TW524816B - Epoxy resins and compositions thereof - Google Patents

Abstract

The specification discloses epoxidized products and compositions of a polyphenol of a phenol and glyoxal wherein the polyphenol prior to epoxidation has an ultraviolet (UV) absorbance of at least 0.260 at 365 nanometers (nm) and/or at least 0.400 at 350 nm. The specification also discloses the manufacture and use of such epoxidized products.

Description

524816 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (丨) This application is a partial continuation of US Patent Application No. 09/298153, filed on September 22, 1998 (which was issued in 1999) April 23, 2011). The present invention relates to an epoxidation product of a phenol-glyoxal condensate, wherein prior to epoxidation, the condensate already has ultraviolet (UV) absorption of at least 0.260 at 365 nm and / or at least 0.400 at 350 nm. The invention also relates to the production and use of the epoxidation product, and to a composition containing the epoxidation product. In the method for manufacturing the condensate of the present invention, an acid catalyst is used to react a molar excess of phenol with glyoxal at a temperature of about 8 ° C to 10'0 ° C, wherein the acid catalyst can be Removed from the reaction mixture by distillation at a temperature lower than about 170 ° C. The reaction was performed by continuously or at least twice adding glyoxal to the phenol, with all of the glyoxal p-phenol added The total molar ratio is about 0.15 to 0.22. During the reaction, the water in the reaction mixture is gradually removed by distillation. Less than about 70% of the total glyoxal to be reacted with phenol is at any time Is added to the reaction mixture. Also, at any one time, less than about 70% of the total aldehyde units supplied to the reaction mixture are present in the reaction mixture along with any ketone units formed in the reaction. The dialdehyde molecule contains two aldehyde units. As defined below, one way to measure the aldehyde units together with the ketone units formed is by measuring the aldehyde equivalent. The aldehyde equivalent in the reaction mixture is kept below total glyoxal. Amount (which is to be added to make the condensation product About 70% of the aldehyde equivalent in the reaction mixture). When the total glyoxal 3 (Please read the precautions on the back before

Order: • Line. This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 524816 A7 _ B7 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs When at least about 85% of the aldehyde equivalents or aldehyde units added to the reaction mixture used to make the condensation product have reacted, the catalyst is removed from the reaction mixture. Removal of the catalyst also removes all or part of the water in the reaction mixture. In the case of trichloroacetic acid as a catalyst, after about 85% of the aldehyde equivalent has been reacted and before the catalyst is removed, a sufficient amount of an alkaline substance is added to the reaction mixture to neutralize the three HC1 released by chloroacetic acid. After the catalyst is removed, the reaction mixture is heated at a temperature of about 175 ° C to 200 ° C for about 0.25 to 3 hours. Moreover, after the catalyst is removed, any unreacted phenol and water are removed at a temperature higher than the temperature required to remove the catalyst. .. The epoxidized phenol-glyoxal condensate laminate can be prepared using conventional methods and ingredients, but using a phenol-glyoxal condensate or its reaction product, such as an epoxidized or glycidyl derivative, as the A part of the resin matrix, in which fibers have been embedded in the resin matrix. Back 5l and previous techniques are polyvalent, such as polyhydric phenols prepared from the condensation reaction of glyoxal and a molar excess of phenol in the presence of an acid catalyst, which have been found to have uses in the same way as other polyphenols, especially It is used for the preparation of epoxidized polyphenols, which can be used in coatings and electronics and as adhesives and laminates in the manufacture of printed circuit boards, for example. Vultures of the invention will typically contain tetraols from about 0 to about 6% and generally from about 1% to about 6% ethane. When the phenol is phenol itself, the tetraphenol-based (p-phenyl) ethyl compound is also called TPE. Although 4 paper sizes of phenol_glyoxal reaction are applicable to China National Standard (CNS) A4 (210 X 297 mm)

524816 A7 B7 V. Description of the invention ii) The reaction product is a mixture, but various polyphenols (such as TPE) and other components can be crystallized from the solution by conventional techniques. Therefore, by the methods well known in the art, the content of tetraphenol ethanes, such as TPE in polyphenols, can be greatly reduced to essentially zero without sacrificing the optical properties provided by the present invention. For example, in this regard, it is effective to use a solvent such as a mixture of an alcohol-aromatic hydrocarbon mixture and a water-miscible ketone-water mixture. The composition system of the present invention is particularly useful when automatic optical inspection (AOI) is used for quality control of the laminate. The polyhydric phenols of the present invention can be used alone or in combination with phenolic resins, or can be used on AOI after epoxidation of polyhydric phenols, like the addition of epoxy resin, and the addition of epoxidized polyphenols and phenolic resins. Thing. AOI is typically performed by measuring: fluorescence in a wavelength range of about 450 nm (nanometer) to about 650 nm, especially at an excitation wavelength of about 442 nm; and / or ultraviolet (UV) light at a wavelength of about 350 to 365 nm absorption rate. The applicant has found a set of process conditions, together with monomers and some catalysts, which can be used to obtain polyphenols and their epoxidized derivatives, which have UV absorption and / or fluorescence within the wavelengths commonly used for AOI quality control It is substantially higher than the phenol-glyoxal condensate prepared by other methods. Photoimageable materials are used with these condensates. High UV absorption is suitable for the manufacture of laminates used in electronic applications, such as high density multilayer printed circuit boards. The advantages of the present invention include: (a) preparing a polyhydric phenol which can be subsequently epoxidized and essentially does not contain metal ions, without the need for catalyst filtration or neutralization and water washing steps, wherein the recovery of phenol is simplified, and In the case where the catalyst does not need to be neutralized with metal ions, it will increase the yield of the reactor; (b) the preparation of polyhydric phenol is applicable to the Chinese National Standard (CNS) A4 specification (21〇χ 297 mm) at 5 paper sizes ( (Please read the precautions on the back first, then this page) Order ·-丨 Line-Printed by the Consumers 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 524816 A7 B7 V. Description of the invention (叱) and its epoxidized derivatives' They show improved optics Properties, such as high fluorescence and / or UV absorbance at the wavelengths used by AOI; and (C) Preparation of polyhydric phenols with increased solubility in organic solvents. The high fluorescence and high UV absorption properties of the epoxidized product and the composition containing the epoxidized product are due to the high fluorescence and high UV absorption of the phenol and ethylene oxide of the present invention. Prior art has revealed many methods for making polyphenols and their epoxidized derivatives. However, the prior art does not use a combination of monomers, reaction conditions, or catalysts of the present invention, and the applicant uses the combination to obtain the desired properties of the products of the present invention. Moreover, the prior art has not revealed a phenol-glyoxal condensate or an epoxidized derivative 'thereof such as a glycidyl derivative having desirable optical properties of the invention. ~ The following terms used herein have the following definitions: (a) "Phenol-glyoxal condensation product" means a phenol-glyoxal reaction product produced by the method of the present invention, wherein the condensate contains less than 5% of Unreacted phenol, preferably less than 3% unreacted phenol, and especially less than 1.5% unreacted phenol. (b) "Aldehyde equivalent" is a method for measuring aldehyde units, and refers to the aldehyde units and the reaction mixture when they are measured by the method described below and in the reaction mixture or in the Intellectual Property Bureau staff of the Ministry of Economic Affairs. Print any ketone units that may be formed in or to be added to the glyoxal. This measurement is usually reported as a hundred percent ratio of the aldehyde equivalents reacted, which is compared to the aldehyde equivalents added or to be added to the reaction mixture. If the measurement of the aldehyde equivalent in the added mixture of glyoxal and phenol is 表现 to show X aldehyde equivalent and the measurement after the reaction of the reaction mixture is 値 to show 1 / 2X aldehyde equivalent, then the aldehyde equivalent in the reaction mixture It is 50% of the added person. During the reaction of this 6th scale, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applicable. 524816 A7 B7 V. During the description of the invention (<), some keto groups may be formed, which are included in the aldehyde equivalent Is measured within the tritium and is considered part of the aldehyde equivalent here. The aldehyde equivalent was measured by taking 1.0 g of the reaction mixture and diluting it with 50 ml of methanol. Dilute sodium hydroxide was then used to adjust the pH to 3.5. Then, add 25 ml of 10% hydroxylamino hydrochloride to the pH-adjusted sample while stirring. The sample was stirred for 10 minutes, and then the sample was titrated back to pH 3.5 with 0,25 equivalent concentration (N) of sodium hydroxide. Calculate the aldehyde equivalent using the milliliter (titration) of the sodium hydroxide solution required to back-titrate the sample to pH 3.5. The milliliter of the sodium hydroxide solution used in the titration was adjusted by correcting the titration of methanol and hydroxylamine hydrochloride used in the test with sodium hydroxide, and this was called a millimeter blank. Then determine the aldehyde equivalent of the sample by the following formula: (2.9x0.25Nx (mlS sodium hydroxide titration minus the sodium hydroxide mls used in the titration blank). Then the amidine obtained by this formula and the aldehyde obtained by the method Equivalents are compared, and the formula is based on one gram of unheated catalyst-free mixture of phenol and glyoxal (based on the weight ratio of glyoxal and phenol used) until time or the time in question, 俾Determines the percentage of aldehyde equivalents of the reaction. Unless otherwise specified, fluorescence measurement in this context means: For a solution of 0.05% of the substance dissolved in tetrahydrofuran (THF), using a cm 1000 instrument, at about 450 When measuring in the range of 650nm, with a detection time of one second at an excitation wavelength of 442nm, its maximum count per second. Cm 1000 is Cure Monitor 1000, which is an instrument manufactured by Spectra Group Co., Ltd. in Maumee, Ohio. The detection time is at the specified 7 paper sizes. The Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applicable (please read the precautions on the back before this page). Social printed 524816 A7

