JP2015189936A - One-component thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a one-component resin composition which can achieve both excellent storage stability and curing speed.SOLUTION: A one-component thermosetting resin composition comprises epoxy silicone resin and heat latent curing catalyst.

Description

  The present invention relates to a one-component thermosetting resin composition.

  The liquid sealing material used for the semiconductor device includes a one-part sealing material in which a base resin and a curing agent are mixed, a liquid containing a base resin composition, and a liquid containing a curing agent. There are two-pack type sealing materials that are used by mixing these liquids (for example, Patent Document 1, Patent Document 2). The two-pack type sealing material usually has an advantage that it can be cured in a short time at a relatively low temperature. On the other hand, it is most important to mix the two-component encapsulant at a predetermined ratio, and in addition to the complexity of weighing and mixing, a weighing error may occur. On the other hand, a one-pack type encapsulant is required to be heated for a long time at the time of curing, but does not require a mixing step, and provides a cured product of stable quality without causing blur due to a weighing error before mixing. Can do.

JP 2006-8888 A JP 2000-347203 A

However, since the one-component encapsulant has a trade-off relationship between storage stability and curing rate, there is a need for a one-component encapsulant that can be stored stably for a long period of time and has a sufficient curing rate. Yes.
The main object of the present invention is to provide a one-component resin composition capable of achieving both storage stability and curing speed.

In order to solve the above-mentioned problems, the present inventors have studied a thermosetting resin and a curing catalyst. By using a combination of an epoxy silicone resin and a specific thermal latent curing catalyst as a sealing material, storage stability is improved. The inventors have conceived that a one-component resin composition capable of achieving both compatibility and curing speed can be obtained. That is, the present invention is as follows.
[1] A one-component thermosetting resin composition comprising an epoxy silicone resin and a heat latent curing catalyst.
[2] The one-component thermosetting resin composition according to [1], wherein the latent heat curing catalyst is a cationic polymerizable catalyst.
[3] The one-component thermosetting resin composition according to [1] or [2], wherein the epoxy group in the epoxy silicone resin includes an alicyclic epoxy.
[4] The one-component thermosetting resin composition according to any one of [1] to [3], including an inorganic filler.
[5] The one-component thermosetting resin composition according to [4], wherein the inorganic filler is a silica filler.
[6] The one-component thermosetting resin composition according to [4] or [5], wherein the inorganic filler is a spherical filler.
[7] A method for producing a cured resin, comprising: heating and curing the one-component thermosetting resin composition according to any one of [1] to [6].

According to the present invention, a one-component resin composition having excellent storage stability and a constant curing rate is provided.
In addition, a one-component resin composition having fluidity is provided even if the filler is contained in a high concentration, and the cured product can achieve high insulation and a smooth surface.

  Hereinafter, the present invention will be described in detail according to embodiments. However, the present invention is not limited to the embodiments explicitly or implicitly described in this specification.

  In the following description, when referring to the insulation of the cured product of the resin composition, it means a volume resistance value (Ω · cm) measured according to JIS K6911.

1. Thermosetting resin composition The liquid resin composition which is the first embodiment of the present invention is a one-component thermosetting resin composition containing an epoxy silicone resin and a heat latent curing catalyst. Moreover, the one-pack type thermosetting resin composition is usually in a liquid state.
In this embodiment, liquid means having fluidity at normal temperature and normal pressure (1 atm, 25 ° C.). More specifically, when the composition is placed in an aluminum cup and tilted by 45 °, the internal composition cannot maintain its shape for more than 10 minutes and causes a change in shape. If not, “no fluidity”.
More specifically, at room temperature and normal pressure, the viscosity is usually 50,000 cp or less, preferably 40,000 cp or less, more preferably 30,000 cp or less, and 20,000 cp or less. More preferably, it is particularly preferably 15,000 cp or less, and most preferably 10,000 cp or less. By satisfying the physical properties in this range, the resin composition can be suitably used particularly for potting.
Hereinafter, the components contained in the thermosetting resin composition will be described.

1-1. Epoxy silicone resin The thermosetting resin used in the present embodiment includes an epoxy silicone resin. In the present invention, by using an epoxy silicone resin, the viscosity of the thermosetting resin composition is suppressed to enable liquid sealing. Hereinafter, the epoxy silicone resin will be described.

  The epoxy silicone resin has an epoxy group in the molecule, and the epoxy group may be a glycidyl group or an alicyclic epoxy group, and from the viewpoint of polymerization rate, preferably an alicyclic epoxy group having a cyclohexyl epoxy group. Including.

