KR900006275B1 - Capsulating composition - Google Patents

Abstract

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Description

Encapsulation Composition

The present invention (A) at least one polyaromatic cyanate; And optionally (B) at least one catalyst for promoting curing of component (A); At least one hydrocarbon polyaromatic cyanate resin as at least part of component (A) is at least 40%, preferably 90 to 100% of the cyanate groups present in component (A) An encapsulating composition, characterized in that it is used as the amount provided by the resin.

In a preferred embodiment, the present invention comprises a filler material (C) in addition to components (A) and (B), wherein component (A) comprises (1) a hydrocarbon novolak resin and (2) a halogenated hydrocarbon novolac Resins, (3) mixtures of (1) and (2), or (4) (1), (2) or (3) and phenol-aldehyde cyanate resins, bisphenol A cyanate resins, halogenated phenol-aldehyde cyanates A product obtained by cyanating a resin, a halogenated bisphenol A cyanate resin, or a mixture thereof; (ii) component (B) is a cobalt salt; (iii) component (C) is present in an amount of from 50 to 80% by weight of the mixed weight of components (A), (B) and (C); (iv) The hydrocarbon polyaromatic cyanate resin or the halogenated hydrocarbon polyaromatic cyanate resin is 90 to 100% of the cyanate group present in component (A), the hydrocarbon polyaromatic or halogenated hydrocarbon polyaromatic cyanate resin or these resins. The encapsulation composition is present in an amount provided by a mixture of

In another preferred embodiment, the invention provides a product obtained by cyanating a product obtained by reacting (i) component (A) with an unsaturated hydrocarbon containing an average of 6 to 55 carbon atoms per molecule of phenol, cresol or mixtures thereof. , Halogenated derivatives of such reaction products, or mixtures of such hydrocarbons or halogenated derivatives thereof, and (ii) component (B) is cobalt naphthenate, cobalt acetylacetonate or cobalt octoate; (Iv) Component (C) relates to the encapsulation composition which is a silica powder.

In another preferred embodiment, the invention relates to (1) component (A) comprising: (a) 70 to 100% by weight of dicyclopentadiene with phenol, cresol or mixtures thereof, C ₉ -C of C ₄ -C ₆ diene; ₁₂ 0 to 30 weight% dimer, 0 to 7 weight% oligomer of C ₄ -C ₆ fluorinated hydrocarbon and optionally 100 weight% C ₄ -C ₆ alkanes, alkenes or dienes Containing a product obtained by cyanating the reaction product with a composition consisting of a balance, (b) a halogenated derivative of the product of component (a), or (c) a mixture of components (a) and (b) (Ii) Component (B) relates to an encapsulation composition which is a silica powder.

In another aspect, the invention relates to electrical and / or electronic components encapsulated with the encapsulation composition.

Hydrocarbon polyaromatic cyanate resins used in the present invention may be prepared by reacting cyanide chloride or cyanide bromide in a suitable solvent (e.g. It can manufacture. In some cases, cyanide reacts a solution of chlorine in chlorinated hydrocarbons with an aqueous solution of alkali metal cyanate at a temperature below 0 ° C., and then separates the chlorinated hydrocarbons, where cyanide chloride is dissolved in alkali metal chloride. Can be dissolved from an aqueous layer). Subsequently, cyanide chloride containing chlorinated hydrocarbons can be used for the reaction.

Examples of suitable hydrocarbon polyphenol resins capable of reacting with cyan chloride or cyanide bromide to form hydrocarbon polyaromatic cyanate resins as used herein are described in US Pat. No. 3,536,734 to Vegter et al. Nelson, US Pat. No. 4,390,680, and Nelson et al., US Pat. No. 4,394,497. Particularly suitable hydrocarbon novolak resins include reaction products of aromatic hydroxyl-containing compounds with unsaturated hydrocarbons having 4 to 55 carbon atoms.

