TW200948858A - Oligomeric adducts of bismaleimide, diamine, and dithiol - Google Patents

Abstract

An oligomeric adduct of a bismaleimide and a diamine is prepared via a Michael addition reaction. The maleimide is extended with the diamine; in some embodiments, the maleimide is extended by an amine in combination with a thiol. The adducts are suitable for use as adhesives, coatings, and encapsulant, particularly for use within the microelectronics packaging industry as a coating for the inactive face of a silicon wafer.

Description

200948858 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention generally relates to a compound of an oligomer, an adduct of a hair amine compound and a diamine. The oligomers are extended by Malay: 醯-end and using amine linkages. These compounds are adhesives, coatings, and semiconductor packages for various manufacturing steps in the industry. ❹ 15 ❹ 20 Bismaleimide is a representative that has been found to be used in microelectronic curable resins. Double maleic amine can carry out homopolymerization under the heat and conditions of the industry, and can be used as a white clay f photoinitiator, and a free radical curing monomer (such as C-explosive vinegar, sulfhydryl) Acrylic vinegar, styrene, ethylene bonds, allylic monomers, olefins, etc. are polymerized. They may also be polymerized via Diels-Alde®, ene reaction, and Michael addition mechanism with the participation of the oxime monomer. As described in this specification and As used in the scope of the patent application, curing will mean polymerization. Commercially available maleic imine thermosetting resins are noted for their high modulus and excellent resistance to thermal degradation. However, such thermosetting compositions It is also brittle, which causes it to be ruptured by vibration after curing. The higher molecular weight of maleimide helps to solve the brittle problem, but for many compositions, the extra molecular weight requires a higher level of diluent to achieve Dispensing. Use a higher level of dilution of the sword to increase the cure_remaining degassing, which increases the likelihood of voids in the cured maleimide. The voids result in an adhesive or encapsulant prepared from maleimide. Potential failures and failure of the final electronic device. Another suitable use for solid maleimide concentrating polymers is next-generation crystal 5 200948858: back side coating (WBC) formulation. WBC formulations are typically cut on wafers. (Smgulate) into individual die (Die) before the semiconductor wafer is directly applied to the silicon surface of the adhesive inactive. This requires better materials comprising a printed open times 5 Ο 10 15

The controlled solubility of 20' allows for a higher degree of cut-off, and improved flow. Therefore, there is a continuing need for maleic amine compounds to address the challenges of the microelectronics packaging industry. SUMMARY OF THE INVENTION The present invention is a filamentary adduct of bismaleimide and di-, bisme 3M! and dibres-dithiol prepared by a Michael addition reaction. Malay

If the female is extended by a diamine or by a combination of a diamine and a dithiol. The oligomer H is used as a binder (4), a coating, and a seal (4) and has a special use in the semiconductor packaging industry. In a specific example, the present invention is a curable composition which is suitable for: adhering a semi-conductive filament crystal or a rotating sealing material to a substrate, and inactively coating the semiconductor wafer before the dicing is performed. Side, known as crystal = cloth ^ BC) / curable composition including bismaleimide and diamine, ^ ^ subtype and - amine and dithiol adduct; curing agent; ; and depending on the solvent required. , Malay (four) bribe amine, or with the amine and mercaptan molar ratio can be any 1 = molecular weight, viscosity, solubility, and diligence for future end uses. § Haibi can be anywhere from 1:1 to 99:1. The ratio of amine to sulfur is chosen in any ratio. In the specific example, the ratio will be within the rail circumference. In another specific example, the ratio will be within the range of 2: in another specific example, the ratio will be 5: i _ . Familiarity 6 200948858 It will be appreciated that as molecular weight increases, solubility decreases and viscosity and toughness (measured by modulus) increase. In the design of bismaleimide and diamine, or bismaleimide and oligomers of diamines and dithiols, practitioners may use one or more pairs in the above molar ratio. Maleimide with one or more diamines and dithiols. The ability to use several bismaleimides, diamines, and dithiols as starting materials to extend the full functionality of the oligomer adduct is open to the practitioner and allows design to have specific properties regarding viscosity, solubility, and bourn Product of performance characteristics. • ° ?-"Ν-Χ- Suitable bimaleimide contains a solid aromatic bismaleimide (ΒΜΙ) resin powder with structure 0 0', where X is an aromatic group. Aromatic group contains each

7 200948858

Bismaleimide resins having such x bridged groups are commercially available and are available, for example, from Sartomer (United States) and HOS-Technic GmbH (Austria) 200948858.

