TW201323B - - Google Patents

Description

-01323 A 6 B6 V. Description of the invention (1) y Inventor of the invention Μ • Λ This invention relates to the use of thermosetting resin and its use-way and. In the manufacture of new composites for enhanced maintenance, invention back # thermosetting resin in its structure Adhesives, high-performance composites and prepregs are well known. Composites and prepregs made of these thermosetting resins and high-strength fibers (such as glass, ceramics, carbon, etc.) have a reduced weight compared to the same objects made of gold. However, objects made with these thermosetting resins are fragile. This feature severely limits their use. In addition, because the viscosity of the thermosetting resin is too high during processing or too low during curing, the expansion of voids and the object are not Integrity makes many objects rejected, and many efforts have been invested to control the viscosity of thermosetting resins. Flow control agents such as fumed silica, lime, whiskers and high molecular weight polymers have been added to thermosetting resins. These reagents increase viscosity in all temperature ranges. This usually causes processing difficulties or inability to process and often impairs the physical properties of the cooked objects. tPlease read the precautions on the back of KI first and then fill out this page) • Ordered · The Ministry of Economic Affairs Central Bureau of Standards Printing ¾ The ester is in. The borrowed acid has a cyanide retention property and _ electrochemical amination and strengthening The resistance of the catalysis membrane of the film is used to protect the middle of the paint and the Arima as a protective compound with a combination of heat and heat, and it is resistant to oxygen in the type of alicyclic or sexual changes. Fan Shu, a fat-sweetening agent, turned this into a meal-quality but fat-heated base glass. The tree and the fat are made of glassy fat, which can be used to fix the tree. The heat-generating agent fat wax can make the tree more effective. It should be viscous and high-fat, anti-structural effect is well-understood. The green knot is high. · Green · A 4 (210Χ 297 public) 201323 A 6 _ B6 V. Description of the invention ": 2) y and fragile, poor impact and fracture Nature. {Please read the precautions on the back and then fill out this page), there are many reference materials in the know-how to teach-show changes _ good curing thermosetting resin • physical properties of first-class thermosetting epoxy resin, this method is Borrow special hardeners and / or add other polymers and / or with inorganic particles. Other reference materials teach the physical properties of improved thermosetting thermosetting epoxy resins. The addition of thermoplastic resins includes the following:-· US Patent No. 3,784,4 33 Shi discloses a composite of unidirectional carbon fiber and solid resin The manufacturing method is to drag the resin onto the carbon fiber in a continuous thin guillotine. The application of heat and pressure causes the resin to flow on the fibers to form a cohesive structure. * The butter is then converted into its solid form, the fusible B-stage. Thermal cycling can be rare because there is no solvent to evaporate, and the thin layer can be cooled quickly. U.S. Patent No. 4,524,181 discloses that it can be thermally converted into a sister compound that reduces mechanical and thermal shock sensitivity, which includes epoxy Resin and colloidally dispersed highly elastic particles. U.S. Patent Ho. 4,588,078 discloses a useful compound as a prepreg, which includes an epoxy prepolymer and a heating agent, and optionally includes a second resin-1, which may exist uniformly or in the form of interpenetrating 5-way . European Patent Application No. D 274 899 reveals a prepreg made of potting-reinforced resin. It has separate phase fine thermoplastic or thermosetting resin particles distributed in the prepreg, preferably the particles are located in the composite In the middle layer of the Ministry of Economic Affairs, Central Central Bureau of Economic and Commercial Printing, polymerized plastic heat-reverse si, the acid and cyanide are divided into 2 0 0, and then exposed in the middle of the ο 36 36 ί 7 blank 15 material 4 'dipping · -i ο ^ N In Lizhizhuan China Yumei District A 4 (210X 297 public issue) Μ 01323 A 6 B6 V. Description of invention ί 3 I. Y, the solution of the substance and disclosed in the US patents Ho. 4,745,215 and 4,780,507 • Λ exposed Jg compound of dicyanate and thermosetting or thermoplastic polymer. European Patent Application No. 30 1 36 1 discloses a rubber-modified cyanate resin and polytriazine derived therefrom and US Patent No. 4,804,740 describes a curable cyanide containing a thermoplastic material Ester formulations: US Patent No. 4, 46 8,497 discloses bis-imide, cross-linking agents, and compatible high elastomers; the sister compounds of these data are used to make prepregs. Μ. T. Bl'ai "et al. Proposed a paper titled in the Qiao International SAMPLE Paper Publication Order (33rd Inter * naf ion a. 1 SAMPLE Symposium, March 7-10, 198S) "PBI's Toughness Effect in BMI Matrix Resin" • Among them, it reveals that t〇% polybenzimidazoline is dispersed in a blend of bismaleimide and 〇, 〇'-diallylbisphenol A This kind of composition does not exhibit the "dissolution temperature" required by the sister compound of the present invention. Briefly, the present invention provides a thermosetting tungsten grease composition whose temperature viscosity during processing and compounding is similar to The viscosity of the unmodified thermosetting resin is significantly increased at higher resin heating temperatures. This thermosetting resin sister- * compound includes a thermosetting resin mixture * which is in the temperature range of 2Q to IDOt: Liquid • The thermosetting resin includes: > (1) one or more thermosetting resins and one or more curing agents, hardeners and catalysts used in the thermosetting resins (the amount is sufficient to cure the thermosetting resins), and. * ( b) 2 to SQ per K »part of thermosetting mixture 2 to other parts having --5-- A 4 (210X 297 male «) {read the back side of the page and then fill Note) - mounted • • · Order 01323 Α6 Β6 five lines, the invention described (4) y..

