TW438874B - Epoxy resins consisting of flexible chains terminated with glycidyloxyphenyl groups for use in microelectronics adhesives - Google Patents

Abstract

This invention relates to flexible epoxy resins that have a structural composition comprising an oligomeric backbone of alkylene or alkyleneoxy repeat units, terminated with an aromatic moiety bearing one or more epoxy functionalities.

Description

4 3 88 7 4 A7 B7 Printed by the Central Standards Bureau of the Ministry of Economic Affairs Λ Industrial Consumer Cooperatives V. Description of the invention (1) The subject of the present invention is a variety of flexible rings for bonding microelectronics with low or no ion pollution. Oxidation synthesis method. One of the steps in the production of semi-conductor integrated circuit is to adhere to the copper frame with a stick or a small piece, and the metal conductive lead is formed by the crystalline sheet and the lead frame assembly enclosed in a polymer sealant inner body. The metal conductor lead is connected to the external circuit. The epoxy compound is connected or encapsulated with an adhesive because of its superior bonding strength. The conventional epoxy resin is aromatic (due to its strength), but these are inherently rigid :: During the process, the adhesive and the matrix undergo repeated thermal cycles: The matrix has a very different coefficient of thermal expansion. Junction failure, substrate curl, or wafer cracking. Therefore, the key requirement for adhesives for sub-components is that they must be strong and flexible f :: stress. A second key criterion is that the adhesive must be able to cure quickly. The rapid curing time required (typically 30-60 seconds is not required) is called rapid curing. This standard combination of flexibility and rapid curing ability) is difficult to adhere together in a single unit. It is also critical that epoxy resin formulations must be free of ions and chloride ions) * and free of chlorine. These contaminated metal leads in soft components Corrosion and eventual component failure. In order to increase flexibility, the epoxy compound can be reacted with a fatty compound; however, this paper is far removed from the Chinese standard (CNS > A4 size (210X297 ^ 1) It can be quickly solidified, and its mixture will extend the silicon wafer out of 0. It has been adhered and is preferably used as a small fragrance epoxy resin through the extension package. It is fragile. ○ In the manufacture. If the adhesive and stress will cause adhesion to the specified micro The electric absorption thermal cycle is in accordance with the adhesive strength of the assembly line at about 2 00. Internal dyes (especially sodium will cause the semi-conductive softener to jointly reduce the strength of the adhesive) (please read the “Cautions on the back side before filling in this Page) 438874 Printed by the Central Bureau of Economic Affairs of the Ministry of Economic Affairs and Industrial and Consumer Cooperatives «. A7 B7__ V. Description of the invention (2) 〇 The addition of a flexing agent also reduces the ability of the adhesive to cure rapidly, because the flexing agent per unit epoxy The base has a high molecular weight. In addition, when aliphatic and aromatic epoxy resins are cured, they may not react together due to differences in reaction rates; low molecular weight compounds may evaporate before curing, while high molecular weight compounds may Complete curing: This combination of factors, sometimes even f: the problem of slow curing formula, is harmful to achieving rapid curing. It is known that the combination of the aromatic part and the aliphatic part in the main chain of the same polymer is some One of these problems may be solved, but currently available polymers of this type have a high aromatic portion to aliphatic minister ratio, resulting in loss of flexibility. In addition, the preparation methods of these materials cause high chlorine pollution, The application of electronic parts is harmful. These polymers also have if: viscosity, and the addition of solvent as a diluent. During rapid curing, the curing is sometimes faster than the complete solvent volatilization, causing voids in the cured adhesive life, And potential failure of microelectronics wafers or small pieces. Therefore, the low viscosity substance that eliminates the need for solvents is better. 0 When building electronic components, the small pieces are bonded to the paper guide. The adhesive of the rack has the smallest weight Loss (no outgassing effect) is also necessary. This is necessary when the chip is cured on the lead frame, and during the wire bonding process (~ 200 υ) or when the circuit is encapsulated or molded. T is important during the two periods of subsequent curing. The weight loss during curing or post-curing should be minimized, so that any volatile substances that escape the adhesive no longer sink on the surface of the sheet. Any redeposition can be made in the mold. The delamination of the top of the chip during or after the printing process. In addition, the outgassing effect after the molding operation but during the reflow of the solder will cause a pressure buildup that will cause cracks in the envelope. CNS) Λ4 specification (210X 297 $ per cent) I 1 1 Order < read the notes on the back before filling out this page) Printed by the Shellfish Consumer Cooperative of the Ministry of Economic Affairs Bureau 438874 A7 ____B7__ 5. Description of the invention (3) The problems associated with providing strength to flexible compounds and rapid curing and thermal stability (low weight loss at high temperatures) are exacerbated as the microelectronics industry advances toward ever-larger wafer sizes. Continuous demand for improved flexible epoxy resin with strength and purity that can be formulated in fast-curing die attach adhesives. Figure 1 shows the DSC pattern of epoxy resin D according to the present invention, showing the exothermic change during curing of the epoxy resin. . There is a linear relationship between curve area and percent cure. Other similar DSCs of the epoxy resin of the present invention are used by the line system to generate the data plotted in Figure 2. Figure 2 is a graph of the percentage cure rate versus curing time of the sample epoxy resin of the present invention. Figure 3 is a test of the present invention. The thermogravimetric analysis graph of a sample epoxy resin, and shows the thermal stability of the epoxy resin when heated at 30'C -20 (TC and maintained at 200 * 0 for 30 minutes per minute. Figure 4 Sample epoxy resin in the presence of curing: (2-ethyl-4-methylimidazole) in the presence of 10 tJ per minute heated by 3 (TC -20 rc thermogravimetric analysis graph. This graph shows the duration of the curing process I: The amount of loss, and it is confirmed that the comparative epoxy resins C and E lose equivalent weight within the range of 200 υ — 25 ′ C (this is the temperature range used for the center line bonding and solder reflow of electronic components). 〇 This invention relates to a variety of flexible epoxy resins that can be used to formulate fast-curing small pieces of bonding adhesives, encapsulants, and coatings. 〇 These epoxy resins are based on a type of pollutants that can be easily removed in the early stages of synthesis. I use epichlorohydrin synthesis route, so compared with the high level The old-fashioned composition of f is applicable to the standard of China National Standard (CNS) A4 (210X297 today thin) — 6 — ------------------------ Order --- --- ^ »-(Please read the notes on the back before filling in this page) 438874 A7 _B7_____ V. Description of the invention (〇 is to produce a low-level quasi-ionic pollutant of less than 0.1% by weight. This is for industrial applications. It is a significant difference. In addition, these synthetic routes allow the preparation of discrete chemical structures, rather than a mixture of various resins. These epoxy resins are liquid at room temperature and less than or equal to 100 eC when cured. Tg 値. In another embodiment, the present invention is an adhesive made of such epoxy resins for use in microelectronics applications. The flexibility of these compounds is used in the preparation of rings with conductive materials such as silver flakes. Oxygen resin is retained and used to bond the silicon wafer to Jinyang's leadframe substrate 0. The cured epoxy resin shows a high radius of curvature, greater than or equal to 350 mm. (The higher the radius of curvature, the smaller the wafer curl, and the Refers to a flexible adhesive. 