An additional exemplary maleimide comprises a general structure which is from 1 to 3 and X1 is an aliphatic or aromatic group. Demonstration of χι 5

The body comprises poly(butadiene), poly(carbonate), poly(carbamic acid vinegar), poly(ether), poly(ester), simple hydrocarbon, and contains functional groups such as carbonyl, carboxyl, lanthanum, uric acid A simple hydrocarbon of an ester, urea, or ether. Resins of this type are commercially available and are available, for example, from National Starch and Chemical Company and Dainippon Ink and Chemical, Inc. Particularly preferred maleic imine contains 10

Wherein C36 represents a linear or branched chain of 36 asbestos atoms (with or without a cyclic moiety >).

; and 9 200948858

Ο 5 10

15 Suitable diamines are those having the structure of ΝΗ2-X~NH2 wherein χ is an aliphatic or aromatic hydrocarbon. The structure and molecular weight of the diamine can be any suitable final composition for use. A wide variety of diamines are commercially available. In several embodiments, the diamine is selected from the group consisting of 2,2-bis[4-(4-aminophenylhydrazino)phenylpropane,], diaminodiphenyl-methane, and 2,2-dual [ 4-(4-aminophenoxy)phenylmethane], 4,4,-diamino-3,3,-didecyldiphenylnonane, 4,4,_(1,3_phenylene) A group consisting of dioxy)-diphenylamine and 1,4-phenylenediamine. Suitable dithiols are those having the SH-X-SH structure, wherein χ is a known or aromatic hydrocarbon. The structure and molecular weight of the dithiol can be any suitable final composition. A widely diversified dithiol is commercially available or consists of a group of Thi 〇 fine G4 from Akcros Che als, when the curable composition of the curable composition of the alkenylcarbamide compound is heated by the scoop ( A thermal initiator) or electromagnetic radiation... a sodium-derived free radical or a cation-initiated species hair styling agent can be formulated to be used in an amount of up to 10% by weight. Booty. The initiator will be coated with an emulsion of L 5 free radical thermal initiator of the total resin, such as benzammonium peroxide, 200948858 5 ❹ 10 15 ❹ 20 peroxide laurel, octyl peroxide, butyl peroctoate, peroxidation Diisopropylbenzene, acetonitrile peroxide, peroxy-p-chlorobenzylhydrazine and di-tert-carboxyperoxybenzoic acid di-tert-butyl ester; l,l-di-(tripentyl-peroxy)_ Cyclohexane; azo compounds such as azoisobutyronitrile, 2,2'-azobispropane, 2,2,-azobis(2-methylbutyronitrile), and m,m'-azo Oxystyrene. Commercially available azo initiators are available from Wak(R) Specialty Company, for example under the tradenames va-044, VA-057, VA-085, V-70, VF-096, V-65, V-6 ( H, V-59, V-40, VF-096, V-30 venders' and those available from Akzo Nobel, for example under the trade names Perkadox ACCN, Perkadox AIBN, Perkadox AMBN-GR venders' and from Dupont Available, for example, under the trade names Vazo-52, Vazo-64, Vazo-67 and Vazo-88. Exemplary free radical photoinitiators are disclosed in (10) CwWwg:: Science and Technology &gt; 1992 » Plenum Press » New York ; SP Pappas, Ed·and less c/ope out / corpse «SWewce Engineerings 11» 187» 1988 &gt; John Wiley and Sons &gt; New York ; HF Mark, NM Bikales, CG Overberger, G· Menges, Eds may also choose a free radical thermal initiator for curing purposes. The exemplary thermal initiators are disclosed in Shao, 211, 1991, John Wiley and Sons, New York; GG Odian ' Ed. In several specific examples, light-induced Both action and thermal initiation can be desirable. For example, curing an adhesive containing a photoinitiator can UV irradiation begins, and in a later processing step 'curing can be done by applying heat to achieve free radical curing. Both UV and thermal initiators can thus be added to the adhesive composition. For some applications, one or more can be used Fillers or spacers 11 200948858 5 10 15 ❹ 20 or rain is added to the curable composition and is usually added for improved rheological properties, stress reduction, and bondline control. Suitable non-conductivity Examples of fillers include alumina, aluminum hydroxide, cerium oxide, feldspar, mica, apatite, calcium carbonate, titania, sand, glass, barium sulfate, cone, carbon black, organic fillers, and organic polymerization. (including but not limited to a toothed 1 ethylene polymer such as tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, vinylidene chloride, and ethylene). Suitable conductive fillers are Ink, gold, silver, copper, Ming 'put, record, charm, carbon cut two stones and alumina. Particles can range from nanometer size to several millimeters of any suitable size> depending on whether it is made into