5. Description of the invention (i) at its wavelength 'its exposure time. Counting is the two basic units used by many optical measurement devices for data output, and it is a digital processing of accumulated signals. If the CCD detector used by Spectra Group, Inc., of Maumee, Ohio, and for the information published here is taken as an example, light will generate a charge on the detector, which is then read by a digitizer. The digital converter is set to record a count of approximately every 10 charge (electron) units it reads. Fluorescence measurements are based on a variety of different materials, such as those described in the tables herein, rather than absolute tritium. Therefore, the fluorescent units of polyphenols in any one of the tables below are relative to those of other polyphenols in the same table, and the polyphenols in different tables cannot be compared with each other. The material in question was dissolved in THF (tetrahydrofuran) at a concentration of 10 mg (mg) / 100 mi (ml) to prepare a sample, and an absorbance measurement was performed at 35 nm or 365 nm to obtain a UV absorbance from the sample. value. SUMMARY OF THE INVENTION In one aspect, the present invention is directed to a method for preparing a polyphenolic product that can be subsequently epoxidized. The polyhydric phenolic product is prepared by increasing the contact and reaction of glyoxal with an excess of phenol in the presence of an acid catalyst. The catalyst can be used at a temperature below about 170 ° C. Distilled to remove from the reaction mixture. The reaction temperature used in the reaction is about 8 (rc to about 10 (rc). Water is gradually removed from the reaction mixture by distillation, while maintaining the aldehyde equivalent in the reaction mixture to less than about 70% (in order to produce polyphenols) The aldehyde equivalent to the total amount of aldehyde to be added to the reaction mixture is used as the reference.) Added to the reaction 8 This paper size applies the Chinese National Standard (CNS) A4 specification (21〇X 297 public love) (Please read the note on the back first) Please fill in this page for further information)--Line-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 524816 A7 ----------- B7 V. Description of the invention (1) The molar ratio of glyoxal in the mixture is per unit One mole of phenol has about 0.15 mole to about 0.22 mole of glyoxal. When at least about 85% of the aldehyde equivalents that have been added to the total glyoxalic acid used to make the condensation product have been reacted, borrow Distillation to terminate the reaction. When trichloroacetic acid is used as the catalyst, 'add alkaline substances to the reaction mixture before neutralization of the catalyst to neutralize any hydrochloric acid that may be released during the removal of the catalyst. In addition to the catalyst, some or all of the water in the reaction mixture is removed. After the catalyst: (a) Distill free or unreacted phenol from the reaction mixture so that the product contains no catalyst and contains less than about 5% phenol; and (b) above about 175 ° C The reaction mixture is heated to a temperature of about 2Ό0 ° ς for 0.25 to 3 hours. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In another aspect, the present invention is directed to the preparation of a polyphenolic product that can be subsequently epoxidized. A method comprising: adding and reacting a solution of phenol and about 0.06 to 0.11 mole of 40% glyoxal dissolved in water in the presence of about 2 to 5% of oxalic acid, wherein the mole of glyoxal is The number is based on the mole number of the phenol added; after a reaction time of about 1 to 5 hours, the reaction mixture is first distilled to remove about 8% to 12% distillate; and 0.06 to 0.11 moles are added. Ear glyoxal (based on the phenol added), so that the total amount of glyoxal added is about 0.15 to 0.22 mole per mole of phenol. Calculated from the time when the first distillation is started, Continue the reaction for about another 5 to 5 hours, and distill the reaction mixture a second time to recover about 6% to 12% of the | And continue the reaction until at least about 85% of the aldehyde equivalent in the total amount of glyoxal (which is to be added to prepare the condensation product) has reacted. The reaction temperature of phenol and glyoxal, including distillation, is 80 ° C to 100 ° C. As discussed above, after at least about 85% of the aldehyde equivalent has reacted, increase the temperature and apply the Chinese National Standard (CNS) A4 specification (210 X 297 mm) at about 9 paper sizes " ~ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 524816 A7 __ B7 V. Description of the invention (2) The reaction mixture is distilled in a temperature range of 130 ° C to about 170 ° C to remove catalyst and water. Removal of unreacted phenol remaining after catalyst removal by distillation at a temperature higher than the temperature used when removing the catalyst, so that the free actinide in the polyphenol condensate does not exceed about .5%, and The reaction mixture is heated at a temperature of about 175 ° C to 200 ° C in a vacuum for about 0.25 to 3 hours to produce the polyphenol of the present invention. In yet another aspect, the present invention relates to a method for preparing an epoxy resin in the form of a glycidyl ether of a polyhydric phenol as described above, which is an epoxidation of polyhydric with a halogen alcohol in the presence of an alkali metal hydroxide such as sodium oxide. John. In another aspect, the present invention relates to a glycidated polyphenol of phenol and glyoxal, wherein the glycidated polyphenol has at least about 0.200 at 365 nm and / or at least 0.300 at 350 nm. UV absorption. In another aspect, the present invention relates to an epoxidized polyphenol prepared from a polyphenol of phenol and glyoxal, wherein before the epoxidation, the polyphenol has at least about 0.260 at 365 nm and / or at 350 nm. UV absorption of at least 0.400. In yet another aspect, the present invention relates to a method for preparing an epoxy resin by reacting the polyphenol of the present invention with a preformed epoxy resin to prepare an epoxy derivative of a polyphenol. In yet another aspect, the present invention relates to a composition containing a polyphenol or an epoxidized derivative containing a polyphenol and a composition having other phenol resins and / or an epoxidized derivative containing the same. On the other hand, the present invention relates to a novel glycidylated 10 paper size applicable to Chinese National Standard (CNS) A4 (210 X 297 public love) (Please read the precautions on the back before this page) ·-丨 Line-524816 A7 B7 V. Description of the Invention (q) The ethylene dicondensate has an ultraviolet absorbance of at least about 0.200 at 365 nm and / or at least 0.300 at 350 nm. In another aspect, the present invention relates to a hardened or unhardened reaction product of a novel polyhydric phenol, such as by glycidation, epoxidation, or phenol-formaldehyde phenolic resin or phenol-ethylene glycol The aldehyde condensate is prepared by reacting it with a glycidylated or epoxidized derivative of a phenolic resin, as well as a laminate of a reinforcing fiber or a resin matrix containing a phenol-glyoxal condensate and its reaction product. Laminate of fiber fabric. Schematic description ‘Figure 1 is a graph of the fluorescence spectra of various epoxidation products. The letter “ΠΑ” indicates the fluorescence spectrum curve of EPON 1031 (CAS: 7328-97-4), which is a commercially available polyphenol epoxy resin with less than 1% free phenol, which can be shown in the drawing. At the same wavelength shown, it is commercially used in AOI fluorescence. EPON 1031 is sold by Shell Chemical Company. The letter "B" indicates the fluorescence spectrum curve of the epoxidation product of Example 5A of this application, where The product was prepared in the same manner as shown in Example 8 herein. The letter "C" indicates the fluorescence spectrum of the epoxide of Example 8. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. It can be seen from FIG. 1 that compared with the polyglycidyl ether product of the commercial product EPON 1031 and Example 5A, the polyglycidyl acid of the fluorene-ethylene diene condensation product of the present invention is When measured in the range of 450 to 650 nm, within a one second detection time, it has an unexpectedly large fluorescence at an excitation wavelength of 442. 11 scales are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) 524816 A7 B7 V. Description of the invention (V0 Manneng details phenol · series monomers. Phenol monomers, also simply referred to as phenols, are It is an unsubstituted or substituted phenol, for example, substituted by an alkyl group, a phenyl group, or an alkoxy group. A typical phenol is a mono- or mono-nuclear monohydroxy phenol having at least one ortho or para position. For bonding. The tritium monomers will typically contain up to about 12 carbon atoms, and preferably up to about 8 carbon atoms. The compounds include: phenol itself; α-naphthol; phenylphenol; cresol, Examples are 2-methylphenol and 3-methylphenol; various xylenols such as 2,5-dimethylphenol and 3,5-dimethylphenol; and other alkylphenols; and alkoxyphenols such as 2 -Methoxy- or 3-methoxyphenol. Mixtures of phenolic compounds can be used. Preferred phenolic compounds are unsubstituted phenols, such as phenol itself. Preferred phenolic monomers can be represented by the formula : Matters needing attention

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R .., consumer cooperation of the Intellectual Property Bureau of the Ministry of Online Economy Integer to 3. When R 'is alkyl or alkoxy, y is 1 to 3, and when Rf is phenyl, y is 1. A mixture of phenol-based monomers may also be used. 12 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 524816 A7 B7 V. Description of the invention (丨 \)

The zrMMMM glyoxal reactants can be in a variety of different forms, such as the relatively pure monomeric glyoxal, polymeric glyoxal, or glyoxal dissolved in water, and mixtures thereof. By way of example, glyoxal is usually used as a 40% solution in water. Acid catalyst · Acid catalyst is a type that can be removed from the reaction mixture by distilling the reaction mixture at a temperature above about 80 ° C but below about 170 ° C (preferably below about 160 ° C). For example, the catalyst may be oxalic acid or tri-acetic acid or a mixture thereof. If oxalic acid is used as the catalyst, the temperature of the reaction mixture, together with the distillation, is raised to above 130 ° C, such as a maximum of about 170 ° C, and the temperature is preferably raised to about 140 ° C to about 16 (TC,俾 Decompose the oxalic acid catalyst into volatile components. Different forms of oxalic acid can be used, such as pure compounds, dihydrates or mixtures thereof, which are all referred to herein as oxalic acid. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Examples of trihaloacetic acid catalysts: Trichloroacetic acid and trifluoroacetic acid. Trifluoroacetic acid may need to be replenished during the reaction because a part of it will be distilled with water. Trifluoroacetic acid forms an azeotropic mixture in water Therefore, when it is intended to remove the trifluoroacetic acid catalyst, it is preferable to perform a series of distillations and add water after each distillation so as to substantially remove all the acids. When trichloroacetic acid is used as the catalyst, After neutralizing any hydrochloric acid formed from trichloroacetic acid, the temperature is raised to about 170 ° C to remove the catalyst. The amount of catalyst used is based on the weight of the phenol added to the reaction mixture. 13 This paper size applies to China Domestic Standard (CNS) A4 Specification (210 X 297 Public Love 1 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Employee Consumer Cooperative 524816 A7 B7 V. Invention Description ((y) The range can be about 1% to about 6%. Add to Based on the weight of phenol in the reaction mixture, the amount of oxalic acid is about 1% to 6%, preferably about 1.5% to about 5%, especially about 2.5% to about 4%. When trihaloacetic acid is used as the catalyst Based on the weight of phenol added to the reaction mixture, the amount of catalyst used is preferably about 1% to about 4%, and especially about 1% to about 3%. Mixtures of acid catalysts can also be used. Reaction conditions The polyhydric phenol of the present invention can be prepared by continuously or individually contacting glyoxal in the presence of an acid catalyst in the presence of a molar excess of phenol. By way of example, for a stepwise reaction, a phenol and an acid catalyst are added to Inside the reactor, a preliminary increase of glyoxal is then added to the reactor while the reaction mixture is maintained at a temperature of about 80 ° C to about 100 ° C. Glyoxal is reacted with phenol and then additional ethane Glyoxal is added to the reaction mixture. The molar ratio of glyoxal to phenol during the manufacture of the phenol-glyoxal condensate is The phenol incorporated has about 0.15 to 0.22 mole of glyoxal, preferably about 0.16 to 0.20 mole of glyoxal for each mole of phenol added. When the reaction mixture is made a total of two Glyoxal in the second increment is based on the total moles of the phenol added, and each increment is preferably about 0.006 to 0.11 mole of glyoxal, especially about 2 moles. Amount of glyoxal. For each mole of phenol added, a total mole ratio of less than about 0.15 mole of glyoxal will produce more tetraphenols, such as TPE, which are above Within the range given by ΑΟΙ quality control, it is essentially lacking in optical properties. For each molol, glyoxal with a specific ratio greater than about 0.22 mol will result in a longer reaction time. National Standard (CNS) A4 Specification (21〇χ297297

