RU2447093C1 - Method of producing ortho-cresol novolac epoxy resin and polymer composition based thereon - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing ortho-cresol novolac epoxy resin and a polymer composition for sealing semiconductor devices which contains said resin. The method of producing ortho-cresol novolac epoxy resin involves polycondensation of ortho-cresol and formaldehyde in equimolar ratio while heating in the presence of an acid catalyst in the medium of n-butanol, reaction of the obtained product with excess epichlorohydrin while heating in the presence of an alkaline catalyst, distillation of epichlorohydrin and extracting the end product. Formaldehyde is used in form of para-formaldehyde. Polycondensation of ortho-cresol and para-formaldehyde is carried out at 115±2°C, first in the presence of 6-8 pts.wt oxalic acid until achieving 35-45% conversion, and then in the presence of 3-5 pts.wt pair-toluene sulphonic acid until complete extraction of the calculated amount of water, n-butanol is then distilled, the reaction mass is neutralised, after which 350-400 pts.wt epichlorohydrin is added and then crushed sodium hydroxide in portions for 1.5-2.0 hours while maintaining temperature in the range of 65-70°C, subsequently holding the reaction mass for 1.0-2.0 hours, distillation of excess epichlorohydrin and n-butanol, washing the resin with chloroform and water and extracting the end product from the chloroform solution by distilling off the chloroform. The polymer composition for sealing semiconductor devices contains ortho-cresol novolac epoxy resin as binder, phenol novolac resin as hardener, quartz filler, glycidyl oxypropyl trimethoxysilane as a finishing agent, triphenyl phosphine as an accelerator, wax and soot.

EFFECT: method of obtaining o-cresol novolac epoxy resin, suitable for producing composite material which can be used in a high vacuum at 105±5°C, with heat resistance of not lower than 160°C and chemical resistance in hot amide solvents.

3 cl, 2 tbl

Description

The invention relates to the production of epoxyphenol resins and composite materials based on them, used in the electrical and electronic industry for sealing semiconductor devices (diodes, triodes, transistors), integrated circuits, etc.

It is known that epoxy molding compounds have several advantages over conventional thermosetting phenol-formaldehyde compounds. They are characterized by good electrical and mechanical properties, high chemical resistance, dimensional stability of the cured material, manufacturability (good fluidity and good compatibility with fillers, curing without the release of volatile components with low shrinkage), etc. Among the disadvantages of epoxy compounds compared to phenol-formaldehyde compositions include: high price, difficulties in removing the product from the mold due to very good adhesion, the need for strict temperature control from due to the strong dependence of fluidity on temperature (Lee X., Neville K. Reference guide to epoxy resins. - M .: ed. Energia, 1973).

The binders that combine the advantages of phenol-formaldehyde and epoxy resins are epoxyphenol resins, the active development of which began in the 60s and continues to develop successfully at present.

Thus, epoxyphenol resins with high heat resistance, tensile strength and alkali resistance were obtained by condensation of phenol (1 mol) with a 36% aqueous formaldehyde solution (2.3 mol) in the presence of aqueous solutions of sodium hydroxides (47% solution) or barium (0.085 mol) at a temperature of 70 ° C with the addition of an epoxy compound - epichlorohydrin (ECG) in an amount of 0.25 mol or diglycidyl ether of butanediol, followed by cooling and neutralization to pH 7.3 (French patent FR 1467840, publ. 1967 g; Chemical Abstracts (hereinafter - S.A.), T. 67, ref. 109261v).

Epoxyphenol resins based on alkyl substituted phenols, in particular, ortho-cresol (hereinafter referred to as o-cresol), are characterized by greater adaptability: at high molecular weights, such resins have a reduced melt viscosity due to the linear structure of the polymer chains and the presence of a substituent in the o-position to the hydroxyl group.