Ts is one of 140C or higher one or more porous thermoplastic polymer resin particles (please read the precautions on the back side and then fill out this page) • To give birth, the dissolution temperature of this particle (as defined below -Γ is _ 5〇t: or higher 'is preferably 7_Qt: or higher, and the particles are substantially insoluble in the thermosetting resin at a temperature of about 1δ 1C (below the dissolution temperature>. This sister compound can be optionally Contains additives for property enhancement. The present invention also provides a pre-preg for structural composites. The impregnated material includes a fiber material fabric impregnated with the thermosetting sister compound of the present invention. Used in the present invention: _ "Dissolution temperature" Refers to the viscosity of the thermosetting resin and thermoplastic particles in the absence of curing agent I for thermosetting resins, hardeners or catalysts, when rising at a rate of about 2t per minute, reaching a minimum value. Thermoplastic particles dissolve and increase in temperature. The method disclosed in the conventional technology to solve the physical disadvantages of heating thermosetting resins does not solve the problems that occur when processing thermosetting resins into objects The viscosity distribution of the thermosetting resin compound is very important when processing the thermosetting resin composition into a prepreg (which can be used to manufacture composite structures). It is suitable for compounding, coating, and impregnating fiber reinforcement. The viscosity of Jun is quite low, but the viscosity is quite high during the aging process. It is very important to let marinate with -1 vacuum to remove volatiles and drag the pressure M to form a composite part without exuding excessive resin (which will cause thermal compounding Part of the gap and incompleteness): The description of Xinjiang Duoxi Wangwang who can explain the purpose of the present invention is shown in the accompanying drawings, where the chart clearly shows the temperature dependence of the viscosity of the composition of the present invention and the conventional art composition 3 -6-A4 (210X 297 佂 没) ^ 01323 A 6 B6 V. Description of the invention f 5 iy in the picture (details and methods of the recipe are described in S Example 1 below), production, curve A (Compared) represents the viscosity of traditional thermosetting resins. As shown in the figure, the viscosity decreases with increasing temperature. Curve B (for comparison) is curve A thermosetting resin sister compound and 8.5 % By weight of polyether amide imide thermoplastic viscosity In this test, during the mixing, the thermoplastic junction has completely dissolved into the thermosetting to form a completely uniform beating compound. The viscosity exhibited by this formula is better than the unmodified thermosetting resin in all temperature ranges. Curve C formula (The present invention) is consistent with the beer line B, however, in this test, the polyetheramide amine thermoplastic is in the form of particles and incorporated into the thermosetting to form a dispersion (in which no thermoplastic is dissolved). Viscosity is unique • The initial viscosity is essentially the same as curve A. However, after the first viscosity minimum occurs • It is the dissolution temperature (Td) * The thermoplastic particles dissolve. This point gives the viscosity of the sister compound It reaches the level of uniform blending of curve B. (Please read the precautions on the back before M fills in this page> k. • Order · Octavia 0 Detailed examples of alfalfa 93 亘 住 明 发 太

N is added to oxygen and its cyclic compound is polyester pre-tree and solid M. Thermal solid ester (a) acid cyanide poly-neutral compound, amine and ether are obviously made by Maben Shuang | |, can be N and solid It is known that heat has turned into a cooked product — 聚 时 # Pre-high and more body or military V oxygen 100 ring is moderate temperature and the body is combined. It was originally combined with Dujie's warm-fat industrial compound, and its base was oxidized and cyclized into a multi-molecule polymerization or pre-polymerization and a single-bonded oxygen ring family. Huan Shang or Nianzu City Xiang Zifang can be divided into a small amount of storage. Green. Printed Armor 4 of the Central Bureau of Economic Development of the Ministry of Economy (210X 297Y) 201323 A 6 B6 V. Description of the invention (6 1 '-0 . '/ \ -CH ——CM- compounds with one or more epoxy groups are preferred. The best epoxy compounds, aromatic polyepoxides are polyglycidyl ethers of polyphenols, aromatic carboxylic acids Glycidyl esters and aromatic amines polyglycidyl derivatives such as N-glycidylaminobenzene, and glycidyl monoglycidyloxybenzene. Polyglycidols including polyphenols are useful as thermosetting resins for the composition of the present invention Derivatives such as 2,2-bis [4- (2,3-epoxypropoxy) phenyl] propane and disclosed in US Patent Nos. 3,018,262 and 3,298,998 and "Handbook of E" (Handbook of E poxy R esins) ”L eean ci N evi 1 1 e, Mc G raw-H i 1 1 Book Company, New York (1 9 6 7). The best polyphenol in the sister compound of the invention The poly (glycidyl ether) is the diglycidyl ether of bisphenol * which has a carbocyclic base ring on the side As disclosed in US Patent No. 3,298,998, this patent has been incorporated herein by reference. An example of this glycidol ϋ is 2,2-bis [4- (2,3-epoxypropoxy) benzene Radical] orthocampane 9, 9-bis [4- (2,3-epoxypropoxy} phenyl] fluoro, and 2,2-bis [4- (2 · 3-epoxypropoxy) stupid Base] Decahydro-Ministry of Economic Affairs Central Bureau of Printing and Printing 1, 4, 5, 8-dimethan naphthalene. The preferred diglycidyl ether is bisphenol-8 ~ A 4 (210Χ 297 public) (please first Read the precautions on the back and fill in this page) 201323 A 6 B6 V. Description of invention ί 7.> A diglycidyl ether.. R Suitable for use in the epoxy resin compound of the invention Examples of glycerylaminobenzene include stupid amine, phenylenediamine, naphthalene amine and naphthalene diamine bis and polyglycidyl derivatives such as N, N-diglycidyl aniline, N.N-diglycidyl naphthalene (Chemical Abstract The ninth episode index, the m-SS volume, page 2660 CS (1 972-76) C Chemical Abstracts 9th Coll. Index], named Nl-naphthyl-N — (ethylene oxide methyl) ethylene oxide methyl Amine) , 1, _4_ bis (with monoglycidylamino> benzene '1' 3-bis (N, R-diglycidylamino) stupid, and bis [4- (diglycidylamino) phenyl] Methane (MY 720TM, Giba Geigy, Inc.). Polyglycidyl derivatives of aromatic aminophenols are described in U.S. Patent Ho. 2.951,825. An example of these compounds is N, N-diglycidyl-4 monoglycidyloxyaniline (ERL0510TM, Chebagagi, Inc.). When the sister part of the sister compound of the present invention < a) contains an epoxy monomer or a prepolymer, it can be used for various thermalizing_thermalizings which are well known in the conventional art. These curing agents and methods of calculation are described in Lee and Neville ·· Epoxy Resin " (" Epoxy Resins ") — in the book • Pages 3S to 140 ”McG" aw-Hill Book Company, Aoyo, 1957. Useful thermalizers include, for example, ethylenediamine , Diethylene triamine, amine ethyl ethanolamine and other amines, diamino ^ phenyl 51, 9 · 9 mono (4-aminophenyl) fluoro, 2, 7_ dichloro mono 9, 9_ bis (4 monoamine Benzyl) fluorine, such as dicyandiamide, amides, organic acids such as adipic acid, phthalic anhydride, and anhydrides of chloric anhydride, and multiple SS such as bisphenol A. If any polymerization of epoxy Occurred at about 1001C but with the rapid temperature -9-A 4 (210X 297 "" (please read the precautions on the back before filling out this page • install ·-fight · green. Σ〇132 ^ Α6 Β6 V. Explanation · f 8 rises to. The range of normalizing agents can also be amines, ions, active thermosetting properties and prepolymers, among which about 1 2 5 t: The amount of epoxy combination can be within 〇. When using thermally active azoles, such as BF3-amine complexing agent, the resin composition is also known to the sisters of the present invention, and many are commercially available There are at least one, preferably two, maleimide groups and when it does occur, a very small amount of curing agent-Λ substance and heating agent Μ stoichiometric_ is used. However, thermal epoxy The catalyst is about 0.1 to 1.5 times the stoichiometric amount of the resin, such as | Lewis acid and test, Lewis acid of the third compound and gold alloy compounds and salts, SbF5, and benzyl dimethylamine. When included Heat with about 0.0 1 stroke of 5% by weight catalyst (the amount of epoxy compound in which M is present is based on) Ν · Ν 'in the compound-bismaleimide monomer whose compound has the general formula (please (First read the notes / items on the back and then fill out this page)