In the present invention, it is preferable to use an epoxy silicone resin synthesized by involving a self-polymerization reaction of an epoxy compound catalyzed by a gallium compound and a silanol supplied from a silanol source compound for at least a part of the curing mechanism. . In addition, although this epoxy silicone resin can be hardened | cured only by this self-polymerization reaction, it is not limited.
Hereinafter, each component of this epoxy silicone resin will be described.

1-1-1. Epoxy compound The epoxy compound is a compound having an epoxy group in the molecule, and preferably an alicyclic epoxy compound having a cyclohexyl epoxy group. Structural formulas of typical alicyclic epoxy compounds are shown in formulas (1) to (3).

エポキシ化合物はグリシジル基を有する化合物であってもよいが、脂環式エポキシ化合物のほうが自己重合反応の活性が高く、好ましい。

The epoxy compound may be a compound having a glycidyl group, but the alicyclic epoxy compound is preferable because it has a higher self-polymerization reaction activity.

  As a suitable example of an epoxy compound having a glycidyl group, a glycidyl ether containing an alicyclic structure as shown in formulas (4) to (8), or an ester compound, and no alicyclic structure as shown in formula (9) There are glycidyl ether compounds, glycidyl ether compounds having a disiloxane skeleton as shown in formula (10), and glycidyl amide compounds having an isocyanuric acid skeleton as shown in formula (11). In the formula (9), R represents an alkylene group having 1 to 20 carbon atoms.

  The epoxy compound may be an aromatic epoxy compound. Examples of such epoxy compounds include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrafluoro as shown in formula (12). Bivalent phenols such as bisphenol type epoxy resins obtained by glycidylation of bisphenols such as bisphenol A, biphenyl type epoxy resins represented by the formula (13), dihydroxynaphthalene, 9,9-bis (4-hydroxyphenyl) fluorene, etc. Glycidylated epoxy resin, 1,1,1-tris (4-hydroxyphenyl) methane trisphenol glycidylated epoxy resin, 1,1,2,2-tetrakis (4-H Rokishifeniru) tetrakis phenols glycidylated epoxy resins such as ethane, phenol novolac, cresol novolac, bisphenol A, novolac, novolac type epoxy resins and novolacs and glycidyl of such brominated bisphenol A novolak and the like. In formula (13), R independently represents hydrogen, an alkyl group having 1 to 3 carbon atoms, or a phenyl group.

エポキシ化合物は、芳香族エポキシ化合物を水素化して得られる脂環構造を有するエポキシ化合物であってもよい。

The epoxy compound may be an epoxy compound having an alicyclic structure obtained by hydrogenating an aromatic epoxy compound.

The epoxy compound may be a silicon-containing compound having an epoxy group. The silicon-containing compound is a silane compound or a siloxane compound.
Examples of the silicon-containing compound having an epoxy group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, (γ-glycidoxypropyl) (methyl) dimethoxysilane, (γ-glycidoxypropyl) (ethyl) dimethoxysilane, (γ-glycidoxypropyl) (methyl) di Ethoxysilane, (γ-glycidoxypropyl) (ethyl) diethoxysilane, [2- (3,4-epoxycyclohexylethyl) (methyl) dimethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] ( Ethyl) dimethoxysilane, [2- (3,4-epoxycyclohexyl) Til] (methyl) diethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethyl) diethoxysilane, (γ-glycidoxypropyl) (methoxy) dimethylsilane, (γ-glycidoxypropyl) ) (Methoxy) diethylsilane, (γ-glycidoxypropyl) (ethoxy) dimethylsilane, (γ-glycidoxypropyl) (ethoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (methoxy ) Dimethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (methoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethoxy) dimethylsilane, [2- (3,4- Epoxycyclohexyl) ethyl] (ethoxy) diethylsilane, [2- (3,4-epoxycyclo Hexyl) ethyl] (dimethyl) disiloxane, 3-epoxypropyl (phenyl) dimethoxysilane, and the like.
Moreover, the organopolysiloxane represented by Formula (14) is also contained in the silicon compound containing an epoxy group.
(R ¹¹ ₃ SiO _1/2 ) _a1 (R ¹² ₂ SiO _2/2 ) _b1 (R ¹³ SiO _3/2 ) _c1 (SiO _4/2 ) _d1 (O _1/2 H) _e1 (14)

In the formula (14), R ¹¹ , R ¹² and R ¹³ each independently represent a monovalent organic group, and at least one is an organic group containing an epoxy group in one molecule.