a filler Or spacer (isolated Code two having more uniform size of the larger size of age). The selection of such dimensions for any particular end use is within the skill of those skilled in the art. The filler can be presented by the practitioner in any amount suitable for the end use selected. — Bare bonding and WBC applications require the addition of strength, toughness, and heat resistance to the oligo-maleimide, but it also dissolves in low-boiling solvents and exhibits excellent processability. The polymerized maleimide of the present invention extended by diamine and dithiol is typically a solid resin and is suitable for the WBC composition. The molecular weight and viscosity of the oligomer of the invention, which is extended by diamine and dithiol, can be appropriately selected from the maleimide and diamine or dithiol addition agent for the wheat addition reaction and Modify the appropriate relative to the molar ratio. The maleidanilide/diamine addition product of the present invention is present in the composition enthalpy in the range of 2% by weight to about % by weight (% by weight) based on the total weight of the composition, in one or more specific examples, one or more The monomer may be present in the composition from 10% by weight to about 90% by weight based on the total weight of the composition. The monomer of the present invention includes, for example, propylene, methyl acetoacetate, maleic imide, ethylene thialate, styrene compound, allyl functional compound, and the like. The time and temperature curing profiles of the various compositions will be diversified, and different f-products can be designed to be applied to the curing curve suitable for the manufacturing process of the shaft industry. In general, such compositions will cure from 70 ° C to 250 ° C and curing will be achieved in the range of ten seconds to three hours. ❹ 15 20 In several embodiments, the adhesive composition may contain additional flexibility and bob. a compound obtained by sigma, which may be any thermal or thermoplastic material having a Tg of 5 〇c or less, and will typically be I. The material is characterized by Freely rotating chemical bonds, the presence of (10) groups, and the absence of rings," "Construction_ such suitable modifiers include polyacrylic acid vinegar, poly (butting), polyTHF ((tetra) tetrahydrogen, also known as silk (μ Glycol)), (iv) n (successive terminal dibutyl acrylonitrile) rubber, and polypropylene glycol. When present, the <RTIgt; </ RTI> compound can be used in an amount up to about 15% by weight of the maleimine diamine adduct of the present invention. The free-radical curing may also be added to the adhesive composition described herein. The useful shelf life of the composition of the compound of the present invention. Examples of such inhibitors include (iv), for example, 2,6•di-tert-butyl-m-methyl-m- 2f-di: tert-butyl-l-methoxyphenol, tert-butylhydroquinone, hydrazine (methylene- (, _-di-dibutyl-4-p-hydroxybenzopropionate)) benzene, s::yl-p-methyl phenyl), and (8)-trimethyl-2, ginseng 2 butyl (4) )benzene. Other useful antioxidants for the administration of hydrogen include the derivatization of p-diphenyldiamine and diphenylamine. The antioxidants are also known to be useful in combination with antimony and metal deactivators. An effective inhibitor package. Examples of suitable oximes include benzoquinone, 2-tert-butyl-154-benzene, 2-phenyl-1,4-benzoquinone, naphthoquinone, and 2,5-dichloro-l,4-benzoquinone. Examples of metal deactivators include N,N'-bis(3,5-di-t-butyl-4-[p-hydroxyphenylpropanyl) 5 oxime, oxalyl bis(benzylidene fluorene), and N-phenyl-N,-(4-toluene)-p-phenylene diamine. Nitroxide free radical compounds such as TEMPO (2,2,6,6-tetramethyl-1-pyraloxy-radical) are also effective as inhibitors at low concentrations. The total amount of antioxidant plus synergist typically falls within the range of from 100 to 2000 ppm by weight based on the weight of the total raw material resin. Other additives, such as adhesion promoters, may also be added in the type known in the art. [Embodiment] In all of the following examples, "η" in the structure is a diversified integer, and each reaction mixture will have an oligomer having a different "η" value. Therefore, 'η is a variable integer for the purposes of this document. Due to this mixing, although the exact integer of each reaction will be undetermined, the average integer can be determined according to the chemical &amp; tens method of the starting material and by the molecular weight of the product. In general, η will be 1 to 5 ❹ Scope. Synthesis of Example 1 14 200948858

