JP2001089640A - Flame-retarded epoxy resin composition and semiconductor sealing material using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retarded epoxy resin composition showing an excellent flame retardance without using any halogen compound nor phosphorus flame retardant, and a semiconductor sealing material using this. SOLUTION: This flame-retarded epoxy resin composition comprises a halogen atom-free epoxy resin which contains at least two epoxy groups within a molecule, a hardener, a compound containing a copper atom and a compound containing a metal atom other than copper as basic components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant epoxy resin composition exhibiting excellent flame retardancy without using a halogen-based compound or a phosphorus-based flame retardant, and a semiconductor sealing material using the same. It is about.

[0002]

2. Description of the Related Art Epoxy resins have a low degree of shrinkage during curing compared to other thermosetting resins such as unsaturated polyester resins and phenol resins, and therefore have good adhesion to metals and inorganic substances, and are used as semiconductor sealing materials. However, in recent years, in many cases, flame retardancy has been imparted to ensure safety against fire. Conventionally, halogen-based compounds such as brominated epoxy resins have been generally used to make these resins flame-retardant.

[0003] Although these halogen compounds have high flame retardancy, aromatic bromine compounds not only release corrosive bromine and hydrogen bromide by thermal decomposition but also decompose in the presence of oxygen. Is a highly toxic polybenzofuran,
Possibility of forming polybromodibenzooxacin. Further, it is extremely difficult to treat aging waste materials and refuse containing bromine.

[0004] For these reasons, phosphorus-based flame retardants have been widely studied as flame retardants in place of halogenated compounds. However, when a phosphate ester or the like is used in the epoxy resin composition, bleeding or hydrolyzability is a problem, causing a drawback that electrical characteristics and reliability are significantly deteriorated.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a flame-retardant epoxy resin composition having a high degree of flame retardancy without adding a halogen compound or a phosphorus flame retardant and which does not deteriorate the properties of products. It is an object of the present invention to provide a product and a semiconductor encapsulating material using the same.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the problems of the conventional flame-retardant epoxy resin composition, and as a result, have found that the epoxy resin composition contains a compound having a copper atom. It has been found that by adding a compound having a metal atom other than copper, the flame retardancy can be remarkably improved, and further studies have been made to complete the present invention.

That is, the present invention provides an epoxy resin (A) having at least two epoxy groups in one molecule and containing no halogen atom, a curing agent (B), a compound (C) having a copper atom, A flame-retardant epoxy resin composition comprising a compound (D) having a metal atom other than copper, and a semiconductor sealing material using the same.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant epoxy resin composition of the present invention and a semiconductor encapsulating material using the same do not use a halogenated compound such as a halogenated epoxy resin or a phosphorus-based flame retardant, and have no constituent components. The main point is to provide flame retardancy by adding a compound (C) having a copper atom and a compound (D) having a metal atom other than copper.

The epoxy resin (A) having at least two epoxy groups in one molecule and containing no halogen atom includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin. Type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, N-glycidyl compound derived from aromatic amine and heterocyclic nitrogen base, for example, N, N-di Glycidyl aniline,
Examples include triglycidyl isocyanurate, N, N, N ', N'-tetraglycidyl-bis (p-aminophenyl) -methane, but are not particularly limited thereto.
These can be used in combination of several types.

However, since the present invention aims at a resin composition containing no halogen-based compound, it goes without saying that halogenated epoxy resins such as brominated bisphenol A epoxy resin and brominated novolak epoxy resin are excluded. However, in the production process of the epoxy resin, chlorine contained in the normal epoxy resin originating from epichlorohydrin is unavoidably mixed. However, the amount is at a level known to those skilled in the art and is of the order of several hundred PPM for hydrolysable chlorine.

As the curing agent (B) used in the present invention, all those known to those skilled in the art can be used.
Particularly, C2 such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.
-C20 linear aliphatic diamine, metaphenylenediamine, paraphenylenediamine, paraxylenediamine,
4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodicyclohexane, bis (4-aminophenyl) Phenylmethane, 1,5-diaminonaphthalene, metaxylenediamine, paraxylenediamine, 1,1-bis (4-
Amines such as aminophenyl) cyclohexane and dicyanodiamide; resole-type phenol resins such as aniline-modified resole resins and dimethyl ether resole resins;
Examples include phenol novolak resins, cresol novolak resins, tert-butylphenol novolak resins, novolak type phenol resins such as nonylphenol novolak resins, polyoxystyrenes such as polyparaoxystyrene, phenol resins such as phenol aralkyl resins, and acid anhydrides. However, the present invention is not particularly limited to these.