C

C Υ Ν ZO Ν Υ

C

C 0 〇 Printed by the Central Bureau of Economic Affairs of the Ministry of Economic Affairs when Υ represents at least two carbon atoms, preferably up to 6 MW carbon atoms, and Z is a divalent containing at least two carbon atoms, usually not more than 20 carbon atoms 10 A 4 (210X297 male; 201323 A 6 _ B6 V. Description of the invention- (9 iy has a chrysanthemum group. Z can be aliphatic, cycloaliphatic, aromatic or heterocyclic. Please pay attention to this page and then fill out this page} * Production groups, these groups can optionally have up to two di-sulfur and _ non-peroxide oxygen heteroatoms. Y can be derived from dicarboxylic acids or anhydrides such as maleic anhydride, Citraconic anhydride 'tetrahydrophthalic anhydride, etc. The representative N, N'-bis-diimide can be 1.2-ethanediamine, 1,3-hexanediamine, trimethyl-1, 6-Hexanediamine, 1,4 monophenylenediamine, 4,4'-methylenebisaniline, 2-methyl-1,4-dibendiamine, 3,3'-methylenebisaniline, 3,3'-sulfose bisbenzamine, 4,4'-sulfonamide bisaniline, 3,3'-oxybisaniline, 4,4'-oxybisaniline, 4,4 'methylenebiscyclohexylamine, 1, 3-benzenedimethanamine, 1,4-phenylenediamine and 4,4 ' Cyclohexane dibenzylamine and mixtures of these N, Ν 'bismaleimides. Other Ν · Ν' bismaleimides and their preparation methods are disclosed in US Patent Hos. 3,562,223, 3,627,780 And 3,839,358. The preparation method of N-N / -bismaleimide is known and has been described in US Patent 4,468,497. N-N, the polymerization method of bismaleimide When it is heated with diamine at a temperature of loot: or lower, it is arbitrarily dissolved into the crosslinking agent of dichloromethane and i. I

The diamines that can be used for the polymerization of Ν, Ν'— 双 马来 藤 IMINE # have been disclosed in US Patent No. 3,562,223: the preferred diamines are those having cycloalkyl or aryl groups and listed above The same diamines • It is printed at the manufacturer Ν, N Central Ministry of Economics Central Bureau of Economics ¾. About the amine amides. Ma Shuang-I 1 11-· Use N- to make, in the N amine aramide To use horse to make Shuangchang _ Tongzhi Jia 4 (210X 297 public) 201323 A 6 B6 V. Description of the invention (10 iv 0.8 diarrhal diamine. • Produced for use in the invention Ν, Ν'- 双 马来The di-unsaturated cross-linking agent in the rattan-imine compound is any di-unsaturated compound having a boiling point of 150 scoops or more under high oxygen pressure and terminal ethylenic unsaturation. The preferred cross-linking agent is di Vinylbenzene, peptidic diallyl and bis (4-allyloxybenzene) mystery. The dicyandiamide monomers and prepolymers that can be used in the sister compound of the present invention are known. Their preparation methods And its use in the manufacture of polycyanates by polycyclic trimerization M has been disclosed in US Patent No. 4,157,360. Dicyanates are compounds of general formula I: H = C0-R-0C = 2 where R is a divalent aromatic hydrocarbon residue and includes at least one aromatic portion, that is, the aromatic ring includes stupid, naphthalene · B · phenanthrene, etc., and R contains up to 40 carbon atoms, including the aromatic portion. For example R can be a 1,4-bis (2'-phenylpropyl) moiety. Its cyanate group is attached to the para position of the phenyl ring of the phenylpropane substituent. M provides one of the compounds of formula I. Example. The aromatic ring R can be replaced by a group that is inert during the polymerization process (ie polycyclotrimerization / process), including halogen, ie fluorine, chlorine * bromine and iodine; Ci-C 4 Alkoxy, which is straight or branched, includes methoxy * ethoxy, isopropoxy and third-butoxy; and ^. Alkylcarbonyloxy, which {please read the back Note and then fill out this page • Installed • • Played. Threads • Printed by the Central Bureau of Economic Development of the Ministry of Economic Affairs and If Base 1 Qian Yi is a heterogeneous acetaminophen with a different number of ¾, which is not based on generation and carbonyl extraction Oxygen is inert, and the ring group group carbonyl aromatic aryl group is used in the process. It is used as a branching group for carbonyl polymerization or oxygen on-line but not more than three. It is No. 4 (210X 297 public) € > 01323 V. Description of the invention- (11 A 6 B6 Aromatic di-molybdate moieties cross-linked triazine polymer after polycyclic trimerization • Production formation -* ''-The so-called "polyurethane trimerization" refers to the formation of cyanurate ring system * It is formed by the condensation of three aromatic cyanate groups by polymerization to form a cross-linked aromatic ring system Or, the basic repeating unit is the general formula BI:

R Ο {Please read the notes on the back before filling this page)

N

N

I

/ \ / \ Ο N 0 / \ R R Economic Department Central Bureau of Standards where the R substituent (as defined above) is attached to the oxygen atom. The method of performing polymerization is known as "including thermal annealing at about 200 fM and has been disclosed in US Patent Mo. 4,157,360-(already described in the foregoing, K 〇" shak reference "). 13 A 4 (210X 297 Gong Mei) 2013 ^^ A 6 B6 Printed by the Central Bureau of Economic Development of the Ministry of Economic Affairs

A 4 (210X 297 male not)-: f ............. h ........: ...................... ............... ¾ ............................... ^ .. ........................... Φ. Ί Please read the note of the plan first. Page) A6 B6 5. Description of the invention (13) When polycyanate is used in the composition of the present invention < a > * Can be used -r any ratio of polycyanate mixture and polycyanate-ester A prepolymer of Hefangyi's monofluoroester (liquid when the processing temperature is preferably between 2Q and 100 f). The prepolymer is prepared by heating the blend with or without a catalyst at a temperature of about 140 ° C to about 220 ° C for a period of time sufficient to cyclotrimerize about 5 to about 50% cyanate functional groups. The catalysts used in the cyclotrimerization of polycyanates to form prepolymers and fully polymerized polycyanurates include zinc cobaltate, tin octoate, zinc stearate 'tin stearate, ethyl IT pyruvate feed , Phenol, catechol's triethylenediamine and iron, cobalt, zinc, feed, magnesium and titanium chelate with two ligand liquids such as catechol. The amount of such catalyst used is from about 0.001 to about 20 parts by weight per 100 parts of polycyanate blend. Other catalysts for the thermalization of polycyanic acid and their uses are disclosed in British Patent No. 1,305,762. However, it is also possible to use only heating without catalyst to form a prepolymer and complete polymerization. Usable cyanate esters include RDX 80352TM, a prepolymer of bisphenol A dicyanate (manufactured by Interez); XU71787TM, a polycyanate ester of polyphenol adduct of dicyclopentadiene (Dow) Manufactured by the chemical company) /; and BT2160TM resin, a prepolymer of bisphenol A dicyanate with a total weight of 10% by weight of 4, 4 'monomethylene dianiline, bissulfonic acid imine, and commercially available from Lingling Qi (please first-«1 read the note on the back and then fill in this page). Install. • Order · * taste_ The central government bureau of the Ministry of Economic Affairs prints the grains to a temperature and a fat level.溍 温 解) -It can be thrown in the ny and but it can be used, the middle aiblM tree 31 parts P sex 1C group 70 solid embolism is better than the S sister more soluble Ga fat in the hot ch, can i. On the tree If the temperature is not high, the temperature is SU, the temperature is SU, the temperature is 50, and the temperature is clear. 3 _ ^ _ V. Description of the invention- (If the vf degree is lower than the beginning of the heating, it varies according to the resin, but it is usually 100 (please read the precautions of the plane before filling this page) • r to 200 t: Between. — — " _ Resin particles are made from an amorphous thermoplastic resin with a glass transition temperature of about 1 400 i〇Μ. Solubility of resin particles with desired solubility characteristics in thermosetting resin Low enough to prevent particles from dissolving when the particles are mixed into the thermosetting resin or during storage of the thermosetting mixture. However, the resin particles also have a solubility sufficient to completely dissolve in the thermosetting resin during the curing cycle of the sister compound. The thermoplastic resin of the resin particles of the present invention is an amorphous thermoplastic resin including polycarbon Esters, Polyesters, Polyarylates, Polyethers, Polyaryls I®, Polyesters, Polyetheramides, Polyamideamides, Polyamides , Polyamides and polyethers 3 The preferred thermoplastic resins are polyetherimides * such as UL TEMTM1000 · available from General Electronics Corporation; polymyridine mills, such as VictresTM4800P · available from ICI, and polyfang Base rollers such as RedelTM A-200 are available from Amoco. The suitability of special thermoplastic resins depends on the aforementioned solubility retention of the thermosetting resin used in the thermosetting resin composition. Resin particles with desired solubility characteristics It can be prepared / prepared by any known method * including grinding solid amorphous thermoplastic resin * spray-drying the solution of amorphous thermoplastic resin or coagulating the latex of amorphous thermoplastic resin. The appropriate particle size is better, the most is rice and the micrometer is 50 It is 5 square meters from the square to the square. 50 is the usual 5 diameter. The diameter is small and the grain is small. The size of the gram is larger or Γ >