Ο

The above maleimide/diamine adduct is derived from the maleimine having the structure •° Λ 5Q 5 f, wherein C36 represents a linear or branched chain of 36 carbon atoms (with or without a cyclic moiety) BMI-1, and 4,4'-diamino-diphenyldecane are hereinafter prepared according to the following procedure. BMI-1 (100.Og, 0.1087 mol), 4,4,-diamino-diphenylnonane (10.77 g, 0.05435 mol) and toluene (100 mL) were charged with a thermometer, a mechanical mixer, And a 500 mL four-neck round bottom reaction flask with a condenser. The reaction flask was purged with nitrogen and mixed at ίο 400 rpms in an oil bath preheated to 90 °C. When the reaction temperature reached 65 ° C, all solids dissolved to form a clear golden solution. Then add five drops of acetic acid. At a temperature of 80 ° C, the reaction time was started, and heating and mixing were continued for 48 hours. During this time, the reaction changed from a clear golden solution to a deep reddish orange solution. After cooling to room temperature, the reaction solution was decanted from the secondary gel on the side of the flask, and the solution was extracted from the solution on a rotary evaporator. The result was 121 g of viscous deep aerated liquid. This product was vigorously mixed in ethanol (300 mL) for 30 minutes and then allowed to stand for 6 minutes. The opaque yellow residual layer was separated from the __ colour base and discarded 1 additional three times of this mixing/clarification/decanting cycle. The ethanol wash was removed according to τιχ (▼ benzene / thf W volume) to remove residual diamine. The solvent was extracted from the product on a Wei rotary evaporator and 60 °C KUgelr〇hr. A 6 〇g dark reddish brown oily product was obtained. The structure was confirmed by 1H NMR. Example 2 Synthesis

ΒΜΙ-2) Preparation. Li-2 (5〇.〇g, 0.0991m〇1), 4,4, diaminodiphenylmethyl 15 (9.81g '〇·〇495ΠΚ>1) and toluene (5_0 are loaded with temperature 16 200948858 Meter, mechanical mixer, and &amp; * Order as a device _ 9 S Π r Reaction flask with nitrogen purge, 〇〇m: L four-neck round bottom reaction flask. Mix. When reaction temperature axis to the oil Add 200 drops of acetic acid in the bath. Then add five drops of acetic acid. Dissolve in solid state to form concentrated gold and heat and mix for 46 hours. This:; ^ time starts, hold into a thin very dark red solution. Then change the reverse color solution Black gel decantation. By, C rotates bursts of J watts: formed on

10

15 =1*3 hours extraction solvent from the red solution, the fruit is mixed with ethanol (15-=0 4. The opaque yellow 6 alcohol is decanted from the brown bottom of the sticky bribe: '. Repeat this three times for further mixing/resting / decantation cycle. Using 40 C known: rotary evaporator and 8 (rCKugelrohr from the product extraction solvent to obtain 6 〇g product. The structure was recognized by 1H NMR tank. Example 3 synthesis

17 200948858

Malay yttrium (hereinafter referred to as BMI-3) and 4,4'-diaminodiphenyl oxime were prepared according to the following procedure. BMI-3 (70.0 g, 0.1203 mol) and 4,4'-diaminodiphenylmethane (11.9 g, 0.0602 mol) were charged in a four-necked round bottom equipped with a thermometer, mechanical mixer, 5 and condenser. Reaction flask. The reaction flask was purged with nitrogen, and mixed at 300 rpms in an oil bath preheated to ll 〇 °C. When the reaction temperature reached 83 ° C, all solids dissolved to form a clear red solution. Then add five drops of acetic acid. Start at the temperature so c 'reaction time, continue heating and mixing for η hours. During this time, the reaction changed from a thin red solution to a thick red-dish solution. After cooling to room temperature, the reaction solution was dissolved in dichloromethane (6 mL). This dialle solution was washed twice with 10% by weight hydrochloric acid to remove residual diamine. The emulsion formed by the washing was destroyed using saline. The organic fraction was dried over sulphuric acid (50 g) and filtered. The solvent was extracted from the clear copper filtrate by 4 (TC rotary evaporator and 6 〇 ° C 〇 Kugelrohr to give a thick amber liquid 15 product. The structure was confirmed by 1H NMR.

The maleimine from the aromatic linkage is extended by the amine-2,2-bis[4-(4-aminophenoxy)phenylpropane]. 20 will be Bismaleimide (from Huntsman Advanced Materials 18 200948858

10 15

Matrimid 5292A, CAS# 13676-54-5, hereinafter referred to as 8]\115292 people) (26.02, 0.0726111〇1), 2,2-bis[4-(4-aminophenoxy)benzene Propane] (14.0 g, 0.0341 mol) and 2-decyloxyethanol (2 〇g) were charged in a 100 mL 3-neck round bottom reaction flask equipped with a thermometer, a mechanical mixer, and a condenser. The flask was fixed in an oil bath preheated to i3〇〇c. The contents were mixed at 300 rpms. The reaction was gradually changed from a yellow paste to a dark brown solution at i 〇 5 °C. Heating was continued for 2.5 hours while maintaining the reaction temperature between 100 and ll 〇 °C. The thick dark red reaction product was allowed to cool to room temperature in a flask. The flask was quenched in dry ice causing the product to freeze and fragment. This allows the cold product to be easily collected from the flask as a hard glass material. The product was placed in a 1 L single-necked flask, and the solvent was extracted on a 70° Clugelr hr for 3 hours. The product was collected, pulverized into a fine gold powder, and dried under vacuum to 8 ° C for a total of 16 hours. Thus more than 35 g of fine gold powder was collected from this reaction. The softening point is 135 to 140. (: Structure confirmed by iHNMR) Example 5 Synthesis