A known method for producing epoxynolac resin without generating powders of derivatives of novolac resins, in particular, based on o-cresol, with a softening temperature of 78.8 ° C, a dynamic viscosity of 76.7 cSt and a degree of polydispersity Mw / Mn 2.12 in three stages:

1) the interaction of o-cresol (I, 100 parts by weight), formaldehyde in the form of formalin (II, 67.6 parts by weight) in the presence of para-toluenesulfonic acid (hereinafter - PTSK, 1.2 parts by weight) at 103 ° C for 6 hours. to obtain novolak A (softening point 125.6 ° C), which is maintained at 160 ° C under nitrogen;

2) novolak B with a softening temperature of 104.5 ° C is obtained from 100 wt.h. I, 61.5 parts by weight II and 1.2 parts by weight PTSK, which is heated to 103 ° C for 5 hours and maintained at 140 ° C under nitrogen;

3) a mixture of 24.6 parts by weight resin A and 75.4 parts by weight resin B is fed into the epoxidation reactor, where the mixture interacts with 539.6 parts by weight of ECG in dioxane (188.8 parts by weight) at 39 ° C and 60 mmHg in the presence of first 19.4 parts by weight 48% potassium hydroxide, and then in the presence of 53.5 parts by weight 48% sodium hydroxide at 60 ° C and 150 mmHg (Sumitomo Chemical Co. Ltd, Japan Application JP 2000 226430, C08G 59/08, publ. 2000, C. A, vol. 133, ref. 151393w).

However, the presence of acid in novolak A upon exposure at 160 ° C under nitrogen and in novolak B upon exposure at 140 ° C under nitrogen results in tarring and blackening of the product and does not provide the desired resin with the desired color.

From British Patent GB 1141979, C08G 29/06, 1969, Dow Chemical Co. (analogue to FR 1553073) a method is known for producing an epoxynovolac resin based on C _1-6 alkyl phenol, phenol, formaldehyde and an epoxidizing agent, preferably ECG, carried out in 3 stages:

1) 1.5-3 mol of formaldehyde in the form of formalin and 1 mol of alkyl phenol are reacted at elevated temperature in the presence of a basic catalyst; the reaction is preferably carried out at a temperature of from 50 to 100 ° C for 1-4 hours;

2) 0.7-2.1 mol of phenol is added to the resulting reaction mixture; a preferred temperature of from 90 to 105 ° C, when the step is carried out in the presence of water as a solvent; it is possible to carry out the step in the absence of solvent at a temperature above the softening point, but below 200 ° C;

3) the novolak obtained at the 2nd stage is epoxidized according to the commonly used technology at an elevated temperature, preferably 100-115 ° C, using ECG in the presence of a basic catalyst, for example, a 50% aqueous solution of sodium hydroxide, calculated as 1.25 mol alkalis per phenolic hydroxyl group; after completion of the reaction, excess epoxidizing agent is removed from the reaction mixture using known separation techniques, including distillation under reduced pressure and elevated temperature; salt is removed to minimize the number of rinses with hot water.

A solid product is obtained that can be stored for a long time without significant changes in physical and chemical properties. Three examples presented in the patent illustrate the preparation of epoxynolac resin only on the basis of p-tert.butylphenol and a 37% aqueous formaldehyde solution with the addition of various amounts of phenol in the second stage (10, 20.8 and 12.2 gram mol respectively examples 1-3).

As a result, epoxynolac resins with the following characteristics were obtained:

- according to example 1: molar weight 1550, functionality 6.2, softening point according to Durran's 96 ° C; novolak, from which this resin is obtained, has a pier. weight 740 and softening point 123 ° C;

- according to example 2: softening point 59 ° C (other indicators are not given);

- according to example 3: softening point 82 ° C (other indicators are not given).

The process is complex and time consuming. first involves obtaining a resol resin in the presence of a basic catalyst (3 hours), then obtaining novolak with the addition of phenol and an acid catalyst (2 hours), followed by complete removal of phenol under a vacuum of 1 mm Hg, includes two stages of three-time washing, etc .; in addition, the claimed method was worked out only on p-tert-butylphenol and no specific information on the process for producing o-cresolwolk epoxies and their characteristics is not contained in the patent description.