- 또는

-환위(ring position)를 함유하는 특정한 화합물을 포함한다. 또한, 이들 화합물은 필요한 경우 치환체 탄화수소 또는 할로겐그룹을 함유할 수 있다.Suitable aromatic hydroxyl-containing compounds that can be used herein include at least one aromatic ring, at least one aromatic ring, at least one phenolic hydroxyl group and at least one hydroxyl group useful for alkylation.

- or

Include certain compounds containing a ring position. In addition, these compounds may contain substituent hydrocarbons or halogen groups, if necessary.

페닐페놀,

페닐페놀,

페닐페놀, 비스페놀 A, 테트라브로모비스페놀 A, 디하이드록시디페닐설폰, 및 이들의 혼합물을 포함한다.Particularly suitable aromatic hydroxyl-containing compounds that can be used herein are, for example, phenol, chlorophenol, bromophenol, methylphenol, hydroquinone, catechol, resorcinol, guoacol, pyrogallol, floro Glucinol, isopropylphenol, methylphenol, propylphenol, t-butylphenol, isobutylphenol, octylphenol, nonylphenol, cumylphenol,

Phenylphenol,

Phenylphenol,

Phenylphenol, bisphenol A, tetrabromobisphenol A, dihydroxydiphenylsulfone, and mixtures thereof.

Suitable unsaturated hydrocarbons in the crude or purified state which may be used herein are, for example, butadiene, isoprene, pipeylene, cyclopentadiene, cyclopentene, 2-methylbutene-2, cyclohexene, cyclohexadiene, methyl Linear and cyclic dimers of cyclopentadiene, dicyclopentadiene, limonene, dipentene, piperylene, methyl dicyclopentadiene, dimethyl dicyclopentadiene, norbornene, norbornadiene, ethylidine nord Bornen, and mixtures thereof. Suitable unsaturated hydrocarbons also include other timers, codlmers, oligomers, and cooligomers of the foregoing unsaturated hydrocarbons.

Particularly suitable unsaturated hydrocarbons which can be used herein are, for example, 70 to 100% by weight of dicyclopentadiene, C ₉ -C ₁₂ dimers or codimers of C ₄ -C ₆ dienes (e.g. cyclopentadiene-isoprene, Cyclopentadienegoperylene, cyclopentadiene-methyl cyclopentadiene, and / or dimers such as isoprene, piperylene, bedyl cyclopentadiene) 0 to 30% by weight, C ₁₄ -C ₁₈ of C ₄ -C ₆ diene 0-7% by weight of trimmers, and 0-10% by weight of aliphatic diolefins (e.g. piperylene, isoprene, 1,5-hexadiene) and cyclic olefins (e.g. cyclopentadiene, methyl cyclopentadiene and cyclopentene) And dicycolopenadiene concentrate containing. Methods for preparing these dicyclopentadiene concentrates and more detailed descriptions thereof can be found in US Pat. No. 3,557,239 to Gebhart et al. And Nelson's US Pat. No. 4,167,542.

In addition, particularly suitable unsaturated hydrocarbons that can be used herein include about 20 to 99 weight percent dicyclopentadiene, 0 to 10 weight percent dimers and dimers of C ₄ -C ₆ hydrocarbons (described above), C ₄ -C ₆ dienes Crude dicyclopentadiene stream containing 0 to 10% by weight of oligomer and an equilibrium to provide 100% by weight of C ₄ -C ₆ alkanes, alkenes and dienes.

In addition, particularly suitable unsaturated hydrocarbons which may be used herein are 30 to 70% by weight piperylene or isoprene, 0 to 10% by weight C ₉ -C ₁₂ dimer or coder of C ₄ -C ₆ diene, and C ₄ -C ₆ Crude piperylene or isoprene streams containing equilibrium to provide 100% by weight of alkanes, alkenes and dienes.

Also particularly suitable hydrocarbon oligomers are reactive components in the hydrocarbon streams described above, for example dicyclopentadiene concentrate, crude dicyulopentadiene, crude piperylene or isoprene, respectively or in admixture with one another or Prepared by polymerizing a mixture with a high purity diene stream.

