JP2015048472A - Thermosetting resin molding material and electronic component device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin molding material capable of forming a cured product which has excellent heat resistance and flame retardancy and is excellent in electrical insulation at a high temperature and adhesion to a metal at a high temperature.SOLUTION: The thermosetting resin molding material contains: an epoxy resin containing a polyfunctional epoxy resin having two or more epoxy groups in one molecule; a cyanate resin containing a polyfunctional cyanate resin having two or more cyanate groups (-OCN) in one molecule; and at least one compound selected from the group consisting of an aromatic carboxylic acid and an aromatic carboxylic acid ester having a phenolic hydroxyl group.

Description

  The present invention relates to a thermosetting resin molding material and an electronic component device.

  Conventionally, epoxy resin molding materials have been widely used in the field of device sealing of electronic components such as transistors and ICs (Integrated Circuits). This is because the epoxy resin has a good balance of electrical properties, moisture resistance, heat resistance, mechanical properties, adhesiveness with inserts, and the like. In particular, a combination of an ortho-cresol novolac type epoxy resin and a novolac type phenol curing agent has an excellent balance between these, and has become the mainstream of a base resin of a thermosetting resin molding material for device sealing. With recent miniaturization, weight reduction, and performance enhancement of electronic devices, mounting density has increased, and accordingly, heat generation of electronic components has become remarkable. In addition, electronic components that operate at high temperatures are also increasing.

  In particular, power semiconductors for in-vehicle use are expected to be exposed to high temperatures for a long time. For power modules for in-vehicle use, it is the mainstream to apply a silicone gel sealing method called gel sealing with a case-type structure. However, such as mass production improvement, vibration resistance improvement, heat resistance temperature improvement, etc. From the viewpoint, sealing by transfer molding using an epoxy resin molding material has been studied. Furthermore, in a power semiconductor, the operating temperature is said to be 200 ° C. or higher by using a silicon carbide (SiC) device that has low power loss and excellent energy saving performance. Therefore, high heat resistance is required for the thermosetting resin molding material for sealing elements used in electronic components, and the cured product is required to have a high glass transition temperature (Tg).

  In order to develop a high glass transition temperature (Tg) with a combination of an epoxy resin and a phenol curing agent, it is effective to increase the crosslinking density of the resin. However, when the crosslinking density is increased, the density of the secondary alcoholic hydroxyl group (OH group) generated in association with the crosslinking reaction also increases. In this case, it becomes very difficult to ensure the electrical insulation of the sealing material at a high temperature of 150 ° C. or higher.

  Cyanate resin is known as a high heat resistant resin. Since the cyanate resin does not generate a secondary alcoholic hydroxyl group with the curing reaction, if it can be used as a thermosetting resin molding material for device sealing, it will lead to ensuring the electrical insulation of the sealing material at high temperatures. Conceivable. However, in order to complete the cross-linking reaction between the cyanate resin and the epoxy resin and the trimerization reaction of the cyanate group itself by heat treatment, a temperature of 200 ° C. or higher is necessary, and the application of the cyanate resin to a thermosetting resin molding material is required. Have difficulty. Therefore, transition metal complexes such as zinc naphthenate and cobalt naphthenate are usually used for the curing reaction of the cyanate resin (see, for example, Patent Documents 1 and 2).

  On the other hand, it is disclosed that the resin composition for circuit boards containing an epoxy resin and cyanate resin shows high heat resistance (for example, refer patent document 3).

JP-A-7-165889 JP-A-7-196793 JP 2011-116910 A

  When a transition metal complex as described above is added in order to achieve a quick cure of the cyanate resin, the metal ion content in the thermosetting resin molding material increases, resulting in a decrease in the reliability of the semiconductor device ( For example, it may lead to a decrease in insulation. Therefore, it is difficult to apply the thermosetting resin molding material using the transition metal complex as described above as a sealing material for power semiconductors that is exposed to particularly severe operating environments. In addition, since the amount of the transition metal complex added is relatively small in the thermosetting resin molding material, it is considered that it is not easy to sufficiently knead or disperse in the material. Also, when using the above transition metal complexes, the curing behavior and various properties of the cured product may vary significantly with slight fluctuations in the amount added, and it is difficult to achieve reproducibility of the various properties with high productivity. it is conceivable that. From the above, it is possible to provide a thermosetting resin molding material containing a cyanate resin without using a transition metal complex as described above as a thermosetting resin molding material applicable also as a sealing material for power semiconductors. It has become extremely difficult and has not yet been put into practical use. Furthermore, the sealing material for power semiconductor sealing is also required to be excellent in flame retardancy.

  The present invention has been made in view of such a situation, and has excellent heat resistance and flame retardancy, is excellent in electrical insulation at high temperatures, and is capable of forming a cured product having excellent adhesion to metals at high temperatures. It is an object of the present invention to provide an electronic component device including a conductive resin molding material and an element sealed thereby.

Specific means for solving the above problems are as follows.
<1>
An epoxy resin containing a polyfunctional epoxy resin having two or more epoxy groups in one molecule;
A cyanate resin containing a polyfunctional cyanate resin having two or more cyanate groups (—OCN) in one molecule;
At least one compound selected from the group consisting of an aromatic carboxylic acid and an aromatic carboxylic acid ester having a phenolic hydroxyl group;
Containing thermosetting resin molding material.

<2>
At least one compound selected from the group consisting of the aromatic carboxylic acid and the aromatic carboxylic acid ester having a phenolic hydroxyl group has an OH group equivalent derived from a carboxyl group and a phenolic hydroxyl group of 30 g / eq to 400 g / The thermosetting resin molding material according to <1>, which is eq.

<3>
The aromatic carboxylic acid includes a benzoic acid compound, a benzene dicarboxylic acid compound, a benzene tricarboxylic acid compound, a benzene tetracarboxylic acid compound, a naphthoic acid compound, a naphthalene dicarboxylic acid compound, a naphthalene tricarboxylic acid compound, a naphthalene tetracarboxylic acid compound, and the like <1> or <2>, which is at least one compound selected from the group consisting of aromatic carboxylic acid compounds having a phenolic hydroxyl group in which one or more OH groups are directly bonded to the aromatic ring of Thermosetting resin molding material.

<4>
The aromatic carboxylic acid ester having a phenolic hydroxyl group is an ester of a benzoic acid compound, an ester of a benzenedicarboxylic acid compound, an ester of a benzenetricarboxylic acid compound, an ester of a benzenetetracarboxylic acid compound, an ester of a naphthoic acid compound, or naphthalenedicarboxylic acid A compound in which one or more OH groups are directly bonded to an aromatic ring of at least one compound selected from the group consisting of an ester of a compound, an ester of a naphthalene tricarboxylic acid compound, and an ester of a naphthalene tetracarboxylic acid compound The thermosetting resin molding material according to any one of <1> to <3>.