524816 A7 B7 5. Description of the invention (π) and may produce products with higher viscosity. The aldehyde equivalents or aldehyde units in the reaction mixture are maintained at at least about 70%, preferably at least about 60%, of the total aldehyde equivalents or total aldehyde units that will be added to the reaction mixture to make the phenol-glyoxal condensate. Therefore, no more than about 70% of the aldehyde equivalents intended to be used in the reaction are present in the reaction mixture at any one time. The catalyst is removed from the reaction mixture after at least about 85% of the total aldehyde equivalents to be added to the reactor have been reacted, and preferably when about 90% to 95% of the aldehyde equivalents have been reacted. The temperature is then usually raised to remove the catalyst. However, when trichloroacetic acid is used as a catalyst, a sufficient amount of alkaline substance is added to the reaction mixture to neutralize any hydrochloric acid (which is a decomposition product formed by trichloroacetic acid before distillation and will Has an impact on catalyst removal). When alkaline substances used to neutralize hydrochloric acid are alkali metal oxides or hydroxides or alkaline earth metal oxides or hydroxides, such as sodium hydroxide or calcium hydroxide, Moore's trichloroacetic acid is used as a catalyst. On an equivalent basis, approximately 80% of the molar equivalent of the base was added. When an amine is used as the basic substance, based on the molar equivalent of trichloroacetic acid used as a catalyst, about 10% to 20% of the amine molar equivalent is added to the reaction mixture to neutralize HC1. The basic substance is preferably an amine so that metal ions such as alkali metal or alkaline earth metal ions are not included in the product. For more demanding electronic applications, the presence of metal ions is detrimental to product applications. As examples of the amine used for neutralizing hydrochloric acid, there can be mentioned amines having a pKa of about 5 to about 11, such as pyridine, formyl, benzyldimethylamine, triethylamine, and hydroxyethyldiethylamine. The total time for the condensation reaction of aldehyde and phenol will typically be about 5 to about 15 hours, and preferably about 8 to 12 hours. 15 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) " (Please read the precautions on the back before this page) Order: 丨 Line. Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 524816 A7 B7 Employees of the Ministry of Economic Affairs and Intellectual Property of the Ministry of Education printed by the cooperative V. Description of the invention (νι \) In the presence of the catalyst, the temperature of the condensation reaction of phenol and glyoxal, including distillation, will be about 80 ° c to about 100 Within the range of ° C, preferably about 85 ° C to 95 ° C, until at least about 85% or more of the equivalent weight in the total amount of ethylene oxide (to be added for the production of the condensation product) has been reacted. After the individual addition of glyoxal to react glyoxal with phenol, the water is continuously or intermittently removed by distillation because water accumulates in the reaction mixture to slow down the reaction. The water system is formed by the condensation reaction of glyoxal and phenol. Other water is usually present in the glyoxal feed. For example, glyoxal is usually used as a 40% solution in water. tThe water content in the reaction mixture is preferably kept below about 8% by weight (based on the phenol added to the reaction mixture), and preferably below about 6% by weight (added on the reaction mixture) Phenol-based). For example, after glyoxal is reacted with an excess of phenol, the reaction mixture is added two or more times, such as 2 to 4 times, and steam f is left to leave water. Preferably, glyoxal is added for the first time before at least about 85% of the total aldehyde equivalent to be used in the production of the condensation product is reacted, which is subsequently reacted, followed by distilled water, and then the glyoxal is added a second time, followed by a single Body response. When the reactant is the same as the catalyst and the operating conditions are in the same range, such as the molar ratio, reaction temperature, catalyst and its amount, water distillation time and distillate amount, the reaction can be monitored without measuring the aldehyde equivalent. The reaction time is used to carry out the reaction. For example, the following steps and timeframes can be used, when the ear to ear ratio of Ethylone is about 0.15 to 0.22; 40% glyoxal solution reacts with the phenol itself at a temperature of 80 ° C to 100t: Make the first addition of glyoxal, continue the reaction of glyoxal and phenol, and distill in time, and then write another I% ,! (Please read the precautions on the back before filling this page) Order:

524816

V. Description of the invention (/) Glyoxal is added, then the reaction is continued, then the distillation is continued, and the reverse is continued until the aldehyde equivalent is consumed to 15% or less of the added amount. Based on the amount of phenol added, glyoxal is added at about 0.006 to 0.08 moles each time. Therefore, after the initial amount of glyoxal is added, the aldehyde is reacted with the phenol for about 1 to 5 hours, preferably 1.5 to 3 hours, and then about 8 is distilled out of the reaction mixture based on the weight of the added phenol. % To 12% of the first observations. After the first distillation (which is carried out at a temperature range of about 80 to 100.): based on the mole number of the added phenol, slowly add another 0.06 to 〇 · ηmol of ethylene glycol Aldehyde is added to the reaction mixture. It is preferred to add approximately equal amounts of glyoxal during each addition. Continue to heat the reaction mixture for another 1 to '6 hours', preferably 1 to 5 to 5 hours. This is the first distillation The starting time meter 'then began a second distillation to remove about 4% to 12% of water (based on the phenol added). After the second distillation, the reaction was allowed to continue for another 0.5 to 6 hours, compared to 1 to 4 hours, this is the time from the start of the second distillation, and then the temperature is increased for distillation, and the catalyst is removed. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the use of 80 ° C to 100 ° C. The temperature is maintained until the temperature needs to be raised and the catalyst or unreacted phenol is removed. Before increasing the temperature used to remove the catalyst, the distillation is performed under vacuum to assist in temperature control. The degree of vacuum may be about 15 to 25 inches or more of mercury. Distillation catalyst removal temperature is less than about 170 ° C, preferably less than about 160 ° C. When oxalic acid is the catalyst, the temperature rises above 135 ° C to about 170 ° C, especially about 155t to about 160 ° C. All or part of it. If oxalic acid is the catalyst, all or substantially all of the water will be removed when the catalyst is removed. 17 This paper is compatible with Chinese National Standard (CNS) A4 (210 X 297) ) '" 524816 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (Mountain) After removing the catalyst, any water system remaining in the reaction mixture was finally removed by distillation to remove phenol. After removing water and all catalysts, unreacted free phenol is removed from the reaction mixture, so that the content of free phenol in the reaction mixture is less than about 5 wt%, preferably less than about 2 wt%, especially less At about 1.5 wt% of the reaction mixture. Conventional methods are used to remove unreacted phenols, such as those used to remove unreacted phenols from phenolic resins, such as heating the reaction mixture at high temperature under vacuum for rapid distillation. , At about 25 to 30 inches of mercury, the temperature can be up to about 19 0 ° C or 200 ° C. The exhaust gas can also be sprayed under vacuum to remove phenol from the product. The reaction mixture is heated simultaneously with the removal of phenol or as a separate step after catalyst removal, and the reaction mixture is heated A temperature of about 175 ° C to about 200 ° C, and preferably a temperature of about 180 ° C to about 195t. The heating system is performed for a time of about 0.25 to 3 hours, preferably about 0.5 to 2 hours. Can be under vacuum All or a part of the heating is performed when phenol is removed. Optionally, a polyphenol having 5% or less of unreacted phenol may be placed in an inert atmosphere and the heating may be performed (the range is about 175 ° C). To 200 ° C for about 0.5 to 3 hours). Examples of the inert atmosphere that may be mentioned are nitrogen or argon. The polyphenols are finally cooled and usually comminuted, for example pressed into a sheet. Polyphenol Product The properties of the polyphenol product of the present invention are as follows: 18 This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm)

524816 A7 B7 V. Description of the invention (\,) Wide range of better quality Mw / Mn 400-600 / 300-390 440-540 / 320-370 Viscosity (cps) at 175 ° C 300-2500 450- 1500 Free phenol (%) 0-5 0.03-1.5 Tetraphenolacetamidine, such as TPE (%) 0-6 1-4 UV absorption in the legs is at least 0.400 at least 0.450 especially> 0.5 UV absorption at 365nm Degrees at least 0.260 at least 0.275 < especially > 0.30 fluorescence: excitation wavelength of 闱 442nm, detection time of 0.5 seconds (as measured by CM 1000 instrument (which is Spectra Group Co., Ltd., Maumee, Ohio), at the maximum Under camping light (approximately 532nm), the fluorescence of the fluorene-oxalic acid condensate is higher than about 70% than that of Acridine Orange Base (Aldrich Chemical). Tifn Acridine Orange Base is used at a concentration of 0.2 mg / L in methanol and phenol-glyoxal condensate is used at a concentration of 0.05 wt% in tetralight furan. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The phenol-glyoxal condensate contains a wide variety of compounds, including polyphenols such as di-, tri-, and tetraphenol. For example, the tetraphenol can be expressed as shown below. 19 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 public love) 524816 A7 B7 V. Description of the invention (\ 务

HO— C C, .〆 C.

C

CH—CH

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, where X is an integer from 0 to 3. When R is alkyl and / or alkoxy, X is 1-3 and alkyl and alkoxy have 1 to 4 carbon atoms. When the reactants are phenol itself and glyoxal, the above polyhydric phenol is a mixture, and the main compound thereof is 4- (4-hydroxyphenyl) ethane (TPE), which is also known as 1,1,2,2-2- ( 4-hydroxyphenyl) ethane. The glycidylation of (4-hydroxyphenyl) ethane produces tetraglycidyl ether of (4-hydroxyphenyl) ethane. The "residue" or "residue" of the acid-glyoxal condensate may mean, for example, the phenol-glyoxal derivative portion of the reaction product in the reaction of an epoxy resin. The amount of residue is the amount of a phenol-glyoxal condensate used to produce a reaction product, such as a resin or compound. For example, if 10 g of a phenol-glyoxal condensate is reacted with 40 g of an epoxide, the phenol-glyoxal condensate residue of the composition will be 10 g. Meanwhile, if 20 g of a phenol-glyoxal condensate is glycidized, the glycidated product will then react with a phenol-formaldehyde phenolic resin, and the phenol-glyoxal residue will be 20 g. The epoxy resin used in the laminated composition of the present invention will have a unit of 20 paper sizes that are applicable to China National Standard (CNS) A4 specifications (21 × X 297 public love) 524816 Α7 Β7 Employee Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printing 5. Description of the invention) The epoxy equivalent weight (WPE) is about 190 to 10,000 and preferably about 190 to 500. · The pressure used to produce the laminate can vary from the contact pressure applied to the tank wall to the high pressure used to make the electronic insulation sheet, such as 1000 psi or more. The temperature used to produce the laminate can vary over a wide range, such as from about room temperature to over 210 ° C. The use of solvents in the laminated composition is optional. Polycyclic chlorides can be prepared by at least two different conventional routes to the epoxidation products of the polyphenols of the phenol and glyoxal of the present invention. One approach is to react a phenol-glyoxal condensate with a halohydrin to form a glycidyl ether of a polyhydric phenol in the presence of an alkali metal hydroxide. The epoxidized product will typically have an epoxy equivalent weight per unit of about 190 to 230, preferably about 205 to 225. Another approach is to react a molar excess of a preformed polyfunctional epoxide with a phenol-glyoxal condensate. The epoxidation product of this alternative route will typically have an epoxy equivalent weight of about 140 to 250, and preferably about 160 to 230. In the first route, the phenol-glyoxal condensate is reacted with an excess of phenol-glyoxal in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide in a temperature range of about 50 ° C to about 80 ° C. Epichlorohydrin can be used to prepare polyepoxide. Any catalyst can be used, such as a quaternary ammonium salt. The reaction can be performed in the presence of an inert solvent, including alcohols such as ethanol, isopropanol, methyl isobutyl ketone (MIBK), toluene, ethers, and mixtures thereof. Another method for preparing polyepoxides via the first route is described in 21 paper sizes applicable to Chinese Standard (CNS) A4 (210 X 297) (please read the precautions on the back first)