Suitable aromatic polycyanate resins which can be used herein as mixtures with hydrocarbon polyaromatic cyanate resins are di- or polyhydroxyl compounds such as resorcinol, catechol, hydroquinone, bisphenol A, bisphenol F, Cyanate derivatives of bisphenol S, phenol or substituted phenol / aldehyde resins, tetrabrodobisphenol A and other halogenated phenolic compounds, and mixtures thereof.

니트로페놀,피로카테콜, 디하이트록시 나프탈렌, 수산화나트륨, 나트륨, 메틸레이트,나트륨 클로라이드, 피리딘-N-옥사이드, 트리부틸포스핀,포스폴린-△³-1-옥사-l-페닐,아연 옥토에이트,주석 옥토에이트, 아연 나프데네이트 및 이들의 혼합물)을 포함한다.Suitable catalysts that can be used to cure the polycyanate resin include acids, bases, salts, nitrogen and phosphorus compounds. Particularly suitable catalysts include, for example, Lewis acids (eg AlC1 ₃ , BF ₃ , FeC1 ₃ , TiC1 ₄ , ZnC1 ₂ , SnC1 ₄ ); Quantum acids (eg HC1, H ₃ PO ₄ ); Aromatic hydroxy compounds (e.g., phenul,

Nitrophenol, pyrocatechol, di height hydroxy naphthalene, sodium hydroxide, sodium methylate, sodium chloride, pyridine -N- oxide, tributyl phosphine, phosphine morpholine - △ ³ -1- oxa -l- phenyl, zinc fertile Ate, tin octoate, zinc naphdenate and mixtures thereof).

Particularly suitable catalysts include, for example, cobalt naphthenate, cobaltacetylacetonate, cobalt octoate, cobalt chloride, 1,4-diazobicyclo- (2,2,2) octane, and mixtures thereof. .

In general, it is preferable to use at least one filler material in the encapsulation composition of the present invention. Suitable filler materials that can be used herein are, for example, finely divided silica powder, quartz, calcium silicate, barium sulfate, hydrated alumina. The choice of fillers will change the effect of moisture permeation through molded or encapsulated parts as they occupy between 50 and 80% by weight of the complete composition.

In some cases, a release agent may be used in the transfer molding composition of the present invention. Suitable examples of such release agents are, for example, stearates (such as glycerol modostearate, calcium stearate) or waxes such as Montan wax or carnauba wax and mixtures thereof.

The encapsulation composition of the present invention is suitable for use in encapsulated electrical and electronic devices and the like. It is particularly suitable for use in encapsulating microcircuit components typically found in dlscrete devices and integrated circuits.

If desired, the compositions of the present invention may also contain flame retardants and coupling agents.

The following examples illustrate the invention and do not limit the scope of the invention in any way.

A. Preparation of Hydrocarbon Polyaromatic Cyanate Resin

400 ml of CH ₂ Cl ₂ is added to a 1 L three-necked flask with a mechanical stirrer, a metered dropping funnel, a gas well and a thermowell equipped with an N ₂ inlet. It is cooled to -1 ° C or lower through a dry ice / ethylene glycol / H ₂ O bath. Then, Cl ₂ (42.6 g, 0.6 mol) is added to the slowly stirring solution through a dispersion tube. A solution of sodium cyanide (NaCN) (29.4 g, 0.6 mol) in 75 ml of H ₂ O was prepared while Cl ₂ addition occurred. After the Cl ₂ addition is complete, aqueous NaCN is added dropwise at a rate of maintaining a temperature of −10 t (approximately 1.8 ml / min addition rate, ie, 03 ml / sec). Watching the pH of the aqueous phase, add NaCN until slightly alkaline (pH 8,9). Separate the aqueous phase and discard.