<5>
Ratio of the number of OH groups derived from a carboxyl group and a phenolic hydroxyl group contained in at least one compound selected from the group consisting of the aromatic carboxylic acid and the aromatic carboxylic acid ester to the number of epoxy groups contained in the epoxy resin The thermosetting resin molding material according to any one of <1> to <4>, in which is 0.10 to 0.60.

<6>
Derived from a carboxyl group contained in at least one compound selected from the group consisting of the number of cyanate groups contained in the cyanate resin and the aromatic carboxylic acid and the aromatic carboxylic acid ester with respect to the number of epoxy groups contained in the epoxy resin; The thermosetting resin molding material according to any one of <1> to <5>, wherein the ratio of the total number of OH groups derived from a phenolic hydroxyl group is 0.70 to 3.50.

<7>
An electronic component device comprising: an element; and a cured product of the thermosetting resin molding material according to any one of <1> to <6> that seals the element.

  According to the present invention, there is provided a thermosetting resin molding material having excellent heat resistance and flame retardancy, excellent electrical insulation at high temperatures, and capable of forming a cured product having excellent adhesion to metals at high temperatures. It is possible to provide an electronic component device including an element sealed by the above.

  In the present specification, a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. Furthermore, the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.

  Moreover, in this specification, an "acid compound" is a compound (however, a compound except an acid ester) containing both an acid and an acid having a substituent. Specifically, for example, a benzoic acid compound is a compound containing both benzoic acid and a benzoic acid having a substituent (however, a compound excluding a benzoic acid ester).

<Thermosetting resin molding material>
The thermosetting resin molding material of the present invention includes an epoxy resin containing a polyfunctional epoxy resin having two or more epoxy groups in one molecule, and a polyfunctional cyanate having two or more cyanate groups (-OCN) in one molecule. A cyanate resin containing a resin and at least one compound selected from the group consisting of an aromatic carboxylic acid and an aromatic carboxylic acid ester having a phenolic hydroxyl group. The thermosetting resin molding material may further contain other components as necessary. The thermosetting resin molding material can be preferably applied to electronic component sealing, and can be more preferably applied to power semiconductor sealing.

  In addition to a polyfunctional epoxy resin having two or more epoxy groups in one molecule and a polyfunctional cyanate resin having two or more cyanate groups (-OCN) in one molecule, an aromatic having an aromatic carboxylic acid and a phenolic hydroxyl group By containing at least one compound selected from the group consisting of group carboxylic acid esters, it has excellent heat resistance and flame retardancy, excellent electrical insulation at high temperatures, and adhesion to metals at high temperatures The thermosetting resin molding material for electronic component sealing which can form the cured | curing material which is excellent in this can be comprised. This is because at least one compound selected from the group consisting of an aromatic carboxylic acid and an aromatic carboxylic acid ester having a phenolic hydroxyl group accelerates the curing reaction of a thermosetting resin molding material containing an epoxy resin and a cyanate resin. It is because it is thought that it is done.

(Epoxy resin)
The thermosetting resin molding material contains an epoxy resin. The epoxy resin contains at least one polyfunctional epoxy resin having two or more epoxy groups in one molecule (hereinafter also simply referred to as “polyfunctional epoxy resin”). The polyfunctional epoxy resin having two or more epoxy groups in one molecule is not particularly limited as long as it is generally used for thermosetting resin molding materials, and can be appropriately selected from commonly used polyfunctional epoxy resins. Can be used. The number of epoxy groups in the polyfunctional epoxy resin may be two or more, preferably 2 to 10, and more preferably 2 to 5.

  Specific examples of the polyfunctional epoxy resin include phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, epoxy resin having triphenylmethane skeleton, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F A compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde, and at least one selected from the group consisting of phenol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene. A novolak-type epoxy resin obtained by epoxidizing a novolak resin obtained by condensation or co-condensation under an acidic catalyst; alkyl-substituted, aromatic ring-substituted or unsubstituted bis Epoxy resin which is diglycidyl ether such as phenol A, bisphenol F, bisphenol S, biphenol, thiodiphenol; stilbene type epoxy resin; hydroquinone type epoxy resin; by reaction of polybasic acid such as phthalic acid and dimer acid with epichlorohydrin Glycidyl ester type epoxy resin obtained; Glycidyl amine type epoxy resin obtained by reaction of polyamine such as diaminodiphenylmethane and isocyanuric acid and epichlorohydrin; Dicyclopentadiene type epoxy which is an epoxidized product of cocondensation resin of dicyclopentadiene and phenolic compound Resin; Epoxy resin having a naphthalene ring; at least one of a phenol compound and a naphthol compound and dimethoxyparaxylene or bis (methoxymethyl) biphenyl Aralkyl-type epoxy resin, which is an epoxidized product of aralkyl-type phenol resin such as phenol aralkyl resin and naphthol aralkyl resin synthesized from the above; Trimethylolpropane-type epoxy resin; Terpene-modified epoxy resin; Olefin bond with peracid such as peracetic acid Examples thereof include linear aliphatic epoxy resins obtained by oxidation; alicyclic epoxy resins and the like. These may be used alone or in combination of two or more.

  Especially, it is preferable that a polyfunctional epoxy resin is a novolak-type epoxy resin from a sclerosing | hardenable viewpoint. Further, from the viewpoint of heat resistance and low warpage, a triphenylmethane type epoxy resin which is a novolac type epoxy resin having a triphenylmethane skeleton is preferable. On the other hand, from the viewpoint of low hygroscopicity and dielectric properties, it is preferably a dicyclopentadiene type epoxy resin.

  The thermosetting resin molding material preferably contains at least one epoxy resin selected from the group consisting of a novolak-type epoxy resin and a dicyclopentadiene-type epoxy resin as a polyfunctional epoxy resin, and an ortho-cresol novolak-type epoxy resin, It is more preferable to include at least one epoxy resin selected from the group consisting of a triphenylmethane type epoxy resin and a dicyclopentadiene type epoxy resin.

  A novolak type epoxy resin can be easily obtained by reacting a novolak type phenol resin with epichlorohydrin. Among these, at least one selected from the group consisting of orthocresol novolac type epoxy resins and triphenylmethane type epoxy resins is preferable.

As an ortho cresol novolac type epoxy resin, it can be obtained as a commercial product under the trade name N-660 of DIC Corporation. When using an ortho-cresol novolac type epoxy resin, the content is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total amount of the epoxy resin in order to exhibit its performance.
Triphenylmethane type epoxy resins are available as Nippon Kayaku Co., Ltd. trade name EPPN-502H, Mitsubishi Chemical Corporation trade name 1032H60, and the like. When using a triphenylmethane type epoxy resin, the content is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 50% by mass or more in the total amount of the epoxy resin in order to exhibit its performance. More preferably.
Examples of the dicyclopentadiene type epoxy resin include trade name HP-7200 of DIC Corporation. In the case of using a dicyclopentadiene type epoxy resin, the content is preferably 20% by mass or more, more preferably 30% by mass or more in the total amount of the epoxy resin in order to exhibit its performance.

