JP3176800B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for electronic and electric parts which has excellent curability and good storage stability at room temperature.

[0002]

2. Description of the Related Art In recent years, epoxy resin compositions have been generally used as sealing materials for semiconductor elements such as ICs and LSIs and electric parts from the viewpoint of balance between properties and costs.

In such an epoxy resin sealing material,
Conventionally used curing accelerators include 2-methylimidazole, 1,8-diazabicyclo [5,4,0] -7-undecene (hereinafter abbreviated as DBU), triphenylphosphine, and the like. The epoxy resin encapsulant using the accelerating agent has poor storage stability at room temperature. Therefore, when stored at room temperature, the flowability deteriorates, causing unfilling failure during molding, breaking the gold wire of the IC chip, and conducting. There were problems such as occurrence of defects.

[0004] For this reason, at present, it is necessary to store the epoxy resin sealing material in a refrigerated state, and at present, enormous costs are required for refrigerated storage and refrigerated transportation.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition for electronic and electric parts which has excellent curability and good storage stability at room temperature.

[0006]

The present invention provides (A) an epoxy resin having two or more epoxy groups in one molecule;
A phenolic resin having two or more phenolic hydroxyl groups in one molecule, (C) a phosphonium ion represented by the general formula (1)

[0007]

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(Hereinafter abbreviated simply as “phosphonium ion.” Also, at least one of R ₁ , R ₂ and R ₃ in the formula
The above is an organic group containing a monovalent aromatic ring, and R ₄ , R ₅
And at least one of R ₆ contains a monovalent aromatic ring.
Represents a non-organic group, may be the same as or different from each other, R in the formula represents an organic group and a divalent substituent selected from the group consisting of aliphatic residue containing bivalent aromatic ring) and , Good
Aromatic carboxylic acid, isocyanuric acid, or 1,2,3-
It contains an ionic bond (hereinafter simply abbreviated as an ionic bond) with an organic anion (a) capable of forming an ion pair of benzotriazole , and (D) an inorganic filler. The equivalent ratio of the phenolic hydroxyl group of the phenolic resin (B) is 0.5 or more and 2 or less, and the weight ratio of the ionic complex (C) is 0.4 parts by weight with respect to 100 parts by weight of (A) + (B). 20 parts by weight or less, and the weight ratio of the inorganic filler (D) is 40 parts by weight or more and 2400 parts by weight or less with respect to 100 parts by weight of (A) + (B). is there.

Specific examples of the epoxy resin (A) include orthocresol novolak epoxy, phenol novolak epoxy, bisphenol A type epoxy,
Examples thereof include a biphenyl type epoxy, but are not particularly limited thereto. Furthermore, phenolic resin (B)
Examples thereof include phenol novolak and cresol novolak. In these (A) and (B), the equivalent ratio of the epoxy group to the phenolic hydroxyl group is 0.5.
Above 2 is preferable, and if it is out of this range, problems such as lowering of glass transition temperature and lowering of curability occur.

In the ionic complex (C) of a curing accelerator, a phosphonium ion and an organic anion (a), two phosphonium ions and an organic anion (a) in one molecule each form at least one ion pair. do it. Examples of the substituents R ₁ , R ₂ , R ₃ , R ₄ , R _5, and R ₆ of the phosphonium ion represented by the general formula (1) include phenyl, tolyl, ethylphenyl, methoxyphenyl, naphthyl, and benzyl groups. Examples thereof include an organic group containing an aromatic ring such as an alkyl group such as an ethyl and butyl group, but from the viewpoint of curability, at least one of R ₁ , R ₂ and R ₃ contains a monovalent aromatic ring. An organic group and R ₄ , R ₅ and R
It is better and more preferable that at least one or more of the _six groups be constituted by an organic group containing a monovalent aromatic ring. The substituents R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be the same or different, and the position of a specific substituent is not limited at all.

[0011] Specific examples of the organic anion (a), Ahn Ikikosan, aromatic carboxylic acid or phthalic acid as an aromatic nucleus to functional groups benzoic acid, trimellitic acid, pyromellitic acid, 2, Polyfunctional aromatic carboxylic acids such as 6-naphthalenedicarboxylic acid, various polymerized carboxylic anions such as polyacrylic acid, isocyanuric acid, 1,2,3-
Benzotriazole anion can be exemplified, Fang aromatic carboxylic acids, isocyanuric acid and 1,2,3-benzotriazole anion is more preferred in view of curability and electrical properties of the resin composition.

