JPH06510819A - Bis-dicyandiamide as a curing agent for Niposhiki resins - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Background of the invention of bis-dicyandiamide as a curing agent for epoxy resins The present invention relates generally to the curing of epoxy resins, and more particularly to the curing of epoxy resins. This invention relates to improvements in curing agents used. Dicyandiamide (also known as cyanoguanidine) Although it is well known as a curing agent for epoxy resins, it has serious drawbacks. It is also known that It, like water, is unusable in most applications. This may be because the solvent is relatively expensive, such as dimethylformamide, or because the solvent is relatively expensive. soluble only in undesirable solvents because they are soluble and environmentally undesirable .

In U.S. Pat. No. 3,553,166, metal salts of imidazole and A curing agent is disclosed in combination with another compound which may be cyandiamide. There is. These hardeners cure at high temperatures and are used in some epoxy compositions. cannot be stored for long periods at ambient temperature.

Another combination of cyandimide and a second compound is disclosed in U.S. Pat. No. 4,311.7. No. 53, where dicyanamide is The present invention provides a curing agent for mixtures of di- and tetrafunctional epoxides in combination with Nidine.

Reaction of dicyandiamide with formaldehyde and amine-terminated polyether The reaction product is an ester, as shown in U.S. Pat. Can be used to cure poxy resins.

A somewhat similar composition is described in Japanese Patent Application No. 61-207425 published in Japan. cyanoguanidine compounds, polyether amines and guanidine compounds. An epoxy curing agent combined with a hardening compound is used.

Two recently published European patent applications are useful as curing agents for epoxy resins It includes certain substituted cyanoguanidines called cyanoguanidines. European Patent No. 306. No. 451 discloses oligomers of substituted 3-cyanoguanidines. . Such compounds are produced by reacting monoisocyanates and diisocyanates. After producing the oligomer, it is reacted with cyanamide to produce a compound with the formula Manufactured by These compounds are oligomeric and The functionality of these compounds is due to the substitution of both terminal amino groups. This is different from that of the present inventor in that the number is decreased. The applicant is The above-mentioned problems inherent in the use of mido, i.e., using unfavorable solvents, The company was aware of the requirements. Novel oligomeric cyanoguanidines can be prepared in suitable solvents. It is said to produce epoxy resins that are sufficiently soluble in water and have a high glass transition temperature. ing. Another published application is European Patent No. 310.545 (U.S. Patent No. 4,859.761), in which the formula Disubstituted cyanoguanidines having the following are said to be useful as curing agents for epoxy resins. It is being said. These substituted cyanoguanidines can be synthesized by disubstituted carbodiimides. Manufactured. Similar to the compound of EP 306,451, these two Substituted cyanoguanidines have both terminal amine groups substituted.

Substituted cyanoguanidines are further described in U.S. Pat. No. 3,734,868. It has been suggested that it is useful in the production of polyurethane.

Additionally, related substances have been used as precursors for various drugs, including - US Pat. No. 4,560,690.

U.S. Pat. No. 2,455,807 describes the bis-dicyandiamidation of the present invention. The present invention relates to a preferred method of manufacturing the compound. Reaction of dicyanamide with desired amine has been shown to produce bis-dicyandiamide.

In co-pending U.S. Patent Application No. 071,557.445, the inventors The use of monosubstituted cyanoguanidine with the following formula as a curing agent for epoxy resins: Disclosed.

C.N. ;1 The present inventor has developed another family of curing agents for epoxy resins, which will be disclosed in detail below. discovered.