When used as a semiconductor encapsulating material, a compound or resin having at least two phenolic hydroxyl groups in one molecule is preferable from the viewpoint of moisture resistance, reliability, etc. Specifically, phenol novolak resin Novolak phenol resins such as cresol novolak resin, tert-butylphenol novolak resin, nonylphenol novolak resin, resol phenol resin, polyoxystyrene such as polyparaoxystyrene, and phenol aralkyl resin.

As the compound (C) having a copper atom used in the present invention, a metal complex or a metal oxide can be used. As the metal complex, specifically, a naphthenic acid complex,
Acetylacetonate complex, ethylenediamine complex, bipepyridine complex, cyclohexanediamine complex, tetraazacyclotetradecane complex, ethylenediaminetetraacetic acid complex, tetraethyleneglycol complex, aminoethanol complex, cyclohexadiamine complex, glycine complex, triglycine complex, naphthyridin complex, At least one complex selected from the group consisting of a phenanthroline complex, a pentanediamine complex, a pyridine complex, a salicylic acid complex, a salicylaldehyde complex, a salicylideneamine complex, a porphyrin complex, and a thiourea complex,
Particularly, an acetylacetonate complex is preferable.

Among the above complexes, those which are more stable to form a chelate ring can be used as metal chelates. For example, those which easily form a ring structure, such as an ethylenediamine complex and an acetylacetonate complex, may be mentioned. On the other hand, as a copper oxide, a monovalent or divalent oxygen compound is easily formed, but a compound in any oxidation state can be used without particular limitation.

As for the compound (D) having a metal atom other than copper, a metal complex or a metal oxide can be used similarly to the compound (C) having a copper atom.
Naphthenic acid complex, acetylacetonate complex, ethylenediamine complex, bipepyridine complex, cyclohexanediamine complex, tetraazacyclotetradecane complex, ethylenediaminetetraacetic acid complex, tetraethyleneglycol complex, aminoethanol complex, cyclohexadiamine complex, glycine complex, triglycine complex At least one complex selected from the group consisting of naphthydiline complex, phenanthroline complex, pentanediamine complex, pyridine complex, salicylic acid complex, salicylaldehyde complex, salicylideneamine complex, porphyrin complex, thiourea complex, etc. Particularly, a naphthenic acid complex, an acetylacetonate complex, a salicylic acid complex, and an ethylenediaminetetraacetic acid complex are preferable.

Among the above complexes, those in which the formation of a chelate ring is more stable are the same as in the case of the copper compound (C).
It can also be used as a metal chelate. For example, those which easily form a ring structure, such as an ethylenediamine complex and an acetylacetonate complex, may be mentioned.

The compound (D) having a metal atom other than copper used in the present invention includes Be, B, Mg, Al, Si,
S, Ca, Sc, Ti, V, Cr, Mn, Fe, Co,
Ni, Zn, Ga, Ge, As, Se, Sr, Y, Z
r, Nb, Mo, Tc, Ru, Rh, Pd, Ag, C
d, In, Sn, Sb, Te, Ba, Hf, Ta, W,
Re, Os, Ir, Pt, Au, Hg, Tl, Pb, B
and a compound having at least one metal atom selected from the group consisting of i and Po. Preferably A
a compound having at least one metal atom selected from the group consisting of 1, Si, Mn, Fe, Co, Ni, Zn, and Sn, and more preferably Al, Co,
And a compound having at least one metal atom selected from the group consisting of Ni and Ni.

The oxide of a metal other than copper is an oxide having any of the metal atoms exemplified as the central metal atom of the metal complex. For example, cobalt is cobalt monoxide, dicobalt trioxide. For example, an oxygen compound having a valence of -1 to pentavalent, such as ordinary cobalt oxide, is formed, and any metal oxide can be used in any oxidation state.

The compounding amount of the compound (C) having a copper atom and the compound (D) having a metal atom other than copper is based on 100 parts by weight of the epoxy resin (A) and the curing agent (B) in total. The total amount of C) and compound (D) is preferably 0.001 to 4 parts by weight, more preferably 0.01 to 1 part by weight, and particularly preferably 0.01 to 0.5 part by weight. However, there is no particular limitation on the ratio between the compound (C) and the compound (D).

The sum of the compound (C) and the compound (D) is 0.
If the amount is less than 001 parts by weight, the effect of flame retardancy cannot be obtained. On the other hand, if 4 parts by weight or more is added, the curability of the resin composition decreases. The compound (C) having a copper atom and the compound (D) having a metal atom other than copper are always contained at the same time, but the compound (C) may be used alone, or two or more kinds may be used. Can be used even if they are mixed. Further, the compound (D) may be used alone or in combination of two or more.