Further, the amount of the curing accelerator (C) to be added is 1% of the total weight of the epoxy resin (A) and the phenol resin (B).
It is preferably from 0.4 to 20 parts by weight based on 00 parts by weight. If the amount is less than 0.4 part by weight, the curability is lowered. If the amount is more than 20 parts by weight, the curing is too fast, and problems such as insufficient filling during molding occur.

Examples of the inorganic filler (D) used in the present invention include alumina, fused silica, crystalline silica, clay and talc, but are not particularly limited thereto. The amount of the inorganic filler (D) to be added is preferably 40 parts by weight or more and 2400 parts by weight or less based on 100 parts by weight of the total weight of the resin components (A) and (B). In such a case, problems such as a decrease in strength are caused. If the amount is more than 2400 parts by weight, fluidity is reduced, and problems such as insufficient filling during molding are caused.

The resin component (A) used in the present invention,
In addition to (B), the curing accelerator (C) and the inorganic filler (D), various additives such as a release agent, a colorant, an antioxidant, and a coupling agent are used as long as the properties are not deteriorated. It goes without saying that it can be blended.

[0015]

The ionic conjugate (C) of the phosphonium ion and the organic anion (a) used in the present invention is 2 in one molecule.
Of the phosphonium ion and the organic anion (a) each form at least one ion pair, and the curing accelerator (C) is an ionic complex of the phosphonium ion and the organic anion (a) at room temperature. Are present in a stable manner, suppress the catalytic action of phosphonium ions, rapidly dissociate this ionic complex during molding when exposed to high temperatures, activate the phosphonium ions, and have the effect of promoting curing. This curing accelerator (C) has a total weight of 10% of the epoxy resin (A) and the phenol resin (B).
The amount is preferably from 0.4 part by weight to 20 parts by weight with respect to 0 part by weight. If the amount is less than 0.4 part by weight, the curability is lowered. The decrease causes problems such as unfilled defects.

[0016]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the catalysts used in Examples and Comparative Examples,

[0017]

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[0018]

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[0019]

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[0020]

Embedded image Was prepared in accordance with a conventional method.

(Example 1) Orthocresol novolak epoxy having a softening point of 65 ° C. and an epoxy equivalent of 210 (EOCN-1025-65 manufactured by Nippon Kayaku Co., Ltd.) 67 parts (hereinafter, all parts by weight are abbreviated as parts), and softening 33 parts of phenol novolac (PR-51470 manufactured by Sumitomo Durez Co., Ltd.) having a hydroxyl group equivalent of 104 at 105 ° C., 2.3 parts of TPPE-BA as a curing accelerator, 300 parts of fused silica, and 2 parts of carnauba wax were blended. The mixture was kneaded with a roll at 90 ° C. for 8 minutes to obtain a molding material. The spiral flow at 175 ° C. by transfer molding of this molding material is 76 cm, 175
The torque after 90 seconds in a 70 ° C curast meter is 71 kg.
f-cm. The spiral flow is a parameter of fluidity, and the larger the value, the better the fluidity. The torque in the curast meter is a parameter of curability, and the larger the value, the better the curability.

Next, the spiral flow of this material after storage at 25 ° C. for 6 months was measured. As a result, the spiral flow was 72 cm, and the residual flow rate (flow after storage at 25 ° C. for 6 months / initial flow × 100 (%)) was 95%.

(Example 2) The curing accelerator TPP of Example 1
Instead of 2.3 parts of E-BA, BDPB-
Except for using 2.4 parts of BA, the material was made by the same operation as in Example 1. The spiral flow of this material is 68
After 90 seconds, the torque was 70 kgf-cm. Also, 2
The spiral flow after storage at 5 ° C. for 6 months was 63 cm, and the residual flow rate was 93%.

Example 3 Curing accelerator TPP of Example 1
Instead of 2.3 parts of E-BA, TPPB-
Except for using 2.4 parts of ICA, all materials were made in the same manner as in Example 1. The spiral flow of this material is 7
The torque after 90 seconds at 0 cm was 72 kgf-cm. Also,
Spiral flow after storage at 25 ° C for 6 months is 69cm,
The residual flow rate was 98%.

Example 4 Curing accelerator TPP of Example 1
Instead of 2.3 parts of E-BA, TPPE-
Except for using 2.1 parts of BZ, the material was converted into a material by the same operation as in Example 1. The spiral flow of this material is 75
After 90 seconds, the torque was 75 kgf-cm. Also, 2
The spiral flow after storage at 5 ° C. for 6 months was 72 cm, and the residual flow rate was 96%.

