phenol resins such as aniline-modified resol resin and dimethyl ether resol resin; novolak-type phenol resins such as phenol novolac resin, cresol novolak resin, tert-butylphenol novolak resin, and nonylphenol novolak resin; phenols containing a phenylene skeleton. Phenol aralkyl resins such as aralkyl resin and biphenylene skeleton-containing phenol aralkyl resin; phenol resins having a condensed polycyclic structure such as naphthalene skeleton and anthracene skeleton can be mentioned.

In addition, as the component (B), polyoxystyrene such as polyparaoxystyrene; alicyclic acid anhydride such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA), trimellitic anhydride (TMA), Acid anhydrides and the like containing aromatic acid anhydrides such as pyromellitic anhydride (PMDA) and benzophenone tetracarboxylic acid (BTDA); polypeptide compounds such as polysulfide, thioester and thioether; isocyanate prepolymers, blocked isocyanate and the like. An isocyanate compound; an organic acid such as a carboxylic acid-containing polyester resin can be mentioned.

Further, when a molded product made of a resin composition or a cured product thereof is used as a semiconductor encapsulating material, the component (B) contains at least two phenols in one molecule from the viewpoint of improving moisture resistance and reliability. A compound having a sex hydroxyl group is preferable. More specifically, as the component (B), novolak-type phenol resin such as phenol novolac resin, cresol novolak resin, tert-butylphenol novolak resin, nonylphenol novolak resin; resol-type phenol resin; polyoxystyrene such as polyparaoxystyrene; Phenolene skeleton-containing phenol aralkyl resin, biphenylene skeleton-containing phenol aralkyl resin and the like are preferably mentioned.

The content of the component (B) in the resin composition can be, for example, as a blending ratio of the components (A) and (B) as follows. That is, from the viewpoint of enhancing the production stability of the resin composition in the present embodiment and from the viewpoint of favoring the performance as the sealing material when the resin composition is used as the sealing material, the components (A) and ( When the total amount of B) is 100 parts by mass, the ratio of the component (A) is preferably 50 to 90 parts by mass and the component (B) is 10 to 50 parts by mass.
The content of the component (B) in the resin composition is preferably 1% by mass or more with respect to the total solid content of the resin composition from the viewpoint of making the curing characteristics of the resin composition preferable. It is more preferably 3% by mass or more, further preferably 5% by mass or more, still more preferably 6% by mass or more, and preferably 22% by mass or less, more preferably 20% by mass or less, still more preferably 17% by mass or less. , Even more preferably 10% by mass or less.

(Component (C))
The component (C) is a curing accelerator. Specifically, the component (C) may be any as long as it promotes the cross-linking reaction between the epoxy resin and the curing agent, and those used in the epoxy resin composition can be used.

The component (C) preferably contains an imidazole-based curing accelerator from the viewpoint of improving the curability at a low temperature.
Specific examples of the imidazole-based curing accelerator include imidazole, 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 2-Phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 -Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimerite, 1-cyanoethyl-2-phenylimidazolium trimerite, 2,4-diamino -6- [2'-methylimidazolyl (1')] -ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl (1')]-ethyl-s-triazine, 2, 4-Diamino-6- [2'-ethyl-4-methylimidazolyl (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl (1')]-ethyl- Isocyanuric acid adduct of s-triazine, isocyanuric acid adduct of 2-phenylimidazole, isocyanuric acid adduct of 2-methylimidazole, 2-phenyl-4,5-dihydroxydimethylimidazole, 2-phenyl-4-methyl-5 -Hydroxymethylimidazole can be mentioned.
Among these, from the viewpoint of improving low temperature curability and filling property, the component (C) is 2-phenylimidazole, 2-methylimidazole, 2-phenyl-4-methylimidazole, and 2-phenyl-4-methyl-. It preferably contains one or more compounds selected from the group consisting of 5-hydroxymethylimidazole, more preferably one or more of 2-phenylimidazole and 2-methylimidazole.
Further, from the viewpoint of improving the balance between low-temperature curability and filling property, the number of functional groups of the imidazole-based curing accelerator is preferably 3 or less, and more preferably 1 or less.

The content of the component (C) in the resin composition is preferably 0.20% by mass or more, more preferably 0, based on the total solid content of the resin composition from the viewpoint of improving the curability during molding. .40% by mass or more, more preferably 0.70% by mass or more. Further, from the viewpoint of improving the fluidity at the time of molding, the content of the component (C) in the resin composition is preferably 3.5% by mass or less with respect to the total solid content of the resin composition, which is more preferable. Is 3.0% by mass or less, more preferably 2.0% by mass or less.

Further, the resin composition may contain components other than the components (A) to (C).
For example, the resin composition preferably further comprises (D) an inorganic filler.

(Component (D))
Specific examples of the inorganic filler of the component (D) include fused crushed silica, molten spherical silica, crystalline silica, secondary agglomerated silica and other silica; alumina; titanium white; aluminum hydroxide; talc; clay; mica; glass fiber and the like. Can be mentioned. Among these, silica is preferable from the viewpoint of improving the production stability and yield of the resin composition and improving the resin characteristics related to reliability such as filling property and volume resistivity during molding of the resin composition, and silica is preferable. Silica is more preferred.

The particle shape of the component (D) is preferable from the viewpoint of improving the production stability and yield of the resin composition and improving the resin properties related to reliability such as filling property and volume resistivity during molding of the resin composition. Is approximately spherical.
The average particle size of the component (D) is not limited, but from the viewpoint of improving the manufacturing stability of the resin composition and when the resin composition is used as a semiconductor encapsulant, the periphery of the semiconductor element in the mold cavity. From the viewpoint of enhancing the filling property into, for example, it is 1 to 100 μm, preferably 1 to 50 μm, and more preferably 1 to 20 μm.