  The ortho-cresol novolac type epoxy resin, triphenylmethane type epoxy resin and dicyclopentadiene type epoxy resin mentioned above may be used alone or in combination of two or more. The content when two or more types are used in combination is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 80% by mass or more, based on the total amount of the epoxy resin.

  The epoxy equivalent of the polyfunctional epoxy resin is not particularly limited. However, the epoxy equivalent of the polyfunctional epoxy resin is preferably 100 g / eq to 1000 g / eq from the viewpoint of balance of various properties such as moldability, heat resistance, and electrical reliability, and is 150 g / eq to 500 g / eq. More preferably. Here, the epoxy equivalent is the mass (g) per mole of epoxy groups contained in the polyfunctional epoxy resin.

  The softening point or melting point of the polyfunctional epoxy resin is not particularly limited. However, from the viewpoint of moldability and heat resistance, the softening point or melting point of the polyfunctional epoxy resin is preferably 40 ° C. to 180 ° C., and 50 from the viewpoint of handleability during preparation of the thermosetting resin molding material. It is more preferable that the temperature is from 130 ° C to 130 ° C.

  The polyfunctional epoxy resin may be used in combination with a known monofunctional epoxy resin having one epoxy group in one molecule. However, when the polyfunctional epoxy resin and the monofunctional epoxy resin are used in combination, the content of the polyfunctional epoxy resin is preferably 85% by mass or more, more preferably 95% by mass or more, based on the total amount of the epoxy resin.

  From the viewpoint of moldability and heat resistance, the content of the epoxy resin in the thermosetting resin molding material is preferably 3% by mass to 15% by mass, and more preferably 5% by mass to 12% by mass.

(Cyanate resin)
The thermosetting resin molding material contains a cyanate resin. The cyanate resin contains at least one cyanate resin having two or more cyanate groups (—OCN) in one molecule (hereinafter also simply referred to as “polyfunctional cyanate resin”). The polyfunctional cyanate resin having two or more cyanate groups in one molecule is not particularly limited as long as it is generally used for thermosetting resin molding materials, and is appropriately selected from commonly used polyfunctional cyanate resins. Can be used. The number of cyanate groups in the polyfunctional cyanate resin may be two or more, preferably 2 to 6, and more preferably 2 to 4.

  Specific examples of the polyfunctional cyanate resin include 2,2-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ethane, and 2,2-bis (3,5-dimethyl-4-cyanato). Phenyl) methane, dicyanate resin such as α, α′-bis (4-cyanatophenyl) -m-diisopropylbenzene; phenol novolac type cyanate resin; dicyclopentadiene type cyanate resin. In addition, as for the cyanate resin used here, the cyanate group of some resin may form the trimer in advance, and may be oligomerized.

Among them, the polyfunctional cyanate resin is preferably at least one selected from the group consisting of a dicyanate resin, a dicyanate resin oligomer, and a phenol novolac type cyanate resin from the viewpoint of balance between curability and fluidity. More preferably, it is at least one selected from the group consisting of bis (4-cyanatophenyl) propane, 2,2-bis (4-cyanatophenyl) propane oligomer and phenol novolac type cyanate resin, Since the balance of fluidity is particularly good, 2,2-bis (4-cyanatophenyl) propane is more preferable. Note that 2,2-bis (4-cyanatophenyl) propane is excellent in terms of cost and productivity.
These polyfunctional cyanate resins may be used alone or in combination of two or more.

  The cyanate equivalent of the polyfunctional cyanate resin is not particularly limited. However, from the viewpoint of balance of various properties such as curability, heat resistance, and electrical reliability, it is preferably 100 g / eq to 1000 g / eq, and more preferably 100 g / eq to 300 g / eq. Here, the cyanate equivalent is the mass (g) per mole of cyanate group contained in the polyfunctional cyanate resin.

  The softening point or melting point of the polyfunctional cyanate resin is not particularly limited. However, from the viewpoints of curability and heat resistance, the softening point or melting point is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability during preparation of the thermosetting resin molding material, it is 50 ° C. to 130 ° C. More preferably.

  The polyfunctional cyanate resin may be used in combination with a known monofunctional cyanate resin having one epoxy group in one molecule. However, when the polyfunctional cyanate resin and the monofunctional cyanate resin are used in combination, the content of the polyfunctional cyanate resin is preferably 85% by mass or more, more preferably 95% by mass or more, based on the total amount of the epoxy resin.

  From the viewpoint of curability and heat resistance, the content of the cyanate resin in the thermosetting resin molding material is preferably 2% by mass to 10% by mass, and more preferably 3% by mass to 8% by mass.

  From the viewpoint of curability and heat resistance, the content of the cyanate resin in the thermosetting resin molding material is preferably 20 parts by mass to 300 parts by mass with respect to 100 parts by mass of the epoxy resin, and 40 parts by mass to 200 parts by mass. More preferably, it is part by mass.

  The equivalent ratio of the epoxy resin and cyanate resin in the thermosetting resin molding material, that is, the content ratio of the number of cyanate groups to the number of epoxy groups (the number of cyanate groups in the cyanate resin / the number of epoxy groups in the epoxy resin) is not particularly limited. The content ratio of the number of cyanate groups to the number of epoxy groups is preferably set in the range of 0.40 to 3.00, and is set in the range of 0.70 to 2.00 from the viewpoint of excellent workability and moldability. It is more preferable. When the content ratio is 0.40 or more, the glass transition temperature (Tg) of the cured product tends to be further improved, and when it is 3.00 or less, the curability is further improved and unreacted in the cured product. The remaining cyanate group tends to be suppressed. Moreover, there exists a tendency for a glass transition temperature (Tg) to improve more.

(Aromatic carboxylic acid or hydroxyl group-containing aromatic carboxylic acid ester)
The thermosetting resin molding material is at least one compound selected from the group consisting of an aromatic carboxylic acid and an aromatic carboxylic acid ester having a phenolic hydroxyl group (hereinafter also referred to as “hydroxyl group-containing aromatic carboxylic acid ester”). (Hereinafter also referred to as “aromatic carboxylic acid or hydroxyl group-containing aromatic carboxylic acid ester”).

-Aromatic carboxylic acid-
The aromatic carboxylic acid is not particularly limited as long as at least one carboxyl group is bonded to an aromatic ring such as a benzene ring or a naphthalene ring.

  The number of carboxyl groups bonded to the aromatic carboxylic acid is preferably 1 to 4.

  It is preferable that one or more OH groups are directly bonded to the aromatic carboxylic acid on the aromatic ring. In that case, the number of OH groups is preferably 1 to 4.

  Examples of aromatic carboxylic acids include benzoic acid compounds, benzenedicarboxylic acid compounds, benzenetricarboxylic acid compounds, benzenetetracarboxylic acid compounds, naphthoic acid compounds, naphthalene dicarboxylic acid compounds, naphthalenetricarboxylic acid compounds, naphthalenetetracarboxylic acid compounds, and the like. The aromatic ring is preferably at least one compound selected from the group consisting of aromatic carboxylic acid compounds having a phenolic hydroxyl group in which one or more OH groups are directly bonded.

