TW438833B - Phosphorus containing flame retardant advanced epoxy resins, preparation and cured epoxy resins thereof - Google Patents

Abstract

A flame retardant advanced epoxy resin was prepared by reacting an active-hydrogen-containing phosphorus compound with a di- or poly-functional epoxy resin via an addition reaction between the active hydrogen and the epoxide group, which has a high glass transition temperature (Tg), suitable for printed circuit board and semiconductor encapsulation applications. The active-hydrogen-containing phosphorus compound is 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide having a chemical structure as follows: formula.

Description

4388 3 3 Α7 Β7 V. Description of the invention (1) Background of the invention Because of its excellent electrical properties, stable shape, high temperature resistance, solvent resistance, acid and alkali resistance, and epoxy resin, it is excellent for metals and silicon wafers. It has the advantages of light weight and low cost, and is widely used in electronics / information, aerospace, construction, and sporting goods. However, epoxy resins are as easy to burn as ordinary plastic materials and endanger human lives. Therefore, the world has strict requirements on the fire resistance of electronic / information materials (such as integrated circuit boards, half-package materials, etc.). For example, UL-94 fire test must meet V-0 regulations. Tetrabromobisphenol A is currently the compound most commonly used to impart flame retardancy to advanced epoxy resins and cured epoxy resins (Cured epoxy resin). Tetrabromopropanol reacts with excess epoxy resin to form two end epoxy epoxy-containing semi-cured products (Advanced epoxy resin) for use with fe-containing glass fibers, and then heat-hardens into the most commonly used flame-retardant laminate (FR_4 ) 'For printed circuit boards. On the other hand, tetrabromopropanediol is also mixed with other epoxy resin hardeners to cure epoxy resins and impart cured epoxy resin flame retardant properties to semiconductor curing materials. The reaction equation of tetrabromopropanediol and excess epoxy resin is as shown in (Π): 111111111 Packing — II If ^ (Please read the precautions on the back before filling this page) Ministry of Economic Affairs t 夬 Standards Bureau staff consumption Printed by the cooperative • 4- This paper size applies to Chinese national standards (CNS > A4 size (210X297 mm) 83.3.10,000 4388 3 3 A7 B7 V. Description of the invention (2)

H2C-CH-CH2: -〇CVq-

{Please read the note ^^^ on the back before filling out this page) (Π: Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs, but halogen flame retardants will produce dioxin or benzofuran when burned ) And irritating, corrosive and harmful gases, and small molecule flame retardants often lead to reduced mechanical properties and photodecomposition, which degrades the material. At the same time, the migration and volatilization of flame retardants in materials will also reduce the physical properties and difficulty In addition, some people have proposed the use of phosphorus-containing diols to carry out the semi-curing reaction (advancement reaction) with epoxy groups, the reaction equation is shown in (in) (JP 1 0-3 00 I7), but using hydrogen and oxygen Group (OH group) for semi-curing reaction with epoxy groups, it is only suitable for bi-functional, if it is used for multi-functional there will be a risk of gelling (gel). And the resulting semi-cured epoxy resin ( advanced epoxy resins) only have a low glass transition temperature, if you want to make a substrate with a high glass transition temperature, you need to add a multifunctional epoxy resin, you must add an additional step, and also consider the hardener for different structures Epoxy Phase separation of the reaction of epoxy groups on different lipid triggered. This paper is suitable scale China National Standard (CNS) A4 size (210X297 mm) 83. 3.10,000 438833 A7 B7 V. invention will be described (

C-C-CH2-〇—0-CH2-C-C

Excess

Q'pnW Ο ΗΟ-Ρ-ΟΗ

Min 〇--cH-Γ.