V Printed by the Central Bureau of Economic Development of the Ministry of Economic Affairs ^ The sons of the surface noodles must be heavier. The sons of the noodles surface noodles " grains of rice noodles 40-shaped to fixed 1 no good 6 丨 Μ A4 (210X 297 public) 201323 A 6 B6 V. Description of the invention (15, y · Control the dissolution rate of the thermoplastic particles into the thermosetting resin M to form a uniform solution. • If the surface area is too small, the dissolution rate will be low. This will make-granules_ thermosetting before dissolution Curing of resin ^ If the particles are not dissolved before the viscosity enhanced by curing, they will not be given. Particles with a high surface area can be prepared by several methods. A small particle has a high surface area. These particles can be ground or It is prepared by coagulating the polymer dispersion. Another method to obtain a high surface area is to prepare porous particles. Porous particles can be prepared by spray-drying a solution of non-shaped thermoplastics. This preparation method is well known in the art The solubility of special resins can be adjusted * that is, by incorporating plasticizers to lower the dissolution temperature, that is, about 5 to 50% by weight of plasticizers are incorporated into the thermoplastic from which the resin particles are made Among resins, it is better that the plasticizer has a functional group that can be copolymerized with the thermosetting resin, that is, a reactive plasticizer. For example, epoxy resin M plasticized particles such as a diglycidyl bond of bisphenol A can be used. Lower its dissolution temperature, that is, increase the rate of its dissolution into the epoxy resin or fluoroester resin compound. For example, you can use amine K plasticized particles to increase their dissolution into Ν, Ν '-bismaleimide The rate of imine monomers and prepolymers. The so-called "substantially insoluble" means that when the sister compound is kept at 15 C below the dissolution temperature for at least 2 hours, substantially less than about 25% of the particles are dissolved, so in thermosetting resins The thermal conductivity of the medium thermoplastic particle composition has not changed significantly. {Please read the precautions on the back side first and then fill out this page.) The Central Bureau of Economic Affairs of the Ministry of Economic Affairs prints the appropriate mold or holds the layer. 〇, use. Staining agent ring is used for sticking and pre-soaking materials. In the structure of the material, it is suitable for the joints of the joints, and the stratification can be closed, the closure can be closed, and the sealing can be replaced by the heat. It is difficult to make a short cut. Preparation of fat in A4 (210Χ 297 g;% *) ^ 01323 A 6 _ B6 V. Description of the invention (16 iy 1 The thermosetting resin compound of the present invention can be used to impregnate woven or nonwoven fabrics, λ, filaments, progenitors The temperature of the yarn is lower than the dissolution temperature of the prepreg-material ring. The fibers that can be thrown into this prepreg include organic and inorganic fibers including, for example, glass fiber, carbon or graphite fiber, ceramic fiber, Boron fiber, silicon carbide Panwei, polyimide fiber, etc., and mixtures of these. The thermosetting composites of the present invention can also be used to coat woven and nonwoven fabrics, films and sheets of organic and inorganic materials including, For example • Organic materials such as polyolefins, polyesters • Polyimide etc. and inorganic materials such as ceramics, feed, spicy and gold etc. These materials are useful in printed electrical technology and bred as structural components of organic maple 〇 · The compound of the present invention may also contain additives to improve the durability of the aging composition. The additives that can be used are inert fillers, tougheners, foaming agents, colorants, dyes and flame retardants Agents such as crushed H fiber such as ceramic fiber, glass fiber • Boron fiber, carbon Pan Wei δ other woven and non-woven fibers; inorganic powders such as kaolin, chalk, silica, antimony trioxide, titanium oxide, carbon; and glass (please first read the notes on the back of the skull before filling in This page) The Central Ministry of Economic Affairs of the Ministry of Economic Affairs of the People's Republic of China ^ The time distribution and the temperature equalization agent are often combined with the temperature and temperature, and the mixing solution is added to the middle device to broadcast this liquid solute fat. Sexuality or degree of granular agent Guxing Castanopsis spp. Temperature neutralization hot line grinds solid fat to catalyze the materials used to dissolve the heat tree, so that it can be applied to sexual agents, such as low-temperature curing or other systems. Grind, '!'. Belonging to it,-it should be placed in a mill for 15 years, and the low-alloying agent must be installed in the older sister but the compound ball holder or porcelain ρ heat is mixed-Baoshi Taogu 60, small fat utensils , Heat to the subtree shearing and combining 2 pieces of 30 tensile high-mix group, the solid body is clearly solid, and the solid Angufa normal plastic heat glue is used to transfer heat, the glass will be dispersed. Opportunity to the armor 4 (210Χ 297 public) 201323 A 6 B6 V. Description of the invention ί i7 丨 ^ r Although the thermosetting sister compound of the present invention is usually processed by hot melt coating technology * production • but also Use organic dissolution processes such as methyl ethyl ketone, toluene, tetrahydrofuran, ethyl acetate, ethyl yeast, etc. for processing. For example, processing solvents may wish to prepare thin adhesive films from these thermosetting sister compounds. Be careful The use of a solvent requires the selection of a solution that dissolves the liquid thermosetting resin but does not dissolve the thermoplastic particles. Suitable substrates for coating the composition of the present invention include polyimide, polypotato, polyolefin, gold foil, etc. Dimensions such as carbon, glass, aramidamide * ceramics, etc. — The purpose and advantages of the present invention will be further explained by the actual implementation of M, but in these examples the special materials and usage M and other conditions and details The content does not limit the scope of the present invention. In these examples, unless otherwise specified, all parts and percentages are by weight and temperature is in degrees Celsius. In the example under Κ, the viscosity is measured with RDA-700TM, Dynamic Machine Analysis Company (Rheometrics, Inc.). 3 The method of throwing in a parallel plate mold is: gap: 1mm · radius: 19.02mm, frequency = 100 rad / sec. Tension = 20%, the temperature ramp is Zt / mU · Initial temperature = 50V Final temperature = 177 t. i When the example 1 is printed by the Central Kneading Bureau of the Ministry of Economic Affairs 31, please read the precautions on the back and then write this page) 35 parts of the thermosetting resin compound 9, 9 a pair [4 one (2, 3-epoxy Propoxy) -Phenyl] Fluorine (DGF) and 35 parts of diglycidyl ether of Bis-A (DGEBA). This · resin sister's combination was subsequently thrown into three formulas: into formula A • no other materials were added; into formula C,-19-A 4 (210X 297 public) ^ 01323 A6 _B6 V. Description of the invention (18. 'y' Will be 8.5% by weight of loose PEI (ULTEM resin • a polyether-brown imine tree (please read the precautions on the back and then fill out this page) * fat production, can be purchased from General Electronics' particle size 3.2 -Micron_ and the surface area is about 5.4 m_2 / g) At S0 t: when dispersed into the resin compound with an air mixer; Formulation B is the same as Formulation C • However, the mixture is heated to 120 t: and stirred Μ The thermoplastic ULTEM is completely dissolved in the resin composition. The viscosity of each formulation is determined by the aforementioned RDA-700 Dynamic mechanical analyzer and made into Table 1. Curve A, the modified resin composition shows that when the temperature of the composition increases Viscosity decreases steadily. • Curve C • The resin composition modified by the bulk thermoplastic shows that when the temperature is above the dissolution temperature, Td, the viscosity of the mixture when the thermoplastic begins to dissolve is about the same as that of the unmodified resin compound Dijiang. The viscosity increases at this temperature Because the dissolved thermoplastic particles only offset the viscosity reduction of the resin compound and prevent the viscosity from further declining in the mixture. Curve B, · The resin composition modified by the dissolved thermoplastic shows a starting viscosity that is better than that of the bulk thermoplastic The viscosity of the high-quality composition is much higher. Therefore, the formulation C provides a low viscosity material with an ideal starting temperature during processing, such as the manufacture of prepreg 12 and a higher viscosity material (that is, controlled flow). At the curing temperature, it is beneficial to ensure that there is no gap to heat the compound. The thermosetting resin compound is produced as shown in Table 1. Printed by the Central Bureau of Economic Affairs of the Ministry of Economy ο 2 A 4 (210X297 public), 01323 A 6 B6 Five , Description of the invention · (19; Table formula thermosetting resin% thermoplastic particles d Tdt minimum viscosity (poise) DEFG Η (a) (a) (b) (b) (c) (C) None None None (e) 115 (e ) 119 (ei 115 0.36 '4.78 0.15 2.551.20 10.60 (please read the notes on the back and then fill in this page) (ai thermosetting resin is 10 0 copies 4' 4 '-tetraglycidyl diamino diphenyl Methane (TGDDM) and 31 parts of 4,4'-diaminodiphenyl milling (DOS) at 120 1C with empty Mix with air mixer to completely dissolve DOS. (B) Thermosetting resin is A "oCy B-30TM, a dicyanate, available from Hi-Tek Polymer Company. (C) Thermosetting resin is Comp imideTM Malay sleeping imine resin can be purchased from Yanyi Chemical Company. (d) PEI thermoplastic particles (disclosed in Example Ha 1). Printed by the Central Bureau of Economic Affairs of the Ministry of Economic Affairs (ei Thermosetting resins without thermoplastic particles show no dissolution temperature Td 2 1 A 4 (210X 297 issued) ^ 01323 A 6 B6 V. Description of invention (2 (^, for the viscosity profile of various formulations RDA-700 Dynamic mechanical extension, measured by strict equipment and the minimum viscosity of each is recorded-in Table J. Each thermosetting resin, _ epoxy, dicyanate + and bismaleimide respectively showed a minimum viscosity of 0.36 , 0.15 and 1.2-poise, the addition of 8.5% by weight of thermoplastic bulk resin to the thermosetting resin shows a dissolution temperature of 115., 119 ° and 115., and the corresponding. The minimum viscosity is 4.78, 2.5 5 and 1 0. 6.0 Po. Example 3 — Fluoroepoxy resin PR-500 thermosetting sister compound (3M) and various thermoplastic resins are mixed with 4.65 parts of each of the thermoplastics listed in Table I using an air agitator at SO f The resin is prepared with 5Q parts of PR-500. The cobalt degree (without the addition of bulk thermoplastics) and the minimum viscosity and dissolution temperature of each mixture and sister compound are recorded in Table K. Please read the back side first Matters needing attention to write this page) • _ • · hit Central Line, Ministry of Economic Affairs Bureau of Indian rubbing quasi armor 4 (210X 297 male hair) ^ 01323 A 6 B6