For the prototype, a technical solution was made on the application of Japan JP 61055113 A, C08G 59/00, C08G 59/08, H01L 23/29, publ. 1986, Japanese patent JP 4034565 B, claimed by Mitsubishi Petrochemical Co., Ltd. In accordance with the said patent, high molecular weight linear o-cresol-wave epoxies with increased mechanical strength, heat-resistant, elastic, impact-resistant, used in the manufacture of elements of electrical and electronic equipment, in particular, used in the Air Force, have been obtained. The method consists in polycondensation of 10.0-1.0 mol of o-cresol and 0-9.0 mol of para-cresol (hereinafter p-cresol) with 0.7-1.0 mol of formaldehyde or a compound generating formaldehyde (such as trioxane), at 95 ° C or higher in the presence of 0.01-20 parts by weight (per 100 parts by weight of cresol) of acid catalyst in 150-300 parts by weight (per 100 parts by weight of cresol) of the solvent (C _3-12 aliphatic alcohol, including n-butanol, C _3-6 glycol ether, benzyl alcohol) with the formation of a linear high molecular weight o-cresol novolak with a softening temperature ≥120 ° C and number average molecular weight Mn≥1500 (determined by the method of vapor pressure in dimethylacetamide (DMAA)), followed by the interaction of the obtained resin with an excess of ECG at 60-150 ° C in the presence of an alkaline catalyst and distillation of ECG. Get the target product with Mn in the range of 2000-7000 and a softening temperature of 100-300 ° C.

In an example illustrating the preparation of epoxynolac resin only on o-cresol, a mixture of 60 parts by weight is reacted. high molecular weight o-cresolwolf resin with a softening temperature> 120 ° C and Mn> 1500 with 462.5 wt.h. ECG and 4.0 parts by weight (CH ₃ ) ₄ NBr at 117 ° C for 2 hours to obtain an epoxy with a softening temperature of 126 ° C and Mn 3950 (S.A., T. 105, ref. 173695w).

However, the o-cresolwolf resins with a softening temperature above 120 ° C used to prepare the epoxy resin are not technologically advanced due to their high viscosity and fluidity.

Information on the specific technology for the preparation of the initial o-cresolwolf resin with a softening temperature of more than 120 ° C in the above abstract S.A. not shown, but from the above information it follows that the prototype process is carried out with the allocation of o-cresolnovolnogo resin and its purification using the operations of washing with water and distillation of the solvent.

In addition, the use at the stage of condensation of o-cresol wave resin with ECG as a catalyst of tetramethylammonium bromide is a highly toxic, expensive (price per 100 g 117.27 US dollars), hygroscopic product that requires special storage conditions, worsens the environmental characteristics of the process and increases its cost .

The technical task of the invention is the development of a method for producing o-cresolwolk epoxy resin suitable for the manufacture of a composite material operable in high vacuum at 105 ± 5 ° C, with heat resistance not lower than 160 ° C and chemical resistance in hot amide solvents at an inexpensive, environmentally friendly receipt.

The technical result of the development, which consists in obtaining o-cresolnobolnogo epoxy with a softening temperature of 50-65 ° C according to a simplified technology that does not provide for the allocation of o-cresolnovolacnogo resin, to reduce the duration of the process and improve environmental performance, is achieved by the fact that in the method of obtaining o- a cresolnobolac epoxy resin, including polycondensation of o-cresol and formaldehyde in an equimolar ratio when heated in the presence of an acid catalyst in n-butanol medium, the interaction was obtained of the reaction product with an excess of ECG when heated in the presence of an alkaline catalyst, distillation of ECG and isolation of the target product, formaldehyde is used in the form of p-formaldehyde, polycondensation of o-cresol and p-formaldehyde is carried out at 115 ± 2 ° C, first in the presence of 6-8 wt. .h. oxalic acid to achieve 35-45% conversion, then in the presence of 3-5 wt.h. PTSK until the calculated amount of water is completely isolated, n-butanol is distilled off, the reaction mass is neutralized, after which 350-400 parts by weight are charged. ECG and portioned for 1.5-2.0 hours crushed sodium hydroxide while maintaining the temperature in the range of 65-70 ° C, followed by exposure for 1.0-2.0 hours, distillation of excess ECG and n-butanol, washing the resin chloroform and water and the selection of the target product from a chloroform solution by distillation of chloroform.