  The aromatic carboxylic acid may further have a substituent in addition to the OH group directly bonded on the aromatic ring. Examples of the substituent in the aromatic carboxylic acid include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, and 6 carbon atoms. -14 aryl groups and the like. These substituents may be further bonded to a carboxyl group, a hydroxyl group or the like.

  Specific examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, merophanic acid, planitic acid, pyromellitic acid, 1-naphthoic acid, 2- Naphthoic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2,3-naphthalenedicarboxylic acid, 1,2,6 -Naphthalenetricarboxylic acid, 1,2,7-naphthalenetricarboxylic acid, 1,3,6-naphthalenetricarboxylic acid, 1,3,8-naphthalenetricarboxylic acid, 2,3,6-naphthalenetricarboxylic acid, 1,4,5 , 8-Naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, salicylic acid, m- Roxybenzoic acid, p-hydroxybenzoic acid, o-pyrocatechuic acid, protocatechuic acid, gentisic acid, α-resorcinic acid, β-resorcinic acid, γ-resorcinic acid, gallic acid, positional isomers of these compounds, substitution of these compounds Examples include the body.

Among them, aromatic carboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, merophanic acid, planitic acid, pyromellitic acid from the viewpoint of curability and heat resistance improvement of the cured product. 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2,3-naphthalenetricarboxylic acid, 1,2,6-naphthalene Tricarboxylic acid, 1,2,7-naphthalenetricarboxylic acid, 1,3,6-naphthalenetricarboxylic acid, 1,3,8-naphthalenetricarboxylic acid, 2,3,6-naphthalenetricarboxylic acid, 1,4,5,8 -Naphthalene tetracarboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid salicylic acid, m-hydroxy ammonium At least one compound selected from the group consisting of perfume acid, p-hydroxybenzoic acid, o-pyrocatechuic acid, protocatechuic acid, gentisic acid, α-resorcinic acid, β-resorcinic acid, γ-resorcinic acid, and gallic acid Is preferred.
Aromatic carboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6 from the viewpoint of fluidity. -Consisting of naphthalenedicarboxylic acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, o-pyrocatechuic acid, protocatechuic acid, gentisic acid, α-resorcinic acid, β-resorcinic acid, γ-resorcinic acid, and gallic acid More preferred is at least one compound selected from the group.

  These aromatic carboxylic acids may be used alone or in combination of two or more.

-Hydroxyl group-containing aromatic carboxylic acid ester-
Hydroxyl group-containing aromatic carboxylic acid ester is an aromatic carboxylic acid ester having a phenolic hydroxyl group, which is an aromatic carboxylic acid ester and a compound in which one or more OH groups are directly bonded on the aromatic ring. If there is no particular limitation.

  The number of carboxyl groups (including esterified carboxyl groups) bonded to the hydroxyl group-containing aromatic carboxylic acid ester is preferably 1 to 4.

  The number of OH groups bonded to the aromatic ring of the hydroxyl group-containing aromatic carboxylic acid ester is preferably 1 to 4.

  Hydroxyl group-containing aromatic carboxylic acid ester includes benzoic acid compound ester, benzenedicarboxylic acid compound ester, benzenetricarboxylic acid compound ester, benzenetetracarboxylic acid compound ester, naphthoic acid compound ester, naphthalenedicarboxylic acid compound ester A compound in which one or more OH groups are directly bonded to the aromatic ring of at least one compound selected from the group consisting of an ester of a naphthalene tricarboxylic acid compound and an ester of a naphthalene tetracarboxylic acid compound. preferable.

  In the hydroxyl group-containing aromatic carboxylic acid ester, the aromatic carboxylic acid ester having two or more carboxyl groups such as dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid, etc. may not have all the carboxyl groups converted to esters. In addition, a carboxyl group and an ester may be mixed.

In a hydroxyl group-containing aromatic carboxylic acid ester, when the carboxylic acid ester structure is represented as —CO—O—R, R is an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon having 6 to 14 carbon atoms. It is preferably a group.
The alkyl group having 1 to 6 carbon atoms represented by R may be linear, branched or cyclic, and is preferably linear or branched. Specific examples of the alkyl group having 1 to 6 carbon atoms include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, and n-hexyl group; isopropyl group, A branched alkyl group such as isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, isohexyl group, sec-hexyl group, t-hexyl group; cyclopropyl group, cyclopentyl group And cyclic alkyl groups such as cyclohexyl and the like.

  Specific examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R include a phenyl group and a naphthyl group.

  The hydroxyl group-containing aromatic carboxylic acid ester may further have a substituent in addition to the OH group directly bonded on the aromatic ring. As the substituent in the hydroxyl group-containing aromatic carboxylic acid ester, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, Examples thereof include aryl groups having 6 to 14 carbon atoms. These substituents may be further bonded to a carboxyl group or an OH group.

  Examples of the hydroxyl group-containing aromatic carboxylic acid ester include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, melophanoic acid, planitic acid, pyromellitic acid, 1-naphthoic acid, 2- Naphthoic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2,3-naphthalenedicarboxylic acid, 1,2,6 -Naphthalenetricarboxylic acid, 1,2,7-naphthalenetricarboxylic acid, 1,3,6-naphthalenetricarboxylic acid, 1,3,8-naphthalenetricarboxylic acid, 2,3,6-naphthalenetricarboxylic acid, 1,4,5 , 8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, etc. An ester compound in which at least one of the sil groups is esterified and one or more OH groups are bonded to the aromatic ring; salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, o-pyrocatechuic acid, Ester compounds in which carboxyl groups such as protocatechuic acid, gentisic acid, α-resorcinic acid, β-resorcinic acid, γ-resorcinic acid and gallic acid are esterified; positional isomers of these compounds; substituted compounds of these compounds, etc. It is done.

Among them, the hydroxyl group-containing aromatic carboxylic acid ester is hemimellitic acid, trimellitic acid, trimesic acid, merophanic acid, planitic acid, pyromellitic acid, 1,2,3 from the viewpoint of improving curability and heat resistance of the cured product. -Naphthalenetricarboxylic acid, 1,2,6-naphthalenetricarboxylic acid, 1,2,7-naphthalenetricarboxylic acid, 1,3,6-naphthalenetricarboxylic acid, 1,3,8-naphthalenetricarboxylic acid, 2,3,6 -One carboxyl group of naphthalenetricarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid and 2,3,6,7-naphthalenetetracarboxylic acid is esterified and one in their aromatic ring Monoester compounds to which the above OH groups are bonded, o-pyrocatechuic acid, protocatechuic acid, gentisic acid, α-res Arsine acid, beta-resorcylic acid, .gamma. resorcinol acid, and at least one carboxyl group of the gallic acid is selected from the group consisting of esterified ester compounds are preferred.
Further, the hydroxyl group-containing aromatic carboxylic acid ester is hemimellitic acid, trimellitic acid, trimesic acid, 1,2,3-naphthalene tricarboxylic acid, 1,2,6-naphthalene tricarboxylic acid, One carboxyl group of 2,7-naphthalenetricarboxylic acid, 1,3,6-naphthalenetricarboxylic acid, 1,3,8-naphthalenetricarboxylic acid, and 2,3,6-naphthalenetricarboxylic acid is esterified, and Monoester compounds having one or more OH groups bonded to their aromatic rings, and o-pyrocatechuic acid, protocatechuic acid, gentisic acid, α-resorcinic acid, β-resorcinic acid, γ-resorcinic acid, and gallic acid More preferred is at least one selected from the group consisting of ester compounds in which the carboxyl group of the acid is esterified.