-CH2-CC (III) Summary of the Invention The present invention provides a phosphorous-containing flame-retardant epoxy semi-cured material-a chemical structure selected from the group consisting of the following formulae (a) to (d): (a) it has an order (please (Please read the notes on the back before filling out this page) Printed by the Central Consumers Bureau of the Ministry of Economic Affairs

h2

h2 m

Ri in the formula: an integer of 0 < m <12; Re hydrocarbon group; 114 and 115 are independently hydrogen methyl groups or this paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) 83. 3.10,000 438833 A7 B7 V. Description of the invention (

Where R1 has the same definition as above; and X = A or B, and at least one X is B, where Λ A = -C H2OH-CH2 OH B = -CH2 ~~ (ifH ~ CHg ~ E where E is

(b)

X

, X---Threading (please read the notes on the back before filling this page) The definition of X in the printed format of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs is the same as above; and Q is CH, '3 -CH — 5 2 '' CH3 1

ΟII 一 〇——S—or —S—, 4 IIο (c)

This paper scale applies Chinese National Standards Rate (CMS) A4 specification (210X297). 83.3.10,000 438833 A7 B7 V. Description of the invention (5) where X and Q have the same definitions as above; and ⑷

The definition of X in the employee consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is the same as above: and Y is-(CH2) n- or phenylene, where n is an integer from 0 to 6. The present invention also provides a phosphorous-containing flame-retardant epoxy resin cured product 'which is prepared by curing the above-mentioned phosphorus-containing flame-retardant epoxy semi-cured product of the present invention with an epoxy resin hardener. Preferably, the hardener is selected from the group consisting of phenolic resin (Pheno1 · formaldehyde novoUc), dicyandi amide, methylenedianiline 'diaminodiphenyl sulfone, acyl A group of phthalic anhydride and hexahydrophthalic anhydride. Preferably, the flame retardant epoxy resin cured product of the present invention is the same amount of the hardener as the flame retardant epoxy resin semi-cured product, and is added at a temperature higher than 150 ° C. Prepared by pre-aging. Preferably, the semi-cured product of the flame-resistant epoxy resin of the present invention has a chemical structure of the chemical formula (a), and in the formula (a): ^ is seven, and R4 is hydrogen. Preferably, the semi-hardened epoxy resin semi-cured material of the present invention has a chemical formula ------------------------- Order (Please read the precautions on the back before (Fill in this page) The paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 4388 3 3 A7 B7 5. The chemical structure of invention description (6) (C), and Q in formula (C) is- C (CH3) 2-. Preferably, the semi-hardened flame retardant epoxy resin of the present invention has phosphorus in an amount of -30% by weight, and more preferably 1-5% by weight. Preferably, the flame retardant epoxy resin cured product of the present invention is in the presence of an epoxy resin curing accelerator and uses 0.01 -1 · 0 weight parts of epoxy per 100 weight parts of the flame retardant epoxy semi-cured material. The resin aging accelerator is prepared by adding aging. One suitable epoxy curing accelerator is triphenylphosphine. The present invention also discloses a method for preparing a phosphorous-containing flame-retardant epoxy semi-cured material, which comprises loading a phosphorus-containing compound having the following formula (I) (please read the precautions on the back before writing this page).

Printed by the Ministry of Economic Affairs of the Central Bureau of Standardization, Shellfish Consumer Cooperative, and printed with epoxy resin materials with the chemical structure of the group consisting of the following formulae (a ') to (d') in molten state or in a common solvent Reaction: (a5)

In the formula: 0 < m < 12 integer iRe Η or CrC4 hydrocarbon group; R4 and R5 are independently hydrogen, -9- This paper standard is applicable to China 囷 national standard (CNS) A4 specification (210X297 mm) 83.3.10,000 438833 V. Description of the invention (methyl or A7 B7

Where R! Has the same definition as above; and Λ X '= —CH2-CH-CH2 (b,)

X ', X, where X' has the same definition as above; and Q is CH, '3

-CH

0II 2 CH3 —〇— —S— or —S—, ^ II 〇 (C,) χΌ

---------- ^ ------ ΪΤ ------ ^ (Please read the notes on the back before filling this page) The definitions of X 'and Q in the assembly are the same as above; and (d,)