0) Consumption by the Central Ministry of Economic Affairs Printed by Sakusha 1 ----- ^ ----- Pack I (Please read the note ^^ on the back before filling this page) The cured epoxy resin also shows good adhesive strength, such as The small piece shear strength is measured. The small piece shear force is a measure of the force required to remove an adhered crystal piece from the metal matrix. For these compounds, it is greater than or equal to 10 MPa. Each epoxy resin can be formulated. It is made into a fast curing adhesive which shows no flexibility or loss of strength. The formulation preferably contains 20-10: parts by weight of a flexible epoxy resin and 80-0 parts by weight of an aromatic 0-glycidyl ether ( (A total of 100 parts by weight), a curing agent, a conductive filler, and a phenol hardener of 20-50 parts per hundred parts of epoxy resin (pphr) as seen. The structural composition of each epoxy resin includes oligomeric backbones of equal length among alkenyl or alkenyl repeating units to provide flexibility, but still maintain sufficient densities to obtain useful adhesive properties. An aromatic moiety bearing one or more epoxy functional groups terminates at one or both ends. Therefore, each compound has no more than two aromatic moieties, the latter of which only exists on this paper standard. Applicable to China National Standard (CNS) A4 (2 丨 0 X 297 mm) -7- 4388 74 Central Ministry of Economic Affairs 橾Printed by the quasi-government industrial and consumer cooperatives ¾ A7 B7 V. Description of the invention (5) Terminals 0 Limit the number of aromatic parts in the main chain of the polymerization Hold the strength imparted by the aromatic part to the cured substance, The flexibility of the cured substance. Discussion of these aliases and discussion of various previously known paths will be advanced-the structure of each compound. The path of flexible epoxy resins is known, including the glycidyl esters and glycidol of tablets. (Glycidyl carbamate). For these materials, it has been found for the present invention that the methoxy moiety is directly attached to the carbonyl group (like the above two). The methoxy moiety is suddenly excited at a high temperature (a temperature close to 200 υ) when the rapid curing of the current electronic component manufacturing is required. The main disadvantage is that the rapid curing system is close to 200 t! The incoming assembly is subjected to a temperature of 200-2 50 'C during the wire bonding process and after the solder reflow operation. Electronic Components I :: The topic Severe Fugitive Volatile Matters must be minimized throughout the entire component operation process. Each of the compounds of the present invention has properties and significantly improved thermal spike characterization at 300 t: temperature. Others for flexible epoxy resins are known to have epichlorohydrin and a diphenol compound with a flexible main chain possessing high-chlorine pollutants (usually > 0.2%). The source of the active ion (including organic, small, and small) is absolutely necessary. In order to achieve the required rapid curing, low stress, and so on, the following sequence is followed in the present invention. The use of an epoxy resin and location to maintain and make fat The steps of the family path synthesis show that the dimerized fatty acid ethyl ester (or amine is inferior, etc.) of the present invention, so it loses weight under the condition of oxiraneization. This is OK and the production of small pieces during the introduction process One of the other interrogating effects (relative to the rapid curing characteristics, in which resin-based preparations are 0. For microelectronics, chlorine should be reduced) to the highest purity and other characteristics. The propane reaction will read the note before reading. The paper size of this page applies to the Chinese national kneading rate (CNS) A4 specification (210X297 mm) -8- 4388 74 A7 B7 V. Description of the invention (6) The oxygen functional group is established on an aromatic ring. This is done on a small molecule Transform As known in the industry, post-treatment by caustic and easy purification by distillation or (re) crystallization. The aromatic ring may have more than one epoxy group and also contains another allowing it to be attached to a flexible Functional group at the end of the chain. This functional group can be a carboxylic acid (derived from benzoic acid) or a hydroxymethyl group (derived from benzyl alcohol). The aromatic ring can optionally carry other non-interfering groups. The attachment of the flexible chain can be carried out as in the case of a benzoic acid derivative by a dehydrating procedure (using a carbodiamido / hydroxyphenyl azide system), where the flexible chain has an amine group 0 at the end. A benzamidine functional group is generated during this coupling procedure. Attachment of the flexible chain can be performed in two ways as in the case of benzyl alcohol. The first is still a dehydration procedure (using carbodiamidine / dimethylamine group). Pyridine system), where the flexible chain bears a carboxyl group at the end. Therefore, a benzyl functional group is generated during this coupling procedure. The second method involves bringing the benzyl alcohol with an isocyanate group at the end. The flexible chain of the group is condensed. Therefore, coupling here During the sequence, a 0-benzyl limbate functional group is produced. 0 The printing is printed in the Ministry of Economic Affairs of China ’s Gradient Masonry Consumer Cooperative (please read the precautions on the back before filling this page). Glycidyl benzyl alcohol and isocyanate Condensation of acid salts is known, but various known methods result in a mixture of diisocyanates and mono- or diol-functionalized phenyl glycidyl ethers. This results in mixed substances at the ends and along the urethane backbone. Mixture of components with epoxy functional groups. Conversely, the compounds of the present invention only have epoxy functional groups at the ends, and the only urethane groups exist at the ends by condensation rather than polymerizing in the resin. In the main chain of the object, each flexible chain contains alkenyl or alkenyl units only. The paper size is in accordance with China National Standard (CNS) A4 (2) 0X297J ^ |) Employee Consumer Cooperative Co., Ltd. Benben 4388 7 4 A7 B7 V. Description of the invention (7) In addition * Various known compounds only illustrate the curing with room temperature of an aliphatic diamine. It is expected that the compounds of the present invention will act as if they have a high degree Rapidly curing epoxy tree with thermal stability , Particularly with respect to the I found inferior thermal spike when used as the glycidyl carbamate 0- shown with the comparative example characterized as natural. The following is a brief description of the preferred synthetic route. The preferred synthetic route for the synthesis of Luzen includes attaching an alkenyl or alkenyl chain to an aromatic compound, the latter being one with one or more glycidyl ethers and one with The aromatic ring of a functional group that reacts with a functional group on the alkenyl or alkenyloxy chain. Typically, the aromatic compound is a glyceryl ether group substituted with a glycidyl ether group and the functional group (preferably an acid Or hydroxy) benzene ring. The benzene ring may also be substituted with a C: _e alkyl, L-6 alkoxy or aryl or alkaryl, Ci-5 perfluoroalkyl, or h_6fluorenyl. As used herein, alkyl refers to a hydrocarbon group derived from an alkane and has the general formula ChH2n + 1; alkoxy refers to an alkyl group that also contains oxygen; aryl refers to a ring structure with the characteristic ring structure of benzene Alkylaryl refers to a group containing both alkyl and aryl structures; perfluoroalkyl refers to an alkyl group in which one or more hydrogens are replaced by fluorine; and fluorenyl refers to a carboxyl group 0H of the group is replaced by some other substitutable group (the benzene ring to which it is attached) the organic acid group c The alkenyl or alkenyl chain may have 10-50 carbon atoms, but typically Is prepared from a dimer acid (a product obtained from the dimerization process of unsaturated fatty acids) of a 3G carbon atom chain, or the chain can be prepared from a dimer diamine or a dimer diisomethane ether in phase f, All these can be purchased in the market. This paper size is free to use the Chinese National Standard (CNS) A4 specification (210X297 mm): -10- ----- I--I-^-pack --- --- Order ------ Mu (please read the note ^^ on the back before filling in this page) 438874 A7 B7 V. Description of the invention (8) Printing of amines by the Central Government Standards Bureau of the Ministry of Economic Affairs End of The alkenyl or alkenyl chain can be substituted with an epoxy group in a benzoic acid coupling procedure. This reaction occurs in the presence, which provides a monoamine bond between the alkenyl or alkenyloxy chain and the substituted benzene. These dehydration systems are the industry's E systems using carbodiamidate, such as dicyclohexylcarbodifluoride), and-hydroxyphenyl azide in a suitable solvent is a better substitute for benzoic acid including glycidyl to f A substituted benzoic acid is 0-preferred compound soft oxybenzoic acid. Alternatively, can the alkenyl or alkenyl chain be in a carboxylic acid? The dehydration carbodioxamine and this pyridine catalyst coupling reaction can react with or benzyl alcohol substituted with glycidyloxy. Another method involves replacing an isocyanate-terminated olefin with a glycidyl group or a glycidyl ether group. The preferred compounds made from these synthetic routes are publicly available, where C-34 and C- 36 is a residual hydrocarbon chain according to the above synthetic pathway sheet. In the reaction, there is a known dehydration system formic acid derivative in the dehydration. 0—Better (hereinafter referred to as DCC medium. Alcohols are substituted with the following structural formula to replace the r-reactive dimer acid (C-36