Order ·· -Line-524816 A7 B7 V. Description of the Invention (W)

Ciba Geigy, Inc., US Patent No. 4,518,762, May 21, 1985. All of them are incorporated herein by reference. In short, in this method, a polyphenol, preferably a purified product of phenol-glyoxal, is at a temperature of 40 ° C to 100 ° C, at any catalyst designated for the formation of a chlorohydrin ether intermediate. In the absence of 2 to 25% by weight (based on the reaction mixture) of a lower alkanol or lower alkoxyalkanol co-solvent, 0.5 to 8% by weight (based on a phenolic hydroxyamidine) In the presence of water, it reacts with an excess of epichlorohydrin and uses 0.9 to 1.15 equivalents of a solid alkali metal hydroxide / phenolic hydroxyl group to produce an epoxy derivative of a polyhydric phenol, and wherein The aqueous system in the reaction mixture is 0.5% to 8% by weight. A bead-shaped solid alkali metal hydroxide having a diameter of about Γ mm is used, which is partly or continuously during the process of gradually increasing the amount of addition. The material was added to the reaction mixture, and then the epoxy novolac resin was separated. In the second route for preparing the phenol-glyoxal-containing condensate-containing epoxy resin of the present invention, a catalyst such as potassium hydroxide, benzyl diacetate is used at about 100 ° C to about 150 ° C. Methylamine, benzyltrimethylammonium hydroxide, methylimidazole, and 2,4,6-p- (dimethylaminoethyl) phenol make one part by weight of the condensate and 4 to .8 parts of polyepoxide reaction. A typical catalyst content is from about 0.1% to about 0.6% based on the weight of the reaction. For polyepoxide-based diglycidyl ether resins that react with polybasic acids of typical acids and oxalic acids, such as bisphenol A, bisphenol F, resorcinol, neopentyl glycol, cyclohexanedimethanol, and others A mixture of diglycidyl ether resins. It is also possible to partially epoxidize the polyhydric phenol of the present invention, and by reducing the amount of base used in the reaction with epichlorohydrin, the desired optical properties are not sacrificed. Example 22 This paper size is applicable to China National Standard (CNS) A4 (21〇X 297 public love) (Please read the precautions on the back before this page) .--• Line_ Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Consumption Cooperative Printed 524816 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Printed A7 B7. 5. In the description of the invention (y |), in the method of the first route above, reduce the charge to about 40% to 70%, and then obtain partial epoxidation. Derivatives. Unless otherwise specified, various resins of the present invention, such as epoxy resins (including glycidated polyphenols) and phenolic resins are reactive, hardenable trees. Unless trichloroacetic acid is used as a catalyst, oxidation with metal ions Or hydroxide to neutralize hydrochloric acid, otherwise the phenol-glyoxal condensate of the present invention will typically have a weight percent concentration of metal ions of less than about: 0.005% sodium; 0.003% calcium; 0.003% Iron; and 0.002% potassium. The polyhydric phenols of the present invention can be used alone to harden epoxy resins, but are preferably used in combination with other epoxy resin hardeners, such as having an ultraviolet absorption of less than 0.260 at 365 nm and / or less than 0 · 400 at 350 nm Degree of phenolic phenolic resin. The other hardener may include about 50% to 97% by weight of the hardening composition and the phenol-glyoxal condensate may include 3% to 50% by weight of the hardening composition. Preferably, the other hardener may include about 50% to 95% by weight of the hardening composition and the phenol-glyoxal condensate may include about 5% to 50% by weight of the hardening composition. About 15 to 30 parts of the hardened composition can be used to harden 100 parts of the epoxy resin. The laminate of the present invention may be a conventional laminate containing a reinforcing agent such as glass cloth and a resin matrix (including epoxy resin and a hardener for epoxy resins such as rhenium-formaldehyde resin), except that the resin matrix will contain about 1 to 35 parts by weight, preferably about 1 to 15 parts by weight and especially about 2 to 10 parts by weight (based on the weight of the resin matrix) of the phenol-glyoxal condensate, residue or mixture thereof. Epoxy resins, hardeners, phenol-glyoxal condensates or their residues, and the size of this paper are applicable to China National Standard (CNS) A4 (210 X 297 mm)-(Please read the precautions on the back first (Fill in this page again) · • Line · 524816 A7

5. Description of the invention (> 〆) The solvent system used for epoxy and hardener will generally include at least 40% of the resin matrix or mixture. The resin matrix of the solvent-containing laminate of the present invention will generally comprise, by weight: (1) about 40 to 80 parts and preferably 50 to 70 parts of epoxy resin; about 1 to 15 parts having Polyphenols of phenol and glyoxal or epoxidized residues of the polyphenols or mixtures thereof at a UV absorption of at least 0.260 and / or a UV absorption of at least 0.400 at 350 nm; (3) about 10 to 35 parts and preferably 15 To 30 parts by weight of solvent; and about 7 to 35 parts by weight of conventional epoxy hardener. The epoxidation residue may be the residue of the glycidylated polyphenol of the present invention or the reaction residue of 4-8 parts of epoxy resin for each part of the polyhydric. The preferred polyepoxide products of the present invention, when used in electronic applications such as laminates for the manufacture of printed circuit boards, will typically include the following compositions based on 100 parts of epoxy resin, such as based on, for example, bisphenol A bis glycidyl ether epoxy resin: (a) about 18-25 parts of hardener for phenol-formaldehyde phenolic resin; printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (b) about 1-30 parts and better It is a member of about 3-15 parts, which is selected from the group consisting of the glycidylated polydrug of the present invention, the reaction product of an epoxy resin and the polyphenol of the present invention, the polyphenol of the present invention, and a mixture thereof. ; And (0 if necessary, epoxide hardening accelerators. Epoxy resins used in lamination and coating formulations are generally solvent-based. Coating formulations can include additives, however, lamination formulations are generally compatible with the type Tu 24 ^ Paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 524816 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ---------- B7 ————— | | Fifth, the invention (> >) material (phenolic compatible finish ) To impregnate multilayer fiber precursors (such as glass cloth). Flame retardants can be produced by the laminates of the present invention by conventional techniques, such as the use of halogenated epoxy resins as the main resin precursor or brominated flame retardant additives or chlorination Flame-resistant additives (such as bisphenol chloride, bisphenol tetrachloride, or tris (2,3-dibromopropyl) phosphate and antimony oxide. Conventional lamination techniques can be used to produce the laminates of the present invention, such as wet Laminate or dry lamination technology. The laminate of the present invention will generally contain about 40% to 80% by weight of the resin matrix material and about 20% to 60% by weight of the reinforcing material, such as glass cloth. The oxyresin may be a conventional epoxy resin, that is, an epoxy resin without the high UV phenol-glyoxal residue of the present invention. The resin may have a WPE ratio of about 190 to about 10,000, and preferably about 190 To about 500. The exemplary traditional epoxy resin, or simple epoxy resin, may be the mentioned diglycidyl ether resin, such as the epoxy resin having the aforementioned WPE 値, which is composed of Presence of compounds and excess epichlorohydrin in alkali metal hydroxides Contact is made to prepare it, wherein the dihydroxy compound may be bisphenol A; brominated bisphenol A; bisphenol F; resorcinol; octylpentanediol; cyclohexanedimethanol and the like; and mixtures thereof The resin may also be based on or derived from a dihydroxy compound, such as bisphenol A. The traditional epoxy resin may be: epoxy phenol novolac resin; epoxy cresol novolac resin; aromatic glycidyl amine resin, such as tris Glycidyl-p-aminophenol; Fan > 1'-tetraglycidyl-4,4, -diaminodiphenylmethane; glycidyl ether of phenolic phenolic resin; glycidyl methyl Poly (glycidyl) copolymerization of acrylic acrylate 25 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)

Order:; Line _ (Please read the precautions on the back before this page) 524816 A7