Example 5 Phenol novolak having 67 parts of a biphenyl type epoxy (YX-4000H manufactured by Yuka Shell Epoxy Co., Ltd.) having a softening point of 95 ° C. and a hydroxyl equivalent of 103 (PR-51714 manufactured by Sumitomo Durez Co., Ltd.) 33 parts, 4.6 parts of TPPE-BA as a curing accelerator, fused silica 2
Except for using 300 parts, a material was produced in the same manner as in Example 1. The spiral flow of this material was 50 cm, and the torque after 90 seconds was 58 kgf-cm. The spiral flow after storage at 25 ° C. for 6 months was 45 cm, and the residual flow rate was 90%.

Comparative Example 1 Curing accelerator TPP of Example 1
A material was produced in the same manner as in Example 1 except that 0.8 parts of triphenylphosphine (hereinafter abbreviated as TPP) was used as a curing accelerator instead of 2.3 parts of E-BA. The spiral flow of this material was 70 cm, and the torque after 90 seconds was 74 kgf-cm. The spiral flow after storage at 25 ° C. for 6 months was 48 cm, and the residual flow rate was 69%.

(Comparative Example 2) In place of 33 parts of phenol novolak and 2.3 parts of TPPE-BA curing accelerator of Example 1, 31.1 parts of phenol novolak and 2.7 parts of phenol novolak containing 30% of DBU as a curing accelerator were used. Except for using a part (SA841 manufactured by San Apro Co., Ltd.), a material was produced in the same manner as in Example 1. The spiral flow of this material was 73 cm, and the torque after 90 seconds was 70 kgf-cm. The spiral flow after storage at 25 ° C. for 6 months was 49 cm, and the residual flow rate was 67%.

(Comparative Example 3) Orthocresol novolak epoxy of Example 1 67 parts, phenol novolak 33
Orthocresol novolak epoxy 30
Parts, and 70 parts of phenol novolak were used, and the same procedure was followed as in Example 1 to produce a material. An attempt was made to measure the spiral flow of this material, but the measurement was impossible due to poor curing.

(Comparative Example 4) The curing accelerator TPP of Example 1
Instead of 2.3 parts of E-BA, TPPE-
Except for using 30 parts of BA, the material was made in the same manner as in Example 1, but the curing was too fast and molding was impossible.

Comparative Example 5 Fused Silica 300 of Example 1
Parts were replaced with materials except that 2500 parts of fused silica were used, but the material was made in the same manner as in Example 1; however, there was almost no fluidity and molding was impossible.

The results of Examples 1 to 5 and Comparative Examples 1 to 5 are summarized in Table 1.

[0033]

[Table 1]

[0034]

The resin composition according to the present invention has excellent curability and excellent storage stability at room temperature. If the resin composition according to the present invention is used as a material for electronic and electric parts,
The merit for industry is great, such as refrigerated storage and refrigerated transportation are not required.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI H01L 23/31 (56) References JP-A-5-148343 (JP, A) JP-A-4-268322 (JP, A) JP-A-4-89818 (JP, A) JP-A-3-296526 (JP, A) JP-A-2-240132 (JP, A) JP-A-2-206667 (JP, A) JP-A-61-204954 ( JP, A) JP-A-54-58795 (JP, A) JP-A-63-248823 (JP, A) JP-A-2-240133 (JP, A) WO 93/15126 (WO, A1) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 59/62 C08G 59/68 C08L 63/00-63/10 H01L 23/29

Claims (1)

(57) [Claims] (A) an epoxy resin having two or more epoxy groups in one molecule, (B) a phenol resin having two or more phenolic hydroxyl groups in one molecule, and (C) a curing accelerator. Phosphonium ion represented by the general formula (1) (Hereinafter simply abbreviated as phosphonium ion. In the formula, R
_{At least one} of R ₁ , R ₂ and R ₃ is monovalent
An organic group containing an aromatic ring, and R _4, R ₅ and R ₆
Wherein at least one or more of them represents an organic group containing a monovalent aromatic ring, and may be the same or different, and R in the formula represents an organic group containing a divalent aromatic ring and a divalent aliphatic group and represents a substituent selected from the group consisting of residues), aromatic Cal
Bonic acid, isocyanuric acid, or 1,2,3-benzoto
Organic anion (a) capable of forming a lyazole ion pair
And an inorganic filler (D), wherein the equivalent ratio of the epoxy group of the epoxy resin (A) to the phenolic hydroxyl group of the phenol resin (B) is 0. 0.5 or more and 2 or less, and the weight ratio of the ionic conjugate (C) is (A) + (B) 100 parts by weight,
0.4 to 20 parts by weight, and the weight ratio of the inorganic filler (D) is 100 parts by weight of (A) + (B).
A resin composition characterized by being at least 40 parts by weight and not more than 2400 parts by weight.