This paper uses the Chinese Cocoon Standard (CNS) Λ4 specification (21〇X297f | t). Please read and read the precautions of < 6 before filling out this page. system

.I ί.! Binding ~ Please read the notes on the back before filling in this page) This paper size is in accordance with China National Standards (CNS) A4 specifications (210X29 ^^ | J 438874 Off-line Consumer Cooperatives, Central Bureau of Procurement, Ministry of Economic Affairs Print

^ ^ Order (’Please read the notes on the back before filling out this page) This paper is applicable to the National Slope of Difficulties (CNS) A4 is now available (210X297 $$ _) The Central Ministry of Economic Affairs is printed by the Consumer Cooperatives

43887 A A7 _B7 _ V. Description of the invention (1 1) 配制 Preparation of curing adhesive The flexible epoxy resin composition of the present invention exhibits good adhesive strength and flexibility, and can be formulated into an adhesive with rapid curing ability. Agent. The preferred fast-curing formula will contain 20-100 parts by weight of flexible epoxy grain fat and 80-0 parts by weight of aromatic 0-glycidyl ether resin (total 100 long weights), a curing catalyst, and optionally One or more fillers 0—In general, the curing catalyst is an imidazole catalyst (existing amount is about 5-10 parts per 100 parts of resin), and the filler is thermally conductive or conductive such as silver flakes, although other conductive or thermally conductive A filler or silica can be used. The filler is preferably present in an amount of about 25 volumes of the adhesive formulation. Aromatic 0-glycidyl (aromatic epoxy resin) will use one or more aromatic rings and optionally one. Or more [a group substituted. The aromatic epoxy resin will have an epoxy equivalent of 200 or less! WPE, per unit epoxy weight] and will be derived from the corresponding phenolic hardener. Examples of the aromatic epoxy resin are bisphenol-F diglycidyl ether, bisphenol to diglycidyl ether, resorcinol diglycidyl ether, and epoxy novolac. The adhesive formulation may further contain 20-50 parts of phenolic hardener per 100 parts of resin, and each unit of the aromatic ring has one or more hydroxyl groups (from which the above-mentioned aromatic epoxy resin is derived). Qi: Examples are commercially available novolacs, bisphenol-F, bisphenol-A, and resorcinol. The addition of phenolic resins improves the adhesive strength of the formula when exposed to moisture and 250 'C thermal shock, and prevents the penetration of flexible epoxy resin from the formula. 0-In general, any effective catalytic amount of effective curing contact All kinds of media can be used. The preferred curing catalyst is imidazole catalyst, and usually about 100 parts of resin is about the size of this paper. Applicable to China National Standard (CNS) A4 (210X297297) ------- ^ ---- ^ ------ 1T ------ ^. ≪-(Please read the note ^^ on the back before filling this page) 438874 A7 B7 V. Description of the invention (12) 5 copies The amount exists. The imidazole catalyst is preferably imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-H--yl. The imidazole filler can be any thermally or electrically conductive material known to be suitable for microelectronic applications, and is used in any effective amount. For many applications, the preferred filler is silver, although other conductive or thermally conductive fillers Or silica can be used, and there is a case where the halo is preferably about the volume of the adhesive formulation. The following examples illustrate various representative epoxy resins. 0 Provide evaluation methods and list execution results. Each example also reveals various contents. Flexible epoxy resin and 0-polyglycidyl ether aromatic epoxy resin fast-curing small piece connection i: mixture formula, and formula containing phenolic resin hardener 0 'test method Central Ministry of Economic Affairs rate for shellfish consumption Printed by the cooperative (please read the note ^ on the back before filling out this page) The amount of hydrolyzable chlorine is determined by the following method: quasi ip Weigh 1 to 5 grams (to the nearest milligram) of resin into an iron Buddha Long e-face magnetic stir bar in a clean 125 ml conical bottle40 ml of 0.1 N KOH dissolved in M alcohol was added and the flask equipped with a reflux condenser was placed in a water bath heated by a magnetic stirrer / hot plate unit. The stirred solution was returned for exactly 15 minutes, then removed from the flask and allowed to cool to room temperature. Liquid I :: was transferred to a clean 250 ml beaker. Rinse the sample beaker * three times with 50 ml alcohol and transfer the liquid to the beaker. Add 1 ml of glacial acetic acid, and titrate the chloride potential to the end with 0.005N AgN〇3 solution: 〇 Calculate the ppm content of hydrolyzable chloride as follows: This paper is used in accordance with China National Standard (CNS) A4 specification (210X297) Xi Meng) 4388 7 4 Printed by the Shellfish Consumer Cooperative of the Central Judging Bureau of the Ministry of Economy U Ί The amount of k in the sample; T — ~ — The total chlorine content is determined by the following method: Accurately weigh 1 to 5 grams (up to the nearest 0.1 mg) of a tree suit — a clean cone with a magnetic stir bar Into a flask. Add 302 liters of hexane and 15 ml of 3N KOH solution in ethanol. Place a flask equipped with a reflux condenser in a 100 ° C water bath heated on a stirrer / hot plate unit. Reflux the internal sample solution for 30 minutes. Remove the flask and allow it to cool to room temperature. Transfer the liquid to a clean 400 ml beaker. Rinse the sample flask with 50 ml portions of methanol three times. Transfer the liquid to a beaker. Add 14 ml of glacial acetic acid. The silver electrode was titrated at a solution potential of 0.005: 8 to the end point. The ppm content of chloride was calculated as described above. Example 1 In this example, 3-glycidyloxybenzoic acid (using Glycerol group and an aromatic ring substituted with an acid group) react with an alkenyl chain terminated with an amine group to form α, ω-bis (3-glycidyloxyJ benzamidine). The alkenyl group is A 36-carbon diamine sold by Henkel under the trademark ersaraine 552. The preparation of 3-glycidyloxybenzoic acid is firstly epoxidized the ethyl ester with epichlorohydrin, and then the ester functional group is hydrolyzed to the acid to The use of epichlorohydrin 1C at the early stages of synthesis and at this low molecular weight makes purification and removal of ionic and bound chlorine contaminants easier.

Versamine 552 diamine 〇 (, ω-bisglycidyloxybenzamine (epoxy Λ) Preparation of this paper is applicable to China National Standard (CNS) A4 size (210X29_7g) (Please read the Note for this page, please fill in this page)-Pack. Order the Ministry of Economic Affairs-8-Printed by the Male Workers' Consumer Cooperatives of the Central Government Bureau 4 3 88 7 4 A7 B7 V. Description of the invention (ι〇

Z Tritium gaseous preparation: Into a 3-liter flask equipped with a mechanical stirrer, a nitrogen flusher and a condenser, inject 3-hydroxybenzene Ej ethyl ester (200 g, 1.204 8 mol), epichlorohydrin (334.6 g), potassium carbonate (261.16 g; ~ 321 sieve powder, pre-dried in a 120 eC air oven for several hours), and methyl ethyl ketone (1 liter). This mixture was heated with a heating mantle overnight to a gentle reflux temperature (~ 85TC). GC analysis (10 m glass capillary, 100 to 2 50 eC, rate at lot / minute) indicated incomplete reaction. An additional 10 ml of epichlorohydrin 3 was added; reflux was continued for 3 hours, at which point it was judged by gas chromatography (GC) traces that f: was complete. The contents are cooled and the salts are removed by suction filtration. Remove the solvent on the spinner_gasifier. The residue was taken up in methyl isobutyl ketone and rinsed with 5% NaOH (2 × 400 ml). The organic phase was dried over magnesium sulfate. The solvent was removed on a 6CTC rotary gasifier. The yellow oil was distilled on Kuge 1 rdhr |: placed at 1 G. It / 0.1 mm Hg was distilled to provide a clear, colorless oil: 176.56 g, 66% yield). H-NMR and IR spectra were consistent with the expected structure.- . Decomposition of ethyl ester: In a liter immersed in a water-bathed one-necked flask with a magnetic stirrer: 3-glycidyloxybenzoic acid (60 g), 0.66 N K0H (400 ml), and epoxy hexane (45 ml). Allow the mixture to stir for 1.5 hours. At this point, borrow the plutonium material on a reverse phase TLC (Whatman MKC1SF reverse phase plate, and wash the solution with 25 ml of f / furan / 25 ml). Water and 10 drops of concentrated phosphoric acid) disappeared as determined to be completely within the rotary gasifier's paper size, using China National Standard (CNS) A4 specifications (210 parent 297_ 曦 _) ί Please read the note on the back first (Fill in this page again)-Install.