V. Description of Invention ί21 I

Table I * Cation Compound *-Formulation. Thermosetting Resin Thermoplastic Particles Td Minimum Bottom Density (Poise)-(Tg) 1-J PR-500f None (e) 0 .30 K PR-500f PES * (230) 1.19 1.61 L PR-500f PCh (154) 74 2.34 Μ PR-5 0 0 f PS 1 (190) 86 6.50 Ν PR-500r PASJ (220) 106 3.76 0 PR-500 ^ PEI11 (217) 106 9.30 Ρ PR-500r 50 PAS / 50PEI 106 4.15 Q PR-500f FPE- (330) 105 2.80 (ei has no inspection of the dissolution temperature (f) available from 3 M aromatic epoxy resin (© V i ctrex 4800 ™ * Can ICI USA Polyether satin L e xan ™ * Polycarbonate (i) Vd e1 ™ P1700 available from General Electronics Co., Ltd. • Polyether can be purchased from Α π 〇c 0 Amoco Performance Products, Inc. ° (j) RADELTM A-200, a polyaryl HI can be purchased from / m〇C〇 performance products {please «read the precautions on the back and then fill out this page>. installed. • Ordered by the Central Bureau of Economic Affairs of the Ministry of Economic Affairs Printing company. (K) UltemTM1000, a polyetherimide can be obtained from General Electronics Co., Ltd. glass transition temperature of ΦΦ thermoplastic resin -23- A4 (210X 297 public) ^ 01323 A 6 B6 V. Description of the invention (22). ≫ '{please read the precautions on the back before writing this page} m-a kind of polyester resin can be Prepared by isophthalic acid / terephthalic acid (SQ / 50 Mo's ear ratio)--"-The data in Table II shows that the unmodified epoxy resin is heated, formula J, and the viscosity drops to the minimum value. 3 0 The viscosity of the thermoplastic compound of the modified epoxy resin is not lower than that of the special thermoplastic when the modified thermoplastic particles (which can be dissolved at the dissolution temperature, Td, and substantially insoluble below this temperature) are used. High value. _ When Example 4. The parts of the formulations J and 0 of Example 3 were evacuated and heated for 4 hours in the plastic film of 177 deaths. Each was measured according to the procedures of ASTM E399-83 and ASTM D638-86 Fracture toughness of pseudo-heated samples, KIC (critical plane-strain fracture toughness in Mode I) and tensile modulus. The values obtained are recorded in Table II.