Summary of the invention Curing agent for epoxy resins with improved solubility, formula % formula % R' and R' are independently -H, -CH3, -CH2CH3, -CH2CH2 CH3, -CH2CH(CH3)2, n is an integer from 2 to 12, a is 0 or an integer from 1 to 5, b is 0 or an integer from 1 to 5, C is 0 or an integer from 1 to 5, d is an integer from 1 to 4, R'' is -H, -CH3, -CH2CH3, -CH2CH2CH3, [phase] ) found in bis-dicyanimide with Bisuzician like this Dimide can be dissolved in various solvents, preferably acetone, methyl ethyl ketone, methyl iso Butyl ketone, cyclohexanone, methanol, ethanol, isopropanol , acetone/methanol, acetone/ethanol, acetone/isopropanol , methyl ethyl ketone/methanol, methyl ethyl ketone/ethanol and methyl Soluble in thyl ethyl ketone/isopropanol. Acts as a hardening agent In this case, the substituted bis-dicyandiamide contains up to about 24% by weight of the epoxy resin precursor. %, preferably from 2 to 16% by weight.

In another aspect, the present invention provides a method of curing an epoxy resin as well as a method for curing an epoxy resin. The amount of reactivity of bis-dicyandiamide defined in The method and curing in amounts up to about 24% by weight, preferably from 2 to 16% by weight. It is a product of curing that occurs under certain conditions.

Description of preferred embodiments Although dicyandiamide (i.e., cyanoguanidine) is widely used, This requires the use of undesirable solvents such as dimethylformamide. has been found to be an undesirable curing agent for epoxy resins. equivalent or If more soluble compounds are discovered that provide improved curing properties, cyanogua can be replaced with ginseng and avoid undesirable solvents. Furthermore, The manufacturing costs, reduced by the use of less expensive solvents, are This can be the result of significant changes. The inventors have discovered significant advantages over currently used compounds. A layer of bis-dicyandiamide with dots was discovered.

Composition of bis-dicyandiamide The inventor has determined that the formula %formula% R' and R' are independently -H, -CH3, -CH2CH3, -CH2CH2 CH3, -CH2CH(CH3)2, n is an integer from 2 to 12, a is O or an integer from 1 to 5, b is 0 or an integer from 1 to 5, C is O or an integer from 1 to 5, d is an integer from 1 to 4, R'' is -H, -CH3, -CH2CH3, -CH2CH2CH3, ) bis-dicyandiamide having an improved solubility over the parent compound. , and still preferably they contain up to about 24% by weight of the epoxy resin precursor. It has been shown that it retains such high curing ability that it is effective at amounts of 2 to 16% by weight. I saw it.

Bis-dicyandiamide of the present invention and the second specification of European Patent No. 310.545 Substituted cyanoguanidines differ in their degree of reactive functionality. The curing agent reacts and crosslinks The amine groups are combined with the epoxide groups to produce an epoxy-based polymer network. react. The degree of reactive functionality of cyanoguanidine is determined by the degree of functionalization of cyanoguanidine. It depends on the degree and is related to the number of exchangeable nitrogen hydrogens of cyanoguanidine. . For example, the specified functionality of dicyandiamide (cyanoguanidine) is 4. , that is, it can be added to four epoxide groups. -Replacement In the case of cyanoguanidine, the degree of functionality is 3, which means that it has three epoxide groups and can be met. European Patent No. 310,545 (U.S. Pat. No. 4,85 9.761)). is 2, which can react with two epoxide groups. The screw of the present invention - The degree of functionality of dicyandiamide is between 4 and 6.

The reactive functionality of the curing agent affects the polymer network produced in the cured polymer system. influence the type of the structural structure and, as a result, improve the performance characteristics in the B stage, i.e. prepreg. properties, e.g. viscosity as a curing function, solvent resistance of the polymer, glass value of the polymer Curing agent of degree 2 (European Patent No. 310,545/U.S. Pat. No. 4,859. 761), the network structure has a high degree of branching with a slightly small degree of branching. It has a linear structure. As in the case of the present invention, the degree of reactive functionality is 3 or more. When using a curing agent, the polymer network can form a highly branched or star-like structure and It has a minimal linear type structure. A branched or star-like structure is a B-stage tree during stacking. Affects resin fluidity (resin flow viscosity) of fat. If the resin flow viscosity is low, the The shaped laminate or composition experiences a high degree of resin flow and is free from voids or resin defects. Produces laminates or compositions with good product. The linear structure in the cured polymer is Inadequate solvent resistance due to solvation of polymer fragments or swelling of the polymer arise. Branched or star-like structures result from the formation of a more highly cross-linked network. Provides improved solvent resistance. A linear structure is more important than a polymer with a branched structure. can produce polymers with low Tg and higher coefficients of thermal expansion. Ru.