-5T Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, printed 438874 A7 B7__ 5. Description of the invention (IS > reduce the mixture to a minimum volume of 30 t! 30 minutes 鉱 0 the residue was rinsed with ether (to Remove any unhydrolyzed material). Then the aqueous layer was acidified to pH ~ 2 with 50% sulfuric acid. Ammonium sulfate was added to almost saturate the aqueous layer, at which point the product began to melt. The product was extracted into ethyl acetate. S ethyl ester (EtOAc) (2X ~ 500ml). Remove the extender on a rotary gasifier, and then use Kugelrohr to remove a small amount of solvent and water. 1 H-NMR and R required product structure, ... 3 ^^. 〇

Versamine 552 α, 〇 > -bis (3-glycidyl_: oxybenzamide preparation: one liter equipped with a mechanical stirrer, 250 ml slow addition funnel, condenser and nitrogen flusher FeiVersamine 552 (47.22 g) in a three-necked flask. To this was added 250 ml of CH212, followed by 3-glycidyloxybenzoic acid (35.04 g) and HOBt 1-hydroxyphenyl azide, 2.4 388 g). Extra 0112 (: 12 washes. This mixture was stirred for 15 minutes, and then a solution of 40.80 g of dicyclohexylcarbodiamide (DCC) in 200 ml of CH2C12 was added dropwise to the reaction. At the beginning of adding DCC, The precipitation of by-product dicyclohexyluria I (DCU) was observed within 15 minutes. The progress of the reaction was monitored by IR spectroscopy, and no appreciable change was detected between 4 and 5 hours of reaction time. Then added 5 1% acetic acid in water (5 ml) quenches the excess DCC, and continues to stir until the absorption of DCC in the Ιβ trace has disappeared (~ 1.5 hours). The solution is cooled and the DCU is removed by suction. The solvent was then removed on a rotary gasifier of 30¾. The residue was taken up in EtOAc. Rinse with 5% NaHC03 (3 x 400 mL), and refrigerate the organic phase overnight. The resulting solution is then ashed with 5% NaHC03 (1 X 400 mL), then 2% triethylamine (1 X 200 mL), and finally This paper uses China National Standards (CNS) A4 specifications (210X297 mm) for this paper. I-18- I--ίϋ. _ Pack one * Order IIII \ ί --- (Please read the notes on the back before filling in this Page) 4388 7 4 at ___B7_____ 5. Description of the invention (16) Rinse with water (IX 400 ml). The organic layer is treated with ammonium sulfate, filtered, and then applied on Amberlys t 15 ion exchange resin (H + form, ~ 100 ml). Dry for 1.5 hours. The resin was removed by filtration. The product was dried over magnesium sulfate, filtered, and the solvent was removed on a rotary gasifier. The remaining solvent was further borrowed by a Kugelrohr device (8 (TC / 0.25 mm Hg). Column / 20 minutes) to remove. The viscous amber oil (7 g, 91% yield) was characterized by 1R, 4 and ^ C-NMR and found to be consistent with the pre-destructed structure. The epoxy resin content was measured as WPE = 481 (Theoretical WPE = M3) 〇Cao Example 1ί 4,7,10-trioxo-1,13 "tridecane diamine 〇c ω-Bis (3- {Please read the note ^^ on the back before filling this page) Preparation of glycidyloxybenzamine (epoxy resin F)

Employees' Cooperatives of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs * ^ This compound was prepared in a manner similar to that of Example 1. 3-Glycidyloxybenzoic acid was prepared as described in Example 1 t. Stirrer, thermometer, slowly add a 250 ml multi-necked flask with a funnel and a nitrogen washer and pour 3-glycidyloxybenzoic acid (11.01 g, 0 ··) in 50 ml of dichloromethane. 101 mol). Diamine (11.01 g, 0.05 mol) and 25 ml of dichloromethane were added. A slight exotherm was observed. The reaction mixture was cooled to 0 in an ice bath, at which time 1-hydroxyphenyl azide (1.35 g, 0.01 mole) was added ', followed by the addition of 1,3-bis in 2.5 ml of dichloromethane over 5 minutes. Cyclohexylcarbodiamine DCC (22.9 g, 0.1111 mol). The addition funnel was washed with an additional 25 ml of dichloroform. The reaction temperature was maintained at 5-20 eC. 〇1 After 5 minutes, the paper was observed to the dicyclohexyl urine paper standard, using the Chinese National Standard (CNS) A4 specification (21〇X29J ^^) 438874 A7 B7. Printed by the Industrial and Commercial Cooperatives. 5. Description of the invention. (17) Signs of the by-products of the reaction. 0 The reaction is monitored by IR and the mixture is passed after three hours: the reaction time, and the solvent is removed on a rotary evaporator under the air. 〇The product was dissolved in 200 ml of ethyl acetate, and 12 ml of water / 3 ml of acetic acid was added to this in three portions over 2 hours, and stirred to quench the excess DCC, which was IR (2112 cm- 1) Make sure c. Then rinse the organic layer with saturated sodium bicarbonate (4 × 100 ml) and saturated sodium sulfate (1 × 100 ml). The organic layer was dried over magnesium sulfate and filtered on Ce〗 ΰ (celite). The solvent was removed on a rotary evaporator at 8 ° C under empty space. The substance was completely removed on a kugelrohr device (90eC / 0 * 25fmHg). The product was separated into a thick yellow oil (2 5.65 g, 90¾ yield). The epoxy resin content was measured as WPE = :: 14 (theoretical WPE = 2 86). The product was characterized by IR and 1H-MMR spectrometry. Example 111 In this example, Glycidyloxybenzyl reacts with a dimer acid (sold by Henkel under the trade name Empol 1024); forms bis (glycidyloxybenzyl) esters of dimer acids. Dimers of dimer acid Preparation of (3-glycidyloxy t methyl) ester (epoxy resin B-1)