The distillation of chloroform is carried out at 65-70 ° C at a pressure of 20 mm Hg with a gradual increase in temperature to 120 ° C at a pressure of 20 mm Hg and exposure under these conditions for 1.0-1.5 hours.

The invention is illustrated by the following example:

In a three-necked flask equipped with a stirrer, reflux condenser and a Dean-Stark trap, 1 mol of o-cresol (108 parts by weight), 1 mol of p-formaldehyde (28.5 parts by weight), n-butanol (250 wt. parts) and oxalic acid (6.0 parts by weight). The resulting mixture is heated under a nitrogen purge at 115 ± 2 ° C until a conversion of 35% is achieved, after which 3 parts by weight are added. PTSK and continue heating until 12 parts by weight are collected in the trap. (82% of theoretical amount) of condensation water. Then, the reflux condenser was replaced with a direct one and 150 ml of butanol were distilled off under normal pressure. The reaction mass is neutralized with an aqueous solution of sodium hydroxide to a neutral reaction with a simultaneous selection of 3.0 wt.h. reaction mass for determining and controlling the softening temperature of the o-cresolobol resin in the reaction mass. Then poured ECG in the amount of 350 parts by weight (3.7 mol). Then the mixture is cooled to 60 ° C and add 3 times 15 wt.h. chopped caustic soda with an interval of 30 min, maintaining the temperature of the reaction mixture 65-70 ° C. ECG and the remaining n-butanol are distilled off. The mixture is cooled, 450 ml of chloroform are added and filtered from crystals of sodium chloride resulting from dehydrochlorination. The chloroform solution is washed with warm distilled water, the lower chloroform layer is separated and the chloroform is first distilled off at 50-70 ° C and 10 mm Hg. with a gradual increase in temperature by 1.5-2 degrees per minute to 120 ° C at 20 mm Hg and incubated under these conditions for 1 hour. An epoxy resin is obtained with a softening temperature of 50 ° C. at a softening temperature of the corresponding novolac resin of 90 ° C.

Information on examples 1-3 are presented in table 1.

The developed method is easy to implement, because it does not provide for the stage of isolation of o-cresol-dandruff resin before its interaction with ECG carried out at 65-70 ° C (versus 110-115 ° C according to the traditional technology using water washing and solvent distillation operations). The total duration of the process is 6.0-7.0 hours versus 9.0-11.0 hours in the case of a process with the isolation and purification of o-cresol-dandruff resin.

The resulting binder with a softening temperature of 50-65 ° C is used to obtain compositions for the manufacture of encapsulating materials for products containing microcircuits operating under high vacuum (2-5 * 10 ^-4 Pa) at a temperature of 105 ± 5 ° C and characterized by increased dispersion heat generated, which prevents overheating of working devices.

Table 1 The parameters of the process for producing o-cresolnobolac epoxy and the characteristics of the resulting product Reagent name and process parameters The number (parts by weight) of reagents and parameter values by examples one 2 3 o-cresol 108 108 108 p-formaldehyde 28.5 28.5 28.5 oxalic acid 6 7 8 p-toluenesulfonic acid 3 four 5 n-butanol 250 ml 250 ml 250 ml epichlorohydrin 350 370 400 ground caustic soda 45 45 45 chloroform 450 450 450 amount of water released 12 13 fourteen the time of adding caustic soda, hour 1,5 1,6 2.0 softening agent for o-cresolwolves resin, ° C 90 95 one hundred softening agent for o-cresolnovolac epoxy resin, ° C fifty 60 65 total process time, hour 7.0 6.5 6.0

Known epoxyphenolic compositions for molding composite materials used in the densification of electronic devices containing epoxy resins of various structures as a binder, phenolic resin as a hardener, inorganic fillers and target additives.