  These hydroxyl group-containing aromatic carboxylic acid esters may be used alone or in combination of two or more.

  One of aromatic carboxylic acid and hydroxyl group-containing aromatic carboxylic acid ester may be used, or both may be used in combination.

  The OH group equivalent derived from the carboxyl group and the phenolic hydroxyl group contained in the aromatic carboxylic acid or hydroxyl group-containing aromatic carboxylic acid ester is not particularly limited, and is 30 g / eq to 400 g / eq from the viewpoint of curability and heat resistance. It is preferable that it is 40 g / eq to 300 g / eq. Here, the OH group equivalent is a mass (g) per mole of OH groups derived from a carboxyl group and a phenolic hydroxyl group contained in an aromatic carboxylic acid or a hydroxyl group-containing aromatic carboxylic acid ester.

  The content of the aromatic carboxylic acid or hydroxyl group-containing aromatic carboxylic acid ester in the thermosetting resin molding material is preferably 0.3% by mass to 3% by mass from the viewpoint of curability and heat resistance. It is more preferable that it is 5 mass%-2 mass%.

  The content of the aromatic carboxylic acid or the hydroxyl group-containing aromatic carboxylic acid ester in the thermosetting resin molding material is 3 to 50 parts by mass with respect to 100 parts by mass of the epoxy resin from the viewpoint of curability and heat resistance. It is preferable that it is 5 to 25 parts by mass.

(Equivalent ratio of each component)
In the thermosetting resin molding material, the equivalent ratio of the epoxy resin to the aromatic carboxylic acid or the hydroxyl group-containing aromatic carboxylic acid ester, that is, the aromatic carboxylic acid or the hydroxyl group-containing aromatic carboxylic acid to the number of epoxy groups contained in the epoxy resin Ratio of number of OH groups derived from carboxyl group and phenolic hydroxyl group contained in ester (number of OH groups derived from carboxyl group and phenolic hydroxyl group in aromatic carboxylic acid or hydroxyl group-containing aromatic carboxylic acid ester / number of epoxy groups in epoxy resin) ) Is preferably set in the range of 0.10 to 0.60, and is set in the range of 0.10 to 0.50 from the viewpoint of obtaining a thermosetting resin molding material that is more excellent in workability and moldability. More preferably. When the equivalent ratio is 0.10 or more, sufficient curability tends to be obtained. Moreover, there exists a tendency for the glass transition temperature (Tg) of hardened | cured material to improve more that an equivalent ratio is 0.60 or less.

  In the thermosetting resin molding material, the equivalent ratio of the epoxy resin to the total amount of the cyanate resin and the aromatic carboxylic acid or hydroxyl group-containing aromatic carboxylic acid ester, that is, included in the cyanate resin with respect to the number of epoxy groups contained in the epoxy resin Ratio of the total number of cyanate groups and the number of OH groups derived from the carboxyl group and phenolic hydroxyl group contained in the aromatic carboxylic acid or hydroxyl group-containing aromatic carboxylate ester ((number of cyanate groups in the cyanate resin + aromatic carboxylic acid or hydroxyl group contained) The number of OH groups derived from carboxyl groups and phenolic hydroxyl groups in the aromatic carboxylic acid ester) / number of epoxy groups in the epoxy resin) is preferably set in the range of 0.70 to 3.50. From the viewpoint of obtaining a thermosetting resin molding material that is more excellent in properties, 0 It is more preferably set in a range of from 80 to 2.50. When the equivalent ratio is 0.70 or more, sufficient curability tends to be obtained. If the equivalent ratio is 3.50 or less, the glass transition temperature (Tg) of the cured product tends to be further improved.

(Other ingredients)
The thermosetting resin molding material may further contain at least one silane compound. Here, as the silane compound, epoxy silane such as γ-glycidoxypropyltrimethoxysilane; mercaptosilane such as γ-mercaptopropyltrimethoxysilane; aminosilane such as γ-anilinopropyltrimethoxysilane; methyltrimethoxysilane Alkyl silanes such as γ-isocyanate propyl trimethoxy silane; vinyl silanes such as vinyl trimethoxy silane; These silane compounds may be used alone or in combination of two or more.

  When the thermosetting resin molding material contains a silane compound, the total content of the silane compound is 0.06% by mass to 2% by mass with respect to the thermosetting resin molding material from the viewpoint of moldability and fluidity. Preferably, 0.1 mass%-0.75 mass% is more preferable, and 0.2 mass%-0.7 mass% is still more preferable. When the total content of the silane compound is 0.06% by mass or more, the fluidity tends to be further improved. There exists a tendency for generation | occurrence | production of shaping | molding defects, such as a void, to be suppressed more that the total content rate of a silane compound is 2 mass% or less.

  The thermosetting resin molding material may further contain at least one curing accelerator. As a hardening accelerator, it is generally used with the thermosetting resin molding material, and there is no limitation in particular. Examples of the curing accelerator include 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] nonene-5, 5,6-dibutylamino-1,8-diazabicyclo. [5.4.0] cycloamidine compounds such as undecene-7; these cycloamidine compounds include maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone Quinone compounds such as 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone; Compound having intramolecular polarization formed by adding a compound having π bond such as phenol resin; benzyldimethylamine, triethanol Tertiary amine compounds such as amine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and derivatives thereof; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, etc. Imidazole compounds and derivatives thereof; organic phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine; maleic anhydride and quinone Phosphorus compound having intramolecular polarization formed by adding a compound having a π bond such as a compound, diazophenylmethane, phenol resin, etc .; tetraphenylphosphonium tetraphenylborate Tetrasubstituted phosphonium tetrasubstituted borates such as tetraphenylphosphonium ethyltriphenylborate and tetrabutylphosphonium tetrabutylborate; tetraphenylboron salts such as 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate and these And derivatives thereof. These curing accelerators may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as an organic phosphine used for the adduct of an organic phosphine compound (tertiary phosphine) and a quinone compound. Examples of organic phosphine compounds include dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, tris (4-butylphenyl) phosphine, tris (isopropylphenyl) phosphine, tris (t-butylphenyl) phosphine, tris (2,4-dimethylphenyl) phosphine, tris (2,6-dimethylphenyl) phosphine, tris (2, 4,6-trimethylphenyl) phosphine, tris (2,6-dimethyl-4-ethoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (4-ethoxyphenyl) phosphi Organic phosphine having an aryl group and the like. Among them, the organic phosphine compound is preferably triphenylphosphine from the viewpoint of moldability.