In the formula (14), R ¹¹ ₃ SiO _1/2 represents an M unit, R ¹² ₂ SiO _2/2 represents a D unit, R ¹³ SiO _3/2 represents a T unit, and SiO _4/2 represents a Q unit. Yes. a1, b1, c1, and d1 are each integers of 0 or more, and a1 + b1 + c1 + d1 ≧ 3.

In the formula (14), R ¹¹ , R ¹² and R ¹³ are preferably a hydrocarbon group having 1 to 10 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and pentyl. Alkyl groups such as hexyl and heptyl groups; alkenyl groups such as vinyl, allyl, butenyl, pentenyl and hexenyl; aryl groups such as phenyl, tolyl and xylyl; benzyl and phenethyl And substituted alkyl groups such as a chloromethyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, and a nonafluorobutylethyl group.

In formula (14), examples of the organic group containing an epoxy group include epoxy alkyl groups such as 2,3-epoxypropyl group, 3,4-epoxybutyl group, and 4,5-epoxypentyl group; 2-glycidoxyethyl Group, glycidoxyalkyl group such as 3-glycidoxypropyl group, 4-glycidoxybutyl group; β- (or 2-) (3,4-epoxycyclohexyl) ethyl group, γ- (or 3-) Examples thereof include an epoxycyclohexylalkyl group such as (3,4-epoxycyclohexyl) propyl group.
In the formula (14), e1 is an integer of 0 or more, and represents the number of hydroxyl groups (silanol) directly bonded to the silicon atom.

  The epoxy compound has a hydrolyzable group bonded to a silicon atom. When the hydrolyzable group is hydrolyzed, the organopolysiloxane represented by the formula (14) (however, e1 ≧ 1) The compound which produces | generates may be sufficient. In other words, in the organopolysiloxane represented by the formula (14) (however, e1 ≧ 1), it may be a compound in which all or part of hydroxyl groups directly bonded to silicon atoms are replaced with hydrolyzable groups. .

  Here, the hydrolyzable group is a group that generates a hydroxyl group (silanol) bonded to a silicon atom by hydrolysis. Specific examples include a hydroxy group, an alkoxy group, hydrogen, an acetoxy group, an enoxy group, an oxime group, A halogen group is mentioned. A preferred hydrolyzable group is an alkoxy group, and particularly an alkoxy group having 1 to 3 carbon atoms, that is, a methoxy group, an ethoxy group, or a propoxy group.

The organopolysiloxane type epoxy compound represented by the above formula (14) can be produced, for example, by the following method.
(Method 1) A method of cohydrolyzing and polycondensing a silane compound having an epoxy group and a silane compound having no epoxy group and / or an oligomer thereof.
(Method 2) A method of adding an organic compound having an epoxy group and a carbon-carbon double bond group to a polysiloxane having a hydrosilyl group.
(Method 3) A method in which the double bond portion of the polysiloxane having an organic group containing a carbon-carbon double bond is oxidized and converted to an epoxy group.
The raw materials that can be used in the production of the polysiloxane type epoxy compound by the method 1 are as follows.

  Examples of the raw material for introducing the M unit include trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane, and triphenylsilanol.

  As raw materials for introducing D unit, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, methylphenyldiethoxysilane, and their hydrolysis condensates (oligomers) Illustrated.

  As dialkylsiloxane oligomers having hydroxyl groups at both ends, compounds having silanol-modified compounds such as polydimethylsiloxane, polymethylphenylsiloxane, dimethylsiloxane-diphenylsiloxane copolymer, and polydiphenylsiloxane are commercially available.

Raw materials for introducing T unit include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, 3,3,3-trifluoropropyl Examples include trimethoxysilane and hydrolytic condensates thereof.

  Examples of the raw material for introducing the Q unit include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and hydrolytic condensates thereof.