solvent The parent compound dicyandiamide is dimethylformamide, dimethylsulfonamide, cid, dimethylacetamide, N-methyl-2-pyrrolidone and methanol. It is soluble only in a small group of commonly available solvents, including: The bis-di of the present invention Cyandiamide is acetone, methyl ethyl ketone, methyl isobutyl ketone, Cyclohexanone, methanol, ethanol and isopropanol or mixture Solvents, e.g. acetone/methanol, acetone/ethanol, acetone/iso Proper tool, methyl ethyl ketone/methanol, methyl ethyl ketone/ethano Methyl ethyl ketone/isopropanol, methyl isobutyl ketone/meth Nor, methyl isobutyl ketone/ethanol and methyl isobutyl ketone/ Soluble in many more desirable solvents including isopropanol or pure epoxy resins It is gender. In particular, acetone, methyl ethyl ketone, methyl isobutyl ketone, Clohexanone, acetone/methanol, acetone/ethanol, acetone/i Sopropatol, methyl ethyl ketone/methanol, methyl ethyl ketone/etha Nor and methyl ethyl ketone/isopropanol are preferred solvents.

The compounds of the invention are generally soluble in these types of solvents in amounts up to about 20% by weight. It is gender. In many cases, the desired amount of substituted cyanoguanidine can be up to about 8 to 20 After dissolving in sufficient solvent to produce a solution containing up to % by weight of the compound, The solution is mixed with the epoxy precursor and cured under curing conditions.

Epoxy resin The bis-dicyandiamide of the present invention can be used with various epoxy compounds known in the art. It can be used with resin precursors. Generally, these include Gigli Diglycidyl bisphenol-A (DGEBA), diglycidyl tetrabromobis Phenol-A, triglycidyltriphenolmethane, triglycidyltrif enol ethane, tetraglycidyltetraphenolethane, tetraglycidyl There are methylene dianilines and their oligomers and mixtures. More details The diglycidyl bisphenol-A (DGEBA) species is the same as the curing agent of the present invention. It was found that both methods gave suitable results.

Catalyst for epoxy resin A catalyst is used to accelerate the reaction between bis-dicyandiamide and epoxy resin. It can prove useful to have a Various catalysts that can be used are known in the art. This product offers unique advantages over others The catalyst they are considering does not contain transition metals. In general, as a catalyst, imidazo 2-methylimidazole, 2-phenylimidazole, 1-cyanoethyl- 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methy imidazole, 4-phenylimidazole, 2-ethylimidazole, 2-ethylimidazole Tyl-4-methylimidazole, benzyldimethylamine, 4-(dimethylamidazole) -N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine Examples include dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, and the like.

Manufacture of laminate products The advantages of the bis-dicyandiamide of the present invention are in the production of reinforced laminates for the electronics industry. cross-links epoxy resins without the need for complex and undesirable solvent use. Their ability to replace dicyandiamide, which is commonly used to Ru. The methods used to manufacture such laminates are well known to those skilled in the art and and the method has been significantly modified to accommodate the bis-dicyandiamide of the present invention. Therefore, there is no need to discuss it in detail here in connection with the present invention. Generally, glass The fabrics used to strengthen laminates typically made from fibers are treated with crosslinkers and and coated with an epoxy resin combined with the desired catalyst. Wear. The cloth is then heated to drive out the solvent and remove the epoxy resin and crosslinking agent. Curing (polymerization and crosslinking). Generally, multi-layered fabrics are combined to create electronic circuits. We provide laminates needed for boards. If only partial curing is carried out, the resulting raw material The composition is often referred to as a "prepreg" or "B-stage" material. further hardens later to complete the laminated product. These processes are batch processes that are familiar to those skilled in the art. carried out in a method or a continuous method.