5. Description of the invention (pair), in which the copolymer includes unsaturated compounds such as acrylate, methacrylate and styrene; and a mixture of various traditional epoxy resins. Non-glycidated epoxy resins can be used. The non-glycidylated epoxy resin includes: ninene dioxide (with an epoxy equivalent weight of 85); vinylcyclohexane—►and compounds (the weight of oxygen is 76), 1,5_ Heptadiene dioxide; 1,7-octadiene dioxide. The non-glycidized epoxide compound is preferably used together with a glycidylated epoxy resin and used as a diluent. The conventional epoxy resin may be a flame-retardant epoxy resin such as a halogenated epoxy resin such as a chlorinated or brominated epoxy resin. An example of a brominated epoxidized resin that can be mentioned is the brominated product of diglycidyl ' ether of bisphenol A, such as EPON 1124 (CAS No: 26265-08-07) from Shell Chemical Company. This brominated epoxy resin can be used in a flame-retardant composition having an epoxy resin. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Preferably, the non-traditional epoxy resins of the present invention include: glycidylated polyphenols of phenol and glyoxal, where the polyphenols have a range of 365 nm before glycidylation. A glycidylated polyphenol of glyoxal and glyoxal with a UV absorption of at least 0.260 and / or at least 0_400 at 350nm; a phenol having a UV absorption of at least about 0.200 at 365nm and / or at least 0 · 300 at 350nm ; And for each portion of phenol having a UV absorbance of at least 0.260 at 365 nm and / or at least 0.400 at 350 nm, and B- · Xingduowu I divided into 'about 4 to 8 parts of the glycidyl ring Reaction products of oxygen resin. The amount of the epoxy hardening accelerator is sufficient to accelerate the hardening of the epoxy resin. Hanging 'is based on 100 parts of epoxy resin, and the amount is about 0.05 to 0.5 parts, and preferably about 0.1 to 0.2 parts. The accelerator includes 2-methylimide 26. The paper size is applicable to Chinese National Standard (CNS) A4 specifications (21G X 297 public love) '--- 524816 A7 B7 V. Description of the invention (〆) azole, 2-ethyl- 4-methylimidazole, amines such as 2,4,6-tris (dimethylaminomethyl) phenol and benzyldimethylamine, and organic phosphorus compounds such as tributylphosphine and triphenylphosphine. Reactive diluents may be present to reduce viscosity and improve processing properties. Examples of the reactive diluent include octyl glycol diglycidyl ether; butanediol diglycidyl ether; resorcinol diglycidyl ether; and cyclohexanedimethanol diglycidyl ether. Various hardeners known in the art can be used in epoxy resins. These include, but are not limited to, aromatic amines, polyamidoamines: polyamines; dicyandiamide; phenol-formaldehyde phenolic resins; and melamine-formaldehyde resins. When phenolic resins are used as hardeners In general, a catalyst (accelerator) can be used and it can be selected from tertiary organic amines such as 2-alkylimidazole; N, N-dimethylbenzylamine; and phosphines such as triphenylphosphine and mixtures thereof . The hardener for phenolic resins is the condensation product of phenol with formaldehyde or ketone. The phenol may be selected from the group consisting of phenol itself, cresol, xylenol, resorcinol, bisphenol-A, p-phenylphenol, and phenol. Its mixture. Substituents for phenol monomers include a hydroxyl group, an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, and a phenyl group. Phenolic resins and dicyandiamide are preferred hardeners. Particularly preferred hardeners are phenol-formaldehyde phenolic resin and o-cresol-formaldehyde phenolic resin, which have a molecular weight of about 300 to 5,000 and preferably about 1,000 to 5,000. The aldehydes which can be mentioned for the preparation of phenolic resin hardeners can be formaldehyde, acetaldehyde, benzaldehyde and hydroxybenzaldehyde. Mention may be made of ketones used in the preparation of phenolic resin hardeners such as acetone, hydroxyacetophenone and metoethylketone. Can use a variety of different solvents, including halogenated solvents, ketones, alcohols 27 This paper size applies to Chinese National Standard (CNS) A4 specifications (210 χ 297 mm) (Please read the precautions on the back before this page) r Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 524816 A7 B7 V. Description of the invention (outside), glycol ethers, glycol acetates, N, N-dimethylformamide. The use of the latter is particularly useful when dicyandiamide is used as the hardener. Ketones include acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone. Reinforcing fibers or fabrics of reinforcing fibers include glass fibers and felt sheets; carbon and graphite fibers, cellulose paper, fiber polyamide sheets, fiber quartz sheets' fiber fabric glass cloth, non-woven glass felt cloth, and the like. Materials such as quartz powder, mica, talc, calcium carbonate, and the like can be added to the resin matrix. (The laminate can be prepared at room temperature or under pressure by adding a layer containing at least one piece of prepreg (containing epoxy resin as an impregnating agent). It is believed that in the high UV absorption and contained From the viewpoint of other desirable properties imparted by the phenol-glyoxal condensate of the invention, the composition containing the phenol-glyoxal condensate of the present invention and the epoxidation product containing the same are novel substances. The gel layer is used. Analyze and use phenolic compounds and polystyrene standards to measure the weight average molecular weight (Mw) and number average molecular weight (Μη) herein. The molecular weight of the sample is prepared as follows: the sample is dissolved in tetrahydrofuran, and the solution is passed through the coagulation Gel chromatography. Any free phenol in the sample is removed from the calculation of molecular weight. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the following methods are used to measure the amount of TPE in different reaction mixtures. (A) The reagent system used Ethylphenol, TPE, and silylating agent. (B) The measurement procedure of TPE is as follows: Prepare silylating agent as follows: In a 25ml (ml) reaction flask, add · 10cc (cubic cm) through a syringe. 3cc Trimethyl Chlorine (TMCS) and 10cc Hexamethyldisilazane (HMDS). Allow it to stay 5 to 1028. This paper size is applicable to China National Standard (CNS) A4 (210 X 297). ) " 524816 A7

V. Description of the invention (η) minutes. (0 Prepare a TPE standard solution as follows: Add approximately 30 mg of each TPE and p-ethylphenol to a vial (suitable for silylation). Add 1cc of a silylating agent. Shake until dissolved (about 10 minutes). Heat at low temperature Overnight. 1 microliter was injected into the gas chromatograph. Methyl ethyl ketone was used as the rinsing agent. The column used for this analysis was Dexsil 300, supplied by Supelco of Belfonte, Pa. To enable those skilled in the art to To better understand the present invention, the following examples are presented. In the examples and the daggers in this case, all parts and percentages are by weight unless otherwise specified. The following examples are used to illustrate the present invention. Some of the examples are called "Comparative Example π in order to show the differences from the examples of the present invention, and does not have to be compared with the prior art. Example 1 Add glyoxal and oxalic acid catalyst once to prepare a phenol-glyoxal condensation product Consumption cooperatives were printed at 90. (2, 1,728 grams (18.36 moles) of phenol and 69.1 grams of oxalic acid dihydrate were added to 227 grams of 40% glyoxal / water (1.57 moles) for 30 minutes. Keep the temperature at 90. C. for another 1.5 hours, then vacuum distill out 185 g of distillate (10.7%, based on the weight of tritium added) from the reaction mixture at 90 ° C for forty minutes. After this heating, add about 79% When the aldehyde equivalent has been reacted, and the amount of water in the reaction mixture is about 4%. Another 227 grams of 40% oxalic acid / water (1.57 mol) is added to the reaction mixture for 25 minutes, the same as the 29 ^ paper scale Applicable to China ^^ 准 (eNS) A4 297 —- 524816 A7 _____ B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. When the description of the invention (,) is maintained at 90t for 1.5 hours, and then at 90 ° C for three Ten minutes of vacuum distillation · 195 grams of distillate (11.3%, based on the weight of phenol added). After this heating, when about 70% of the added aldehyde equivalent has reacted, and the amount of water in the reaction mixture is About 3.5%. With respect to the total amount of glyoxal added twice, the molar ratio of glyoxal to phenol is 0.17. The temperature of 9 ° C is maintained for another 1.5 hours. After this heating, 90% is added to Aldehyde equivalents in the reaction mixture have reacted and the water content is about 4.5%. Then evaporate at atmospheric pressure | The reaction mixture was kept at 160 C and maintained at 160 ° C for one hour. Then the reaction mixture was vacuum-evaporated at 155-160 ° C to remove most of the unreacted. Continue vacuum distillation up to a temperature of 190t, and keep at this temperature for one Hours until the phenol in the reaction mixture is less than 1%. The obtained phenol-ethylene disulfide condensation product is then pulverized, for example, pressed into a sheet. During the reaction, the aldehyde equivalent in the reaction mixture remains less than ethyl About 70% of the aldehyde equivalent in the total amount of dialdehyde (to be added for the production of the gadolinium glyoxal condensation product). The following table shows the properties of the fluorene-glyoxal condensation products. This example is also referred to as Example 1 in the following table. Example 2 (comparative example) at 90 ° C ,,: __ Adding acetic acid in one time and _ Xingli catalyst to prepare west cent _ glyoxal polyphenols at 85 ° C, 5 ? 6 grams (6.22 moles) of phenol and 23 grams of oxalic acid dihydrate, add 151.4 grams of 40% glyoxal / water (104 moles) for about an hour, during which the temperature is gradually increased to 9 (TC. The molar ratio of glyoxal to pyrene is 〇_Π. Immediately apply a vacuum at 90-95 ° C for 60 minutes to remove 1230. (Please read the precautions on the back before

. Line _ This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 524816 A7 B7_______ 5. Description of the invention (> /) Grams of distillate. Maintain a temperature of 90-92 ° C for 225 hours. After this time, about 82% of the aldehyde equivalent added has been reacted. Vacuum was then applied for 15 minutes to remove 13.3 grams of distillate. Continue heating at 90 ° C to 91t for 1.25 hours. After 1.25 hours, about 88% of the aldehyde equivalent added had been reacted. A vacuum was then applied for 6 minutes to remove 6.68 grams of distillate. Continue heating at 90 ° 0 for 5 hours and at 100 ° C for one hour. After this one hour of heating, about 94% of the aldehyde equivalent added to the reaction mixture had reacted. The reaction mixture was distilled at atmospheric pressure to 160 ° C. Keep at a temperature of 160 ° C for one hour. The reaction mixture was then subjected to vacuum distillation at 155-160 ° C to remove most of the unreacted phenol, and the vacuum distillation was continued at 19 ° C until the phenol in the reaction mixture was less than 1%. During the vacuum distillation, the reaction mixture was heated at a temperature of about 175 ° C to 192 ° C for about 0.25 hours. The reaction mixture is discharged from the reactor and then pulverized, for example, pressed into a sheet. The properties of the polyphenol product of this example are shown in the following table, and this example can be referred to as Example 2. Example 3 (comparative example) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs at 102 ° C and reflux (103-104 ° C) with one-time addition of glyoxal and oxalic acid catalyst to prepare phenol-glyoxal Polyphenols_ At 90 ° C, add 576 grams (6.12 moles) of phenol and 23 grams of oxalic acid dihydrate, add 151.4 grams of 40% glyoxal / water (1.04 moles) for one hour, and allow the temperature to rise to Reflux (103-104 ° C). The molar ratio of glyoxal to phenol is 0.17. The reaction mixture was kept at reflux for 10 hours. After this reflux, about 89% of the aldehyde equivalent had reacted. Then increase the temperature to ll (TC, and remove 31) The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 524816 A7 B7 V. Description of the invention (f) 55.5 grams of observed material approximately 22 Minutes. The temperature is maintained at 110 ° C for one hour, and then the reaction mixture is distilled at atmospheric pressure to 160 ° C. The reaction mixture is held at 160 ° C for one hour. The reaction mixture is then subjected to vacuum distillation at 155-160 ° C. To remove most of the unreacted phenol, and continue vacuum distillation at 176 ° C until the phenol in the reaction mixture is less than 3%. During the reaction, the aldehyde equivalent in the reaction mixture is kept less than the total amount of glyoxal (To be added for the production of condensation products) about 70% of the aldehyde equivalent. The reaction mixture is discharged from the reactor and then pulverized, for example, pressed into a sheet. The following table shows the properties of the polyphenol product of this example, and this The example can be referred to as Example 3. Fen example 4 (comparative example) The phenol-glyoxal polyphenol was prepared at a temperature of 102 ° C and reflux at no. At C, 576 grams (6.12 moles) of phenol and 6.23 grams of 18.5% H In C1 (0.20 / 〇HC based on phenol), force D into 151.4 g of 40% glyoxal / water (1.04 mol) for one hour, while allowing the temperature to rise to reflux (103-104 ° C). The molar ratio of glyoxal to phenol is 0.17. After two hours of reflux, about 93% of the aldehyde equivalent added had reacted. The reaction mixture was then vacuum distilled to raise the temperature to 11 ° C. to remove 116 · 4 grams of aqueous HC1 distillate. Then 100 grams of hot water was added to the reaction mixture, and the distillation was continued to 150 ° C. under atmospheric pressure. The hydrochloric acid (HC1) catalyst and water were co-distilled from the reaction mixture. Then, vacuum distillation was performed to 180 ° C, and unreacted phenol was removed so that the residual amount in the reaction mixture was less than 4%. The reaction mixture was discharged from the reactor. , Then pulverized, pressed into a sheet, and produced. The following table shows as many as 32 paper sizes of this paper are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) ii # · — 1 (Please read the back first Please pay attention to this page and fill in this page)--Line-Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 524816 A7 B7 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy It can be referred to as Example 4. Example 5 (Comparative Example) Phenol-glyoxal polyphenol was prepared by adding glyoxal at one time and using a phenolsulfonic acid catalyst at 102 ° C and reflux (103-104 ° C). At 90 ° C, 576 grams (6.12 moles) of phenol and 5.76 grams (1.5% Based on phenol) 65% phenolsulfonic acid (as catalyst), 151.4 g of 40% glyoxal / water (1.04 mole) was added for one hour. The molar ratio of glyoxal to phenol was 0.17. The reaction mixture was allowed The temperature rises to reflux (103-104 ° CV, hold for several hours and the conversion rate of phenol equivalents rises to about 96% of those added. Then neutralize the catalyst, cool to 65 ° C and use Rinse with distilled water to remove salt. Distill to 160 ° C at atmospheric pressure, then vacuum distill at about 176 ° C to reduce the amount of unreacted phenol in the reaction mixture to about 1%. The reaction mixture is finally crushed, for example, Compressed into tablets. Example 5A (Comparative Example) Follow the procedure of Example 5 above, but replace phenolsulfonic acid with 1.25 g (0.22%, based on phenol) of anhydrous methanesulfonic acid. Before neutralizing the catalyst, approximately 97% was added Aldehyde equivalents have been reacted. Basically, equivalent properties, molecular weight, viscosity, and TPE% are obtained. The properties of the phenol-glyoxal condensation product are shown in the following table. This example can be referred to as Example 5A. Example 6 Large-scale production of glycol · · glyoxal condensation products 33