This paper size applies to China's national gradient (CNS > A4 size (2l0X29Zf | t) ------, ---- ^ 1 ----- 1T ------ S5t · (Please first listen (Please read the notes on the reverse side and fill in this page) Please contact the Central Government Bureau of the Ministry of Economic Affairs to pay for the cooperation Du Yin 11 4388 7 4 A7 ___B7___ V. Description of the invention (l8) 3-Glycidyl benzyl alcohol · * This epoxidation step was performed similarly to that described in Example I. Into a two-liter multi-neck flask equipped with a mechanical decanter, a condenser, and a thermometer, epichlorohydrin (277 ml, 3.5 12 moles) was injected. And 250 ml of methyl ethyl ugly. Add solid 3-hydroxybenzene [alcohol (200 g, 1.61 mol) and wash with 500 ml of methyl ethyl ugly. Then add potassium carbonate powder (320 g, 2.31 mol, in Dry in an empty oven to 120 t: / 3 hours). The mixture was heated to a lighter reflux temperature (~ 80t :) with an oil bath. After 6 hours at the reflux temperature, the absence of starting phenylalcohol in the GC trace (5 m glass capillary, 150 to 200 eC rate in minutes) was determined to be complete reaction. The mixture was cooled § room temperature and filtered with methyl Rinse with ethyl alcohol. Remove the release agent on a rotary gasifier and re-dissolve the residue in methyl isobutyl ketone (350 ml). 0 pieces of 5% NaOH (1 x 2000 ml) rinse the organic layer and Causes severe emulsification. Allow the system to settle and remove the entire aqueous layer. Then rinse the organic layer with 10% sodium sulfate (5 x 200 ml) until the pH is ~ 7. The organic layer is dried over sodium sulfate, filtered, and 8 (The solvent was removed from the rotary gasifier of TC. The distillate was collected on the Kug: lrohr unit at 120 to 140 · 0/2 · ϋmm Hg (110 mm Hg was first tried to distill) as the product c The clarified almost colorless oil (190.6 g, 66% yield) was characterized by IR and U13C-NMR and found to confirm the specified structure. The epoxy resin content was measured as WPE = 180 (theoretical WPE = 180). Preparation of double (3-glycidyl chloride, chlorate, beetle, and some) j (epoxy resin B-1): a mechanical stirrer, a thermometer, and slowly add the paper size to the paper ^ National Standards (CNS) Μ Specifications (210 × 29 · 7 | ^) —.ϋ I 1 · —JII Packing II —Booking —i— I ^ (Please read the note $ on the back before filling Page) 4388 7 4 A7 B7 «Central Ministry of Jibei printed for shellfish consumer cooperatives V. Description of the invention (is) Inject 3_glycidyloxybenzene with a one-liter multi-necked flask using a funnel and a nitrogen flusher Methanol (91.62 g, 0.509 mol) and Empo] 1024 dimer acid (143.71 g). 250 ml of 0112 .:] 2 and 〇〇〇〇〇 (dimethylamino sulfanimide; 0.61 g , 1 mol%, based on C0 0 H), and the mixture was immediately cooled in an ice bath to maintain the temperature throughout the reaction at 4 to 0 in a one-hour period by slowly adding a DCC solution (DCC) via a slow addition funnel. : 104.85 g, 0.509 ml, at 60¾ liters of CH2C12 *) 〇 Four hours after the slow addition was completed, the g_p absorption in the IR trace became maximum and the DCC absorption was minimum. Then the reaction mixture was filtered and washed with CH2Cl2. The filtrate was stirred on 30 ml of Amberlyst 15 ion exchange resin (按, form) and stirred for 30 minutes and filtered. To this filtrate was added 50 mM aqueous acetic acid (5 ml), and it was stirred until DCC lost in the IR trace (30 minutes). To this was added solid sodium bicarbonate and stirred until P "was ~ 70. It was filtered to remove salts and the filtrate was stored in a cold storage tank. The organic layer was dried over magnesium sulfate and filtered and washed with CH2C. The solvent was removed on a rotary gasifier and then on a Kugelrohr unit (110 ^ / 0.25¾ mHg). The final product was a brown oil (217.8 g, 9.% yield), and the specified structure was confirmed by 1R, iH and " C-NMR spectrometry. The epoxy resin content was measured as WPE = 448 (theoretical WPE = 4 53) 〇 Dimer acid bis (.2-Glycidyloxyxan: methyl) -----------: ---- ^ ------ 1T ---- -^ J _ (Please read the notes on the back before filling out this page) Preparation of ester (¾ oxygen resin)

438874 A7 B7 V. Description of the invention (20) Preparation of 2-Nylon-glyceryloxybenzyl alcohol printed by the Ministry of Economic Affairs of the Tiegao Automobile Bureau Λ Industrial Consumer Cooperative Co., Ltd. • This compound is prepared as above, except that The 2-hydroxybenzyl alcohol product was separated and purified by distillation (36¾ yield). It was characterized by IR and 1 H-NMR spectrometry. The epoxy resin content is measured as WPE = 18D. Bishenic acid bis (2-glycidyloxybenzyl) _j: Preparation: This material is prepared exactly as above, except that 2-glycidyloxybenzyl alcohol is used. . The product was separated into 90% yield and characterized by IR and 1 H-NMR. The epoxy resin equivalent weight was measured as WPE = 456 (theoretical WPE = 450). Preparation of bis (4-glycidyloxymethyl) ester of dimer acid (epoxy resin B-3) 〇y— C. 34 -(4-Glycidyloxy preparation of a benzyl alcohol: This compound is prepared as described above, except that the starting phenol is 4-hydroxybenzyl alcohol. The product is separated and purified by distillation. This material is formed at this point. A white crystalline solid (45% yield). Qualitative analysis was performed by IR and iH-NMR spectroscopy. The epoxy t-lipid content was measured as WPE = 179 〇 Dimeric acid bis (4-glycidyloxy certain benzyl) g: Preparation: This material was prepared exactly as above, only 4-glycidyl bismuth group was used. Benzyl alcohol. The product was separated into 91% yield and characterized by IR and U MR. The epoxy equivalent is measured as WPE = "5 (theoretical WPE = 45〇) 〇 ------: '----- meal ------. 1T ------ ball. (Please First read the note f on the back, and then fill out this page.) The standard of this paper is Chinese national standard {CNS > A4 specification (210X292; ^^) 438874 A7 B7 V. Description of the invention (21)

Example IV In this example, diisocyanate i from dimer acid: (sold by Henkel under the trademark DDI-1410) and H2-diisocyanate dodecane and 3-glycidyloxybenzyl alcohol Reaction to form the corresponding aminomethyl I: ester. Preparation of dimerized diisocyanate bis-0- (3-glycidyloxybenzyl) carbamate (epoxy resin D)

Dimer diisocyanate (DIH-1410, 146.52g · U.4 898 烨 NC NC0 > Weigh directly into a 500 ml multi-necked flask equipped with a mechanical stirrer, thermometer and nitrogen flusher. 0 Then add 3-glycerol oxybenzyl alcohol (90 g, 0.499 6 moles) and U0 ml tombenzene. Made from a plastic two small straws and discarded to this heterogeneous mixture Loga-drops Dibutyltin dibutyl laurate (DBTDL). The mixture became completely clear and homogeneous 20 minutes after the addition of DBTi L. 0 A slight exotherm was observed to 28 X when the flask was submerged in cold water. The temperature was not allowed to exceed 30 eC. 〇 After a reaction time of seven hours (NC0 disappeared in the IR trace), the reaction mixture was passed through a silica column in a one-liter slow addition funnel. The latter was prepared by first ~ 250 ml of 30-60 sieve silica The stone was slurried in EtOAc, and then layered on top of ~ 150 ml of 70-230 sieve silica. The product was washed with ~ 1.5 liters of EtOAc. The solvent was first placed on a rotary gasifier and then in a Kug] rohr device. (IK Zhang scale is applicable to China National Standard (CNS) A4 specification (210 > &29; 29_ ^ 考) — ------------- ^ ------ 1T-X 锖 read the note on the back ^^ item 畀 fill in the note 肓) * 济 部 t 央 央 准 ί Industrial and Consumer Cooperatives, Printed Oxygen and Chemicals, a 4388 74 A7 B7 V. The description of the invention (22) 128 · 0! / 0.1 mm Hg is removed. 0 The product is a pale yellow viscous oil (231.5 g, 98.6¾ Yield), solidified when stored in a cold E device and the structure was determined by 1 R, 1 H, and 1 3 C_NMR spectroscopy. The measured epoxy resin content was WPE = 475 (theoretical WPE = 479). Preparation of bis-0- (3-glycidyloxybenzyl) carbamate (epoxy resin K) of dodecane cyanate C12 Rugged} Human ^^ 1,12-diisocyanate Dodecane (14.58 g, 0.0577 mol), 3-glycidyloxybenzyl alcohol (21.86 g, 0.1 21 mol), and 32.5 ml of toluene were weighed into a pair equipped with a thermometer and a magnetic stir bar and a rubber septum. An airtight milliliter filled flask was stirred. In a lt) -2 (TC cold water bath), the turbid mixture was stirred. At this time, a 9-inch glass suction end was immersed in the tin catalyst, and then the end of the straw was mixed into the reaction mixture "λ Tin dilaurate After the ester 0 was mixed for 5 hours, the mixture turned into a solid white mass. The solid was broken with a spatula and introduced into 50 ml of E | benzene to facilitate stirring. After a total reaction time of 7 hours, IR traces indicated that All the isochate functional groups have been reacted. The milky mixture is transferred to a single-necked rb flask using toluene (80 ml) and dichloromethane (WO ml). Remove the solvent on a rotary evaporator. Continue removing solvents and unreacted on the KugelrtTir device (120 X; 0.1 mm Hg); alcohol. Product content (please read the notes on the back before filling this page) This paper uses the Chinese national standard (CNS > A4 size (210X29 $ | n 438874 A7 B7) V. Description of the invention (23 _ 成 99% Yield of a white solid, and qualitatively measured by 1 {1 and 1114 {^: spectrophotometry. Epoxy resin equivalent is WPE: 319 (theoretical WPE =; 06.31). Example V In this example, glycidyloxy Benzyl alcohol I. Preparation of various flexible diacids. Preparation of bis (3-glycidyloxybenzyl) ester of undecanoic acid, lauric acid and sebacic acid (epoxy resin C)