Production of bis-dicyandiamide The curing agents of the present invention can be manufactured by various methods known to those skilled in the art. Wear. For example, May (J, Or, Chem, 12.437-44 2.442-445 (1947)) and Curd (J, Chem , Soc, 1630-1636 (1948)), aryl isothiocyane N-cyanamide was obtained by reaction with sodium cyanamide followed by reaction with methyl iodide. The method for producing ano-8-methyl-N'-arylisothiourea is based on ammonia Cyanoguanidine is produced by reaction with Cards (J, Chem, Soc .

, 729-737 (1946)) and Rose (24 national special editions) No. 577.843) is a method in which an aryldiazonium salt and a dicyandiazonium salt are Substituted aryl-azo-dicyandiamides or triases using reaction with amides which is pyrolyzed to produce nitrogen and the corresponding substituted cyanoguanidine. do.

The inventors are familiar with the work of Redmon et al. in U.S. Patent No. 2. 455.　 Special features when the method disclosed in No. 807 produces bis-dicyandiamide I think it depends on the fixed value. This method generally follows the following reaction by Redmon et al. It can be described by

In fact, metal salts of dicyanamide (CN-NH-CN), e.g. Preferably, anamides are used. In the present invention, bis-dicyandiamide is dia in a suitable solvent such as butanol, ethanol, propatool and water. Manufactured by dissolving or mixing with hydrochloric acid to form a slurry be done. Sodium dicyanamide is added in approximately chemical amounts. The reaction is about 75℃ To complete the reaction at a temperature of ~110°C and a pressure of ~2068 kPa atmospheric pressure. It will be carried out for the required time. Preferably, a temperature of about 100°C to 110°C is used to conduct the reaction. The time is about 2-24 hours. The solvent, if used, is then distilled off and the bis- Dicyandiamide is recovered by crystallization and washing. When using hydrochloric acid, solid After the body is filtered and washed, it is redissolved and crystallized from the solution.

2.2-dimethyl-1,3-propanediamine hydrochloride 50. 0g (0,28 6 mol), sodium dicyanamide 55.27 g (0.56 mol) and water 3 0 mL into a 500 mL three-bottom flo-maru equipped with a mechanical stirrer and heating mantle. in the bottom flask. Temperatures were raised to 100°C under air flow to aid water removal. I raised it. After removing the water, add 80 mL of butanol to the flask and mix The material was heated at 105° C. for 17 hours. Add 300 mL of water and add butanol. Removed by boiling distillation. Cooling precipitated a light brown gum. decant the water and the product was dissolved in methanol. Pour this solution into the rotary Evaporate in a rotor to leave 55.3 g (81.8%) of a pale yellow amorphous powder. Ta.

Example 2・ 4.4'-Methylene-bis(cyanoguanidinocyclohexane) (MCDICY D 4.4'-methylene-bis(cyclohexylamine) 51. 0g (0, Addition funnel, condenser, machine The mixture was placed in a 50QmL three-lobe flask equipped with a mechanical stirrer and a heating mantle. blend After stirring until dissolved, add 40 concentrated HCl diluted with 50 mL of isopropanol. ．． 0 mL (0,484 mol) was added dropwise to form a white precipitate. nato1no 47.4 g (0,532 mol) of umciscyanamide was added and the mixture was refluxed. I let it happen. After the mixture was refluxed for 4 hours, the water was azeotropically distilled. Cool the mixture and A white precipitate was formed. Remove the solvent on a rotary evaporator and add water. The salts were leached from the product A. The second liquid phase is denser than the water produced; Then, it is separated in a rotary evaporator and striated to form a white amorphous material. 11 g (13% yield) of resin remained.