This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 524816 A7 B7 V. Description of the invention (π) The phenol-glyoxal condensation product of Example 6 is prepared in substantially the same manner as in Example 1. In addition to preparing it with large equipment that can produce hundreds of pounds of product, and spraying with vacuum steam at 190 ° C to reduce phenol to less than 0.1%. The insoluble matter percentage of the phenol-glyoxal condensation product of this example is 0.04%, and other properties are listed in the following table, where this example may be referred to as Example 6. The insoluble matter was tested by essentially dissolving 15 g of the condensate in 285 ml of isopropanol, filtering through No. 42 Whatman filter paper, and then drying the filter paper in an oven at 75 ° C to 100 ° C for 30 minutes. Example 7 Preparation of the phenol-glyoxal condensation product in the manner of 篁 M. 丄. · The phenol-glyoxal condensation product of Example 7 was prepared in substantially the same manner as in Example 6, except that it was prepared at a different time. . The percentage of insoluble matter in the product was 0.01%, and other properties are listed in the following table, where this example can be referred to as Example 7. The insoluble matter test was performed in the same manner as in Example 6 above. Treasure 8 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs n II n ϋ L— ϋ nn ϋ n · nn (Please read the precautions on the back before filling this page) • Wire · Polyglycidyl ether resin (cyclohydrogen resin Preparation) In a one-liter flask, 75 g of the flake reaction product of Example 6, 200 g of isopropanol, and 52.5 g of water were added to form a reaction mixture. The reaction mixture was heated to 55 ° C. After 10 minutes, 388.5 grams of epichlorohydrin was added. The reaction mixture was reheated to 55 ° C and then 30 grams of a 20% sodium hydroxide / water solution was added while maintaining the temperature at 55 ° C. Maintain a temperature of 55 ° C. 34 This paper size is in accordance with Chinese National Standard (CNS) A4 (21 × 297 mm). 524816 A7 B7 5. Description of the invention (w) Another 30 minutes. 90 grams of a 20% sodium hydroxide / water solution was then added. The reaction mixture was held at 55 ° C for another hour, heated to 65 ° C for a minute, and then transferred to a separatory drain. The upper clear brown organic layer (145.6 g) was stirred with 150 g of water and 50 .g of dry ice. The water layer was discarded, and the organic layer was washed a second time, and then vacuum-cracked to recover excess epichlorohydrin and 105 g of the dark resin of the epoxidation product of Example 6. This epoxy resin has unit epoxy equivalent weights of 203.1 and 225.8. This is compared with EPON 1031's unit epoxy equivalent weight of 210. The following Table 1 shows the comparison of the viscosity and unit epoxy equivalent weight (WPE) of the epoxy resin of this Example 8 and other epoxy resins prepared from polyfluorene. This example can be referred to as Example 8. Example 9 (Comparative Example) Preparation of a phenol-glyoxal polyphenol using an acidic (sulfonic acid) ion-exchange tree J at a temperature of 90 ° C for 30 minutes at 709.3 g of amidine (7.54 moles) and 35.5 g Amberlyst 15 (which is a dry sulfonic acid ion exchange resin sold by Rohm & Haas) was charged with 93 g of 40% glyoxal / water (0.64 mol). This resin was selected because resin resins used as catalysts in US Patent Nos. 5,012,016, 5, Η 6,006, and 5,191, 1; 28 (all granted to S. Li) were not obtained, and this resin appears to be the closest to that. Resin. The temperature was maintained at 90 ° C for another 1.5 hours. After this time, 88% of the aldehyde equivalent added has been reacted. 42 grams of distillate was then distilled off under vacuum. After the distillation was completed, 95% of the aldehyde equivalent added to the reaction mixture had reacted. Add another 93 grams of 40% ethylene glycol / water calendar for 31 minutes, while maintaining the temperature at 90 ° C for 1.5 hours. After 1.5 hours, 81% of the aldehyde equivalent added to the reaction mixture. 35 This paper size is in accordance with China National Standard (CNS) A4 specifications (210 X 297). 丨 4. 丨 (Please read the note on the back first Please fill in this page again for matters)-trD, ·-Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 524816 A7 B7 V. The description of the invention (Ya) has been reflected. Then 70 g of distillate was distilled off under vacuum at 90 ° C for 30 minutes. The temperature of 90 ° C was maintained for another 30 minutes, after which time 91% of the aldehyde equivalent added to the reaction mixture had reacted. For a total of two glyoxal additions, the molar ratio of 'glyoxal to phenol is 0.17. The catalyst was allowed to settle, and a fairly clear liquid (687 g) was poured out, and neutralized to pH 6 with 2.6 g of 50% sodium hydroxide. 650 grams of the neutralized solution was added to the flask, and atmospheric distillation was performed at 160 ° C. The reaction mixture was then vacuum distilled to 175 ° C to remove phenol. During the reaction, the aldehyde equivalent in the reaction mixture was maintained at less than about 70% of the aldehyde equivalent in the total amount of glyoxal (to be added for the production of polyphenols). The yield of the product was 263 grams. The obtained polyphenol is then pulverized, for example, to form a sheet. The properties of the polyphenol product of this example are shown in the following table, where this example can be referred to as Example 9. Example 10 (Comparative Example) Glyoxal and oxalic acid catalysts were added twice, and the total glyoxal / phenol mol ratio of the first part was 0.22, and the second part was phenol added to reduce Φ7, dialdehyde / phenol Molar ratio to 0.17 to prepare a phenol-glyoxal condensation product. In 9 (TC, 1419 g (15 mol) of phenol and 56.5 g of oxalic acid dihydrate, 240 g of 40% glyoxal / water (1.655 mol Ear) for 30 minutes. Maintaining the temperature at 90 ° C for another 1.5 hours, and then vacuum distilling 148.3 g of distillate from the reaction mixture for 50 minutes at 90 ° C. After this 50 minutes, about 62% plus The aldehyde equivalent to the reaction mixture has reacted. An additional 240 grams of 10% glyoxal / water (1.655 moles) is added to the reaction mixture for 22 minutes while maintaining the temperature at 90 ° C for 1.5 hours. Here This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) Word Γ Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives 524816 A7 B7 V. Invention Explanation (> <) Approximately 58% of the employees ’cooperatives in the Intellectual Property Bureau of the Ministry of Economy printed 1.5 hours after printing The awakening equivalent in the reaction mixture has reacted. Then, 212.2 g of extracts were vacuum distilled out at 90t for 45 minutes. After 45 minutes, about 65% of the awakening equivalent added to the reaction mixture had reacted. For all glyoxal additions, the molar ratio of glyoxal to phenol is 0.22. The temperature of 9 ° C is maintained for another 5 hours. After this 5 hours, about 87.% of the aldehyde equivalent added to the reaction mixture Already reacted. The reaction mixture was then divided into two parts. 214 g of rhenium was added to half (794 g) to adjust the glyoxal / phenol molar ratio to 0.17. The phenolic reaction mixture was heated at 90 ° C for 2.5 After hours, 89% of the aldehyde equivalent added to the reaction mixture had reacted. The percentage of water in the reaction mixture was 4.9%. The Chiang reaction mixture was then heated to 160 ° C for 25 minutes and held at 160 ° C for one hour, after which Distilled under vacuum at 175 ° C to remove most of the phenol. The product was then discharged from the flask. The remaining half of the reaction mixture without phenol added was heated to 160 ° C as described above and vacuum evaporated to 175 ° C to remove Except for discretionary use. 0.22 mole of acetic acid to acid The resulting phenol-glyoxal condensation product is referred to in these tables as Example 10.22, and the phenol-glyoxal condensation product prepared using a molar ratio of glyoxal to phenol of 0.17 is shown in the table. It is called Example 10.Π. During the reaction, for Example 10.Π and Example 1022, the aldehyde equivalent in the reaction mixture was maintained to be less than the total amount of glyoxal (to be added for the production of the phenol-glyoxal condensation product) About 70% of the aldehyde equivalent in). The properties of the polyhydric ·· are shown in the following table. The polyphenols of Example 10.17 and Example 10.12 were heated under complete vacuum at 19 ° C for one hour. The properties of these products are shown in the following table. The heated sample of Example 10.17 is called Example 10.17Η, and the sample of Example ι22 is called Example 10.22Η. It can be seen from the table that the heated sample exhibits improved optical properties. 37 This paper size is in accordance with the Chinese National Standard (cnS) A4 specification (21G X 297 male f ^ " 524816 A7 ___B7___ V. Description of the invention (private) Example 11 Preparation of phenol-glyoxal condensation product, which is added with secondary ethylene The glyoxal-glyoxal-phenol mowa ratio is 0.17. HC was removed at 90 ° C using trichloroacetic acid catalyst and alkaline materials. 709.3 g (7.54 moles) of phenol and 17.7 g of trichloride In acetic acid (2.5%, based on the weight of the phenol added), 92.9 g of 40% glyoxal (0.64 moles) / 7jc was added for 27 minutes. The temperature was maintained for 1.5 hours, and after 1.5 hours, 58% aldehyde The equivalents have reacted. Subsequently, 62.2 g of distillate was vacuum distilled from the reaction mixture for 26 minutes at 90 ° C. After distillation, 70% of the aldehyde equivalents added were reacted (converted), and the The amount of residual water is about 3.5%. Another 92.9 grams of 40% glyoxal (0.64 moles, 1.28 moles in total) are added for half an hour while maintaining the temperature for 1.5 hours. The total mole of glyoxal to phenol in this example The ear ratio is 0.17. After this heating, about 62% of the aldehyde equivalent added to the reaction mixture has reacted. Then at 90 ° C for 25 minutes 81.6 grams of distillate was distilled off in vacuum. After distillation, 72% of the added aldehyde equivalent was converted and the residual water in the reaction mixture was 3.5%. Maintaining a temperature of 90 ° C for another 1.5 hours, after this 1.5 hours About 88% of the aldehyde equivalents added have reacted. After half an hour, 1.0 g of pyridine is added. At this time '88% of the aldehyde equivalents that have been added to the reaction mixture have reacted. The temperature has risen to 125 ° C. Keep it at this temperature for 70 minutes, then raise it to 160 ° C for 1.5 hours, and keep it at this temperature for 23 minutes to complete the decomposition of the acid. Under complete vacuum, heat phenol-ethyl at 190 ° C. The dialdehyde condensation product was removed for one hour to remove unreacted phenol and to prepare a phenol-glyoxal condensation product, which is also referred to as Example 11 in the following table. During the reaction, the aldehyde equivalent in the reaction mixture was maintained at less than ethylene _About 70% of the aldehyde equivalent in the total amount (to be added for the production of phenol-glyoxal condensation products) 〇38 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Please read the back first (Notes on this page) Γ Member of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the Consumer Cooperative 524816 A7 B7 V. Description of the invention (a) Example 12 (comparative example) The preparation of a phenol-glyoxal condensation product, in which glyoxal is added twice, and the glyoxal-phenol molar ratio is 0.17, Trichloroacetic acid catalyst was used to remove HC1 without using alkaline substances. The procedure of Example 11 was followed, except that basic materials (such as pyridine) were not added to the reaction mixture until the temperature was raised to 125 ° C and the catalyst was removed; the final temperature after removal of phenol was 175 ° C. The treatment of this example was discontinued when heated to 175 ° C because of the high viscosity. This example is also referred to as Example 12 in the table. Table 1, some phenol-glyoxal polyphenols 1 (Please read the precautions on the back before