In addition, as components other than the components (A) to (D), coupling agents such as silane coupling agents; natural waxes, synthetic waxes, higher fatty acids or metal salts thereof, demolding agents such as paraffin and polyethylene oxide; silicone oils. , Low stress agent such as silicone rubber; Colorant such as carbon black; Ion trapping agent such as hydrotalcite, bismuth oxide, yttrium oxide; Inorganic flame retardant (for example, hydrated metal compound such as aluminum hydroxide) , Halogen-based flame retardants, phosphorus-based flame retardants, organic metal salt-based flame retardants, etc .; phenol-based antioxidants (dibutylhydroxytoluene, etc.), sulfur-based antioxidants (mercaptopropionic acid derivatives, etc.), phosphorus-based oxidation Antioxidants such as antioxidants (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.) can be mentioned, and the resin composition may contain one or more of these components. It may be included.
The amount of each of these components in the resin composition can be about 0.1 to 10 parts by mass, respectively, when the total amount of the components (A) and (B) is 100 parts by mass.

Next, the thermal characteristics of the resin composition will be described.
The resin composition in the present embodiment has a maximum heat generation start temperature of 70 ° C. or higher and 90 ° C. or lower when the temperature is raised from 25 ° C. to 200 ° C. under the condition of a heating rate of 5 ° C./min in differential scanning calorimetry. The heat generation temperature is 90 ° C. or higher and lower than 130 ° C.
Here, the heat generation start temperature and the maximum heat generation temperature of the resin composition can be obtained from the DSC curve obtained by measuring the resin composition under the above conditions using a differential scanning calorimeter.

The heat generation start temperature of the resin composition is 70 ° C. or higher, preferably 72 ° C. or higher, from the viewpoint of maintaining a low viscosity of the resin composition during curing at a low temperature and improving the filling property during molding. It is preferably 75 ° C. or higher.
From the viewpoint of improving the low temperature curability, the heat generation start temperature of the resin composition is 90 ° C. or lower, preferably 89 ° C. or lower, more preferably 88 ° C. or lower, and preferably 81 ° C. or lower. ..
Here, the heat generation start temperature is the heat generation height when the difference between the heat generation height H1 at 60 ° C. and the heat generation height Hmax at the maximum heat generation temperature is ΔH1 and the heat generation height H1 is used as a reference. Is the temperature when it reaches 10% of ΔH1.

Further, in the DSC curve of the resin composition, the number of exothermic peaks exceeding 30% of ΔH1 is preferably one from the viewpoint of improving the production stability of the resin composition.

Further, in the DSC curve of the resin composition, the peak height at the maximum heat generation temperature is represented by the difference in heat generation amount between the heat generation amount at 60 ° C. and the heat generation amount at the maximum heat generation temperature.

The maximum heat generation temperature of the resin composition is 90 ° C. or higher, preferably 92 ° C. or higher, from the viewpoint of maintaining a low viscosity of the resin composition when cured at a low temperature and improving the filling property during molding. , More preferably 95 ° C. or higher.
From the viewpoint of improving the low temperature curability, the maximum heat generation temperature of the resin composition is less than 130 ° C., preferably 120 ° C. or lower, more preferably 118 ° C. or lower, and further preferably 115 ° C. or lower.

In the heat generation curve obtained by DSC of the resin composition, the temperature when 50% of ΔH, which is the difference between the heat generation height Hmax at the maximum heat generation temperature and the heat generation height Hs at the heat generation start temperature, is reached is low. From the viewpoint of achieving both fluidity and curability during forming and improving storage stability during storage, the temperature is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 85 ° C. or higher, and further. More preferably, it is 90 ° C. or higher.
Further, from the viewpoint of achieving both fluidity and curability during low-temperature molding and storage stability during storage, the temperature when the heat generation curve obtained by DSC reaches 50% of ΔH is preferably 150. The temperature is less than or equal to 147 ° C., more preferably 147 ° C. or lower, still more preferably 140 ° C. or lower, still more preferably 130 ° C. or lower, still more preferably 125 ° C. or lower.
Further, from the same viewpoint, among the temperatures when 50% of ΔH is reached, the temperature on the lower temperature side and the temperature on the higher temperature side than the maximum heat generation temperature are both in the range of 80 ° C. or higher and 150 ° C. or lower. Is more preferable, and it is more preferably in the range of 80 ° C. or higher and 145 ° C. or lower, and further preferably in the range of 90 ° C. or higher and 140 ° C. or lower.

In the heat generation curve obtained by DSC of the resin composition, among the temperatures when 50% of ΔH, which is the difference between the heat generation height Hmax at the maximum heat generation temperature and the heat generation height Hs at the above-mentioned heat generation start temperature, is reached. The temperature on the lower temperature side than the maximum heat generation temperature is preferably 80 ° C. or higher, more preferably 82 ° C., from the viewpoint of achieving both fluidity and curability during low-temperature molding and storage stability during storage. Above, more preferably 85 ° C. or higher.
Further, from the viewpoint of achieving both fluidity and curability during low-temperature molding and from the viewpoint of storage stability during storage, the temperature on the lower temperature side than the maximum heat generation temperature among the temperatures when reaching 50% of ΔH is For example, it is 110 ° C. or lower, preferably 105 ° C. or lower, more preferably 95 ° C. or lower, and preferably 92 ° C. or lower or 90 ° C. or lower.
Here, the temperature on the lower side than the maximum heat generation temperature among the temperatures when the temperature reaches 50% of ΔH is, specifically, 50% of ΔH in the temperature zone between the heat generation start temperature and the maximum heat generation temperature. It means the temperature when it reaches.

In the present embodiment, by appropriately selecting the constituent components of the resin composition and the production method, it is possible to obtain a resin composition in which the heat generation start temperature and the maximum heat generation temperature in the DSC are in a specific range.
In particular, in the method for producing a resin composition, it is important to form a particulate, preferably core-shell particulate resin composition in the procedure described later in order to control the heat generation start temperature and the maximum heat generation temperature in the DSC. Is. Further, as a result, for example, the heat generation start temperature and the maximum heat generation temperature of the resin composition can be set within a specific range. The reason for this is not necessarily clear, but it is considered that the curing characteristics of the resin composition are affected by the control of the resin composition.
Hereinafter, a method for producing the resin composition will be described.