  As raw materials for introducing an epoxy group, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltriethoxysilane, (γ-glycidoxypropyl) (methyl) dimethoxysilane, (γ-glycidoxypropyl) (ethyl) dimethoxysilane, (γ-glycidoxypropyl) (methyl) Diethoxysilane, (γ-glycidoxypropyl) (ethyl) diethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] (methyl) dimethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl ] (Ethyl) dimethoxysilane, [2- (3,4-epoxycyclohexyl) Ethyl] (methyl) diethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethyl) diethoxysilane, (γ-glycidoxypropyl) (methoxy) dimethylsilane, (γ-glycidoxypropyl) ) (Methoxy) diethylsilane, (γ-glycidoxypropyl) (ethoxy) dimethylsilane, (γ-glycidoxypropyl) (ethoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (methoxy ) Dimethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (methoxy) diethylsilane, [2- (3,4-epoxycyclohexyl) ethyl] (ethoxy) dimethylsilane, [2- (3,4- (Epoxycyclohexyl) ethyl] (ethoxy) diethylsilane, [2- (3,4-epoxysilane) Examples include (rohexyl) ethyl] (dimethyl) disiloxane, 3-epoxypropyl (phenyl) dimethoxysilane, and the like.

  As an epoxy silicone resin, 1 type may be used independently and 2 or more types may be used together.

1-2. Thermal latent curing catalyst The one-component thermosetting resin composition of the present invention contains a thermal latent curing catalyst.
The heat-latent curing catalyst of the present invention is a compound that exhibits catalytic properties by heating and serves as an epoxy polymerization initiator, or a compound that can accelerate an epoxy polymerization reaction and cure a thermosetting resin.
If a latent curing agent such as an amine adduct that reacts one-on-one with an epoxy is used, the influence of the physical properties of the latent curing agent component on the physical properties of the cured product will increase, resulting in a decrease in the insulation of the cured product, etc. Is concerned. In addition, since the latent curing agent component in the resin composition increases, the viscosity of the resin composition increases, so that uniform mixing cannot be performed or a smooth film cannot be formed. In the present invention, by using a thermolatent curing catalyst, it is possible to achieve both the storage stability and the curing speed of the one-component thermosetting resin composition, and the resulting cured product has high insulation and smoothness. it can. Further, when an amine adduct latent curing agent is used, the resin composition or cured product has an unpleasant amine odor, but the resin composition of the present invention is uncomfortable by using a thermal latent curing catalyst. Has no amine odor.
The heat latent curing catalyst of the present invention includes, for example, a Lewis acid, a compound obtained by neutralizing a proton acid with a Lewis base, a compound obtained by neutralizing a Lewis acid with a Lewis base, a mixture of Lewis acid and trialkyl phosphate, and a sulfonate ester. , Organic sulfonium salts, organic phosphonium salts, onium compounds, imidazole derivatives, inorganic compounds, and the like. The thermal latent curing catalyst is preferably one that exhibits catalytic activity at a temperature of 80 ° C. or higher.

Specifically, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4-diamino-6- [2′-methylimidazolyl- (
1 ')] Imidazoles such as isocyanuric acid adducts of ethyl-s-triazine; organophosphorus compounds such as diphenylphosphine, triphenylphosphine, triphenyl phosphite; benzyltriphenylphosphonium chloride, tetra- n-butyl phosphonium bromide, methyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium bromide, n-butyl triphenyl phosphonium bromide, tetraphenyl phosphonium bromide, ethyl triphenyl phosphonium iodide, Ethyl triphenyl phosphonium acetate, methyl tributyl phosphonium dimethyl phosphate, tetrabutyl phosphonium diethyl phosphodithionate, tetra-n-butyl Quaternary phosphonium salts such as phosphonium benzotriazolate, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate; 1 , 8-diazabicyclo [5.4.0] undecene-7 and diazabicycloalkenes such as organic acid salts thereof; organometallic compounds such as zinc octylate, tin actylate, aluminum acetylacetone complex; tetraethylammonium bromide, tetra- Quaternary ammonium salts such as n-butylammonium bromide; Boron compounds such as boron trifluoride and triphenyl borate; Metal halide compounds such as zinc chloride and stannic chloride, addition of dicyandiamide and amine with epoxy resin Things High melting point dispersion type latent curing accelerators such as amine addition type accelerators; Microcapsule type latent curing in which the surface of curing accelerators such as imidazoles, organophosphorus compounds and quaternary phosphonium salts are coated with a polymer Accelerators; amine salt type latent curing accelerators; latent curing accelerators such as high temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts other than gallium compounds, Bronsted acid salts, etc. Can do.

Since strong catalytic activity is required, it is preferably an inorganic compound, more preferably a cationic polymerizable catalyst, and particularly preferably boron trifluoride (BF ₃ ) -amine complex, represented by the following formulas (15) to (17): And BF ₅ salt, SbF ₆ salt, and PF ₆ salt, respectively. Use of a cationically polymerizable catalyst is preferable because it can achieve both storage stability and a curing rate, can further increase the insulation of the cured product, and can reduce the linear expansion coefficient.