The flame-retardant epoxy resin composition of the present invention is obtained by using a compound having a copper atom (C) and a compound having a metal atom other than copper (D) in combination with a halogen-based compound or a phosphorus-based flame retardant. Without adding, it is possible to achieve a high degree of flame retardancy and does not deteriorate the characteristics of the product, it is suitable as a sealing material for semiconductor elements,
Encapsulation materials, coating materials, insulating materials for electronic and electrical components,
It can also be suitably used for a laminate, a metal-clad laminate, and the like.

The semiconductor encapsulating material of the present invention is basically composed of the flame-retardant resin composition and a filler. Specific examples of the filler include silica powder such as fused silica, alumina, and talc. , Calcium carbonate, clay, mica, etc. If necessary, natural waxes, synthetic waxes, metal salts of linear aliphatic acids, acid amides, esters, release agents such as paraffins, carbon black,
Additives known to those skilled in the art, such as a coloring agent such as redwood, various curing accelerators, and a coupling agent, are used in combination.

The flame-retardant epoxy resin composition of the present invention, a filler, and other additives are selected to have an arbitrary composition ratio, and are sufficiently mixed by a mixer or the like. Alternatively, a semiconductor encapsulating material can be obtained by performing a kneading process using a co-kneader, cooling, solidifying, and pulverizing to an appropriate size. In the preparation of the flame-retardant resin composition, the epoxy resin (A) and the curing agent must be prepared in advance in order to improve the dispersibility of the compound (C) having a copper atom and the compound (D) having a metal atom other than copper. It may be used by being melted and mixed with (B).
The obtained semiconductor encapsulating material is suitably used for encapsulating a semiconductor element by transfer molding, injection molding or the like.

[0024]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited thereto. First, a predetermined amount of each component is blended and kneaded, and for the obtained molding material for semiconductor encapsulation, the spiral flow and curability of the molding material, the flame retardancy and reliability of the cured product are evaluated for the property evaluation. It was measured. Each test method and conditions were as follows.

(1) The spiral flow was measured at 175 ° C. and 70 kgf / cm ² using a mold conforming to the EMMI standard. (2) The curability was measured by measuring the Barcol hardness of the molded article when molded at 175 ° C. for 120 seconds. (3) Flame retardancy was evaluated by the vertical method according to UL94 standard. After the measurement sample was molded at 175 ° C for 3 minutes,
A 1.6 mm thick flame resistance test sample that had been post-cured at 175 ° C. for 8 hours was used. (4) The reliability of the monitor IC (1
6pDIP) was formed and evaluated by the number of defects (eg, chip shift) after leaving it for 1000 hours at 121 ° C. and 100% hot and humid conditions.

(Example 1) 85 parts by weight of fused silica, biphenyl type epoxy resin (YH-
4000H, epoxy equivalent 195 g / eq) 7.6 parts by weight,
Phenol aralkyl resin (Mitsui Chemicals XL-225,
6.8 parts by weight of hydroxyl equivalent (175 g / eq), 0.01 parts by weight of copper acetylacetonate (manufactured by Wako Pure Chemical Industries, Ltd.) (based on 100 parts by weight of epoxy resin (A) and curing agent (B) in total) 0.07 parts by weight), iron acetylacetonate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.01 parts by weight (0.07 parts by weight based on 100 parts by weight of epoxy resin (A) and curing agent (B) in total) Parts by weight), 0.3 parts by weight of a release agent (natural carnauba wax), 0.2 parts by weight of a colorant (carbon black), and a coupling agent (A-18 manufactured by Nippon Unicar)
6) 0.3 parts by weight were blended and kneaded using a hot roll to obtain a molding compound for semiconductor encapsulation.

(Examples 2 to 5) Instead of iron acetylacetonate used in Example 1, zinc acetylacetonate (Kanto Chemical Co., Ltd.), zinc-ethylenediaminetetraacetic acid (Wako Pure Chemical Industries, Ltd.), A molding material was prepared in the same manner as in Example 1 except that manganese-acetylacetonate (manufactured by Wako Pure Chemical Industries, Ltd.) and manganese salicylate (manufactured by Wako Pure Chemical Industries, Ltd.) were used and blended according to Table 1. Prepared and evaluated for spiral flow, curability, flame retardancy, and reliability.

(Comparative Examples 1 to 5) In the same manner as in Example 1 except that the components were blended according to Table 1, such as an example using a phosphorus-based flame retardant and an example using a compound having a metal atom,
Molding materials were prepared and evaluated for spiral flow, curability, flame retardancy, and reliability.