B_1L Ministry of Economic Affairs Central Bureau of Preservation and Printing-the temperature of the fat tree at the time of breaking is dissolved and melted on the but-solubilized but not PE, the proton solid particles are molded under the heat. The temperature is said to be in ® but Explained by the hot thermoplastic compound KI c tension modulus 4 formula solid resin particles MPa-m1 " 2 GPa J PR-500 None 0.644 3.52 0 PR-500 8.5¾ PE I 0.909 3.42 A 4 (210X 297 g; § ) ^ 01323 A6 B6 V. Description of the invention (23 iyr

There is no increase in crack toughness about the material. There is a loss in tensile modulus. When the FS formulation PR-500 epoxy resin and 8.5% by weight PEI particles were measured as described above using the RDA-700 Dynamic analyzer, except that the temperature increased by 2 t per minute: until the temperature of the formulation increased by Μ °, the temperature was published at this time · Maintain a residence time of 2 hours. During this residence period, the viscosity of the formula remains unchanged. After increasing the temperature, the characteristic Td appears and the viscosity of the formula is increased.

g Li R means to control the dissolution temperature by controlling the surface area of the thermoplastic particles. The surface area of the prepared PEI particles is about 1.0 to 9.0 square meters per gram (as shown in Table IV, measured by WBET (Brunauer, Ennett, and Teller)), and the surface area is in the Quantasorb BETTM surface analyzer (manufactured by Quantachrome) Get on). Each of the sister compounds was mixed in 6.01 by mixing 4.65 parts of the particles into other parts [? -500 epoxy resin (as described in Example 3) and their viscosity was measured by RDA-700. The dissolution temperature and Td of each sister compound are listed in Table IV. {Please read the notes on the back and then fill in this page) Printed by the Central Bureau of Economic Development of the Ministry of Economic Affairs 5 2 A 4 (210X 297 Public Issue) A 6 B6 V. Description of Invention (24)

Table F: Surface area of sister compound (: n2 / g)-Dissolution temperature (υ > R. '1.01 127 S 2.65 114 T 2.73 108 U 3.60 107 V 4.73 95 W 8.98 92 (please read the back side first Please pay attention to this page.) After Table IV, you can see the thermoplastic polyetherimide. PEI resists the surface area from about 1.0 to 9.0. The dissolution temperature of the composition is also controlled to 127 ° to 32. gili 7 (hh For bells) The viscosity of the bulk thermoplastic polyimide, 10% by weight of DurUidTM (in PR-500 epoxy resin) (available from Rogers) was measured with RDA-700. No dissolution temperature was observed This composition therefore illustrates the thermosetting sister compound not included in the present invention. Vmp, (Buh is more suitable) Printed by the Central Kneading Bureau of the Ministry of Economic Affairs to prepare 50 parts of PR-500 epoxy resin and 5.56 using the aforementioned method Partially ground thermosetting compound of polyimide-imide thermoplastic resin (surface area is 0.3 m 2 / g and its viscosity is obtained. · No dissolution temperature is observed, as the temperature rises to the beginning of epoxy resin Viscosity decreased during the polymerization. From -26-A4 (210X 297 g; «) 01323 Α6 Β6 V. Description of the invention (25). Γ '(please read the precautions on the back before filling in this page) The prepreg prepared by this sister compound has voids and intermittentness. This is not the case-modified by thermoplastics Epoxy resins are similar .. In Example 9, the three thermosetting sister compounds of PR-500 epoxy resin and poly Zhaoyi imine (PEI) particles (surface area of 4.73m2 / s) are mixed with air, Υ and Zn The device is prepared by mixing the sister parts at SQ t :. The sister compounds X, Y and Z in 50 parts of PR-500 epoxy resin respectively contain 2.63 parts (5.0%), 4. 65 parts (8.5%) and 5.56 parts (0.5%) PEI. The concentration of each sister compound was obtained and the minimum viscosity was observed to be 3.5 poises, 10 0.3 poises And 2 1. 2 2 Po. This point shows that the control of viscosity is very important during the early processing operations (such as the manufacture of prepreg rings made with the sister compound of the present invention). G Example 10, order, practice The thermosetting resin compound is prepared by mixing 91.5 parts of PR-500 epoxy resin and 8.5 parts of bulk polyimide (surface area is 5.371112 / 8). This mixing system is connected to a mirror mixer under vacuum at 3510 get on. The resin film is further processed into a resin film approximately 66 mm thick. This film is laminated into continuous carbon using a traditional 30cm prepreg machine (which can be concealed from California Graphite Machines, Inc.) Pan Wei (Hercnles Co., IMTTM Fiber). The 16 layers of prepregs prepared by this method are cyclically matured with a blasting autoclave to form a glass transition temperature of 205 T. It can be used as a non-void (hole) compound for structural parts in machinery panel. -2 7 _ A 4 (210Χ 297Υ «) ^ 01323 A 6 _B6 V. Description of the invention _ (26 v (please read the note on the back ^ matters before filling in this page) When the method of Example 10 uses undispersed granular thermoplastic Resin-modified prepreg-When the production is repeated, the resulting panel has a lot of voids due to excessive resin flow-Example 11 This example illustrates the control of the dissolution temperature by plasticizing thermoplastic particles. Plasticized polyethylene pyrimidine thermoplastic particles (PEI / DGF > The preparation method is to make 90 parts by weight of PEI and i〇r child parts double C_ 4 — (2, 3-epoxypropoxy) phenyl] Fluorine is dissolved in 300 parts of dichloromethane, latexed in water and coagulated by pouring human enzyme. Obtained particles with an average diameter of 3 microns and a surface area of 5.40〇12 / 8. At 3〇10〇 these particles will be 4.658 Divide into 5 (^ PR-50 0 epoxy resin and obtain the viscosity of the mixture. The dissolution temperature of the unplasticized polyetheracetimide particles is exemplified by the example. The present example after plasticization is 9 51 When Example 12 formulas ΑΑ, ΒΒ and CC, each containing 35% bis [4- (2,3-glycidoxy) phenyl] fluorine (DGP) and 65% bisphenol six bis glycidyl ether / ( DGEBA) of 50 parts of epoxy resin mixture and 4.65 parts of poly (PS), PEI / DGF (epoxy plastic polyether amide imide described in Example 1) and polyether amide imide PEI ( Example 3 The polysilimide that was thrown out) was prepared by mixing with an air agitator at 60t: hour. Each MRDA-700 viscosity was printed by the Central Bureau of Economic Affairs of the Ministry of Economic Affairs. Solution stop The dissolution period of the time including the time and the temperature at the beginning and the beginning of the temperature is at the low end of the week P. At 15 o'clock, the temperature is about two degrees. The jiajia 4 (210X 297 public), 01323 A 6 B6 V. Description of the invention _ (27 temperature and viscosity