Extension of a maleic amine from an aromatic linkage to an amine- 2,2-bis[4-(4-aminophenoxy)phenylpropane] (from National Starch and Chemical Co) Obtained SR525, CAS#3006-93-7, hereinafter referred to as BMI525) (26.0g, 0.0969mol), 2,2-bis[4-(4-aminophenoxy)phenylpropane] (i4.〇 g, 0.0341 mol), and 2-methoxyethanol (20 g) were charged in a 100 mL three-neck round bottom reaction flask equipped with a thermometer, 19 20 200948858 mechanical mixer, and a condenser. The flask was solidified in an oil bath preheated to 125 C. The contents were mixed at 300 rpms. Gradually, the reaction was changed from a yellow slurry to a deepened orange slurry at 10 °C. Heating was continued for 6.0 hours while maintaining the reaction temperature between 105 and 丨^. The 5 reaction product, a thick dark orange-red syrup, was cooled to room temperature in a flask. The product solution was transferred to a 250 mL one-necked flask. The solvent was extracted at 6 (TCKiigelrohr for 1 hour. After a brief burst of foaming, the product was collected as a dark orange solid' pulverized and dried under vacuum at 60 to 80 ° C for a total of 16 Hour. More than 35 g of fine gold powder was obtained from this reaction. The observed softening point was 115 to 125. (: ίο The structure was confirmed by hNMR. Example 6 Synthesis

The maleimine from the aromatic linkage is extended by the amine-2,2-bis[4-(4-aminophenoxy)phenylpropanone]. 15 Bismaleimide (from 5100, CAS# 105391-33-1 from Daiwakasei Industry Co. Ltd., hereinafter referred to as BMI 5100) (26.0g, 0.0588111〇1), 2,2-double [4- (4-Aminophenoxy)phenylpropane] (14. (^, 0·0341πιο1), and 2-decyloxyethanol (20 g) were charged in 100 mL of a thermometer equipped with a thermometer, a mechanical mixer, and a condenser. The flask was shaken in a flask. The flask was fixed in an oil bath preheated to 125 ° C, and the contents were mixed at 200 rpm. Gradually, the reaction was changed from a brownish yellow slurry to a clear dark red solution at 10 °C. Heating was continued for 75.0 hours while maintaining the reaction temperature between 105 and 120 ° C. 20 200948858 When the amine was consumed, the reaction product was a thick dark red liquid. To aid recovery, the reaction flask was quenched in dry ice. The viscous liquid was frozen, chipped and readily obtained from the reaction flask. The solid was then transferred to a 1000 mL single-necked flask placed on Kugelrohr. The solid was melted back to the liquid and the residual solvent was extracted at 80 ° C. The product was collected as a brown powder and dried under vacuum at 60 to 80 ° C. The reaction is obtained having a softening point of more than 35g of 180 to 185 ° C of the product. Structure confirmed by 1H-NMR is. Example 7 Synthesis of

The maleimide from the aromatic linkage is extended by the amine-4,4,-diaminodiphenylnonane. BMI5292A (30.00 g, 〇. 〇 838 mol), 4,4,-diaminodiphenyl decane (8.3 g, 0.0419 mol), and 2-methoxyethanol (19 g) were charged with a thermometer and a machine. A 10 mL round neck reaction flask with a mixer and a condenser. The contents of the reaction flask were mixed at 300 rPms in an oil bath preheated to 125 °C. When the reaction temperature reached 丨, the mixture formed a dilute deep red solution. At this temperature, the reaction time begins, heating and mixing are continued. Thin layer chromatography (nonyl/tetrafurfuran, 1/1 volume) was used to monitor the reaction. After 7 hours, all amines were consumed and the reaction changed from a yellow paste to a viscous dark red liquid. The reaction was transferred to a 500 mL reaction flask by cooling solidified and clay-like solids. The residual solvent was extracted from the flask using a rotary evaporator for 2 hours followed by Kugelr hr 1.5 hours (both at 6 ° C). Then, the gold brown solid obtained by pulverizing 21 200948858 'removed the residual solvent using a vacuum oven of 8 (TC) to obtain almost 35 g of a pale brown powder having a softening point of 180 to 19 (TC. The structure was confirmed by b NMR. Example 8 Synthesis