Specifically, the resin composition can be obtained by a production method including the following melt-mixing step, charging step and granulation step. Hereinafter, a case where the resin composition contains the components (A) to (D) will be described as an example.
(Melting and mixing step) Step of obtaining a melt mixture (M) of the epoxy resin of the component (A) and the curing agent of the component (B) (Additional step) The curing accelerator and the component of the melt mixture (M) and the component (C). The inorganic filler of (D) and components other than the components (A) to (D) as appropriate are charged into the stirring device after the step (granulation step) charging device of the stirring device provided with the stirring blades. The linear velocity of the tip of the stirring blade is 0. For example, the mixture is driven at a speed of 1 m / s or more and heated while mixing to bring the temperature to, for example, 110 ° C. or higher, and the molten mixture (M) is contained outside the core containing the components (C), (D) and other components as appropriate. The process of obtaining core-shell particles with a shell

Although the detailed mechanism is unknown, in the granulation process, for example, the molten mixture (M) moderately softened at a temperature of 110 ° C. or higher is larger due to stirring at a constant speed or higher (specifically, rotation of the stirring blade). It is considered that by receiving the shearing force, the surface of the core containing the components (C), (D) and other components as appropriate can be easily coated thinly and uniformly. Then, it is considered that core-shell particles having a substantially uniform shell thickness can be obtained.

In addition, the components (C), (D) and other components are appropriately mixed by a large shearing force with stirring at a constant speed or higher. As a result, a shell of the molten mixture (M) can be formed around the core containing the components (C), (D) and optionally other components. That is, it is considered that if the core-shell particles are produced by the above-mentioned method for producing a resin composition, it becomes easy to include the components of the resin composition in one particle in a well-balanced manner. This is preferable not only in terms of particle homogeneity but also in terms of component distribution homogeneity.
Hereinafter, each of the above-mentioned steps, steps that may be optionally included, and the like will be described in more detail.

(Melting and mixing process)
In the melt-mixing step, the components (A) and (B) are used, and a melt-mixture (M) thereof is obtained by an appropriate method.
The method of melt mixing is not limited. For example, (1) first, the components (A) and (B) are placed in a suitable container, for example, a heat-mixable container such as a heating pot, (2) then they are heated and mixed, and (3) then A molten mixture (M), which is a pulverized product, can be obtained by a three-step method of producing a pulverized product through cooling and pulverization steps. The shape of the obtained pulverized product is, for example, granular or particulate.
In addition, premixing may be performed before the above-mentioned step (1).

The heating and mixing in the above step (2) is carried out under the conditions of 120 to 180 ° C. for 1 to 60 minutes, for example, by providing a jacket in a heating pot to circulate the heat medium oil and then using a stirrer with a stirring blade. Can be done at.
In the cooling and crushing step of the above step (3), for example, the mixture obtained in the above step (2) is cooled to 40 ° C. or lower, preferably 10 ° C. or lower, and then a known crushing device such as a granulator is used. And so on. After the crushing step, a step of adjusting the particle size by removing coarse particles and particles that are too fine may be performed, and such a step can be, for example, a classification step using a sieve or the like.

The average particle size of the molten mixture (M), which is a pulverized product, is preferably 5 mm or less, more preferably 0.1 to 2 mm. By reducing the average particle size of the molten mixture (M) to some extent, it tends to be easier to make the thickness of the shell more uniform in the granulation step described later.

In the melt-mixing step, at least the components (A) and (B) are used as raw materials to obtain a melt mixture (M), but raw materials other than these may be additionally used.
Examples of the raw material that can be additionally used include the above-mentioned coupling agent, mold release agent, and low stress agent. When these raw materials are used, the amount thereof can be, for example, about 0.1 to 10 parts by mass when the total amount of the components (A) and (B) is 100 parts by mass.

From the viewpoint of suppressing deterioration of the raw material and stability over time, the melt mixture (M) preferably does not contain the component (C) which is a curing catalyst of the epoxy resin.

(Input process)
In the charging step, at least the above-mentioned molten mixture (M), component (C), (D) and other components as appropriate are charged into a stirring device equipped with a stirring blade.
Specific examples of other components that can be used in the charging process include the above-mentioned colorants, ion scavengers, flame retardants, and antioxidants.

The stirring device provided with the stirring blade (hereinafter, also simply referred to as “stirring device”) is provided with a stirring blade capable of stirring the molten mixture (M), the components (C), (D) and other components as appropriate, and also. When the stirring blade is driven, the linear velocity at the tip of the blade may be set to, for example, 0.1 m / s or more in the granulation step described later, and is not limited. Here, the stirring blade is often also referred to as a "stirring blade". The linear velocity at the tip of the blade will be described in detail later.
Since the pressure may be reduced in the granulation step described later, it is preferable that the stirring device can be stirred under reduced pressure.

As for the stirring device, for example, FIGS. 1, 2 (i), 2 (ii) and the like can be shown. These figures are cross-sectional views schematically showing an example of a stirrer.
The stirring device 1 includes a stirring blade 2, a shaft 3, and a tank body 4. Further, although not shown, a motor for rotating the stirring blade 2 and the shaft 3; a speed reducer for reducing the rotation of the motor to a rotation speed suitable for stirring; a lid for stirring in a closed state; depressurization or Equipment for pressurization; equipment for temperature control such as heaters, cooling devices, thermometers; and other necessary equipment can be provided.

The shape of the stirring blade 2 is not limited to the shape shown in FIGS. 1, 2 (i) and 2 (ii), and includes an anchor shape, a helical ribbon shape, a propeller shape, a disc turbine shape, and an inclined paddle shape. Various types known in the field of agitators, such as edged turbine shapes, can be used.