So, by Sumitomo Bakelite Co. Developed epoxy compositions for semiconductor seals with good resistance to moisture and soldering, containing:

a) 85-92% (to the total weight of the composition) of inorganic fillers and target additives (88 g fused silica powder, 0.3 g carbon black, 0.5 g carnauba wax, 0.2 g triphenylphosphite);

b) at least 8% of a mixture of two epoxy resins of different structures, 20-80% of each (one of which is o-cresol epoxy);

c) at least 20% of a phenolic hardener (calculated as a binder);

d) curing accelerator.

A sample of material in the form of a piece has a spiral fluidity of 80 mm (Korean application KR 9700092 C08L 63/00, publ. 1997; C. A, t.123, ref. 259312b).

Fire-resistant molding materials for sealing electronic devices with good moisture and heat resistance (Japanese application JP 2000 226499, C08L 63/00, publ. 2000, S.A., t.133, ref. 151764t), proposed by Hitachi Chem. Co., Ltd., contain, per 100 g of o-cresol-wave epoxy, 53.0 g of novolak, 15.7 g of tricalcium salt of nitrilo-tris (methylene) phosphonic acid, and 530 g of SiO ₂ (UL 94 VO).

Known developed by Mitsubishi Petrochemical Co., Ltd. epoxy compositions for a composite material with a glass transition temperature of 183 ° C (according to the application of Japan JP 0234626, C08G 59/62, publ. 1990) used for sealing electronic devices, characterized by low shrinkage during crosslinking and high heat resistance, containing 1 equivalent epoxy resin 0, 5-2.0 equiv of polyphenols and 0.01-20 wt.h. N- (imidazolyl) alkylurea. In the example (S.A., t.113, ref. 133840x) the following composition is given, parts by weight:

o-cresolnobolac epoxy, in particular Epicote 180 80 phenolic novolak (Tamanol 752 with hydroxy equivalent 104) fifty BREN (brominated phenolic novolak) twenty glycidyloxypropyltrimethoxysilane 0.5 fused quartz 300 antimony trioxide 5 stearic acid 2 soot 1,5 N, N ¹ bis (2-methylimidazolyl-1-ethyl) urea (I) 1,5

The material is obtained by mixing the starting components in the melt, grinding and injection molding at 175 ° C.

Characteristics of the material obtained in accordance with the application of Japan JP 0234626:

glass transition temperature, ° C 183 bending strength, kg / mm ² 14.1 shrinkage when stitching,% 0.30 linear expansion, 1 / ° C twenty specific volume resistance, Ohm * cm 3.5 * 10 ¹⁶ (20 ° C) 8.0 * 10 ¹³ (150 ° C)

Mitsubishi Denki K.K. and Shin-Etsu Chem. Co., Ltd. proposed composition (European application EP 955675, H01L 23/29, publ. 1999), the closest in composition to the claimed. The composition includes an epoxy resin (preferably epoxycresol-dabbing), a crosslinking agent (preferably a phenolic novolac resin) and an inorganic filler in an amount of at least 70% by weight. (preferably 70-92% by weight.) In this case, at least one epoxy resin and / or one crosslinking agent (but both are better) have a molecular weight distribution of Mw / Mn <1.6, the content of binuclear compounds is less than 8% by weight ., and the content of seven or more nuclear compounds is more than 32% by weight.