The maleimide from the aromatic linkage is extended from the amine-4,4,-diaminodiphenylnonane in a 50% solids solution. 81^1 5292 八(30.00§'〇.〇838111〇1), 4,4'-diaminodiphenyl decane (8.3g, 0.0419mol), and propylene carbonate (38 3g) were packed in 10 A 500 mL four-neck round bottom reaction flask equipped with a thermometer, mechanical mixer, and condenser. The contents of the reaction flask were mixed at 200 rpms in an oil bath preheated to 125 °C. When the reaction temperature reached it, the mixture formed a thin, deep reddish orange solution. At this temperature, the reaction time begins and heating and mixing are continued. Thin layer chromatography (nonylbenzene/tetrahydrofuran, 1/1 volume) was used to monitor the ||15 reaction. After 9 hours, all amines were depleted and the reaction changed from the initial yellow slurry to a viscous dark red liquid. When hot, the viscous product is transferred to the HDPE bottle. Nearly 65 g of the product was obtained as a 5 % solution in propylene carbonate. Solutions of BMI/amine adducts are expected to provide greater efficiency in preparation, processing and formulation. The structure was confirmed by iNMR. 20 Example 9 Synthesis 22 200948858

Ο

BMI 5292A is extended from two different aromatic linkages of maleimine (ΒΜΙ 5292Α, ΒΜΙ 5100) via amine-2,2-bis[4-(4-aminophenoxy)phenylpropane] 15. 〇g, 〇.〇4i9mol), BMI 5100 ( 18.5g, M419mol), 2,2-bis[4-(4-aminophenoxy)phenylpropane] (17 2g, 0.0419mol), and 2-methoxyethanol (26 g) was charged in a 250 mL three-necked round bottom reaction flask equipped with a thermometer, a mechanical mixer, and a condenser. The flask was fixed in an oil bath preheated to 125 C and the contents were mixed at 3 rpm. Gradually, the reaction was changed from a yellow mixture to a pale orange slurry at 105 C. Heating was continued for about 9 hours while maintaining the reaction temperature between 1 and 5 and 115. In the daytime. The reaction product - thick dark red (four) - was transferred to a 25 GmL single-bottle. It was washed with 2-methoxyacetone. The thief will make the solvent from the reaction. The product was collected as a dark orange powder and was between 6 Torr and 8 Torr. [Drying under vacuum for a total of 16 hours. From this reaction, more than 4 g of a powder having a softening point of 15 to 160 ° C was obtained. The structure was confirmed by iH NMR. Example 10 Synthesis 23 15 200948858

马 In a 50% solids solution, two aromatic linked maleimides (BMI 5292A and BMI 5100) are amine- 2,2-bis[4-(4-aminophenoxy)phenyl Propylene] extended. 5 BMI 5292A (15.0 g, 〇. 〇 419 mol), BMI 5100 ( 18.5 g, 0.0419 mol), 2,2-bis[4-(4-aminophenoxy)phenylpropane] (17.2 g, 0.0419 mol) And propylene carbonate (5 〇.7g) were packed in a 500 mL four-neck round bottom reaction flask equipped with a thermometer, mechanical mixer, and condenser. The contents of the reaction flask were mixed at 200 rpm in an oil bath preheated to 125 °C. When the reaction temperature reached 105 ° C, the mixture formed a thin dark red orange solution. At this temperature, the reaction time begins and heating and mixing are continued. Thin layer chromatography (toluene/tetrahydrofuran, 1/1 volume) was used to monitor the reaction. After 31.5 hours, all amines were consumed. The reaction changed from a golden yellow syrup to a viscous dark red syrup. When hot, the viscous product is transferred to a HDPE plastic bottle. The structure was confirmed by 1H NMR. A nearly 50 g solution of nearly 95 g of product was obtained. Solutions of BMI/amine adducts are expected to provide greater efficiency in preparation, processing and formulation. Example 11 Synthesis 200948858

Maleimide (BMI 5292A, BMI © 5100) from two different aromatic linkages was extended via amine-4,4'-diaminodiphenylmethane. BMI5292A (15.0g' 0.0419mol), BMI5100 (18,5g, 5 0.0419m〇l), 4,4,-diaminodiphenylnonane (8.3 g, 0.0419 mol), and 2-decyloxy Ethanol (50 g) was loaded in a 500 mL four-neck round bottom reaction flask equipped with a thermometer, mechanical mixer, and condenser. The flask was fixed in an oil bath preheated to 125 C, and the contents were mixed at 200 rpms. Gradually, the reaction was changed from a yellow-orange mixture to a thin, clear red-orange solution at 105 C. Continue to add 10 heat for 7.5 hours' while maintaining the reaction temperature between 105 and 115 °C. The reaction ❹ product, a thick dark red liquid, was transferred to a 500 mL one-necked flask. Rinse with 2_mercaptoethanol. At 60 to 70.自 Extract the solvent from the reaction using a rotary evaporator. The product was collected as a dark amber powder and dried under vacuum at 75. From this reaction, more than 35 g was obtained with a softening point of 130 to 14 Å. (: Powder. 15 Structure confirmed by hNMR. Example 12 Synthesis 25 200948858