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Example Molecular weight Mw / Mn Phenol% TPE,% II Viscosity cps (175 ° C) 1 451/331 0.15 4.15 480 2 464/347 (465 / 362f 0.29 5.10 510 3 468/351 2.05 8.53 300 * 4 572/387 3.46 13.21 900 * 5A 538/376 1.13 10.1 891 6 494/353 0.04 1.73 530 7 508/358 0.04 2.74 670 9 475/356 0.19 10.42 2,400 10.17 485/348 3.80 5.5 350 * 10.17H 496/357 < 0.05 5.79 1088 10.22 518 / 364 3.88 5.60 400 * 10.22H 528/366 < 0.05 4.83 1700 11 518/363 0.3 4.85 2040 12 552/357 0.30 1.02 > 9,000 I (a) 値 before catalyst removal * These examples have high phenol content 39. • Line-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 524816 A7 B7 V. Description of the invention) Examples 1, 6 and 7 given in Table 1 above give The lowest TPE percentage, even though Examples 1-3 use the same catalyst and the same reactant mole ratio. Conventional catalysts such as HC1 (Conventional Example) and Acid Expansion (Conductive Examples 5A and 9) give a very high degree of TPE. Even when oxalic acid is not used, the addition of glyoxal and the removal of distillate also give high TPE.値 (Example 3). Post-heating at 190 ° C in Examples 10.17H and 10.22H showed no significant effect on molecular weight or no TPE 'but reduced free phenol content and increased viscosity. Table 2 _ Camphor light data of 0.05% winter phenol or epoxidized polyphenols in tetragas sulfan (THF), the detection time is one second, and the excitation wavelength is 1. Please read memorandum

¥ Page I 442nm Example or product The maximum intensity count wavelength is the largest 计数, nm 1 11232 526 5A 6516 532 6 11502 538 7 10535 532 Epon 1031 and 6403 528 —_ * EPON 1031 (CAS: 7328-97-4) is an inclusive (Through phenyl) E-order

The polyphenols of alkane tetraglycidyl ether are printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and sold by Seh11 Petroleum Company of Emeryvile, California. From Table 2 above, it can be known that the fluorescence of Examples 1, 6 and 7 (these are acid-glyoxal condensation products of the present invention) is about 70% higher than that of Example 5A. Example 5A was prepared using a sulfonic acid catalyst. The same results are shown in Tables 3 and 4 below. 40 This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 524816 A7 ____B7_ V. Description of the invention (;? /) Table 3 0.05% epoxy polyphenols The fluorescence of the solution in THF, the excitation wavelength is 442nm and the detection time is 1.0 second. The maximum intensity count wavelength of the material is the largest, nm EPON 1031 9640 527 Example 8 14,600 535 As can be seen from Table 3 above, the product of Example 8 is an example. 6 Θ spoon epoxidation product, showing a fluorescence of about 50% over the commercial EPON · 1031. Table 4 Fluorescence data obtained from a solution of 0.05% polyphenol in tetrahydrofuran (THF). The detection time is one second and the excitation wavelength is 442 nm. The data in Table 4 are different from those in Tables 2 and 3. Concentration of polyphenols obtained by date (% by weight) Maximum intensity Counting wavelength maximum nm 1 0.0500 16640 530 1 0.0500 16300 531 2 0.0503 13550 530 2 0.0503 13510 529 3 0.0500 12860 536 3 0.0500 12640 532 4 0.0500 13960 523 4 0.0490 13850 525 5A 0.050 9920 535 5A 0.050 9620 530 41 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

524816 A7 B7 V. Description of the invention (π) 2 · 0.0498 6940 540 3 * 0.0501 5130 530 3 * • 0.0501 5280 527 5A * 0.0503 5010 530 * These actinides belong to the reaction mixture before catalyst removal. As can be seen from Table 4 above, the fluorescence of Example 1 is substantially higher than that of other examples, including Examples 2 and 3 (they use the same catalyst and the same reactant mole ratio). Table 5 · Ultraviolet (UV) absorption data in dilute tetrahydrofuran (10 mg / ml) Material at 350 nm at 365 nm Example 1 0.544 0.300 Example 2 0.470 0.258 Example 3 0.500 0.270 Example 5A 0.367 0.220 Example 5A EF 0.290 0,168 Example 6 0.515 0.288 Example 8 0.400 0.223 Example 9 0.266 0.134 Example 10.17 0.385 0.216 Example 10.17H 0.416 0.224 Example 10.22 0.418 0.239 Example 10.22H 0.470 0.258 Example 11 0.728, 0.739 0.395, 0.404 Example 12 0.465 0.317 EPON 1031 0.273 0.161 Pure TPE 0.000 0.000 Epoxy can be known from Table 5 above. Examples 1 and 11 are at 350 and 365nm. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm). Please read the notes on the back first. Printed by Bureau Consumers Cooperative

524816 A7 ________________ B7 5. The invention description (M) shows the highest absorption. Compared to the products of Examples 5A and 9 catalyzed by sulfonic acid, all oxalic acid catalyzed products showed higher absorption. Other properties are equal, the higher the concentration of TPE, the lower the optical properties. Moreover, it should be noted that TPE. Has no absorbance under the test conditions. It can also be known that the phenol-glyoxal condensation products of Examples 10 and 11 (which were heated at 190 ° C for one hour) compared with the products before heating, that is, the products of Examples 10.17 and 10.22, that is, Example 10. · ΠΗ, Example 10.22H, and Example 11 have better optical properties. In addition, it can be known that the epoxidation product of Example 1, that is, 1 * glycidylated Example 8, exhibits a higher degree of absorption than the commercial EPON 1031. Although the product of Example I2 exhibited high absorption 値, its viscosity was too high, i.e., it exceeded 9000 cps (at 175 ° C), as shown in Table 1 above, and was therefore unacceptable. Table 6 Degrees and Units of Hydrogen Perylene (WPE) I i I-ϋ l · — 1 I IT II nnn · ϋ I (Please read the precautions on the back before filling out this page) * Line · Intellectual Property Bureau of the Ministry of Economic Affairs Printed by employee consumer cooperatives ~~ Material Mw / Mn Viscosity ^ cps WPE EPON 1031 895/395 14880 (100 ° C) 997 (125 ° 〇172 (150 ...) 216 Epoxy of Example 6 576/348 12210 (100 ° C) 1580 (125 ° 〇440 (aviation) 214 Example 15A Epoxide 767/374 11580 (100 ° 〇821 (125 ° 〇142 (150 ° 〇233 43 $ Paper size applies to Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) 524816 A7 B7 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (4> 〇 Table 7 Fluorescence data obtained from a solution of the product in 0.05% THF, But the emission wavelength is 442nm, and the detection time is half a second. The maximum product intensity is below the maximum counting wavelength. Example 6 19,960 531 Example 11 17,390 532 Example 10.22 19,040 530 Example 10.22H 19,940 530 Example 10.17H 20,120 530 Table 8 Measure the dissolution of different phenol-glyoxal condensates in 50% acetone 10 grams of each acetone and solid were added to a large glass bottle with an inner diameter of 7/8 inches, warmed under vigorous stirring, and then allowed to settle at room temperature for a day. The total height of the mixture was 1.75 inches. The upper layer is reported in millimeters (mm). Lower thorium shows lower solubility. Material clear liquid Example 1 32 Example 2 30 Example 4 8 Example 5A 23 Example 10.17 17 Example 10.22 22 Example 6 41 Example 9 7 Example 11 24 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 524816 A7 B7 V. Description of the invention (to) Test the 50% solubility of several materials in methyl ethyl ketone. After 10 days, the products of Examples 1-3 and 11 were still completely dissolved at room temperature. The product of Example 5A deposited some products after being left for 3 days. Table 9 Polyphenols and EPON] Metal ions containing epoxide metal EP 31 〇n Ion example 1 Bud example 6 Example 7 Example 5Α + i〇li Na 0.003 0.001 0.002 0.017 0.028 Ca 0.002 0.001 0.001 • < 0.001 0.001 Fe < 0.001 < 0.001 0.001 < 0.001 < 0.001 K 0.008 < 0.001 < 0.001 < 0.001 0.001 * its Example 13 Preparation of pre-SBS material bad product of Example 5A of large equipment for producing a compound of formula and see below to prepare a resin matrix of the prepreg laminate and bad. (Please read the precautions on the back before filling this page) ί Line · Weight percentage of printed materials of employees' cooperatives in the Intellectual Property Bureau of the Ministry of Economic Affairs 1. Brominated epoxy resin (EPON 1124 A80, Shell Chemical Company) 60.0 2. Phenol- Glyoxal condensate (PGC) 3.0 3. Phenolic lacquer resin hardener (Durite SD1711, Borden Chemical Co.) 14.4 4. Acetone 15.05 5. Methyl ethyl ketone 7.45 6.2-methylimidazole 0.2 Preparation of two viscosities of 2000cps (25.〇 solution, where two different 卩 0 (: '3.? 〇 (:, 3 (phenol-glyoxal condensate) for Example 6 and Example 45) This paper size applies the Chinese National Standard (CNS ) A4 specification (210 X 297 public love) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 524816 A7 B7 V. Description of Invention (kiV) Example 5A (as shown in the previous examples) of epoxide (glycidyl) Derivatives). The epoxide system of Example 6 was prepared by the method of Example 8 and the epoxide system of Example 5A was prepared by substantially the same steps. The series of properties of the two materials is in Experiment 13A.