By appropriately adjusting the amount ratio of the molten mixture (M), component (C), (D) and other components charged into the apparatus in the charging process, the homogeneity of the particles such as the uniformity of the thickness of the shell The sex can be further enhanced.

For example, the proportion of the molten mixture (M) in all the components charged into the stirring device 1 in the charging step can be, for example, 50% by mass or less, preferably 30% by mass or less, and more preferably 15% by mass or less. , More preferably 0.1 to 10% by mass, and even more preferably 0.1 to 5% by mass, the homogeneity of the particles such as the uniformity of the thickness of the shell can be further enhanced.
The amount of the component (D) to be charged is preferably 40 to 99.9% by mass, more preferably 50 to 99.9% by mass, still more preferably 50 to 99.9% by mass, based on all the components charged to the stirring device 1 in the charging step. Is 85-99.9% by mass.
The amount of the component (C) to be charged and other components is preferably 0.1 to 3% by mass, more preferably 0.1 to 1% by mass, respectively, among all the components charged to the stirring device 1 in the charging step. Is.

(Granulation process)
In the granulation step after the charging step, the components charged into the stirring device 1 in the charging step are heated while being mixed by driving the stirring blade 2 to, for example, 110 ° C. or higher. This temperature is preferably 110 to 180 ° C, more preferably 120 to 170 ° C. When the temperature is, for example, 110 ° C. or higher, the molten mixture (M) is moderately softened, and it becomes easy to coat a uniform shell. Further, when the temperature is, for example, 180 ° C. or lower, deterioration of the raw material and the like can be suppressed, and the performance of the finally obtained core-shell particles and the resin composition using the same can be further improved.
Here, "the component charged into the stirring device 1 in the charging step is set to 110 ° C. or higher" means that the component itself charged into the stirring device 1 in the charging step, that is, the component itself finally granulated. It means that the temperature becomes 110 ° C or higher. This can be confirmed, for example, by temporarily suspending the granulation process and measuring the temperature of the contents in the stirring device 1. Alternatively, a stirring device 1 having a viewing window may be used, and the temperature may be measured by measuring the temperature from the viewing window with a radiation thermometer.

In the granulation step, the shaft 3 and the stirring blade 2 are rotated at a somewhat large rotation speed so that the linear velocity at the tip of the stirring blade 2 is, for example, 0.1 m / s or more. As a result, the appropriately softened molten mixture (M) receives a large shearing force by stirring at a high speed. Then, it is considered that core-shell particles having a shell (thickness is substantially uniform) containing the molten mixture (M) can be obtained on the outside of the core containing the components (C), (D) and other components as appropriate. Also, due to the large shear force, the components (C), (D) and other components are appropriately mixed, and as a result, melt around the core containing the components (C), (D) and other components as appropriate. It is believed that a shell of the mixture can be formed.

The "tip of the stirring blade 2" is supplemented.
The tip of the stirring blade 2 is typically the portion where the moving distance per unit time is the largest when the stirring blade 2 rotates. In other words, it can be expressed as a portion that moves fastest when the stirring blade 2 rotates, specifically, a portion that shows the fastest linear velocity.
In the stirring blade 2 of FIG. 1, both ends thereof, that is, the right end and the left end in the figure are “tips”.
In the case of FIG. 2 (i), there are three stirring blades 2 in form, but the tip of the bottom stirring blade 2 in the figure, which has the largest turning radius, corresponds to the "tip of the stirring blade 2". To do.
In the case of FIG. 2 (ii), the stirring blade 2 shown in the figure has five protrusions symmetrically with respect to the axis 3, and among them, the bottom protruding portion. The moving distance is the largest when the tip is rotated, and corresponds to the "tip of the stirring blade 2".

In addition, "the linear velocity at the tip of the stirring blade 2" will be supplemented.
The linear velocity of the tip of the stirring blade 2 typically means the maximum value of the relative velocity of the tip of the stirring blade 2 with respect to the tank body 4. Here, the tank body 4 is usually fixed.
When there is one rotation axis, the value obtained by the formula of πND / 60 is the value of the stirring blade 2 where the diameter (rotation diameter) of the stirring blade 2 is D (m) and the rotation speed is N (rpm). The linear velocity at the tip (m / s). Here, π is the pi.
For example, when the stirring blade rotates and revolves like a planetary mixer, the linear velocity at the tip of the blade cannot be calculated by the above simple formula, but the rotation velocity and the revolution velocity are appropriately combined. The maximum value of the relative speed of the tip of the stirring blade may be obtained by such means. Alternatively, the linear velocity at the tip of the blade may be obtained by actual measurement instead of calculation. For example, the stirring device 1 may be driven without a material to be inserted to take a moving image of the movement of the tip of the blade, and the moving image may be analyzed.

The linear velocity of the tip of the stirring blade 2 may be, for example, 0.1 m / s or more, preferably 0.4 m / s or more, and more preferably 1.0 m / s or more. The upper limit of the linear velocity is not limited, but from the viewpoint of device restrictions and the like, it is preferably 10 m / s or less, more preferably 8 m / s or less, and further preferably 5 m / s or less.

Normally, there is a clearance, that is, a gap between the tip of the stirring blade 2 and the tank body 4. In FIGS. 1, 2 (i) and 2 (ii), the size of this clearance is specified as a. Although the details are unknown, it is presumed that due to the appropriate clearance, the components colliding with the stirring blade 2 appropriately escape to the clearance during the granulation process, which further promotes granulation. It is considered that this makes it possible to further align the particle size distribution of the particles.
Specifically, the size of the clearance is preferably 0.5 to 10 mm, more preferably 1 to 8 mm.

In the granulation step, the time for keeping the component charged into the stirring device 1 at, for example, 110 ° C. or higher, specifically, the time for keeping the component at 110 ° C. or higher is preferably 5 to 200 minutes, more preferably. It takes 10 to 180 minutes, more preferably 20 to 150 minutes. By setting this time to 10 minutes or more, it becomes easy to form a shell having a sufficient thickness, and the thickness of the shell can be made more uniform. Further, by setting this time to 200 minutes or less, deterioration of the material and the like can be suppressed. Therefore, when the core-shell particles are applied to the resin composition, various performances can be further improved.