In the description, it is noted that practically all known types of epoxy and phenolic resins are used in the preparation of the claimed composition, but out of seven examples that differ in various combinations of epoxy and phenolic resins and the amount of filler (not counting comparative examples), only one composition contains o-cresol epoxy with a softening point of 72 ° C and a Mw / Mn of 1.41 (resin A) in combination with a phenolic wave resin with a softening point of 98 ° C and a Mw / Mn of 1.24 (resin D).

The composition of a specific composition based on resins A and D (example E7 described in the description of the invention), the following (parts by weight):

resin A 54.75 resin D 35.25 filler, 300 including: - fused silica with an average particle size of 10 microns 20% wt. - spherical. fused silica with an average particle size of 30 microns 75% wt. - spherical. fused silica with an average particle size of 0.5 microns 5% wt. antimony trioxide 10.0 wax Wax E 1,5 soot 1,0 brominated epoxyphenol novolak with bromine content of 35.5% 10.0 glycidyloxypropyltrimethoxysilane 1,0 triphenylphosphine 0.8

Note: 1) the sum of resins A, D and brominated novolak is 100 parts by weight; 2) the molar ratio of phenolic hydroxyl groups in the phenolic resin to epoxy groups in the epoxy resin is 1.0

The percent filling of the compositions of the examples in accordance with the invention is 67.1-85.7.

When filled with 75.1% (Example E7), the spiral fluidity is 141 cm, and the hardness at elevated temperatures is 78 (on the Barkola scale). Spiral fluidity was measured according to the EMMI standard when forming a composition in a mold at 180 ° C and a load of 70 kgf / cm ² .

The technical problem of the invention (in terms of composition) is to develop, on the basis of domestic raw materials, the composition of the polymer composition for a material operable under high vacuum at a temperature of 105 ± 5 ° C ° with increased heat dissipation, which prevents the product from overheating during operation.

The composition of the prototype is designed to provide effective formability that does not require post-stitching, and its use to obtain material that is workable in the above conditions, i.e. to solve a completely different technical problem mentioned above, it is not possible due to the fact that the composition includes:

- a complex scarce three-component quartz nanofiller, consisting of fused silica (particle size 10 μm) and spherical fused silica (particle size 30 μm and 0.5 μm),

- Wax E grease with a dropping point of 75-87 ° C; however, when exposed to a deep vacuum at 105 ± 5 ° C, volatiles may be released from the cured material, and therefore the use of lubricants with a dropping point below 105 ° C is undesirable.

In addition, the material according to the prototype has a spiral flow of 141 cm (filling 75.1% by weight), and a spiral flow of more than 100 cm is also an undesirable indicator, because during pressing, the amount of flashing increases, the cost of removing it increases, and, as a result, the cost of the material increases.

In accordance with the claimed invention, the stated technical problem is solved by the fact that the polymer composition comprising o-cresolnobolac epoxy resin as a binder, phenolic novolac resin as a hardener, quartz filler, glycidyloxypropyltrimethoxysilane as a coupling agent, triphenylphosphine as an accelerator, and wax as a binder contains o-cresol-wave epoxy resin with a softening temperature of 50-65 ° C, obtained by polycondensation of o-cresol with p-formaldehyde in equimolar ratio at 115 ± 2 ° C first in the presence of 6-8 parts by weight oxalic acid to achieve 35-45% conversion, then in the presence of 3-5 wt.h. PTSK until complete release of the calculated amount of water, distillation of n-butanol, neutralization of the reaction mixture, followed by loading 350-400 wt.h. ECG and batch loading of ground sodium hydroxide for 1.5-2.0 hours while maintaining the temperature in the range of 65-70 ° C, followed by exposure for 1.0-2.0 hours, distillation of excess ECG and n-butanol, washing resins with chloroform and water and the selection of the target product from a chloroform solution by distillation of chloroform, carried out at 50-70 ° C at a pressure of 10 mm Hg with a gradual increase in temperature to 120 ° C at a pressure of 20 mm Hg and exposure under these conditions for 1.0-1.5 hours, as a hardener, the composition contains phenol novolac resin brand SF-015, oxidized polyethylene wax as wax, and additionally N, N ^I dimethyl-3-chlorophenylurea and hexagonal boron nitride in the following ratio of components of the composition (wt%):