χ (8,9,10 ------------- ^-Please read the note on the back before filling in this note) * tr. I Industrial Consumer Cooperatives, Central Bureau of Fengfeng, Ministry of Economic Affairs 5- system

Undecaneedioic acid, lauric acid, and adducts of sebacic acid can be purchased from Aldrich Chemical Company under the tradename CORFREE M1, and are DuPont products. The bis (3-glycidyloxybenzyl) ester was prepared as described above except that CORFREE M1 was used instead of the dimer acid. The yield of the product was 98%, and it was characterized by IR and iH-NMR spectrometry. Measure epoxy equivalent weight fv WPE = 2 6 9.4 (theoretical WPE = 265.5) 〇3,6,9-trioxoundecanoic acid bis (3-glyceryloxybenzyl) ester (epoxy Preparation of Resin H). Fly X

This paper size uses Chinese national kneading rate (CNS M4 specification (210XW $ |: _) 438874 A7 B7

V. Description of the invention (24) 3,6,9-trioxoundecane diacid is an experimental substance that can be purchased from 110 ° (6) and is used to replace dimer acid. Fish: Diacid (30 g) and 3-glycidyloxybenzyl alcohol (44.54 g) were combined with dicyclohexylcarbodiamidate (50.88 g) as described above and its catalytic properties in difluoromethane 4-dimethylamino α-pyridine (DMAP) (0.29 98 g) Degree: The product was separated into a yield of 89%, and the epoxy resin was measured by IR and 1 H-NMR spectrometry. Equivalent is WPE = 285.1 (theoretical WPE = 286.3). Preparation of bis (_3-glycidyloxymethyl) octanoate (epoxy resin. 1) II

------ „---- ^ 1 — (锖 Please read the precautions on the back before filling out this page) Central Bureau of Standards of the Ministry of Economic Affairs βίχConsumer Cooperation Du Printing Pack " XX Compound 1 Preparation of this product It is similar to epoxy resin C and fluorene and can be used as a reactive diluent. Caprylic acid (30 g) and 3-glycidyl I :: oxybenzyl alcohol (38,24 g) are added to dicyclohexylcarbodiamine ( 4 3.74 5 :) Treatment with catalytic DMAP ('0.257 231) in dichloromethane under dehydrating conditions. The product was separated into 98% yield as described above and qualitatively measured by 1R and spectrometry. Epoxy was measured Resin equivalent is WPE = 3ϋ6.2 (theoretical WPE = 306.4). Preparation of bis (3 glycidyloxybenzyl) ester (epoxy resin J) derived from poly (tetrahydrofuran) trimer

This paper is scaled to the standard of Chinese households (CNS) A4 Washing (210X297 public dream) 0 Order 4388 7 4 A7 A7 ______B7_ V. Description of the invention (25) For a machine equipped with a mechanical stirrer, thermometer, cold yttrium, A 250 ml flask equipped with a nitrogen flusher was charged with poly (tetrahydrofuran) terpolymer (p0ly THF-25 0, available from BASF; 0H # = 479.2; 25 g, 0.213 mol hydroxyl functional group), succinic anhydride (21.5 G, 0.2156 mol), and toluene (20 ml). Heating to maintain a gentle reflux temperature. After a reaction time of 3.5 hours, the anhydride absorption has disappeared from the IR traces. The mixture is cooled and additional is added to this. 70 ml of toluene, 3-glycidyloxybenzyl alcohol (39.32 g), and DMAP (0.268 g). The mixture was further cooled to 0-5C, at which point the addition of the DCC solution (44. SO grams of DCC was dissolved in 50 ml of toluene). After 35 minutes, the addition was completed, and the mixture was stirred for 4 hours. IR traces showed no change in DCC and ester absorption from the previous profile, so the reaction was filtered to remove dicyclohexyl. Urea '〇 added Amlnrlyst 15 (Η + form, 14 mmol ), Stirred for 30 minutes and filtered square 6 plus acetic acid (2 ml of 50% aqueous solution) and stirred until the residue DCC spike ί; I R disappears. Solid sodium bicarbonate and then sodium carbonate were added until pH 7 was obtained. The mixture was filtered, dried over magnesium sulfate, filtered, and the solvent was removed on a rotary evaporator. The solvent and unreacted benzyl alcohol were further removed from the Kugelrohr device (122 mm Hg) in the Ministry of Economic Affairs and printed by the Gap Bureau Consumer Cooperatives _ {Read the notes on the back and then fill out this page). Health Λ: The product is separated into 96% yield, and qualitatively determined by UMK and III spectrometry, and the $ has epoxy equivalent WPE = 394 (theoretical WPE = 380).

Example VI This example provides the preparation of an epoxy resin T that does not contain terminal benzene groups. The di-bis- (glycidyl) carbamate (epoxy resin c) of a dimeric diisomate: The paper size is prepared using the Chinese National Standard (CNS > A4 size ([10x 297 ^ # "'4388 7 4 A7 B7 V. Description of the invention (26)