Table 1 shows the compositions and evaluation results of the examples and comparative examples. As is clear from the evaluation results, in Comparative Example 1 using a phosphorus-based flame retardant and Comparative Example 5 using a copper compound and a compound having a metal atom other than copper, the flame retardancy was UL94V-0. But Comparative Example 1
Was inferior in reliability and Comparative Example 5 was poor in curability. In Comparative Example 4, sufficient flame retardancy was not obtained because the amounts of the copper compound and the compound having a metal atom other than copper were small. On the other hand, in all the examples, the flame retardancy achieved V-0, and other various physical properties were also good.

[0030]

[Table 1]

[0031]

The flame-retardant epoxy resin composition of the present invention comprises:
By adding a compound having a copper atom and a compound having a metal atom other than copper without adding a halogen-based compound, sufficient flame retardancy can be obtained. Furthermore, the flame-retardant epoxy resin composition as a non-halogen, non-phosphorus material which is more reliable than the case where a phosphorus-based flame retardant conventionally used is blended, and a semiconductor encapsulation using the same. Provide materials.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) H01L 23/29 H01L 23/30 R 23/31 F-term (Reference) 4J002 CC042 CC052 CC072 CD051 CD061 CD111 CD131 CD141 CE002 DE078 DE097 DE098 DE138 DE149 DE239 DJ019 DJ039 DJ049 DJ059 DK008 EC077 EC078 EE047 EE048 EG087 EG088 EJ067 EJ068 EN036 EN037 EN038 EN076 EN107 EN108 EN117 EN118 ET006 EU007 EU008 EU047 EU048 EU077 EU078 EV127 EV128 EV226 FD001 FD019 FD019 FD0140A EA02 EB03 EB06 EB07 EB08 EB09 EB12 EB19 EC01 EC20

Claims (8)

[Claims] 1. An epoxy resin (A) having at least two epoxy groups in one molecule and containing no halogen atom, a curing agent (B), a compound (C) having a copper atom,
And a flame-retardant epoxy resin composition comprising a compound (D) having a metal atom other than copper. 2. The flame-retardant epoxy resin composition according to claim 1, wherein the curing agent (B) comprises a compound or resin having at least two phenolic hydroxyl groups in one molecule. 3. The flame-retardant epoxy resin composition according to claim 1, wherein the compound (C) having a copper atom comprises a metal complex or a metal oxide. 4. The compound having a copper atom (C) is a naphthenic acid complex, an acetylacetonate complex, an ethylenediamine complex, a bipepyridine complex, a cyclohexanediamine complex, a tetraazacyclotetradecane complex, an ethylenediaminetetraacetic acid complex, a tetraethyleneglycol complex, From aminoethanol complex, cyclohexadiamine complex, glycine complex, triglycine complex, naphthyridin complex, phenanthroline complex, pentanediamine complex, pyridine complex, salicylic acid complex, salicylaldehyde complex, salicylideneamine complex, porphyrin complex, and thiourea complex The flame-retardant epoxy resin composition according to claim 1, wherein the composition is at least one complex compound selected from the group consisting of: 5. Compound (D) having a metal atom other than copper
Is a metal complex or a metal oxide. The flame-retardant epoxy resin composition according to claim 1, wherein 6. Compound (D) having a metal atom other than copper
But naphthenic acid complex, acetylacetonate complex, ethylenediamine complex, bipepyridine complex, cyclohexanediamine complex, tetraazacyclotetradecane complex, ethylenediaminetetraacetic acid complex, tetraethyleneglycol complex, aminoethanol complex, cyclohexadiamine complex, glycine complex, tri At least one complex compound selected from the group consisting of glycine complex, naphthyridin complex, phenanthroline complex, pentanediamine complex, pyridine complex, salicylic acid complex, salicylaldehyde complex, salicylideneamine complex, porphyrin complex and thiourea complex. The flame-retardant epoxy resin composition according to claim 1 or 5, characterized in that: 7. Compound (D) having a metal atom other than copper
Are Be, B, Mg, Al, Si, S, Ca, Sc,
Ti, V, Cr, Mn, Fe, Co, Ni, Zn, G
a, Ge, As, Se, Sr, Y, Zr, Nb, Mo,
Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, S
b, Te, Ba, Hf, Ta, W, Re, Os, Ir,
7. The compound according to claim 1, which is a compound having at least one metal atom selected from the group consisting of Pt, Au, Hg, Tl, Pb, Bi and Po. The flame-retardant epoxy resin composition according to any one of the above. 8. A semiconductor encapsulation material comprising a flame-retardant epoxy resin composition according to claim 1 and a filler.