Further, when the thermosetting resin has a silanol group, a gallium compound can also be used as a catalyst. The gallium compound is not particularly limited as long as it is a compound containing gallium as a metal atom, and various forms such as an oxide, a salt, and a chelate complex can be used. Specifically, gallium acetylacetonate, gallium acetate, gallium sulfate, gallium nitrate, gallium oxyacetate, triethoxygallium, triisopropoxygallium, tris (8-quinolinolato) gallium, tris (2,2,6,6- Examples thereof include tetramethyl-3,5-heptanedionato) gallium (III), gallium (III) trifluoromethanesulfonate, gallium oxalate, gallium ethylxanthate, diethylethoxygallium, and gallium maleate. Of these, gallium acetylacetonate and gallium acetate are particularly preferable. Two or more kinds of gallium compounds can be used in any combination.

  When the thermosetting resin in the thermosetting resin composition has a silanol group and further contains a silanol source compound, the gallium compound also serves as a catalyst for siloxane condensation and is preferable because the crosslinking system proceeds simultaneously. Further, it has good compatibility with siloxane and silica and contributes to silica dispersion. Furthermore, when epoxy silicone is reacted with a gallium catalyst, the linear expansion coefficient of the resulting cured product becomes constant over a wide range.

  The content of the curing catalyst in the thermosetting resin composition is preferably adjusted to be 0.01% by weight to 1.0% by weight with respect to 100% by weight of the thermosetting resin composition.

1-3. Other components In addition to the above-mentioned components, the thermosetting resin composition according to the embodiment of the present invention includes a dispersant, an antioxidant, an antifoaming agent, a colorant, from the viewpoint of improving physical properties and imparting functions. You may further contain additives, such as a modifier, a leveling agent, a light-diffusion agent, heat conductivity, a flame retardant, a reactive or non-reactive diluent, adhesion | attachment, an adhesive improvement agent, or various fillers.

1-3-1. As the filler, both general organic fillers and inorganic fillers can be used. Examples of the organic filler include styrene polymer particles, methacrylate polymer particles, ethylene polymer particles, propylene polymer particles, synthetic polymer particles such as polyamide, starch, natural products such as wood flour, cellulose that may be modified, Examples include various organic pigments. The inorganic filler is not particularly limited as long as it is an inorganic substance or a compound containing an inorganic substance. Specifically, for example, quartz, fumed silica, precipitated silica, anhydrous silicic acid, fused silica, crystalline silica, ultrafine powder amorphous silica. Silica-based inorganic fillers such as alumina, zircon, iron oxide, zinc oxide, titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass fiber, glass flake, alumina fiber, carbon fiber, mica, graphite, carbon black , Ferrite, graphite, diatomaceous earth, clay, talc, aluminum hydroxide, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, potassium titanate, calcium silicate, inorganic balloon, silver powder and the like.

  These may be used alone or in combination of two or more. Moreover, you may perform a surface treatment suitably. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a silane coupling agent, and the like, but are not particularly limited.

  By using a filler, the strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical properties, light reflectance, flame retardancy, fire resistance, thixotropy, and gas barrier of the molded product obtained Various physical properties such as properties can be improved.

Although the addition amount of a filler is not specifically limited, From a viewpoint of the linear expansion coefficient and insulation of the hardened | cured material obtained, 50 weight% or more of inorganic fillers with a linear expansion coefficient of 20 ppm / K or less are included in a thermosetting resin composition. Preferably, it is contained 70% by weight or more, more preferably 80% by weight or more. Control of particle size distribution can be used as means for increasing the amount of addition. That is, a higher filling rate can be obtained by mixing fillers having different particle sizes.
The particle size distribution of the filler is measured by using a Particle Size Analyzer CILAS 1064 (manufactured by CILAS, Model 1064) as a laser scattering / diffraction particle size distribution measuring apparatus, and is measured at least 1 to 1 to 10 μm and at least 1 to 10 to 100 μm. It is desirable to have two peak tops. Further, nano-sized ultrafine particles may be included.

  Moreover, when the addition amount of a filler increases, the viscosity rise of a composition will become remarkable. Depending on the application and molding method, it is necessary to suppress the increase in viscosity, but in that case, the shape and surface structure of the filler greatly affect. By selecting a spherical shape rather than a fibrous or irregular shape, the viscosity can be kept low. Further, depending on the type and amount of the surface functional group of the particle, the interaction between the particles and between the matrix compositions composed of the particles and the epoxy resin can be controlled to obtain an appropriate viscosity. Here, the spherical shape may be a true spherical shape, an elliptical shape, or a substantially spherical shape including an oval shape. Specifically, an aspect ratio (ratio of major axis to minor axis) is usually used. 2 or less, preferably 1.5 or less.