Compound C Printed by the Central Labor Bureau of the Ministry of Economic Affairs, Zhengong Consumer Cooperative. Dimeric diisocyanate (DDI-141D, 200 g, 0.6686 mole NCO) was directly weighed into a device equipped with a mechanical stirrer, thermometer, and nitrogen flusher. Put 500 ml in an RB flask. Water glycerol (68 g, 1.003 mol) and 100 ml of toluene were then added. Add a drop of tin dibutyl laurate (DBTDL) to the heterogeneous mixture from a plastic straw that was discarded after use. 80% of the mixture became completely clear and homogeneous after DBTDL was added. 0 The flask was submerged in a cold water bath. A slight exotherm was observed at 30 ° C, and some dry ice was added to keep the temperature below 3 (TC ° after a reaction time of 7.5 hours (NC0 disappeared in the IR trace). Slowly add the silica column in the funnel. The latter method is to first pulp ~ 250 ml of 30-60 sieve silica in EtOAc, and then layer this ~ 150 ml of 70-230 sieve silica. The top 0 product was washed with ~ 1.5 liters of EtOAc. The solvent was first removed on a rotary gasifier and then on a Kngelrohr unit (8 (TC / 2.0 mm Hg). The product was a pale yellow viscous oil (245.6 G, 99.8% yield), and the structure was determined by 1R, H, and nC-NMR spectrometry. The epoxy resin content was measured as WPE = 405 (theoretical WPE = 368). Preparation of diglycidyl dimer ( Post-epoxy resin E) 1 > ^ ° ° ^ < 1 This substance can be Epone 871 from Shell Chemically available or as described above-IIII i 1 (please read the "$" on the back side before filling out this page) The paper size is free to use China National Leap Year (CNS) 8-4 Specification (210X29J ^ |) Central Ministry of Economic Affairs搮 Rate Bureau Shellfish Consumer Cooperative Print 438874 A7 B7 V. Description of the invention (27) Prepared as a low-air pollutant. In either case, the substance behaves similarly in terms of curing rate and thermal stability. Low-air dimer acid (Empol 1024) Preparation of two oleyl esters: A multi-necked round bottom flask equipped with a mechanical stirrer, thermometer, nitrogen flusher, and slow addition funnel was charged with 50.00 g (U.0868 mole) of Empol 1024 dimer acid, 19,29 g (0.2604 moles) glycidol, 200 ml of toluene, and a catalytic amount (0,212 g, 0,0017 mol) of 4-dimethylaminopyridine. The reaction was cooled to 0. — 5 _C, and a solution of 36.48 g (0.1771 mol) of 1,3-bicyclic L-based carbodioxamine in 100 ml of toluene was added over one hour. After the slow addition was completed, the reaction was maintained at 0- 5 to 15 minutes. The reaction solution was then kept at 10-15 C for two hours. It was determined to be incomplete by IR (the ester exists at 17 3 cm · i) and the disappearance of 1.3-dicyclohexylcarbodiamidate (2120 cm〃): 〇 Then the product solution was cooled to 0-5'C , Keep for 15 minutes, and then filter back to remove 1,3-dicyclohexyl urea by-product. Then the resulting solution is cooled to 10-151C and stirred, and 20 ml of 50:50 water: methanol and 34 ml are added to this. Amb βΓ-ΐ yst 15 (Η * form) solution. The reaction was then filtered and the solvent was removed using a rotary evaporator at low pressure. The product was then allowed to dissolve in 30 ml of toluene and stored in a refrigerator overnight, and the solvent was filtered under a cold day, and then the solvent was removed under a low pressure using a rotary evaporator. Residual solvents and residual glycidol were removed using a Kugelrohr device (80TC / 0.1 — 0.2 | :: mHg). The product was separated into an oily substance (46.48 g, 78% yield) and characterized as follows: IR spectrum: 1735 cm. Epoxy equivalent: WPE = 359 (theoretical 値 = 344) 〇 This paper size is applicable to China _ furniture ratio (CNS) A4 specification (210X297 $), I · — — Pack 11 I Order I Ϊ .¾ (Please read first Note on the back, please fill out this page again.) Printed by the Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, f ft 43RR 7 4 V. Description of Invention (28)

Example VII The gas content of the test sample was tested for the total chlorine and hydrolyzable chlorine content of several epoxy resin samples according to the test method described in this specification, and the results are listed in II 0 Chlorine (ppm) Hydrolyzable chlorine (ppm) Combined chlorine (ppm) A 283 26 257 B 319 39 280 3-glycidyloxybenzyl alcohol 805 82 723 C 282 185 97 D 674 352 322 In the table above, 3-shrinking Glyceryloxybenzyl alcohol and]: The derivative of the epoxy resin B refers to the total nitrogen content of the epoxy resin to the beginning of the reaction (often the weight of the epoxy resin when it is converted into this ester). The chlorine content of the epoxy resin B contains i .. almost equal to the calculated dilution factor. For example, 805 ppmx (360/9) 6) = 320 ppm. Therefore, any purification operation that can be performed to reduce the chlorine content of 3-glycidyloxybenzyl alcohol will be available in Low chlorination of ore in finished epoxide finished products. Purification of 3-glycidyl alcohol and certain methanol: In the above preparation of 3-glycidyloxybenzyl alcohol, the product is based on 1: Characterized by UNMR and found to have WPE = 178 and total chlorine = 317 ppm 1 hydrolyzable chlorine = 120 ppm. This product (50 g) and methyl isobutyl S (50 ml) and the paper size are in use »_ house standard (CNS > Λ4 grid (2Ι0 × 29 ^ &) I nn 11 ϋ ϋ n ϋ I ^ I · M.i Please read the notes on the back before filling this page) 438874 A7 ____B7___ V. Description of the invention (29) · (Please read the notes on the back before filling this page) IN KOH (50ml) add A 250 ml flask equipped with a mechanical stirrer and a thermometer. The mixture was thoroughly stirred and heated to 40-4 5 t: 逹 4 hours. The flask was cooled and the contents were transferred to a separating bucket. The phases were separated. And rinse the 栌 layer with 10% sodium sulfate (3 × 100 ml) until ρΗ = 7. The organic layer was dried over magnesium sulfate, filtered, and the solvent was removed on a rotary evaporator. The purified product was 110 kn in the Kngelrohr device: / (0.25 mm Hg). The purified substance was found to have WPE: 177, total chlorine = 129 ppm and hydrolyzable chlorine = not detected. If a fluorene-purified epoxy alcohol product is used to produce epoxy resin B, then epoxy resin B has a total chlorine = 51 ppm. This is calculated as follows: 129 ppmx (360/906) = 51 ppm.

Example W: The flexibility, strength, and rapidity of epoxy resins are tested to determine the suitability of these epoxy resins for microelectronic applications. The method is to measure their use in silver wafers and to bond silicon wafers to Flexibility and strength behind the lead frame of the gold tincture. 0 Adhesive formula printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative: Formulated the sample epoxy resin-a small piece of bonding adhesive containing the following weight: part ring Oxyresin, 30 parts of f-phenol A diglycidyl ether (Bis-A) (a product of Shell Company, sold under the trade name EPON 828), 5 parts of 2-ethyl-4-methylimidazole (2E4MZ); it formula with 80 The weight% silver flakes are mixed until the silver is completely wetted. Mixture Ϊ: Let it air out at room temperature for 15-20 minutes, then let it stand at room temperature, and stir with spread spectrum for 60 minutes. Measure of flexibility and strength Taken from the fast curing ring f ... Resin. The measurement of flexibility is to measure the radius of curvature, which is greater than 300 mm c (the radius of the curvature of the paper applies Chinese National Standard (CNS) A4 specifications (210X29J ^ |) 4 3 88 7 4 A7 ______B7__ V. Description of the invention (3〇) Large> The smaller the wafer bend, This in turn implies that it is a flexible adhesive). The indication of flexibility is also provided by the glass transition temperature (Tg), which is too low for the cured epoxy resin. 0 The strength is based on the small shear strength and the wafer to be bonded. The force required to remove the gold tincture substrate; for these epoxy resin tires, the small piece shear force is greater than or equal to 10 MPa when it is rapidly cured and greater than or equal to 25 MPa when it is cured in the oven. As required by 100% curing When used, these epoxy resins can be rapidly cured. Small pieces of shear force: one side of a silicon wafer (80 x 80 square mils) is coated with an adhesive formulation and placed in a copper lead frame (D / L) ”_., And at 175 t: curing in the oven for one hour. Each specimen was tested for shear strength at 1 ° C after curing. The small piece shear strength was measured with Hybrid Machine Manufacturing's small piece shear tester (type 17 50) / Chatillon DFI 50 iridium force gauge. The force required to remove the sticky pieces is read in kilograms, and converted into ten samples. The average piece of shear force in megapascals is strong. 0 The better piece of shear is 兆 5 MPa or more. 〇Fast curing samples were prepared in a similar way, except that the samples were cured at 180 C on a preheated hot plate. ------ IT > * .. (Please read the note on the back before filling this page) Curvature Radius: Each epoxy resin to be tested is prepared as described, outgassing, and aging. hour. An adhesive was coated on one side of a silicon wafer (200 × 60ϋ square mils), placed on a lead frame, and cured in an 175 ° C oven for one hour. Curvature radius of the cured sample, measured by Tokyo Seimitsu Corporation's SURFFC0M surface texture measuring instrument, and the average of the three samples is reported in millimeters. The preferred radius of curvature appears to be 300 mm or greater. Glass transition temperature: Slope transition temperature (h) is h Perkin Elmer The paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 ^ || Π 4 3 88 7 4 A7 B7 V. Description of the invention (31) DSC measurement. In the pure resin In the case, the sample is preheated to 50 and then quenched to -70 υ 〇 and then heated at a speed of 2 (TC & per minute until Tg is reached. To measure the Tg 'of the cured resin, 5? Parts by weight The 2-ethyl-4-methylimidazole preparation sample was then heated to 2000 ° ('to ensure complete curing. After quenching to -40 t :, the sample was yttrium at a rate of 201C per minute Heat until Tg is reached. The following table 1 lists the small pieces of some samples with strong shear force, rapid curing time, radius of curvature and Tgo. Table 1, (Please read the precautions on the back before filling the page)-Install · 4 %% ^ ^ is fine to turn 1 »Gray I hot box @ 175 * 急速 @ 1βΟβ 洗清 A chip failur e 38 · 3 1.0 points 316 • 10.73 51.93 IB 35.2 15,4 2.0 404 -51.10 -9/46 C 16.3 5.7 1.0 490 -40.03 • 17,63 D 32 · 0 11,3 1,5 323 -28.97 16.82. E 17.3 4.7 2 · 0 344 -39.97 • 25.31 G 42.5 17.4 1.25 334 G " 28.6 11.8 1.75 498 H 32.3 13.6 1.5 428 Β ^-^ 3 ^ Β9B0 · «α; Order