马 50% solid solution t, from two aromatic linked maleimide (BMI 5292A and BMI5100) extended by amine-4,4,-diaminodiphenyl decane. BMI 5292A (15.0 g, 〇. 〇 419 mol), BMI 5100 ( 18.5 g, 5 〇. 〇 419 mol), 4,4'-diaminodiphenyl decane (8.3 g, 0.0419 mol), and propylene carbonate The ester (41.8 g) was packed in a 500 mL four-neck round bottom reaction flask equipped with a thermometer, mechanical mixer, and condenser. The contents of the reaction flask were mixed at 200 rpms in an oil bath preheated to 125 °C. When the reaction temperature reached 105 ° C, the mixture formed a thin reddish orange solution. At this temperature, the reaction is started for a period of time, and heating and mixing are continued. Thin layer chromatography (nonylbenzene/tetrahydrofuran '1/1 volume) was used to monitor the reaction. After 12 hours, all amines were consumed and the reaction changed from a golden yellow slurry to a viscous dark red syrup. When hot, the viscous product is transferred to a high density polyethylene bottle. The structure was confirmed by 1H NMR. Thus, nearly 80 g of a 50% solution in propylene carbonate was obtained. The hydrazine/amine adduct 15 solution is expected to provide greater efficiency in the preparation, processing and formulation. Example 13 Synthesis 26 200948858

Maleimide-bonded maleimide (BMI 5292A) via two different amines, 2,2-bis[4-(4-aminophenoxy)phenylpropane] and 4,4,-diamine Diphenyl decane is extended. 5 BMI5292A (40.0g, 〇.lll7mol), 2,2-bis[4-(4-aminophenoxy)phenylpropane] (11.5g, 〇.〇 279mol), 4,4,-diamine Diphenylpyrene (5.5 g '〇.〇 279 mol) and 2-methoxyethanol (30 g) were charged in a 250 mL three-neck round bottom reaction flask equipped with a thermometer, a mechanical mixer, and a condenser. The flask was fixed in an oil bath preheated to 125 ° C and the contents were mixed at 10 200 rPms. Gradually, the reaction is at 1〇5. (: Change from pale yellow paste to dark red solution. Continue to heat and mix for 2 hours while maintaining the reaction temperature between 105 and 115. Transfer the reaction product - dark red orange liquid to ❹ 500 mL single-necked flask The solution was rinsed with 2_methoxyethanol. The solvent was extracted using a rotary evaporator for 4 hours at 6 ° C. The product was collected and pulverized to a golden orange powder 15 and then stepped at 75. (: vacuum Drying. More than 40 g of powder were obtained from this reaction. The structure was confirmed by 1H NMR. Example 14 Synthesis 27 200948858

Maleic amines from aromatic linkages via two different amines - 2,2-bis[4-(4-aminophenoxy)phenylpropane] and 4,4,-diaminodiphenyl Base 曱 ❹ ❹ ❹ BMI 5100 (49.4g, 〇.iii7mol), 2,2-bis[4-(4-aminophenylbenzeneoxy)phenylpropane] (U.5g '0.0279mol), 4, 4,-Diaminodiphenyl oxime (5.5g, 〇.〇 279mol), and 2-methoxyethanol (3〇g) are packed in a thermometer equipped with a thermometer, mechanical mixer, and condenser. mL three-neck round bottom reaction flask. The flask was fixed to preheat to 125. In the oil bath of 〇, the contents were mixed at 200 rpms. With heating, the reaction was changed from light yellow slurry to i〇5t&gt;c to a clear red solution. Heating and mixing were continued for 28 hours while maintaining a reaction temperature between 105 and 115 °C. The reaction product - dark red viscous liquid. Transfer to a 5 GG mL single neck flask. Rinse with 2-methoxyethanol. The solvent was extracted by rotary evaporation at 6GC for 4 hours. The product was collected, pulverized into a gold-colored powder, and further dried at 75 to a thief vacuum. Since then, reaction 15 has been paid in excess of 4 〇g with a softening point of 145 to 155. (: powder) The structure was confirmed by 1 NMR. Example 15 Synthesis