Part or all of the granulation step is preferably carried out under reduced pressure. Specifically, part or all of the granulation step is preferably under a reduced pressure of 30 kPa or less, more preferably under a reduced pressure of 0.01 to 20 kPa, still more preferably under a reduced pressure of 0.05 to 15 kPa, even more preferably. Is carried out under reduced pressure of 0.1 to 10 kPa.
For depressurization, for example, by using a stirrer 1 capable of depressurizing during stirring, the granulation step can be performed under reduced pressure.
The depressurization is preferably carried out for at least half or more of the total time of the granulation step.

It is considered that the water content contained in the components charged into the stirring device 1 is further reduced by performing a part or all of the granulation process under reduced pressure. More specifically, it is considered that most of the water adhering to the charged component (D) and the like is removed by depressurization (and heating at, for example, 110 ° C. or higher). As a result, the situation where the molten mixture (M) solidifies only in a part of the core containing the components (C), (D) and other components as appropriate is further suppressed, and a shell having a more uniform thickness can be formed. Conceivable.
Above all, when the component (D) is silica, it is considered that water removal by decompression (deaeration) is preferable because silica easily adsorbs water due to its nature.

Here, in the granulation step, since the charged components are heated at, for example, 110 ° C. or higher, a certain amount of water is removed without reducing the pressure. That is, decompression is not essential in the granulation process. However, it is preferable to reduce the pressure from the viewpoint of further reducing the water content.

From the viewpoint of "removing water", a water reduction step for reducing the water contained in the component (D) or the like may be provided. The above-mentioned "decompression" may correspond to this water removal step, but the water contained in the component (D) or the like may be reduced by a method different from the decompression.
For example, before the charging step, it is conceivable to heat the components (C), (D) and other components as appropriate to sufficiently dry the water before charging. Further, before the charging step, the components (C), (D) and other components may be degassed as appropriate to reduce the adhering water content.
However, from the viewpoint of simplification of the manufacturing process and cost reduction, it is preferable to reduce the water content by reducing the pressure in the granulation process.

By the above procedure, the resin composition of the present embodiment can be obtained as core-shell particles.

(Cooling and stirring process)
Further, in the present embodiment, the method for producing the particulate resin composition is preferably a cooling stirring step in which the stirring blade 2 is rotated to cool the components in the stirring device while stirring after the granulation step. Including. As a result, agglomeration and formation of agglomerates during cooling of the core-shell particles obtained in the above-mentioned granulation step can be further suppressed.

The speed at which the stirring blade 2 is rotated in the cooling stirring step is not limited, but the linear velocity at the tip of the stirring blade 2 is appropriately in the range of, for example, 0.01 to 10 m / s, preferably 0.1 to 5 m / s. Can be set.
The time of the cooling and stirring step is not limited and can be set as appropriate. For example, it is 10 to 200 minutes, preferably 20 to 180 minutes, and more preferably 30 to 150 minutes.

The core-shell particles are preferably cooled to a temperature equal to or lower than the softening point of the molten mixture (M) by a cooling and stirring step. Typically, the core-shell particles are preferably cooled to 60 ° C. or lower, more preferably 55 ° C. or lower, even more preferably 50 ° C. or lower, to room temperature by a cooling and stirring step. It is even more preferable to be cooled.

In the cooling and stirring step, as in the granulation step, decompression may be performed in part or in whole. The pressure at the time of depressurization is, for example, 20 kPa or less, preferably 0.01 to 20 kPa, and more preferably 0.05 to 15 kPa. It is considered that the reduction of water content and the reattachment of water content can be suppressed by reducing the pressure even during cooling, and as a result, the agglomeration of particles and the like can be further reduced.

(Crushing process)
Further, if the particles obtained in the granulation step are agglomerated, for example, when two or more core-shell particles are attached to each other, a crushing step for crushing the agglomerates may be performed.
The specific method of pulverization is not limited, but for example, an impact type such as a hammer mill can be used. The raw material supply rate can be set to 1 to 1000 kg / h.
Further, at the time of pulverization, a ball mill such as a vibrating ball mill, a continuous rotary ball mill or a batch type ball mill; a pot mill such as a wet pot mill or a planetary pot mill; a roller mill or the like may be used.

The shell thickness of the core-shell particles of the resin composition finally obtained through each of the above steps is, for example, 0.1 to 10 μm, preferably 0.5 to 5 μm, and more preferably 1 to 3 μm. The thickness of the shell and the uniformity of the thickness of the shell appear on the polished cut surface, for example, by cutting a core-shell particle embedded in a resin with a cutting machine and polishing the cut surface. It can be evaluated by observing the cross section of the core-shell particles (those in which the cut surface of the particles can be observed). For observation, for example, an electron microscope such as a magnifying glass, an optical microscope, or a scanning electron microscope can be used.

The average particle size of the core in the finally obtained core-shell particles is, for example, 2 to 55 μm, preferably 4 to 50 μm, and more preferably 10 to 45 μm.
The average particle size of the finally obtained core-shell particles is, for example, 3 to 60 μm, preferably 5 to 50 μm, and more preferably 10 to 45 μm.
For the average particle size of the core-shell particles, for example, a volume-based particle size distribution data is acquired by a laser diffraction / scattering type particle size distribution measuring device (for example, a wet particle size distribution measuring machine LA-950 manufactured by Horiba Seisakusho Co., Ltd.). It can be obtained by processing the data.

It is obtained as core-shell particles by the production method described above. The core-shell particles are used as constituents of the resin composition in this embodiment. Then, the core-shell particles include a shell containing the components (A) and (B) on the outside of the core containing the components (C), (D) and other components as appropriate. The average particle size of the core-shell particles, the average particle size of the core, the thickness of the shell, and the like are as described above.