Test 13A

Epoxide Mw / Mn viscosity, cps WPE Example 6 576/348 12210 (100 ° C), 214 Example 5A 767/374 11580 (100 ° 〇233 By using BGF643 coating (finish), 2116 type glass (E -Glass) manual impregnation method to prepare two layers of 7-8mils thick, 11.5 square inches. Typical hardening conditions need to meet the International Institute of Electronics Manufacturing (NEMA) FR4 specifications, which means that for prepregs, the 1.5 minutes in an oven at 325-350 ° C. The prepreg is then cooled to room temperature and heated for more than 45 minutes to 350 ° F, and then maintained at this temperature for about 30 minutes before cooling to room temperature The resin content of the laminate is about 60% by weight. The laminate is then cut to 4 square inches and detected by an automatic optical inspection (AOI) instrument. In the case of ultraviolet absorption, the following instrument can be used : Hewlett-Packard ^ HP BV 3000, Teradyne's 5539 and Orbitech's VT 8000. The results of the AOI fluorescence test are shown in Test 13B, in which the test is performed twice or three times. 46 This paper standard is applicable to the Chinese National Standard (CNS) A4 specification ( 210 X 297 Public Love 1 _

524816 Printed by A7 B7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs. 5. Description of the Invention (叱 <) Test 13B Strong epoxide PGC in the formula of fluorescein—epoxide of Example 6 192.2 194.7 Ring of Example 5A Oxide 130.8 125.4 135.5 The data in the above test IIB show that the formulation using the epoxide of Example 6 shows a 48% higher fluorescence than the formulation using the epoxide of Example 5A. '' Replace the epoxide of Example 6. with an unepoxidized material, and even the AOI discussed above, the phenol-glycol condensation product of Example 6 in the laminated formulation and the phenol of Example 5A will be used. Compared with the ethylene glycol condensate, it is shown that the phenol-ethylene glycol condensate of Example 6 is higher than about 50% to 70% of the fluorescence obtained from Example 5A, and can be used for the CCD of A0I instrument ( A charged couple device camera provides better images. The brominated epoxides used in the foregoing formulations can be partially or completely replaced with bisphenol-A epoxy resins having similar epoxy equivalents to achieve similar results. The formula of Example 13 is the preferred formula. However, the brominated epoxy resin can vary from about 40% to 80% by weight of the formulation, and the resin can be substituted with different halogens, such as chlorine. However, if the flame retardancy is desired, the epoxy resin need not be halogenated, and the flame retardancy can be obtained by adding a conventional flame retardant. The phenol-glyoxal condensate can vary from about 1% or 2% to about 15% and can be fully or partially substituted with the same amount of phenol-glyoxal residue. The amount of phenolic resin hardener may vary from about 7% to about 35%, and the amount of the solvent system may vary from about 10 to about 35%, all percentages or parts being weight ratios. 47 Dynamic range Interference degree 2.0 2.0 1.6 1.5 1.8 (Please read the precautions on the back before

«-Line · This paper size is in accordance with Chinese National Standard (CNS) A4 specification (21〇X 297 public love) 524816 A7 ____B7 V. Description of the invention (4) Example 14 The fluorescence analysis compared with acridine orange-based is implemented here In the example, a solution of 0.05% by weight of a sample dissolved in tetrahydrofuran (THF) at the spectral level was used to collect all spectra. The solution can be prepared by dissolving the solid in the necessary amount of .THF to produce the desired concentration. Standard Aldrich Orange (Aldrich Chemical Co., Milwaukee, WI ·) solution (0.78 // M) can be prepared by diluting the concentrated dye solution in methanol. The standard concentration can be confirmed by absorption spectrum. The CM 1000 was set to provide 442 nm excitation and a 0.5 second detection time was used for measurement. Table 14 represents the measurement results of fluorescence intensity, which are reported in counts per second, that is, the percentage of intensity at individual wavelengths. Table 14 Results of fluorescence analysis using CM1000 In this table, the excitation wavelength is 442 nm; the detection time is 0.5 seconds and the concentration is 0.05 wt%. The maximum fluorescence of the sample, the intensity of nm, the count / s relative to the intensity standard of D-Yazu orange,% acridine orange 0.78 // 528 24000 M (0.2mg / L) dissolved in methanol (maximum) 23800 524 24000 530 23800 532 23400 535 The condensate of Example 5A 532 24000 100 The condensate of Example 6 532 40 600 170 48 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -------- r -------- (Please read the notes on the back before filling in this page) Order ·-· Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Claims (1)

A8B8C8D8 524816 6. Scope of patent application The oil-based ether resin is based on glycidyl bisphenol A. (Please read the notes on the back before writing this page) 8. According to the resin of item 1 of the patent application, where the polyepoxy resin is a glycidyl methacrylate poly (glycidylated) copolymer and One member is selected from the group consisting of acrylates, methacrylates, phenethyl stores, and mixtures thereof. 9. The resin ' according to item 1 of the scope of patent application has at least an epoxy equivalent weight per unit. 10. A glycidylated polyphenol of phenol and glyoxal. The glycidylated polyphenol has an ultraviolet absorption of at least 0.200 at 365 nm and / or at least 300 at 350 nm. 11. The polyphenol according to item 10 of the application, wherein the phenol of the polyphenol is the phenol itself. Line 12. A composition comprising an epoxy resin and, for each 100 parts of the epoxy resin, also: (a) 18 to 25 parts of a hardener for an epoxy resin; and (b) 1 to One of the 30 members is selected from the group consisting of: glycidylated polyphenols of phenol and glyoxal, wherein the polyphenols have at least 0.260 at 365 nm and / or at 365 nm before glycidylation. UV absorbance of at least 0.400 at 350nm; a reaction product of each part of phenol and glyoxal polyphenol and 4 to 8 parts of glycidyl epoxy resin, wherein the polyphenol has Polyphenols of phenol and glyoxal having a UV absorption of at least 0.260 at 365 nm and / or at least 0.400 at 350 nm; and a polyphenol of glyoxal at a wavelength of at least 0.260 at 365 nm and / or at least 0.400 at 350 nm; and mixtures thereof. 13. The composition according to item 12 of the scope of the patent application, in which the hard ----------- 7 _____ This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 public variable) 524816 A8 B8 C8 D8 6. The scope of patent application is phenol-formaldehyde phenolic resin or p-cresol-formaldehyde resin or mixture. (Please read the precautions on the back before writing this page) 14. According to the composition of the scope of application for item 12, the hardener is dicyandiamide. 15. The composition according to item 13 of the scope of patent application, which includes an epoxy hardening accelerator, in an amount sufficient to accelerate the hardening of the epoxy resin. 16. A hardened composition of a composition according to item 15 of the scope of patent application, wherein for every 100 parts of epoxy resin, there are: (a) 18 to 25 parts of hardener, which is a selection of free phenol-formaldehyde novolac Resin or p-cresol-formaldehyde resin or a mixture thereof; and (b) one to 30 members, selected from the group consisting of: glycidylation of phenol and glyoxal A polyhydric phenol in which, prior to glycidylation, the polyhydric phenol has an ultraviolet absorption of at least 0.260 at 365 nm and / or at least 0.400 at 350 nm; a polyphenol of glyoxal and 4 to 8 parts per phenol The reaction product of a glycidyl epoxy resin, wherein before the glycidation, the polyphenol has an ultraviolet absorbance of at least 0.260 at 365 nm and / or at least 0.400 at 350 nm; it has an absorbance of at least 0.260 at 365 nm and / or at Polyols with a UV absorption of at least 0.400 and polyhydric phenols of glyoxal at 350mn; and mixtures thereof, and wherein the composition includes an epoxy hardening accelerator in an amount sufficient to accelerate the hardening of the epoxy resin. 17. The composition according to item 12 of the scope of patent application, in which 100 parts of epoxy resin is roughly bisphenol A having an epoxy equivalent weight of 190 to 10,000. 18. A hardened composition according to item 17 of the scope of the patent application, wherein the composition includes epoxy resin (which is roughly the size of this paper applicable to the Chinese National Standard (CNS) A4 specification (210 X 297) (%) 524816 8s8 D8 6. Scope of patent application (please read the precautions on the back before writing this page) 190 to 10,000 units of epoxy equivalent weight of bisphenol a, of which for every 100 parts of epoxy Resin having: (a) 18 to 25 parts of hardener, which is selected from the group consisting of free phenol-formaldehyde phenol resin or p-cresol-formaldehyde resin or mixtures thereof; and (b) 1 to 30 parts A member is selected from the group consisting of glycidylated polyphenols of phenol and glyoxal, wherein the polyfluorene has at least 0.260 and / or 350 nm at 365 nm before glycidylation. A UV absorption of at least 0.400; a reaction product of each part of phenol and glyoxal polyhydric phenol and 4 to 8 parts of glycidyl epoxy resin, wherein the polyphenol has a temperature of 365 nm before glycidylation At least 0.260 and / or at 3 UV absorbance of at least 0.400 at 50nm; polyphenols of phenol and glyoxal having UV absorbance of at least 0.260 at 365nm and / or at least 0.400 at 350nm; and mixtures thereof, and wherein the composition includes portions sufficient to accelerate Epoxy hardening accelerator for epoxy resin hardening 19. A composition comprising: (a) 50 to 97 parts by weight of ultraviolet absorption having less than 0.260 at 365nm and / or less than 0.4Ό0 at 350nm Degree of phenolic phenolic resin; and (b) 3 to 50 parts of polyphenols of phenol and glyoxal having an ultraviolet absorbance of at least 0.260 at 365 nm and / or at least 0.400 at 350 nm. 20. According to the scope of patent application The composition of item 19 includes 100 parts of epoxy resin for each of 15 to 30 parts of the phenol-based phenolic resin and polyhydric phenol in the scope of patent application. 21. A composition according to item 20 of the scope of patent application Hardened composition of materials, wherein the composition includes: (a) 50 to 97 parts by weight with ______4 ________ This paper size applies the Chinese National Standard (CNS) A4 specification (210 x 297 mm) A8B8C8D8 524816 Six Patent applications for phenolic phenolic resins with an ultraviolet absorbency of less than 0.260 at 365nm and / or 0.400 at 350nm; and (b) 3 to 50 parts with at least 0.260 and / or 365nm Polyphenols of phenol and glyoxal with an ultraviolet absorptivity of at least 0.400 at 350nm; and for every 15 to 30 parts of the phenolic phenolic resin and polyphenols, the composition additionally contains 100 parts of epoxy resin . 22. A method for manufacturing an epoxy resin, comprising a glycidylated phenol-glyoxal condensation product, which has at least 0.26 ° at 365 nm and / or at least 35 ° nm before being glycidylated. · UV absorption of 400. 23. A method for manufacturing an epoxy resin, comprising reacting 4 to 8 parts of a polyepoxide for each part of a phenol and glyoxal condensation product, which has at least 0_260 and / or at 365 nm before epoxidation. Ultraviolet absorption at 350 nm of at least 0.400. ------------------------- i (Please read the precautions on the back before writing this page ^), Yi Ding Thread paper size is applicable China National Standard (CNS) A4 (210 X 297 mm)