A solution of hydrocarbon novolac (93.0 g, 0.56 equiv) in 250 ml CH ₂ Cl ₂ is cooled to ˜0 ° C. Subsequently, the solution is added to the CNC1 / CH ₂ Cl ₂ prepared above. Triethylamine (60.6 g, 0.6 mole) is added dropwise while stirring the CNCl / novolak / CH ₂ Cl ₂ solution (-500 rpm) (rate -1.2 ml / min) , 0.02 ml / sec). After the addition is complete, the cold bath is removed and the contents are stirred for 1 hour (3600 seconds). Add 250 ml of H ₂ O, then stir the mixture for 5 minutes (300 seconds). The mixture is transferred to a separatory funnel. The aqueous phase is removed and the organic phase is washed successively with two 250 ml portions of 0.2N HC1 and two 250 ml portions of H ₂ O, followed by drying over MgSO ₄ . After filtration, the CH ₂ Cl ₂ is removed on a rotary evaporator.

B. Preparation of Unfilled Molding Compositions

To 350 g of the hydrocarbon polyaromatic cyanate resin prepared in A above in molten state (80 ° C.) was added 0.025% by weight of high-balt naphthenate as a 6% by weight solution in mineral spirits. The resulting mixture is poured into a 1/8 inch (3.175 mm) thick mold, then cured at 175 ° C. for 1 hour (3600 seconds) and then further at 225 ° C. for 2 hours (7200 seconds). The results are shown in Tables I, II, III and IV.

[Comparison Experiment A]

For comparison, 400 g of cresol epoxy novolac resin having an epoxide equivalent of 216 and an average functionality of 5.5 was mixed with 92.6 g of methylenedianiline to prepare an unfilled molding composition. The mixture is poured into a mold as described in Example 1-B and then cured for 16 hours (57,600 seconds) at 55 ° C, 2 hours (7200 seconds) at 125 ° C and 2 hours (7200 seconds) at 175 ° C. . The results are shown in Tables I, II, III and IV below.

[Comparison Experiment B]

Also for comparison, diglycidyl ether (400 g) of bisphenol A having an epoxide equivalent of 189 was mixed with methylene dianiline (105.8 g), followed by 16 hours at 55 ° C (57,600 seconds) and 2 hours at 125 ° C. (7200 seconds) and cured at 175 ° C. for 2 hours (7200 seconds). The results are shown in Table IV below.

[Comparison Experiment C]

Also for comparison, the polyglycidyl polyphenols of novolak resins having an epoxide equivalent of 179 and an average functionality of 3.6 are cured for 2 hours (7200 seconds) at 175 ° C. The results are shown in Table IV.

TABLE 1

Thermal properties

_a Tg is measured by differential scanning calorimetry (DSC). _b

The sample is heated at a rate of 10 ° C./min. Decomposition start temperature is defined as the temperature at which rapid weight loss occurs for the first time.

TABLE 2

Electrical characteristics

TABLE 3

Moisture weight gain *

Coupons of 1 in x 3 in x 1/8 in (25.4 mm x 76.2 mm x 3.175 mm) are exposed to 250 ° F. (121.1 ° C.) and 15 psig (103.4 kPa) steam for 500 hours (1,800,000).

TABLE 4

Equilibrium moisture weight gain *

Samples are exposed by dipping in water at 80 ° C. The exposure time is over 1000 hours (3,600,000 seconds) for all samples to reach an equilibrium moisture content increase.

Claims (4)

An encapsulation composition for encapsulating an electrical component, comprising the following components (a) and (b): (a) 70 to 100% by weight of phenol, cresol or mixtures thereof and dicyclopentadiene, 0 to 30% by weight of C ₉ -C ₁₂ dimer of C ₄ -C ₆ diene, oligomer of C ₄ -C ₆ amorphous hydrocarbon At least one polyaromatic cyanate resin obtained by cyanating the reaction product with a composition consisting of 0 to 7% by weight and a balance to provide 100% by weight of C ₄ -C ₆ alkanes, alkenes or dienes, (b) at least one catalyst for promoting curing of component (a). The encapsulation composition of claim 1, further comprising a halogenated derivative of component (a). The encapsulation composition of claim 1, further comprising cobalt naphthenate as catalyst (b). The encapsulation composition of claim 1, further comprising silica powder as filler material.