  There is no restriction | limiting in particular as a quinone compound used for the adduct of an organic phosphine compound (tertiary phosphine) and a quinone compound. Examples of the quinone compound include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, anthraquinone, and the like. Among them, the quinone compound is preferably p-benzoquinone from the viewpoint of moisture resistance or storage stability.

  When the thermosetting resin molding material includes a curing accelerator, the content of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved. The content of the curing accelerator is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the epoxy resin, cyanate resin, and aromatic carboxylic acid or hydroxyl group-containing aromatic carboxylic acid ester. 3 mass parts-6 mass parts are more preferable. When the content of the curing accelerator is 0.1 parts by mass or more, it tends to be easier to cure in a shorter time. When the content of the curing accelerator is 10 parts by mass or less, the curing rate does not become too fast, and a better molded product tends to be obtained.

  The thermosetting resin molding material may further contain at least one inorganic filler. By further including an inorganic filler, a reduction in hygroscopicity, a reduction in linear expansion coefficient, an improvement in thermal conductivity, and an improvement in strength are achieved more effectively. The inorganic filler is not particularly limited as long as it is generally used for thermosetting resin molding materials. Inorganic fillers include fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, Examples thereof include powders such as spinel, mullite, and titania, beads formed by spheroidizing these, and glass fibers. These inorganic fillers may be used alone or in combination of two or more. Among these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. The shape of the inorganic filler is preferably spherical from the viewpoint of fluidity during molding and mold wear. In particular, from the viewpoint of a balance between cost and performance, the inorganic filler is preferably spherical fused silica.

  When the thermosetting resin molding material contains an inorganic filler, the content of the inorganic filler is in the thermosetting resin molding material from the viewpoint of flame retardancy, moldability, hygroscopicity, linear expansion coefficient reduction and strength improvement. 70 mass%-95 mass% is preferable with respect to it. There exists a tendency for a flame retardance to fully improve that the content rate of an inorganic filler is 70 mass% or more. When the content of the inorganic filler is 95% by mass or less, better fluidity tends to be obtained.

  The thermosetting resin molding material may further contain other additives such as an anion exchanger, a release agent, a flame retardant, and a colorant, if necessary.

  The thermosetting resin molding material can further contain an anion exchanger as required. By including the anion exchanger, it is possible to further improve the moisture resistance and high temperature storage characteristics of the IC. There is no restriction | limiting in particular as an anion exchanger, A conventionally well-known thing can be used. Examples of the anion exchanger include hydrotalcite compounds, hydrated oxides of metal elements selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. These anion exchangers may be used alone or in combination of two or more.

  When the thermosetting resin molding material contains an anion exchanger, the content of the anion exchanger is not particularly limited as long as it is a sufficient amount that can capture anions such as halogen ions. 0.1 mass part-30 mass parts are preferable with respect to 100 mass parts of epoxy resins, and, as for content of an anion exchanger, 1 mass part-5 mass parts are more preferable.

  The thermosetting resin molding material may further contain at least one release agent as required. Examples of the release agent include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000, such as trade name PE and PED series of Clariant Japan Co., Ltd., which is an oxidized or non-oxidized polyolefin. Other examples of the mold release agent include carnauba wax, montanic acid ester, montanic acid, stearic acid, and the like. These release agents may be used alone or in combination of two or more.

  When the thermosetting resin molding material contains an oxidized or non-oxidized polyolefin as a release agent, the content is preferably 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the epoxy resin. 1 mass part-5 mass parts are more preferable. If the content is 0.01 parts by mass or more, sufficient releasability tends to be obtained. There exists a tendency for adhesiveness to improve more that content is 10 mass parts or less.

  When the thermosetting resin molding material contains another release agent in addition to the oxidized or non-oxidized polyolefin as a release agent, the total content of the release agent is 0 with respect to 100 parts by mass of the epoxy resin. 1 mass part-10 mass parts are preferable, and 0.5 mass part-3 mass parts are more preferable.

  The thermosetting resin molding material may further contain at least one conventionally known flame retardant as required. Examples of flame retardants include red coated with at least one of brominated epoxy resin, antimony trioxide, red phosphorus, aluminum hydroxide, magnesium hydroxide, zinc oxide, and other inorganic substances, and thermosetting resin such as phenol resin. Phosphorus compounds such as phosphorus and phosphate esters; melamine, melamine derivatives, melamine-modified phenolic resins, compounds having a triazine ring, nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives; phosphorus and nitrogen-containing compounds such as cyclophosphazene; water Examples thereof include compounds containing metal elements such as aluminum oxide, magnesium hydroxide, zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, and dicyclopentadienyl iron. These flame retardants may be used alone or in combination of two or more.

  When the thermosetting resin molding material contains a flame retardant, its content is not particularly limited. 1-30 mass parts is preferable with respect to 100 mass parts of epoxy resins, and, as for content of a flame retardant, 2-15 mass parts is more preferable.

  The thermosetting resin molding material may further contain a colorant such as carbon black, an organic dye, an organic pigment, titanium oxide, red lead, or bengara. Furthermore, the thermosetting resin molding material may contain a stress relaxation agent such as silicone oil and silicone rubber powder as other additives as required.

  The thermosetting resin molding material can be prepared by any method as long as various components can be dispersed and mixed. As a general technique, there can be mentioned a method in which components of a predetermined blending amount are sufficiently mixed with a mixer or the like, melt-kneaded using a mixing roll, an extruder, or the like, and then cooled and pulverized. The thermosetting resin molding material is prepared by stirring and mixing components of a predetermined blending amount, kneading with a kneader, roll, extruder, etc. that have been heated to 70 ° C. to 140 ° C. in advance, cooling, pulverizing, etc. It can also be obtained by the method. The thermosetting resin molding material is easy to use if it is tableted with dimensions and mass that meet the molding conditions.

<Electronic component device>
The electronic component device of the present invention includes an element and a cured product of the thermosetting resin molding material of the present invention that seals the element. Electronic component devices having elements sealed with thermosetting resin molding materials include lead frames, wired tape carriers, wiring boards, glass, silicon wafers, and other support members such as semiconductor chips, transistors, diodes, thyristors. Examples thereof include an electronic component device in which elements such as active elements such as capacitors, passive elements such as capacitors, resistors, and coils are mounted and necessary portions are sealed with the thermosetting resin molding material of the present invention. In particular, the thermosetting resin molding material of the present invention can be suitably used for power semiconductor applications exposed to harsh operating environments from the viewpoints of heat resistance, electrical insulation and the like.
As a method for sealing an element using the thermosetting resin molding material of the present invention, a low-pressure transfer molding method is the most common, but an injection molding method, a compression molding method, or the like may be used.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

<Examples 1-24, Comparative Examples 1-26>
Each material shown below is mix | blended by the mass part shown in following Table 1-7, respectively, knead | mixing temperature 80 degreeC, kneading | mixing time 10 minutes, roll kneading | mixing, Examples 1-24 (Tables 1-3) and Thermosetting resin molding materials of Comparative Examples 1 to 26 (Tables 4 to 7) were prepared. In addition, the blank in a table | surface represents not mix | blending.