Here, the fact that the core-shell particles are used as a constituent component of the resin composition includes both of the following.
(I) Using the core-shell particles alone as a resin composition (ii) Mixing and kneading the core-shell particles and other components, or both, and using the core-shell particles as a resin composition.

Examples of the "other components" in the case of the above (ii) include the melt mixture (M) described in the above-mentioned melt-mixing step, the above-mentioned components (C) and (D), a colorant, an ion scavenger, and a cup. Examples include ring agents, curing catalysts, mold release agents, low stress agents, flame retardants, antioxidants and the like.

Further, in any of the above cases (i) and (ii), the core-shell particles or the resin composition obtained as a mixture / kneaded product of the core-shell particles and other components can be used when put into practical use. It may be locked in a suitable form.

In the resin composition obtained in the present embodiment, the ratio of the maximum torque of 10% arrival time T1 before and after storage at 25 ° C. for 3 days, which is measured under the following conditions, is a viewpoint for improving the storage stability of the resin composition. Therefore, it is preferably 0.85 or more, more preferably 0.88 or more, and further preferably 0.9 or more. From the same viewpoint, the ratio of T1 is preferably 1.15 or less, preferably 1.12 or less, still more preferably 1.1 or less, still more preferably 1.0 or less, and even more preferably. It is less than 1.0.
(conditions)
When the TAB size is 35φ, the mold temperature is 100 ° C., the measurement time is 5 minutes, the torque range is 300 kgf · cm, and the torque value when reaching the maximum is 100%, the arrival time of 10% is defined as T1.

(Molded body)
In the present embodiment, the molded product comprises a cured product of the resin composition according to the above-mentioned embodiment.

(Structure)
In this embodiment, the structure has a molded body according to this embodiment. That is, the structure has a cured product of the resin composition according to the present embodiment.
The structure is not limited, but in addition to semiconductor packages, modules with indicators such as liquid crystal displays (LCD) and light emitting diodes (LEDs); modules or devices with batteries such as dry batteries and coin batteries; plastic lens composite infrared sensors, Examples include cameras.
Further, in the present embodiment, the structure can also be used, for example, in a product having a heat resistance of 100 ° C. or lower or a component thereof.

FIG. 3 is a cross-sectional view schematically showing the structure of a semiconductor device using a resin composition as an example of the structure. In the semiconductor device 10 shown in FIG. 3, the semiconductor element 11 is fixed on the die pad 13 via the die bond material cured body 12. The electrode pad of the semiconductor element 11 and the lead frame 15 are connected by a bonding wire 14. The semiconductor element 11 is sealed by a molded body 16 made of a cured product of the resin composition of the present embodiment.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.

Hereinafter, the present embodiment will be described in detail with reference to Examples and Comparative Examples. The present embodiment is not limited to the description of these examples.

First, the raw materials used in the following examples are shown.
(Epoxy resin)
Epoxy resin 1: Orthocresol novolac type epoxy resin, manufactured by Changchun Artificial Resin Co., Ltd., CNE-195LL
Epoxy resin 2: Triphenol methane type epoxy resin, manufactured by Mitsubishi Chemical Corporation, E-1032H60
Epoxy resin 3: Biphenylene skeleton-containing phenol aralkyl type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., NC3000

(Inorganic filler)
Inorganic filler 1: Crystalline silica, manufactured by Morimura Brothers, CH-A
Inorganic filler 2: Spherical alumina, manufactured by Denka, DAM-40K
Inorganic filler 3: silica, manufactured by Admatex, SC-2500-SQ
Inorganic filler 4: Silica, manufactured by Denka, FB-105FC

(Hardener)
Hardener 1: Phenolic novolac resin, manufactured by Sumitomo Bakelite, PR-55617
Hardener 2: Phenylene skeleton-containing phenol aralkyl resin, manufactured by Nippon Kayaku Co., Ltd., GPH-65

(Curing accelerator)
Curing Accelerator 1: Imidazole Curing Accelerator (2-phenylimidazole), manufactured by Shikoku Kasei Co., Ltd., 2PZ-PW
Curing Accelerator 2: Imidazole Curing Accelerator (2-methylimidazole), manufactured by Shikoku Chemicals Corporation, 2MZ-H
Curing accelerator 3: Catalyst (tetraphenylphosphonium 4,4'-sulfonyl diphenolate), manufactured by Sumitomo Bakelite, C03-MB

(Additive)
Additive 1: Coupling agent, manufactured by Toray Dow Corning, CF4083
Additive 2: Release agent obtained in Production Example 1

Additive 3: Colorant, manufactured by Mitsubishi Chemical Corporation, carbon # 5
Additive 4: Low stress material, manufactured by Toray Dow Corning, FZ-3730
Additive 5: Release agent, manufactured by Toa Kasei Co., Ltd., C-WAX
Additive 6: Coupling agent, manufactured by Chisso, GPS-M

(Manufacturing Example 1)
The above additive 2 (release agent) was obtained by the following method.
300 g of a copolymer of maleic anhydride and a mixture of 1-octacosene, 1-triacontene, 1-tetracontene, 1-pentacontene, 1-hexacontene, etc. (Diacarna (registered trademark) 30 manufactured by Mitsubishi Chemical Industry Co., Ltd.), 141 g of stearyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved at 100 ° C., 5 g of a 10% aqueous solution of trifluoromethanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was reacted at 160 ° C. for 8 hours, and then 160 ° C. under reduced pressure. By carrying out the reaction for 2 hours, 436 g of a mold release agent and a softening point of 55 ° C. were obtained.

(Examples 1 to 4, Comparative Examples 1 and 2)
(Manufacturing of resin composition)
(Examples 1 to 4 and Comparative Example 2)
For each example, a core-shell resin composition was produced by the following procedure based on the components and formulations shown in Table 1.