The Central Ministry of Economic Affairs of the Ministry of Economic Affairs of the Central Bureau of Shellfish Consumer Cooperation Du Yin A * Pure and Unmixed Double A Epoxy Resin Example VIII Thermal Characteristic DSC Analysis: Using Perkin-E] mer Differential Scanning!:. The calorimeter borrows DSC analysis test Several samples of epoxy resin formulated as an adhesive: the ability to cure rapidly. Dsc measurement is equivalent to the onset and initiation of heat release from curing. 0 The example is based on the Chinese paper standard remotely using China National Standards (CMS) A4 specifications. (4388 74 B7 V. Description of the invention (32) The formula described in the DSC plate is 180 t: fixed on a hot plate: a predetermined time. Then the DSC traces will be operated to determine the degree of reaction. Residual exothermic 揷: ΔΙΙ initial residual X100% =% curing △ H curing time that initially occurs within a span of 50TC or below refers to the rapid curing of these formulas. The exothermic start and end of the samples are shown in Table 2 And shows the ability of several epoxy resins to cure rapidly when used in imidazole-catalyzed formulations. The data from the DSC curve is shown in Figure 1 as% cure versus time, and the cure rate of each compound of the present invention is shown again. Meet the requirements of t-speed curing. As is generally understood, the steeper the slope of the curve, the faster the curing. 0 For the test sample, the curing order is C ~ A > D > B >] 〇 Table 2 (Fill in this page) Packing and ordering

δΗ kJ / mol E 79 ·. 198-C f 130.0eC 139.9 A 100.0 148.5 131.0 83 · 6 B 97.0 199.0 146.7 76.2 C 92.4 148,4 124.2 87.2 D 100.7 148.4 129.7 84.6 G 108.7 157.8 141.0 82.0 Η 125.4 169,8 147.2 64.9 Note: kJ / mo] = Kilojoules / mol TGA analysis: Thermogravimetric analysis (TGA) • Perdn Elmer TGA sheet is used ^ Lai Zhunjia 29

438874 A7 __B7 V. Description of the invention (33) The assembly is performed on several samples. TG A is the replacement loss when the sample is subjected to a heating cycle. The formulation described in Example VU1 was analyzed at 3 ° C to 200 t: heating and heating for 50 minutes at a temperature increase of 10XJ per minute, and 200 ° C for 30 minutes. The results are shown in the table. 3 is plotted in Figures 3 and 4, and shows that each sample shows far superior thermal properties, whether it is a pure substance or even more significantly in the presence of an imidazole curing catalyst. Table 3 Ring Qing 6 TGA to 175 ° C 1〇 · / 蠓 TGA · / · 囔 Blessing to 200.C ·. TGA% tender loss @ 200 ° C. TGA% gold 1 sand to 200¾ and 2E4MZ E 0.548 1.41 4 * 25 3.356 A 0 * 108 0.299 0.93 0.303 B 0.269 0,547 1.70 0.377 C 0.588 0.682 7J0 1.398 D 0,034 0.196 1.34 ΓΙ--ιι · " ^ ::-丨 · 11 ·· 0.314 Note: TGA = thermogravimetric analysis; 2E4MZ = 2-ethyl- 4-methylimidazole graphical element symbol description A, B, C, D, E, G, H: Epoxy resin paper scale, free use, BI family-like (CNS 丨 A4 specification (2 丨 ximeng) —4 — ^ 1-κ '^ in ϋ Please read the note on the back page first) 11 Central Elevator of the Ministry of Economic Affairs of the People ’s Republic of China 屌.

Claims (1)

ail A8B8C8D8 6. Scope of patent application 0 I) \ ^ 0-C-NA J hi. --------- ^ .- I ------ Order · ------ i I. (Jing Xian first read the note on the back Please fill in this page again) Du Yinlong Where * indicates the point of attachment to the flexible chain; and the flexible chain is Cu-5. Alkenyl or alkenyl groups; and η is an integer of 1-3. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 feet) A8 438874 _ D8 6. Application for patent scope 2 The flexible epoxy compound of the scope of application for item i has the following structural formula: 3. If the flexible epoxy compound of item 1 of the patent application scope has the following structural formula: < Jing first read the precautions on the back before filling out this page) Printed by the Employees' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 0 Wuhe Chemical Aliphatic Oxygen Concentration Item Fan Lizhuan: Please apply the structure such as knot 4 * with a-line. This paper size applies the Chinese National Standard (CNS) A4 specification (2) ϋ X 297 public ") 438874 A8 B8 C8 D8 VI. Application scope 0 0 ^^. 5. If the flexible epoxy compound of item 1 of the patent application scope has the following structural formula: CC. 0 II CT (Jingxian read the notes on the back of the results before filling this page) I --- -Order --------- Line-DuPont Printed by Shellfish Consumer Cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. If the flexible epoxy compound '1 in the scope of patent application has the following structural formula: ϋ η Ί ， 1 1 '乂, J This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 43 88 7 4 as Β8 C8 D8 VI. Patent application scope 7 · If item 1 of the patent application scope The flexible epoxy compound 'has the following structural formula: 8. The flexible epoxy compound' such as item 1 of the scope of patent application has the following structural formula: ο ^ 111 —In -I! K ^^^ 1- nn ^ —. (Xu first read the notes on the back before filling in this tile) 9. If the scope of the patent application has the following structural formula: 0 K Printed by the Central Laboratories of the Ministry of Economic Affairs of the People ’s Republic of China, printed by the Shellfish Consumer Cooperative 1 〇. The flexible epoxy compound 'such as the scope of application for patent No. 1 has the following structural formula: CNS > Λ4 specification (2tox 29-7 including #) ABCD 43 88 74 Patent application scope 11. If the flexible epoxy compound of the first patent application scope has the following structural formula: 1 2. As claimed in the patent scope The flexible epoxy compound of item 1 is used as a binding agent for the application of microelectronics. 0 Binding; Class J. (please read the precautions on the back first and then 5? For this tile) Central Ministry of Economic Affairs Consumption Cooperatives Printed This Paper Standard Use "National Slope (CNS) A4 Specification (210X292 ^^)