o-cresol bracer epoxy 25.0-27.0 phenolic novolac resin brand SF-015 12.5-13.5 ground quartz 32.0-35.0 glycidyloxypropyltrimethoxysilane 0.29-0.70 triphenylphosphine 0.46-0.59 oxidized polyethylene wax 0.36-0.40 technical carbon (soot) 0.62-0.68 N, N ^I -dimethyl-3-chlorophenylurea 0.06-0.08 hexagonal boron nitride 22.1-27.6

An example of obtaining a polymer composition and composite material based on it:

Powdered powdered quartz (grade BMP) commercially available is washed in a dilute solution of hydrochloric acid, followed by washing with water, dried, and added to a suspension of quartz in chloroform with 1.0% glycidyloxypropyltrimethoxysilane, followed by removal of chloroform and drying. In a ball mill with ceramic balls, 26.0 wt.% Of o-cresolnobolac epoxy resin, 13 wt.% Phenolic novolac resin SF-015 (GOST 18694-80), previously subjected to free phenol purification in vacuum at 150 ° C, 32 are placed, 32 , 6 (including a sizing of 0.6) wt.% Of the finished KMP grade B, 0.46 wt.% Triphenylphosphine, 26.9 wt.% Hexagonal boron nitride, 0.06 wt.% N, N ^I -dimethyl- 3-chlorophenylurea, 0.36 wt.% Wax and 0.62 wt.% Soot and stirring until the resulting powder completely passes through a 0.5 mm sieve. Then the powder is homogenized on rollers with electric heating with a shaft diameter of 100 mm, a length of the working part of 200 mm and a gap of 0.5-1 mm, with a roll temperature of 90-95 ° C for 2 minutes. The material obtained after rolling in the form of flakes is re-mixed and sieved through a 0.5 mm vibrating screen. Curing cycle: 120 s at 175 ° C and curing for 1 hour at the same temperature.

The compositions of the examples and characteristics of all the materials obtained are presented in table 2.

table 2 The compositions and characteristics of the materials as examples Component Names The number of components, wt.% example 1 example 2 example 3 o-cresol bracer epoxy 26.0 25.0 27.0 phenolic novolac resin brand SF-015 13.0 12.5 13.5 ground quartz 32,0 33.0 35.0 glycidyloxypropyltrimethoxysilane 0.60 0.29 0.70 triphenylphosphine 0.46 0.48 0.59 oxidized polyethylene wax 0.36 0.38 0.40 technical carbon (soot) 0.62 0.68 0.63 N, N ^I -dimethyl-3-chlorophenylurea 0.06 0,07 0.08 hexagonal boron nitride 26.9 27.6 22.1 Characteristics of materials: glass transition temperature, ° C 169 170 168 spiral flow, ° C 55 fifty 60 bending strength, N / m ² 90 90 95 coefficient of linear thermal expansion, 10 ^-6 deg ^-1 23 25 28 thermal conductivity, W / m * deg 1,5 1,6 1.4

A material based on a composition of a developed composition combining a specially prepared binder, SF-015 resin as a hardener and a filler, additionally including hexagonal boron nitride, makes it possible to use it for sealing microelectronic products, in particular integrated circuits, which are operable under high vacuum at 105 ± 5C ° with increased heat dissipation.

Hexagonal boron nitride is described in the technical literature as a material with high thermal and electrical insulation properties, low coefficient of linear thermal expansion, used as a high-temperature lubricant, as a separating medium in various processes with ceramics, metal and glass, and refractory coating in precision metallurgy, and also as thermal insulation in the field of dielectrics. Based on these properties, the introduction of hexagonal boron nitride into the composition should not improve the heat dissipation characteristics, which takes place in our case, which confirms the non-obviousness of the use of boron nitride in the composition.