  The order of mixing the filler is not particularly limited, but it is desirable to mix with the epoxy compound in the absence of a curing catalyst in order to prevent the progress of the curing reaction due to heat generation during mixing.

  The means for mixing the filler is not particularly limited. Specifically, for example, a two-roll or three-roll, a planetary stirring and defoaming device, a homogenizer, a dissolver, a planetary mixer, etc., a plastmill Such as a melt kneader. Mixing may be performed at normal temperature, may be performed by heating, may be performed under normal pressure, or may be performed under reduced pressure. If the temperature during mixing is high, the composition may be cured before molding.

1-3-2. Antioxidant The thermosetting resin composition according to the embodiment of the present invention may contain an antioxidant in order to suppress yellowing under the use environment.

  Phenol antioxidants, phosphorus antioxidants, hindered amines and the like are preferably used. Phenolic antioxidants and hindered amines act as radical scavengers. The phosphorus antioxidant acts as a peroxide decomposer.

  Examples of the phenolic antioxidant include 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, and n-octadecyl-3- (3 ′, 5′-di- t-butyl-4′-hydroxyphenyl) propionate, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate)] methane, tris (3,5-di-t -Butyl-4-hydroxybenzyl) isocyanurate, triethylene glycol-bis- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 2,2'-methylenebis- (4-methyl -6-tert-butylphenol), 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3-methyl-6-tert-butyl) Phenol), 4,4'-thiobis (4-methyl -6-t-butylphenol), 4,4'-butylidene bis (3-methyl -6-t-butylphenol) and the like.

  The hindered amine system is considered to be stabilized by the oxidation of the nitroxy radical by capturing the radical. Examples of the nitroxy free radical compound include 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1-piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1,1,3,3- Examples thereof include tetramethyl-2-isoindolinyloxy radical and N, N-di-t-butylamineoxy radical. A hindered amine system exhibits a synergistic effect when used in combination with a phosphorus-based antioxidant and improves weather resistance.

  Examples of phosphorus antioxidants include triphenyl phosphate, triisodecyl phosphate, isodecyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, trisnonyl phenyl phosphate, distearyl pentaerythritol diphosphate, tris ( 2,4-di-t-butylphenyl) phosphate and tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene-diphosphate.

  Among these, a hindered phenol antioxidant having an alkyl group at one or both ortho positions of the phenol hydroxyl group is particularly preferably used. Examples of the hindered phenol antioxidant include [3- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propanoyloxy] -2,2-bis [3- (3 5-di-t-butyl-4-hydroxyphenyl) propanoyloxymethyl] propyl] 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, octadecyl-3- (3,5-di -T-butyl-4-hydroxyphenyl) propionate.

1-3-3. Epoxy resin curing catalyst In the present invention, a thermal latent curing catalyst and a catalyst used for ordinary epoxy resin curing can be used in combination. Examples of such catalysts include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, and triethanolamine; 2-methylimidazole, 2-n- Heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole 1- (2-cyanoethyl) -2-ethyl -4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-phenyl-4,5 -Di [(2'-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenylimidazolium trimellitate 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 2, 4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'- Chiruimidazoriru - (1 ')] ethyl -s- triazine.

1-3-4. Curing aid The thermosetting resin composition of the present invention may contain a curing aid in order to promote the reaction between the thermosetting resin and the heat latent curing catalyst. Examples of the curing aid include amines, polyamide resins, acid anhydrides, and phenols. From the viewpoints of reducing the linear expansion coefficient, controlling the polymerization rate, and reducing the viscosity, it is preferable to use an acid anhydride. Examples of the acid anhydride include aliphatic acid anhydrides, alicyclic acid anhydrides, aromatic acid anhydrides, and halogen acid anhydrides.
Although there is no restriction | limiting in particular as content of an acid anhydride, when too much, Tg of an acid anhydride may affect the linear expansion coefficient of the hardened | cured material obtained.

  Examples of the alicyclic carboxylic acid anhydride include compounds represented by formula (18) to formula (23), 4-methyltetrahydrophthalic acid anhydride, methyl nadic acid anhydride, dodecenyl succinic acid anhydride, Examples thereof include Diels-Alder reaction products of alicyclic compounds having a conjugated double bond such as α-terpinene and alloocimene and maleic anhydride, and hydrogenated products thereof.