Example 3: Danjigo Sanbo U Emimunyuyo Ebize 4 rainbows and 1 serving 430.0 g (3,70 mol) of 1,5-diamino-2-methylpentane was Placed in a 2L round bottom flask equipped with a mechanical stirrer and addition funnel. frass Place the container in a water bath, add 615 mL (7.40 mol) of concentrated HCI drop by drop, and A bright yellow solution was obtained. Sodium dicyanamide 658.8g (7.40mol ) was added to the solution at 30°C and the temperature was increased to 100°C. Move water removal The mixture was placed under a stream of nitrogen and the mixture became very viscous. 5 hours plus After heating, add 3 liters of water and 1.51 sotol of 1-pentanol to the flask. ; and the mixture was cooled. The aqueous phase was separated and the organic phase was dissolved in 5% NaOH ( Washed with 2 L of 5% acetic acid (aqueous) and 2 L of 5% acetic acid (aqueous). Organic phase over sodium sulfate and rotary evaporate to leave a yellow glass-like resin. did. Yield was 662 g (71.4%). Elemental analysis, actual value C48.4 8%, N7.78%, N39.80%, calculated value C47.97%, N7.26%, N44.77% 1.3-xylene diamine 103. 2g (0°758 mol) and 800 mL of butanol in a condenser, addition funnel, mechanical stirrer and heat. It was placed in a 2000 mL three-day round bottom flask equipped with a mantle. butanol 20 Add one drop of 47.3 mL (0,849 mol) of concentrated sulfuric acid diluted with 0 mL to the flask. I added one. Next, 158.7 g (1.78 mol) of sodium dicyanamide and 35 mL of diluted water was added and the mixture was heated to 100°C. helps remove water The nitrogen flow was started. After 2 hours, the temperature was increased to 110°C and the water An additional 35 mL was added. This temperature was maintained for 6 hours. Add 1.5L of water and add butano. was removed by azeotropic distillation. Upon cooling, a white solid precipitates and a Buchner leak occurs. Collected at Doo. The solid was dissolved in 400 mL of 5% NaOH (aqueous), 400 mL of 5% acetic acid and Washed with 1.5 L of hot ethanol. 49 g (24% yield) of fine white powder m, p, 204-207°C were collected. Elemental analysis, actual value C53, 88%, 85.72 %, N40.19%, calculated value C53, 31%, N5.23%, N41.46%.

Example 5: Synthesis of 1.6-bis(cyanoguanidino)hexane (DAHDICY) = 1.6 -Hexanediamine hydrochloride 50.0g (0,264 mol), sodium disia 51.7 g (0,581 mol) of Namide and 30 mL of water were added to the nitrogen inlet, mechanically Placed in a 250 mL three-day round bottom flask equipped with a stirrer and heating mantle. warm The temperature was gradually increased to 100°C under nitrogen flow and the water was removed. Next, the pig 75 mL of alcohol was added and the temperature was maintained at 100° C. for 6 hours. Cool the mixture and turn white A colored solid was collected and recrystallized from aqueous ethanol. Melting range is 177-1 38 g of product (57% yield) was collected at 90°C. Elemental analysis, actual value C47°9 8%, H7, 75%, N41.88%, calculated value C47,97%, H7, 26%, N44.77%.

23.58 g (0,238 mol) of sodium dicyanamide in 35 mL of water, 250m equipped with mechanical stirrer, condenser, addition funnel, thermometer and nitrogen purge Pour into a L-fluoro round bottom flask. For this reaction, 1,2-dianilinoethane 2 5.3 g (0,119 mol) and the mixture was heated to 80°C while mixing. Heated. Dilute 19.6 mL of concentrated hydrochloric acid with 20 mL of water and add 3 mL of concentrated hydrochloric acid to the heated mixture. Added over 0 minutes. The mixture was heated for an additional hour and a precipitate began to form. Ta. The mixture was cooled, the water was decanted, and the resin precipitate was taken up in acetone. .

The solution is filtered to remove insoluble materials, dried, and washed with acetone. 25 g of brown solid (60.6% of theory) removed by tally evaporation. left behind. Elemental analysis, actual values C66, 88%, H6, 82%, N24.24%, Calculated values: C62.4%, H5.2%, N32.4%.