Solid novolac resin SF-015 is usually used in the production of binder shell molds and cores to produce high-quality castings that accurately reproduce the shapes of models, which allows them to be widely used in the automotive industry, as well as for the manufacture of abrasive products, and therefore its introduction into the composition of the developed press compositions are also not obvious.

Claims (3)

1. A method of producing an ortho-cresol-wave epoxy resin, including polycondensation of ortho-cresol and formaldehyde in an equimolar ratio by heating in the presence of an acid catalyst in n-butanol, reacting the resulting reaction product with an excess of epichlorohydrin when heated in the presence of an alkaline catalyst, distilling off epichlorohydrin and isolating the target product, characterized in that formaldehyde is used in the form of para-formaldehyde, the polycondensation of ortho-cresol and para-formaldehyde is carried out at (115 ± 2) ° С sleep ala in the presence of 6-8 parts by weight oxalic acid to achieve 35-45% conversion, then in the presence of 3-5 wt.h. para-toluenesulfonic acid until the calculated amount of water is completely isolated, n-butanol is distilled off, the reaction mass is neutralized, after which 350-400 parts by weight are charged. epichlorohydrin and chopped sodium hydroxide portionwise for 1.5-2.0 hours while maintaining the temperature in the range of 65-70 ° C, followed by exposure for 1.0-2.0 hours, distillation of excess epichlorohydrin and n-butanol, washing the resin chloroform and water and the selection of the target product from a chloroform solution by distillation of chloroform. 2. A method of producing an ortho-cresol-wolf epoxy resin according to claim 1, characterized in that the distillation of chloroform is carried out at 50-70 ° C at a pressure of 10 mm Hg with a gradual increase in temperature to 120 ° C at a pressure of 20 mm Hg and exposure under these conditions for 1.0-1.5 hours 3. A polymer composition for sealing semiconductor devices, including ortho-cresol-woven epoxy resin as a binder, phenolic novolac resin as a hardener, a quartz filler, glycidyloxypropyltrimethoxysilane as a sizing agent, triphenylphosphine as an accelerator, wax and soot, characterized in that the binder contains an ortho-cresol-wave epoxy resin with a softening temperature of 50-65 ° C obtained by polycondensation of ortho-cresol with para-formaldehyde in equimolar Ohm ratio at (115 ± 2) ° C, first in the presence of 6-8 parts by weight oxalic acid to achieve 35-45% conversion, then in the presence of 3-5 wt.h. para-toluenesulfonic acid until complete release of the calculated amount of water, distillation of n-butanol, neutralization of the reaction mixture, followed by loading 350-400 wt.h. epichlorohydrin and a batch charge of ground sodium hydroxide for 1.5-2.0 h while maintaining the temperature in the range of 65-70 ° C, followed by exposure for 1.0-2.0 h, distillation of excess epichlorohydrin and n-butanol, washing resin chloroform and water and the selection of the target product from the chloroform layer by distillation of chloroform, carried out at 50-70 ° C at a pressure of 10 mm RT.article with a gradual increase in temperature to 120 ° C at a pressure of 20 mm Hg and exposure under these conditions for 1.0-1.5 hours, as a hardener, the composition contains phenol novolac resin brand SF-015, as wax - oxidized polyethylene wax and, in addition, N, N ^I- dimethyl-3-chlorophenylurea and hexagonal boron nitride in the following ratio of composition components, wt.%:
o-cresol bracer epoxy 25.0-27.0 phenolic novolac resin brand SF-015 12.5-13.5 ground quartz 32.0-35.0 glycidyloxypropyltrimethoxysilane 0.29-0.70 triphenylphosphine 0.46-0.59 oxidized polyethylene wax 0.36-0.40 technical carbon (soot) 0.62-0.68 N, N ^I -dimethyl-3-chlorophenylurea 0.06-0.08 hexagonal boron nitride 22.1-27.6