In addition, arbitrary structural isomers and arbitrary geometric isomers can be used as the Diels-Alder reaction product and hydrogenated products thereof.
In addition, the alicyclic carboxylic acid anhydride can be used after being appropriately chemically modified as long as the curing reaction is not substantially hindered.
By containing an acid anhydride, effects such as control of the epoxy reaction rate, handling, improvement of leveling, and prevention of coloring may be obtained. Although there is no restriction | limiting in particular as content of an acid anhydride, It is preferable that it is 1.5 equivalent or less with respect to the amount of epoxy. More preferably, it is 1 equivalent or less, More preferably, it is 0.8 equivalent or less.

1-3-5. Silane Coupling Agent The thermosetting resin composition of the present invention can contain a silane coupling agent in order to improve the adhesion to metal parts and inorganic fillers.

  Specific examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Examples include aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane.

2. Production method of thermosetting resin composition The production method of the thermosetting resin composition of the present invention is not particularly limited, and the thermosetting resin, the thermal latent curing catalyst, and, if necessary, a filler, a diluent, and an antioxidant. It can manufacture by mixing other components, such as an agent.

3. Method for Curing Thermosetting Resin Composition and Cured Product The method for producing a resin cured product of the present invention includes a step of heating and curing the one-component thermosetting resin composition of the present invention. The thermosetting resin composition according to the present invention involves a self-polymerization reaction of a thermosetting resin by a thermolatent curing catalyst in at least a part of the curing mechanism. This one-component thermosetting resin composition can be cured only by the self-polymerization reaction, but is not limited thereto.

Since the thermosetting resin composition according to the present invention has fluidity, the molding method is not limited and can be used for casting and potting.
The heating method for curing the thermosetting resin composition according to the embodiment of the present invention to obtain a molded body is not particularly limited, and for example, hot air circulation heating, infrared heating, high frequency heating, etc. The conventionally known method can be employed.

The heat treatment condition is not limited as long as the thermosetting resin composition can be brought into a desired cured state.
The time for maintaining the curing temperature (curing time) is determined according to the catalyst concentration, the thickness of the member to be formed with the composition, and the like. Usually, it is 1 hour or more, preferably 2 hours or more, more preferably 4 hours or more.
The curing temperature is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 150 ° C. or higher. By setting the curing temperature to about 100 ° C. at first and then to about 150 ° C., foaming due to residual solvent or dissolved water vapor in the composition can be prevented. In addition, since the difference in curing speed between the deep portion and the surface can be reduced, a cured product having a smooth surface and no wrinkles and a good appearance can be obtained. When the difference in curing speed between the deep part and the surface is small, the cured state becomes uniform, so that the generation of internal stress in the cured product is suppressed, and the generation of cracks can be prevented.

4). Use of 1-component thermosetting resin composition The use of the thermosetting resin composition according to the embodiment of the present invention is not particularly limited, and is used as a sealing material for various semiconductor devices including power devices. be able to.

  The cured product of the one-component thermosetting resin composition according to the embodiment of the present invention has a constant linear expansion coefficient in a wide temperature range by having a high concentration of filler, and has a low linear expansion coefficient. In addition, since it has high thermal conductivity and insulation and is excellent in reliability, it is particularly suitable for power devices. The power device formed by sealing using the one-component thermosetting resin composition according to the embodiment of the present invention is sealed with a cured product having a substantially constant average linear expansion coefficient over a wide temperature range. It has high mechanical reliability and can withstand use under high temperature and high pressure current.

  Hereinafter, the present invention will be described in detail by way of examples.

<Synthesis Example 1>
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (64.8 g), trimethylethoxysilane (40.1 g), isopropyl alcohol (45 g) and 1N hydrochloric acid (24.39 g) were mixed and stirred at room temperature for 3 hours. .51 g and 148 g of isopropyl alcohol were added, and the mixture was heated and stirred for 4 hours under reflux conditions of isopropyl alcohol. Thereafter, the reaction solution was neutralized with an aqueous sodium dihydrogen phosphate solution (10% by mass), washed with water until the washed water became neutral, volatile components were removed under reduced pressure, and Mw = 1000. Polysiloxane EpSi-1 was obtained.