Here, in Tables 1 to 7, “number of epoxy groups” indicates the number of epoxy groups contained in the epoxy resin. “Cyanate group” indicates the number of cyanate groups contained in the cyanate resin. The “number of OH groups derived from a carboxyl group and a phenolic hydroxyl group” indicates the number of OH groups derived from a carboxyl group and a phenolic hydroxyl group contained in an aromatic carboxylic acid or a hydroxyl group-containing aromatic carboxylic acid ester.
That is, “the number of cyanate groups / the number of epoxy groups” indicates the ratio of the number of cyanate groups contained in the cyanate resin to the number of epoxy groups contained in the epoxy resin. “Number of OH groups / number of epoxy groups” indicates the ratio of the number of OH groups derived from a carboxyl group and a phenolic hydroxyl group contained in an aromatic carboxylic acid or hydroxyl group-containing aromatic carboxylic acid ester to the number of epoxy groups contained in the epoxy resin. "(Cyanate group number + OH group number) / epoxy group number" refers to the number of cyanate groups contained in the cyanate resin relative to the number of epoxy groups contained in the epoxy resin and the carboxyl group-derived and phenolic groups contained in the aromatic carboxylic acid or hydroxyl group-containing aromatic carboxylic acid ester. The ratio of the total number with the number of OH groups derived from a hydroxyl group is shown.
However, in the comparative example using the phenol resin instead of the cyanate resin, the “number of cyanate groups” indicates the “number of hydroxyl groups of the phenol resin”. In a comparative example using a phenol compound instead of an aromatic carboxylic acid or a hydroxyl group-containing aromatic carboxylic acid ester, “OH group number” indicates “hydroxy group number of phenol compound”.

  The details of each material used in each example are shown below.

(Polyfunctional epoxy resin)
Epoxy resin 1: Triphenylmethane type epoxy resin having an epoxy equivalent of 170 g / eq and a softening point of 67 ° C. (trade name EPPN-502H of Nippon Kayaku Co., Ltd.)
Epoxy resin 2: Orthocresol novolac type epoxy resin having an epoxy equivalent of 200 g / eq and a softening point of 60 ° C. (trade name N-660 of DIC Chemical Industries, Ltd.)
Epoxy resin 3: Epoxy equivalent 258 g / eq, dicyclopentadiene type epoxy resin having a softening point of 60 ° C. (trade name HP-7200 of DIC Corporation)
Epoxy resin 4: Naphthalene-modified novolak epoxy resin having an epoxy equivalent of 250 g / eq and a softening point of 58 ° C. (trade name HP-5000 of DIC Corporation)
Epoxy resin 5: Dicyclopentadiene type epoxy resin having an epoxy equivalent of 286 g / eq and a softening point of 104 ° C. (trade name HP-7200HHH of DIC Corporation)
Epoxy resin 6: Orthocresol novolak type epoxy resin having an epoxy equivalent of 209 g / eq and a softening point of 96 ° C. (trade name YDCN-704A of Nippon Steel & Sumikin Chemical Co., Ltd.)

(Multifunctional cyanate resin)
Cyanate resin 1: 2,2-bis (4-cyanatophenyl) propane having a cyanate equivalent weight of 139 g / eq, a cyanate group number of 2, and a melting point of 80 ° C. (trade name Primaset BADCy of Lonza Japan Co., Ltd.)
Cyanate resin 2: 2,2-bis (4-cyanatophenyl) propane oligomer having a cyanate equivalent of 240 g / eq and a softening point of 95 ° C. (trade name Primaset BA-200, Lonza Japan Co., Ltd.)
Cyanate resin 3: Phenol novolac-type cyanate resin having a cyanate equivalent of 131 g / eq and a softening point of 80 ° C. (trade name Primaset PT-60, Lonza Japan Co., Ltd.)

(Phenolic resin: Phenolic resin used in the comparative example instead of cyanate resin)
Phenolic resin 1: Hydroxyl aldehyde type phenolic resin having a hydroxyl equivalent weight of 103 g / eq and a softening point of 88 ° C. (trade name MEH-7500 of Meiwa Kasei Co., Ltd.)
Phenol resin 2: phenol aralkyl resin having a hydroxyl group equivalent of 175 g / eq and a softening point of 70 ° C. (trade name MEH-7800 of Meiwa Kasei Co., Ltd.)

(Aromatic carboxylic acid)
Aromatic carboxylic acid 1: gallic acid (number of OH groups derived from carboxyl group and phenolic hydroxyl group: 4)
Aromatic carboxylic acid 2: terephthalic acid (carboxyl group-derived and phenolic hydroxyl group-derived OH group number 2)

(Aromatic carboxylic acid ester having a phenolic hydroxyl group)
Aromatic carboxylic acid ester derivative 1: methyl γ-resorcinate (number of OH groups derived from carboxyl group and phenolic hydroxyl group is 2)

(Phenol compound and metal complex: phenol compound and metal complex used in place of aromatic carboxylic acid or hydroxyl group-containing aromatic carboxylic acid ester in Comparative Example)
-Phenol compound 1: phenol (number of hydroxyl groups 1)
-Phenol compound 2: Catechol (number of hydroxyl groups 2)
-Phenol compound 3: resorcinol (2 hydroxyl groups)
-Phenol compound 4: Hydroquinone (number of hydroxyl groups 2)
Metal complex 1: cobalt naphthenate ((hydroxyl equivalent 0, hydroxyl number 0)

(Other additive components)
Silane compound 1: γ-glycidoxypropyltrimethoxysilane Curing accelerator 1: Betaine-type adduct of triphenylphosphine and p-benzoquinone Inorganic filler 1: Average particle diameter of 17.5 μm, specific surface area 8 m ² / g spherical fused silica release agent 1: montanic acid ester (trade name HW-E of Clariant Japan KK)
Colorant 1: Carbon black (trade name MA-600 of Mitsubishi Chemical Corporation)

<Evaluation>
The thermosetting resin molding materials of Examples and Comparative Examples obtained above were evaluated by the following various characteristic tests (1) to (5). The evaluation results are shown in Tables 8 to 14 below. The thermosetting resin molding material was molded by a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds unless otherwise specified. Further, post-curing was performed at 180 ° C. for 6 hours.

(1) Heat hardness (curability)
The thermosetting resin molding material was molded into a disk having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and was measured immediately after molding using a Shore D hardness meter (HD-1120 (type D) from Ueshima Seisakusho Co., Ltd.). .

(2) Glass transition temperature (Tg) measurement (dynamic viscoelasticity)
The thermosetting resin material was molded into a size of length 80 mm × width 10 mm × thickness 3 mm under the above conditions and post-cured. Next, it is cut into a width of 5 mm and a length of 55 mm with a diamond cutter, and using a viscoelasticity measuring device RSA3 (TA Instruments Inc.) in a three-point bending mode under conditions of a temperature rising rate of 5 ° C./min and a frequency of 6.28 rad / s. It was measured. The temperature at which the maximum value (peak top) of loss tangent (tan δ) obtained by this dynamic viscoelasticity measurement was shown was the glass transition temperature (Tg).