Table V Recipe Td Residence temperature no) Viscosity (poise) (r) Start and end AA 86 .70-10.8 11.0 BB 95 80 4.3 -4.5 CC 106 90 2. 8 2. 8 (Please read the notes on the back side first Fill this page>. Pack. The data in Table V shows that the dissolution temperatures of the thermosetting resin composition and thermoplastic particles of the present invention are 86, 95 and 106, respectively. Ό can be maintained at a temperature of about 15C below the dissolution temperature for at least 2 hours without Significantly changes the viscosity of the sister compound. G Μ 13 (hh for use) PR-500-thermosetting sister compound of aromatic epoxy resin (available from 3M) and 8.5% by weight of polybenzimidazole (PBI) particles The preparation method is to mix 4.65 parts (JltrafUe ΡΒΙ Celanese Co.) with an air stirrer at 60t: and its surface area is 12.3in2 / g and 50 parts of PR-500. Cobalt of this composition There is no evidence of PBI dissolution. This image is related to the book issued by Yin Nujing from the Central Bureau of Economic Affairs of the Ministry of Economic Affairs. The difference between -tg and the difference is that only the replacement and the sister change 00 Change -5 kinds of R Γ P of each quality, and change it to Benwei 4 (210X 297 male) A6 B6 Fifth, the description of the invention (28 is clear. It ’s very good to say that the r art of the family is here (please read the precautions on the back and then fill out this page > .51 · • 打 · sf. Printed by the Central Bureau of Economic Development Armor 4 (210X 297 gong)

Claims (1)

A revision-free version (mm A7 B7 C7 D7 .......................... {................ installed .................................................................. .... Practice (please read the precautions on the back before filling in this page). Printed by the Central Squash Bureau of Suiji Ministry L A hot-melt thermosetting resin (a) A thermosetting mixture of 100 parts, the surrounding is liquid , This mixture includes epoxy, cycloaliphatic epoxy, Ν, Ν'- sister compound, including its temperature at the kind of or more maleic acid double 2. 3 ester thermosetting (b) 2 to ester poly Acrylics and higher grains. The temperature rise of the resin sister avoids increasing. The average diameter of the thermalization sister is based on the application. The amine is based on the application. The third is based on the application. The third is based on the application of monomers and pre-resin. 50 One part of the class, polyacetamides, polyimines, polyethers and polyethers have the highest insolubilities in their dissolution temperature, and the poly-patent range of amorphous resins that do not contain up to the dissolution temperature is 0.5 to 5%. The thermosetting agent, hardening species or more of the thermosetting tree of 槻 榇 gold amines and wrong patents are selected from polyamines, polyimides, and polyaryl esters The amorphous thermoplastic has a surface temperature of 1.0 m2 / s less and decreases at a temperature below the degree of the thermoplastic particles in the thermosetting resin, and as the lipid particles are completely solvated, the matrix is essentially the first item. In a 50-micron fan garden. Sister acids or anhydrides of item 1 or 2 or multiple compounds or salts, Lewis acids of Selenium 1 or 2 sister fats *, agents and catalyzed esters , Polyammonium polymer dissolves in the dissolved knot: 20 to 100. Other species are selected from aromatic imines, and polycyanide one or more of the chemical agents; and polyboats, polycarbodiimides and Class, resin particles of polyaryl smear · and solvents with 5G t or temperature of 15 TC, and whose viscosity is higher than the dissolution temperature and is uniform in the matured compound and r. Among them, the resin Compound of particles, in which the curing agent phenol, and in which the catalyst is acid or test class, imidazole compound, in which the resin particles A 4 (210X297 Gongguang), 01323 A7 B7 C7 D7 VI. Patent application Fan Yuanzi It also includes effective plasticizers. 5 · According to patent application No. 1 or 2 The sister compound, which further includes an effective amount of at least one inert filler, stabilizing agent, foaming agent, colorant, dye, and flame retardant. 6 According to the patent compound of the patent application item 1 or 2, It is used for one of the prepregs including reinforcing fibers. 7 · According to the sister compound of item 1 or 2 of the patent application scope, it is used as a coating on suspected suspects. 8. The sister compound according to item 1 or 2 of the patent application is used as a coating on a non-suspect male. 9. The sister compound according to item 1 or 2 of the patent application scope is used as a coating on the film. 10. The sister compound according to item 1 or 2 of the patent application is used as a coating on the sheet. (Please read the precautions on the back before filling in this page) • Call .Line · Printed by the Central Bureau of Standards of the Ministry of Economic Affairs 2 f 4 (210X 297 Gonghu)