19.83 g of sodium dicyanamide (0,200 mole) dissolved in 35 mL of water ) equipped with a mechanical stirrer, condenser, addition funnel, thermometer and nitrogen purge. It was placed in a 250 mL 309-bottomed flask. N, N’ for this reaction mixture -diphenyl-1,4-7 22-diamine 26.1g (0,100 mol) and the mixture was heated to 80° C. with stirring. 16.5 mL of concentrated hydrochloric acid Diluted with 20 mL of water and added to the heated mixture over 30 minutes. blend The mixture was stirred at temperature for an additional hour and a gray solid began to precipitate. Cool the mixture and The solids were mixed with acetone and filtered. Rotor the acetone solution Dry in a evaporator and strip to give 24 g of gray powder (theoretical 60 g). ．． 8%) remained. Elemental analysis, actual value C80, 95%, H6, 38%, NIL, 53%, calculated value C67.0%, H4.6%, N28.4%.

Example 8: All bis-dicyandiamide derivatives and their unsubstituted parent compounds (DICY) The solubility test was carried out using a weight ratio of dicyandiamide to solvent of 1:10. Therefore, it was carried out. For example, substituted dicyandiamide 0. 1 gram of solvent ．． Added 0 grams. The samples were agitated slightly and dissolution was recorded at 25°C. vinegar That is, the grade of complete dissolution is 10, partial dissolution is +δ, and non-dissolution is -. etc. is spelled. The sample was then heated to 50°C for 30 minutes and the same grade system The solubility was recorded using TEM.

and heated to 50° C. with stirring for 30 minutes. 2-methyl-imi Dazole (2Mf) 0.044g and methyl ethyl ketone (MEK) 6.92 g was added to the above solution with stirring.

Part B: Dow epoxy 71881 resin (diglycidyl bisphenol A (DGEBA) and brominated DGEBA) 50.0 g.

Part A and Part B were mixed together and aged for 24 hours. Then volatile The varnish was B-staged on a hot plate in a thin casting pan. Grinding B-stage resin After being pulverized into a fine powder, it was cured at 170°C in a hydraulic press at 200 psj. Ta.

Polymers develop the following properties as a function of curing.

Final polymer properties after 360 minutes of curing at 170°C Tg (DSC) = 136°C , Tg (TMA) = 120±7℃, α=5D±12ppm/'C1α180 =103±3ppm/'C0 and heated to 50° C. with stirring for 30 minutes. 2-methyl-imi Dazole (2MI) 0,11g and methyl ethyl ketone (MEK) 11.15 g was added to the above solution with stirring.

Part B: Dowepoxy 71881 resin (diglycidyl bisphenol A (DGE) BA) Brominated DGEBA) 50.0 g.

Part A and Part B were mixed together and aged for 24 hours. Then volatile The varnish was B-staged on a hot plate in a thin casting pan. Grinding B-stage resin After being pulverized into a fine powder, it was cured at 170°C in a hydraulic press at 200psi. I set it.

Polymers develop the following properties as a function of curing.

Final polymer properties after 360 minutes of curing at 170°C: Tg (DSC) = 127 °C, Tg (TMA) = 113 ± 3 °C, α8 = 44 ± 2 ppm/’C1α18 o=96±2 p p m/℃.

Example 11: Part A: 2.30 g of DIANEDICY, 1-methoxy-2-fluor/- A, 50g, methyl ethyl ketone 7.50g and 2-Mlo, 054g (7) Dissolved in the mixture with stirring.

Part B: Dowepoxy 71881 resin (diglycidyl bisphenol A (DGE) BA) and brominated DGEBA) 25.0 g.

Part A and Part B were mixed together and aged for 24 hours at room temperature. next, The volatile varnish was B-staged on a hot plate in a thin casting pan. B stage resin was crushed to a fine powder and then heated to 170'C in a hydraulic press at 200psi. hardened.

Polymers develop the following properties as a function of curing.

7-Characteristics: Tg (DSC) = 180 minutes after 170°C tenocuring 106°C mi 3.46 and tan δ = 0.006 and relative humidity 50% Then ε′=3.54 and tanδ=0.002.