(3) Volume resistivity The thermosetting resin material was molded into a disc having a diameter of 100 mm and a thickness of 2 mm under the above conditions, and post-cured to obtain a test piece. Next, based on the JIS K 6911 (1995) standard, an electrode of an insulation resistance measuring instrument was attached to this test piece, a voltage of 500 V was applied, a current value for 1 minute was measured, and a volume resistivity was calculated by the following formula: did. The measurement was performed at 150 ° C. and 180 ° C.
Rv = 500 / Iv
ρv = (πd2 / 4t) × Rv
Here, Iv: measured current value (A), ρv: volume resistivity (Ωcm), d: outer diameter of inner circle of main electrode (cm), t: thickness of test piece (cm), Rv: Volume resistance (Ω), π: Circumference ratio (3.14) are shown, respectively.

(4) Flame Retardancy Evaluation Based on the UL-94 standard, a thermosetting resin material is molded to a size of 127 mm long × 12.5 mm wide × 6.35 mm thick under the above conditions, and post-cured to obtain a test piece. It was. Next, the test piece was hung perpendicularly to the clamp, held over a flame with a height of 19 mm for 10 seconds, the flame was moved away, the afterflame time of the test piece was measured, and after flame was put on the flame again for 10 seconds together with extinction. Time was measured. This was performed 5 times per sample. When the fire reached the clamp, it was written as “Clamp” in the table. The maximum afterflame time is V-0 when the maximum afterflame time (maximum afterflame time) is 10 seconds or less and the sum of all afterflame times (total afterflame time) is 50 seconds or less. Was set to V-1 when 30 seconds or less and the total afterflame time was 250 seconds or less, and the others were determined to be out of specification.

(5) Measurement of adhesive strength with metal at 200 ° C. and 250 ° C. Thermosetting resin molding material on the copper plate, on the silver-plated copper plate or on the nickel-plated copper plate, respectively, with a bottom surface of 4 mmφ and a top surface of 3 mmφ, height The test piece was molded into a size of 4 mm and post-cured. With a bond tester (Daisy Japan Co., Ltd. series 4000), the shear adhesive strength was measured at a shear rate of 50 μm / s while maintaining the temperature of various copper plates at 200 ° C. or 250 ° C.

  From the above evaluation results, all Examples were superior to Comparative Examples in glass transition temperature, flame retardancy, shear adhesive strength, and volume resistivity.

  In addition, "-" of Comparative Examples 5 to 8 in Table 11 and Comparative Examples 17 to 24 in Table 13 indicates that the data could not be acquired because the curability was poor and the test piece could not be molded. These are considered to have a poor curability because they do not contain, for example, an aromatic carboxylic acid or an aromatic carboxylic acid ester having a phenolic hydroxyl group, and a molded product could not be obtained.

In addition, since Comparative Examples 25 and 26 in Table 14 in which the metal complex 1 (cobalt naphthenate) was used instead of the aromatic carboxylic acid or the aromatic carboxylic acid ester having a phenolic hydroxyl group, the predetermined evaluation could not be performed. In Table 14, “−” is shown except for the hardness at the time of heating. In Comparative Example 25, the kneaded product taken out after the roll kneading was in the form of a bowl and was not pulverized. Although this was heated at 180 ° C. for 2 minutes or more, curing did not proceed, and it was impossible to measure the hot hardness, rather than obtaining a predetermined molded product. On the other hand, in Comparative Example 26, the kneaded material hardened rapidly during the kneading of the roll. The kneaded product taken out was heated at 180 ° C., but it did not melt and was almost completely cured, so that a predetermined molded product could not be obtained.
The content of the metal complex is 0.5 parts by mass in Comparative Example 25 and 0.7 parts by mass in Comparative Example 26 with respect to 100 parts by mass of the epoxy resin. Thus, the curing behavior changed significantly. For this reason, even if a moldable sealing material is obtained using a metal complex, it is considered difficult to ensure the curability and reproducibility of other characteristics.

Claims (7)

An epoxy resin containing a polyfunctional epoxy resin having two or more epoxy groups in one molecule;
A cyanate resin containing a polyfunctional cyanate resin having two or more cyanate groups (—OCN) in one molecule;
At least one compound selected from the group consisting of an aromatic carboxylic acid and an aromatic carboxylic acid ester having a phenolic hydroxyl group;
Containing thermosetting resin molding material.   At least one compound selected from the group consisting of the aromatic carboxylic acid and the aromatic carboxylic acid ester having a phenolic hydroxyl group has an OH group equivalent derived from a carboxyl group and a phenolic hydroxyl group of 30 g / eq to 400 g / The thermosetting resin molding material according to claim 1, which is eq.   The aromatic carboxylic acid includes a benzoic acid compound, a benzene dicarboxylic acid compound, a benzene tricarboxylic acid compound, a benzene tetracarboxylic acid compound, a naphthoic acid compound, a naphthalene dicarboxylic acid compound, a naphthalene tricarboxylic acid compound, a naphthalene tetracarboxylic acid compound, and the like 3. The compound according to claim 1, wherein the compound is at least one compound selected from the group consisting of aromatic carboxylic acid compounds having a phenolic hydroxyl group in which one or more OH groups are directly bonded on the aromatic ring. Thermosetting resin molding material.   The aromatic carboxylic acid ester having a phenolic hydroxyl group is an ester of a benzoic acid compound, an ester of a benzenedicarboxylic acid compound, an ester of a benzenetricarboxylic acid compound, an ester of a benzenetetracarboxylic acid compound, an ester of a naphthoic acid compound, or naphthalenedicarboxylic acid A compound in which one or more OH groups are directly bonded to an aromatic ring of at least one compound selected from the group consisting of an ester of a compound, an ester of a naphthalene tricarboxylic acid compound, and an ester of a naphthalene tetracarboxylic acid compound The thermosetting resin molding material according to any one of claims 1 to 3.   Ratio of the number of OH groups derived from a carboxyl group and a phenolic hydroxyl group contained in at least one compound selected from the group consisting of the aromatic carboxylic acid and the aromatic carboxylic acid ester to the number of epoxy groups contained in the epoxy resin Is 0.10-0.60, The thermosetting resin molding material of any one of Claims 1-4.   Derived from a carboxyl group contained in at least one compound selected from the group consisting of the number of cyanate groups contained in the cyanate resin and the aromatic carboxylic acid and the aromatic carboxylic acid ester with respect to the number of epoxy groups contained in the epoxy resin; The thermosetting resin molding material according to any one of claims 1 to 5, wherein the ratio of the total number of OH groups derived from phenolic hydroxyl groups is 0.70 to 3.50.   An electronic component device comprising: an element; and a cured product of the thermosetting resin molding material according to any one of claims 1 to 6, which seals the element.