1. 1. Melt-Mixing Step Of the raw materials shown in Table 1, an epoxy resin, a curing agent and an additive 2 (release agent) were put into a heating pot and heated with a heat medium oil at 150 ° C. Stirring with a stirring blade was started when the material temperature exceeded 100 ° C., Additive 1 (coupling agent) was added when the material temperature exceeded 120 ° C., and then the mixture was stirred for 5 minutes.
After the stirring was completed, the mixture was transferred to another container and cooled at 10 ° C. The material was cooled to 20 ° C. or lower, and then pulverized with a hammer mill.
From the above, a pulverized product of the molten mixture having an average particle size of 700 μm was obtained.

2. Loading process In the tank body of the stirrer, the above 1. The pulverized product, curing accelerator, inorganic filler, additive 3 (colorant) and additive 4 (low stress material) of the melt mixture obtained in the above were added.
As the stirring device, a device having a clearance (distance between the tip of the stirring blade and the tank body) of 3.0 mm was used. This stirring device was equipped with a motor and speed regulator for stirring, a lid for stirring in a closed state, a pump for depressurization, a heater for temperature control, a viewing window, and the like.

3. 3. Granulation process 2. The components charged into the tank body were mixed by rotating the stirring blades so that the linear velocity at the tip was 1.0 m / s, and heated by the heater provided in the stirring device. The temperature of the contents in the tank body was maintained at 120 ° C., and the stirring blades were continuously rotated under normal pressure for 30 minutes. The temperature of the contents inside the tank body was confirmed with a radiation thermometer from the viewing window provided in the stirring device.
As a result, core-shell particles having a shell (average thickness 0.1 to 10 μm) containing a molten mixture were granulated on the outside of the core containing the inorganic filler and the additive 3 (colorant).

4. Cooling and stirring process 3. After the above step, the heating of the heater was weakened, and then the stirring blade was rotated so that the linear velocity at the tip became 1.0 m / s, and the core-shell particles were cooled for 120 minutes until the temperature of the core-shell particles became 45 ° C. or lower.

5. Crushing step If partial agglomeration of core-shell particles is confirmed, the above 4. The core-shell particles cooled in 1 were put into a hammer mill for processing.
Through the above steps, the resin compositions of each example were obtained.

(Comparative Example 1)
First, each of the raw materials blended according to Table 1 was mixed at room temperature using a mixer, and then roll-kneaded at 70 to 100 ° C. Then, the obtained kneaded product was cooled and then pulverized to obtain a powdery and granular resin composition.

(DSC)
The thermal properties of the resin compositions obtained in each example were measured by DSC.
Using a differential scanning calorimeter (manufactured by SII, DSC7020), a 10 mg resin composition was measured under a nitrogen stream under a temperature range of 25 ° C. to 200 ° C. at a heating rate of 5 ° C./min. When the difference between the calorific value height H1 at 60 ° C. and the calorific value height Hmax at the maximum heat generation temperature is ΔH1 and the calorific value height reaches 10% of ΔH1 when the calorific value height H1 is used as a reference. Was defined as the heat generation start temperature. The exothermic peak was assumed to exceed 30% of ΔH1.

(Curast torque)
For the resin composition obtained in each example, using a curast meter (Curast meter MODEL7 manufactured by A & D Co., Ltd.), TAB size 35φ, mold temperature 100 ° C., measurement time 5 minutes, torque range 300 kgf. The torque value of the resin composition was measured over time under the condition of cm, and the maximum torque 10% arrival time T1 (s) was determined from the start of the measurement.
The measurement was carried out at 25 ° C. before and after storage for 3 days, and the ratio of the above T1 before and after storage was calculated.

(Curing characteristics at low temperature)
The curing characteristics of the resin composition obtained in each example at low temperature were evaluated by the following methods and criteria. The evaluation results are also shown in Table 1.
(Spiral flow)
The spiral flow measurement of the resin composition obtained in each example was carried out. In a low-pressure transfer molding machine (KTS-30, manufactured by Kotaki Seiki Co., Ltd.), use a mold for measuring spiral flow according to EMMI-1-66, set the mold temperature to 100 ° C., and measure for 5 minutes. The resin composition was charged and the flow length (cm) was measured.
In Comparative Example 1, when the mold temperature was 100 ° C., the measurement was not performed because the mold could not be cured in 5 minutes, and the mold temperature was set to 175 ° C., and the measurement according to the above method was 140 cm. It was.
In Comparative Example 2, when the mold temperature was 100 ° C., the measurement was not performed because the curing was not possible in 5 minutes, and the mold temperature was set to 120 ° C., and the measurement according to the above method was 15 cm. It was.

(Bending strength / Elastic modulus)
For the resin composition obtained in each example by measurement by molding, the resin composition was cured at a mold temperature of 100 ° C. and a measurement time of 5 minutes to obtain a molded product, and then JIS was performed in an atmosphere of 25 ° C. A three-point bending test was carried out by a method conforming to K6911. It was evaluated whether the cured product of each example had sufficient bending strength (MPa) and elastic modulus (MPa) even when molded at a lower temperature than the cured product of Comparative Example 1.
Here, the cured product of Comparative Example 1 was evaluated by the following method. That is, with respect to the resin composition obtained by the measurement by molding the molded product, the resin composition was cured at a mold temperature of 175 ° C. and a measurement time of 3 minutes to obtain a molded product, and then the resin composition was subjected to JIS K6911 in an atmosphere of 25 ° C. A three-point bending test was carried out by a method based on the method, and the bending strength (MPa) and elastic modulus (MPa) of the cured product of the resin composition of Comparative Example 1 were evaluated. The result was a bending strength of 165 MPa and an elastic modulus of 17,500 MPa.
In Comparative Example 2, the resin composition obtained by the measurement by molding the molded product was cured at a mold temperature of 120 ° C. and a measurement time of 3 minutes to obtain a molded product, and then in an atmosphere of 25 ° C. , A three-point bending test was carried out by a method according to JIS K6911, and the bending strength (MPa) and elastic modulus (MPa) of the cured product of the resin composition of Comparative Example 2 were evaluated. The result was a bending strength of 105 MPa and an elastic modulus of 19000 MPa.