Example 12: Part A: I) JANEDICYl, 28g, 1-methoxy-2-propertool 7.50 g, 7.50 g of methyl difluorketone and 0.054 g of 2-Ml. Dissolved in the mixture with stirring.

Part B: Dowepoxy 71881 resin (diglycidyl bisphenol A (DGE) BA) and brominated DGEBA) 25.0g0 parts and parts B are mixed together. The mixture was combined and aged for 24 hours at room temperature. Next, apply a thin casty of volatile varnish. brought to B stage on a hot plate in a baking pan. After grinding the B-stage resin into a fine powder, 20 Cured at 170° C. in a hydraulic press at 0 psi.

Polymers develop the following properties as a function of curing.

Nie Masa Shikoryu Final polyv-properties after 180 minutes of curing at 170°C: Tg (DSC) = 116 °C = 3.51 and tan δ = 0.010, and at 50% relative humidity ε '=3.61 and tan δ=0.010.

Example 13: Part A: 1.46 g of DIPPDICY, 1-yl + sea 2-proper/- Lua.

50g, methyl ethyl ketone 7.50g and U2-MI 0.054g (7) Dissolved in the il1 mixture with stirring.

Part B: Dowepoxy 71881 resin (diglycidyl bisphenol A (DGE) BA) and brominated DGEBA) 25.0 g.

Part A and Part B were mixed together and aged for 24 hours at room temperature. next, The volatile varnish was B-staged on a hot plate in a thin casting pan. B stage resin was ground to a fine powder and then hardened at 170°C in a hydraulic press at 200psi. turned into

Polymers develop the following properties as a function of curing.

Time (minutes) Final polymer properties after 180 minutes of curing at 170°C: Tg (DSC) = 117°C , Tg (TMA) = 79±3°C. Induction at 1 MHz, 25°C and 0% relative humidity The electrical properties are: ε’=3.60 and tanδ=0.0067, and the relative humidity At 50% degree, ε' = 3.71 and tan δ = 0.005.

Example 14: Part A: 2.62 g of DIPPDICY, 7° of 1-methoxy-2-propasol 50g1 in a mixture of 7.50g methyl ethyl ketone and 2-Mlo, 054g Dissolved while stirring.

Part B: Dowepoxy 71881 resin (diglycidyl bisphenol A (DGE) BA) and brominated DGEBA) 25.0 g.

Part A and Part B were mixed together and aged for 24 hours at room temperature. Next layer , the volatile varnish was B-staged on a hot plate in a thin casting pan. B stage tree After crushing the moonfish into a fine powder, it was placed in a hydraulic press at 200 psi at 0 to 170°C. hardened with.

Polymers develop the following properties as a function of curing.

Time (minutes) Tg (℃) Final polymer properties after 180 minutes of curing at 170°C: Tg (DSC) = 86°C , 8 ppm/'COIMHz, 25°C and 0% relative humidity, the dielectric properties are ε' = 3.80 and tan δ = 0.011, and at 50% relative humidity ε′ = 3.85 and tan δ = 0.005.

Example 15: Part A: 2.30 g of DIANEDICY, 1-methoxy-2-propatool 7 ．． 50g, a mixture of 7.50g methyl ethyl ketone and 2-Mlo, 054g Dissolved in the mixture with stirring.

Part B, Dowepoxy 71881 resin (diglycidyl bisphenol A (DGE) BA) and brominated DGEBA) 25.0 g.

Part A and Part B were mixed together and aged for 24 hours at room temperature. next, The volatile varnish was B-staged on a hot plate in a thin casting pan. B stage resin was crushed into a fine powder and then heated at 170°C in a hydraulic press at 200 ps i. hardened.

Polymers develop the following properties as a function of curing.

Time (minutes) Tg (℃) Final polymer properties after 360 minutes of curing at 170°C: Tg (DSC) = 112 °C Part A: 1.46 g of DIPPDICY, 1-methoxy-2-propertool 7 ゜50g1 Mixture of 7.50g of methyl ethyl ketone and 2-Mlo, 054g Dissolved in the mixture with stirring.