28 200948858 In a 50% solid solution, a maleimine from an aromatic linkage is extended with an amine 2,2-bis[4-(4-aminophenoxy)phenylpropane]. 5 ❹ 10 BMI 5292A (360.0g, l. 〇〇 56mol), 2,2-bis[4-(4-aminophenoxy)phenylpropane] (206.4g, 〇.5028mol), and propylene carbonate The ester (566.4 g) was loaded into a 2 L four-neck round bottom reaction flask equipped with a thermometer, mechanical mixer, and condenser. The contents of the reaction flask were mixed at 200 rpms in an oil bath preheated to i25 °C. When the reaction temperature reached i 〇 5 ° C, the mixture formed a thin dark red orange solution. At this temperature, the reaction time begins and heating and mixing are continued. (Note: The temperature of the contents gradually increased to about 122t). The reaction was monitored by measuring the viscosity of the solution at 5 ° C from samples taken every hour. After 21.5 hours, the viscosity of the solution at 50 ° C was measured to be 4580 mPa·s (cPs), and the reaction was terminated. When hot, it is easy to discharge dark red sticky products. A nearly 50 g solution of nearly 90 g of product was obtained and the sample was characterized. The structure was confirmed by ijj NMR. The Mw is determined by GPC to be 20,646 and the MWD is 7.3. Example 16 Synthesis

15 ❹ In a 50% solids solution, the aromatic-linked maleimide (bmi 5292A) is extended by the amine-2,2-bis[4-(4-aminophenoxy)phenylpropane] BMI 5292A (360.0 g, 1.056 mol), 2,2-bis[4-(4-aminophenoxy)phenylpropanone] (206.4 g, 0.5 〇 28 mol), and propylene carbonate (566.4 g) A 2 L four-neck round bottom reaction flask equipped with a thermometer, mechanical mixer, and condenser was charged. The contents of the reaction flask were mixed in an oil bath preheated to 200 rpms. When the reaction temperature reached l 〇 5 ° C, the mixture 29 20 200948858 5 形成 formed a thin dark red orange solution. At this temperature, the reaction time begins and heating and mixing are continued. (Note: The temperature of the contents gradually increases, and during most reactions, the temperature range is between 130 and 132 ° C). The reaction was monitored by measuring the viscosity of the solution at 50 ° C from samples taken every hour. After almost 7 hours, the viscosity of the solution at 50 ° C was measured to be 4915 mPa·s (cPs) and the reaction was terminated. When hot, it is easy to discharge dark red sticky products. Approximately 5 〇〇g of product was obtained as a solution of 5 〇 % solution and the sample was characterized. The structure was confirmed by NMR. The Mw of the product determined by GPC was 28,161 and the MWD was 10.19. Example 17 Synthesis

10 in a 50% solids solution, from the aromatic linkage of maleimine by amine-2,2-bis[4-(4-aminophenoxy)phenylpropane] extension BMI 5292A (360.0g ' l. 〇〇 56 mol), 2,2-bis[4-(4-amine 15 ❹ basic oxy) ketone propyl] (206.4 g ' 〇.5028 mol), and propylene carbonate (566.4 g) A 2 L four-neck round bottom reaction flask equipped with a thermometer, mechanical mixer, and condenser was charged. The contents of the reaction flask were mixed in an oil bath preheated to 200i*Pms. When the reaction temperature reached 丨 still, the mixture formed a dilute deep reddish orange solution. At this temperature, the reaction time begins and heating and mixing are continued. (Note: The temperature of the contents gradually increases, and during most ruminations, the temperature range is between 123 and 125. (:). The solution is measured at 5 (TC viscosity) by monitoring the reaction from a sample taken every two hours. After 1 hour and 15 minutes, the viscosity of the solution at 50 ° C was measured to be 4536 mPa·s (cPs), and the final reaction was 1. 30 20 200948858 When it was hot, it was easy to discharge the deep red viscous product. Thus, nearly 900 g of Example 24 was obtained. % solution, and the sample was characterized. The structure was confirmed by NMR. The Mw of Example 24 was determined by GPC to be 19,975 and the MWD was 7.44.

In one embodiment, the invention is a semiconductor germanium wafer having an active face and an inactive face, the inactive face to include one or more of the present inventions of bismaleimide and monoamine, or double malayan The amine and the composition of the diamine and the oligomer addition product of the dithiol are coated. Coating can be carried out by any of the techniques used to add material to the backside of the wafer, and includes stencil printing, spray coating, ink printing, and the like. Although the present invention has been described with respect to the specific embodiments, it will be apparent that other modifications and changes may be made without departing from the spirit of the invention.

31

Claims (1)

200948858 X. Patent application scope: 1. A curable composition comprising (a) a compound selected from the group consisting of the following groups 32 200948858 33 200948858 〇 34 200948858 35 5 200948858 and And (b) a curing initiator. 5 2. A semiconductor germanium wafer having an active surface and an inactive surface, wherein the inactive surface is coated with the composition according to item 1 of the patent application. 36 200948858 VII. Designation of representative representatives: (1) The representative representative of the case is: ( ). None (2) Simple description of the symbol of the representative figure: None 10 〇 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None ❹ 4