From Table 1, the resin compositions obtained in each example were superior in curing characteristics at low temperatures as compared with those in the comparative examples.

1 Stirrer 2 Stirrer blade 3 Shaft 4 Tank body 10 Semiconductor device 11 Semiconductor element 12 Die bond material Cured body 13 Die pad 14 Bonding wire 15 Lead frame 16 Molded body

This application claims priority on the basis of Japanese Application Japanese Patent Application No. 2019-052396 filed on March 20, 2019, and incorporates all of its disclosures herein.

According to the present invention
(A) Epoxy resin and
(B) Hardener and
(C) Curing accelerator and
A resin composition for a molding material containing
The component (C) contains an imidazole-based curing accelerator and contains an imidazole-based curing accelerator.
When the differential scanning calorimetry of the resin composition for molding material was performed at 25 to 200 ° C. under the condition of 5 ° C./min.
The heat generation start temperature is 70 ° C or higher and 90 ° C or lower.
A resin composition for a molding material having a maximum exothermic temperature of 90 ° C. or higher and lower than 130 ° C. is provided.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.
Hereinafter, an example of the reference form will be added.
[1]
(A) Epoxy resin and
(B) Hardener and
(C) Curing accelerator and
A resin composition for a molding material containing
When the differential scanning calorimetry of the resin composition for molding material was performed at 25 to 200 ° C. under the condition of 5 ° C./min.
The heat generation start temperature is 70 ° C or higher and 90 ° C or lower.
A resin composition for a molding material having a maximum heat generation temperature of 90 ° C. or higher and lower than 130 ° C.
[2]
The resin composition for a molding material according to the above [1], wherein the ratio of the max torque 10% arrival time T1 before and after storage at 25 ° C. for 3 days measured under the following conditions is 0.85 or more and 1.15 or less. Stuff.
(conditions)
TAB size 35φ, mold temperature 100 ° C, measurement time 5 minutes, torque range 300kgf ・ cm
[3]
In the heat generation curve obtained by the differential scanning calorimetry, the temperature when 50% of ΔH, which is the difference between the heat generation height Hmax at the maximum heat generation temperature and the heat generation height Hs at the heat generation start temperature, is reached. The resin composition for molding material according to the above [1] or [2], wherein the temperature on the lower temperature side and the temperature on the higher temperature side than the maximum heat generation temperature are both in the range of 80 ° C. or higher and 150 ° C. or lower.
[4]
In the heat generation curve obtained by the differential scanning calorimetry, the temperature when 50% of ΔH, which is the difference between the heat generation height Hmax at the maximum heat generation temperature and the heat generation height Hs at the heat generation start temperature, is reached. The resin composition for a molding material according to any one of the above [1] to [3], wherein the temperature on the lower temperature side than the maximum heat generation temperature is 80 ° C. or higher and 95 ° C. or lower.
[5]
The resin composition for a molding material according to any one of the above [1] to [4], wherein the component (C) contains an imidazole-based curing accelerator.
[6]
A molded product made of a cured product of the resin composition for a molding material according to any one of the above [1] to [5].
[7]
A structure having the molded product according to [6].

According to the present invention
(A) Epoxy resin and
(B) Hardener and
(C) Curing accelerator and
A resin composition for a molding material containing
The component (C) contains an imidazole-based curing accelerator and contains an imidazole-based curing accelerator.
When the differential scanning calorimetry of the resin composition for molding material was performed at 25 to 200 ° C. under the condition of 5 ° C./min.
The heat generation start temperature is 70 ° C or higher and 90 ° C or lower.
The maximum exothermic temperature is me 90 ℃ more than 130 ℃ less than Der,
Provided is a resin composition for a molding material, wherein the resin composition for a molding material is a core-shell particle having a shell containing the components (A) and (B) outside the core containing the component (C). To.

Claims (7)

(A) Epoxy resin and
(B) Hardener and
(C) Curing accelerator and
A resin composition for a molding material containing
When the differential scanning calorimetry of the resin composition for molding material was performed at 25 to 200 ° C. under the condition of 5 ° C./min.
The heat generation start temperature is 70 ° C or higher and 90 ° C or lower.
A resin composition for a molding material having a maximum heat generation temperature of 90 ° C. or higher and lower than 130 ° C. The resin composition for a molding material according to claim 1, wherein the ratio of the max torque 10% arrival time T1 before and after storage at 25 ° C. for 3 days measured under the following conditions is 0.85 or more and 1.15 or less. ..
(conditions)
TAB size 35φ, mold temperature 100 ° C, measurement time 5 minutes, torque range 300kgf ・ cm In the heat generation curve obtained by the differential scanning calorimetry, the temperature when 50% of ΔH, which is the difference between the heat generation height Hmax at the maximum heat generation temperature and the heat generation height Hs at the heat generation start temperature, is reached. The resin composition for a molding material according to claim 1 or 2, wherein the temperature on the lower temperature side and the temperature on the higher temperature side than the maximum heat generation temperature are both in the range of 80 ° C. or higher and 150 ° C. or lower. In the heat generation curve obtained by the differential scanning calorimetry, the temperature when 50% of ΔH, which is the difference between the heat generation height Hmax at the maximum heat generation temperature and the heat generation height Hs at the heat generation start temperature, is reached. The resin composition for a molding material according to any one of claims 1 to 3, wherein the temperature on the lower temperature side than the maximum heat generation temperature is 80 ° C. or higher and 95 ° C. or lower. The resin composition for a molding material according to any one of claims 1 to 4, wherein the component (C) contains an imidazole-based curing accelerator. A molded product comprising a cured product of the resin composition for a molding material according to any one of claims 1 to 5. A structure having the molded product according to claim 6.

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