Part B: Dowepoxy 71881 resin (diglycidyl bisphenol A (DGE) BA) and brominated DGEBA) 25.0g0 Part A and Part B mixed together and aged for 24 hours at room temperature. Next, a thin cast of volatile varnish B stage was achieved on a hot plate in a gourd pan. After grinding the B-stage resin into a fine powder, 200 Cured at 170° C. in a hydraulic press at psi.

Polymers develop the following properties as a function of curing.

Time (minutes) Final polymer properties after 360 minutes of curing at 170°C: Tg (DSC) = 104 ℃ member A + 2.62 g of DIPPDICY, 1-methoxy-2-propatool 7 ゜50g1 Mixture of 7.50g of methyl ethyl ketone and 2-Mlo, 054g Dissolved in the mixture with stirring.

Part B: Dowepoxy 71881 resin (diglycidyl bisphenol A (DGE) BA) and brominated DGEBA)25. Og.

Part A and Part B were mixed together and aged for 24 hours at room temperature. next, The volatile varnish was B-staged on a hot plate in a thin casting pan. B stage resin was ground to a fine powder and then hardened at 170°C in a hydraulic press at 200psi. turned into

Polymers develop the following properties as a function of curing.

Time (minutes) Final polymer properties after 360 minutes of curing at 170°C: Tg (DSC) = 101 ℃ amendment translation submission form (Article 184-8 of the Patent Law) May 12, 1994-Kan

Claims (10)

[Claims] 1. It is a curing agent for epoxy resin, and there are formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is ▲There are mathematical formulas, chemical formulas, tables, etc.▼,, -(CH2)-n, ▲Mathematical formulas, chemical formulas, tables, etc. There are ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. Yes▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc. ▼、▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ and X is a sigma bond, O, S▲There are mathematical formulas, chemical formulas, tables, etc.▼, R' and R'' are independently -H, -CH3, -CH2CH3, -CH2CH 2CH3, -CH2CH(CH3)2, where n is an integer from 2 to 12. , a is 0 or an integer from 1 to 5, b is 0 or an integer from 1 to 5, c is 0 or an integer from 1 to 5, d is an integer from 1 to 4, R''' is -H, -CH3, -CH2CH3, -CH2CH2CH3, ▲ formula, There are chemical formulas, tables, etc.▼ ) The above curing agent. 2. A method of curing an epoxy resin, the method comprising: quantity formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -(CH2)-n, ▲Mathematical formulas, chemical formulas, tables, etc. There are ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼、▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼ , ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ and X is a sigma bond, O, S, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, R' and R'' are independently -H-CH3, -CH2CH3, -CH2CH2 selected from CH3, -CH2CH(CH3)2, n is an integer from 2 to 12, a is 0 or an integer from 1 to 5, b is 0 or an integer from 1 to 5, c is 0 or an integer from 1 to 5, d is an integer from 1 to 4, R''' is -H, -CH3, -CH2CH3, -CH2CH2CH3, ▲ Formula , chemical formulas, tables, etc.▼ ) and bis-dicyandiamide having the following properties. 3. The bis-dicyandiamide may be present in an amount up to about 24% by weight. The method described in item 2 of the scope of the request. 4. R is -CH2-C(CH3)2-CH2- and R''' is H. The method described in item 2 of the scope of the request. 5. Request that R is ▲There is a mathematical formula, chemical formula, table, etc.▼ and R′′′ is H The method described in item 2 of the scope. 6. R is -CH2-CH(CH3)CH2CH2- and R''' is H The method according to claim 2. 7. Request that R is ▲There is a mathematical formula, chemical formula, table, etc.▼ and R′′′ is H The method described in item 2 of the scope. 8. R is ▲There is a mathematical formula, chemical formula, table, etc.▼, and R′′′ is ▲Mathematical formula, chemical formula, etc. The method according to claim 2, which includes formulas, tables, etc. 9. R is -CH2CH2- and R''' is ▲a mathematical formula, chemical formula, table, etc. The method according to claim 2, which is ▼. 10. In claim 2, R is -(CH2)6- and R''' is H. Method described.