[Example 1]
0.76g of said EpSi-1, YED216D (Mitsubishi Chemical Corporation alkyl glycidyl ether) 0.09g, true spherical filler HL-3100 (Tatsumori Co., Ltd.) 7.4g was stirred and mixed. Furthermore, latent cationic polymerization initiator Sun-Aid SI-B3 (manufactured by Sanshin Chemical Industry Co., Ltd.) (0.008 g) was added and stirred and mixed to obtain a curable composition No-1. The curable composition No-1 did not smell. Table 1 shows the composition of the curable composition No-1.

[Comparative Example 1]
0.76g of said EpSi-1, YED216D (Mitsubishi Chemical Corporation alkyl glycidyl ether) 0.09g, true spherical filler HL-3100 (Tatsumori Co., Ltd.) 7.4g was stirred and mixed. Furthermore, 0.17 g of amine adduct-based latent curing agent Amicure PN-40J (manufactured by Ajinomoto Fine Techno Co., Ltd.) was added and stirred and mixed to obtain a curable composition No-2. Curable composition No-2 had an unpleasant amine odor. Table 1 shows the composition of the curable composition No-2.

[Comparative Example 2]
The same procedure as in Comparative Example 1 was used except that 2.13 g of Amicure MY-24 (Ajinomoto Fine Techno Co., Ltd.) was used in place of the amine adduct-based latent curing agent Amicure PN-40J used in Comparative Example 1 above. Thus, a curable composition No-3 was obtained. Curable composition No-3 had an unpleasant amine odor. Table 1 shows the composition of the curable composition No-3.

<Evaluation of fluidity before heat treatment>
About 2 g of the composition was put in an aluminum cup having an inner diameter of 5 cm and allowed to stand at room temperature for 3 days. Thereafter, when the aluminum cup was held at an angle of about 45 degrees and held for 10 minutes, it was judged as “fluid” when the internal composition flowed, and “no fluidity” when it did not flow.

<Fluidity evaluation after heat treatment>
About 1 g of the composition between two SUS plates sandwiching a spacer with a thickness of 1.5 mm, in a thermostatic bath at 80 ° C. for 30 minutes, 120 ° C. for 120 minutes, 150 ° C. for 60 minutes, and 200 Curing was performed by sequentially heating at 60 ° C. for 60 minutes. After that, when it is taken out from the thermostatic bath and kept at a tilt of about 45 degrees for 10 minutes when the temperature is lowered to room temperature, it is “fluid” when the internal composition flows, and when it does not flow, “flow” No sex ”.
<Properties of cured film>
Visually, the thickness uniformity of the cured product and the surface smoothness were judged.

<Insulation evaluation after heat treatment>
For the evaluation of insulation, the volume resistance was measured from the volume resistance measured at room temperature using a digital ultrahigh resistance / microammeter 5451 and a resiliency chamber 12708 (manufactured by ADC Corporation) in accordance with JIS K6911. The rate was calculated. The results are shown in Table 2.

As is clear from Table 2, the one-component thermosetting resin composition of the present invention was fluid even after standing at room temperature for 3 days, and lost fluidity after heat treatment. That is, it was a composition having both storage stability and heat curing rate. On the other hand, it was found that the resin composition of the comparative example lost its fluidity after standing at room temperature for 3 days and was inferior in storage stability.
Further, the cured product obtained from the resin composition of the present invention formed a smooth and uniform film and exhibited excellent insulating properties. On the other hand, the cured product obtained from the resin composition of the comparative example formed a film having irregularities on the surface and a non-uniform thickness, and the insulation was also inferior to the cured product of the present invention.

  The application of the resin composition provided by the present invention is not particularly limited, and may be used for any application, but can be suitably used for the sealing of semiconductor elements, and particularly power. It can be suitably used for a device.

Claims (7)

  A one-pack type thermosetting resin composition comprising an epoxy silicone resin and a heat latent curing catalyst.   The one-component thermosetting resin composition according to claim 1, wherein the thermolatent curing catalyst is a cationic polymerizable catalyst.   The one-component thermosetting resin composition according to claim 1 or 2, wherein an epoxy group in the epoxy silicone resin contains an alicyclic epoxy.   The one-component thermosetting resin composition according to claim 1, comprising an inorganic filler.   The one-component thermosetting resin composition according to claim 4, wherein the inorganic filler is a silica filler.   The one-component thermosetting resin composition according to claim 4 or 5, wherein the inorganic filler is a spherical filler.   A method for producing a cured resin, comprising the step of heating and curing the one-component thermosetting resin composition according to claim 1.