-10- This paper size applies the Chinese National Standard (CNS) M Washer (210X297 mm) 83. 3.10,000 4388 3 3 Printed A7 B7 by the Consumers ’Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (8) X 'in the formula has the same definition as above; and Y is-(CH2) n- or phenylene, wherein π is an integer from 0 to 6. In the above method of the present invention, 'preferably, the reaction is performed at 100 t to 200 t, and the epoxy group of the epoxy resin material reacts with the active hydrogen of the phosphorus-containing compound of formula (I) (bonded to phosphorus Above), the equivalent ratio is between 2: 1 and 〖〇: 1. This reaction can be performed in the presence of a catalyst. The catalyst is 2-phenylimidazole, 2-methylimidazole, triphenylphosphine, quaternary phosphorus or quaternary amine compound. In the present invention, the reactive hydrogen of the phosphorus-containing compound (I) is used to directly bond epoxy groups of a bifunctional or multifunctional epoxy resin by an addition method to form an epoxy semi-cured product (Advanced epoxy resin). This semi-cured epoxy resin not only imparts the flame-resistant epoxy resin cured material (Cured epoxy resin) obtained by its curing, but also provides thermal stability, does not migrate, increases the thermal cracking temperature, and does not produce toxic or Corrosive gas is an environmentally friendly and flame-resistant material, suitable for circuit board manufacturing and semiconductor packaging materials. DETAILED DESCRIPTION OF THE INVENTION The present invention utilizes an active hydrogen-containing phosphorus-containing compound having the formula (I) and directly reacts with an epoxy group through an addition method, and is suitable for use in difunctional and polyfunctional epoxy resins. The reaction formula is as shown in (IV): -11- This paper size is applicable to the China National Standard (CNS > A4 size (210 X 297 mm)) | Binding »Thread (please read the notes on the back before filling in (This page) 438833 Α7 Β7

ch2-ch-ch2-o- I OH 5. Description of the invention (

Η (IV) This reaction (IV) is suitable to be carried out at 100 ° C-200 ° C, and is preferably 150 ° C-18 (TC), or can be carried out with a small amount of catalyst. Suitable catalysts such as 2- Phenyl imine (2- 卩 1 ^ 11 > ^ 1111 £ 1 & 2〇 丨 6), 2-methylimidazole, triphenylphosphine, or quaternary phosphorus and quaternary Amine salts (quarternary phosphonium and ammonium compounds), such as ethyl trisphenol based iodine phosphide, ethyl trisphenol based phosphide, ethyl trisphenol based bromide ... and other quaternary phosphorus salts; benzyltrimethylamine Chlorine, benzyltriethylamine chloride > quaternary amine salts such as tetrabutylamine chloride, etc. The resulting semi-cured flame retardant epoxy resin is suitable as a matrix for fiber-reinforced resins for manufacturing circuit boards (Matrix) Resin The semi-hardened flame retardant epoxy resin obtained by the reaction (IV) can be mixed with a conventional epoxy hardener and then heated (for example, 15 (TC or more)) to mature to form a hardened flame retardant epoxy resin. The conventional epoxy resin hardeners suitable for the present invention are typically, for example, phenol-formaldehyde -12----------- ^ ------ 'ΤΓ --- --- 0 (Please read threshold first Please fill in this page again.) The paper printed by the Central Bureau of Standards of the Ministry of Economic Affairs and the Consumers' Cooperative Printing Co., Ltd. The paper Λ degree is applicable to the Chinese National Standard (CMS) A4 specification (210X297 mm) 83.3.1, 0.00 Printed by the employee consumer cooperative 438833 A7 B7 V. Description of the invention (10) novolac), dicyandiamide, methylenedianiline, diaminodiphenyl sulfone, acid anhydride ( phthalic anhydride), and hexahydrophthalic anhydride, etc. Cured epoxy resins are used for semiconductor packaging materials. Raw materials required for the manufacture of semi-cured and cured products of flame retardant epoxy resins — — Epoxy resin can be any epoxy resin, such as bisphenol A, bisphenol F, bisphenol S, bisphenol S, biphenol, etc. Epoxy compounds; and polycyclic epoxy resins (phenol formaldehyde novolac epoxy), cresol formaldehyde novolac epoxy (functional groups 4-18), and many other rings Oxygen resin or mixtures thereof. The present invention can be further understood by the following examples, which are used for illustration purposes only and are not intended to limit the scope of the present invention. I. Preparation Example of Phosphorus-containing Flame Retardant Epoxy Semi-cured Product 1: Diglycidyl ether bisphenol A epoxy resin (DGEBA) reacts with DOPO to form epoxy semi-cured product IIPK containing Phosphorus content 1% by weight) was prepared in a condenser with a calcium chloride drying tube, nitrogen gas was passed into the tube's thermoelectric 隅 temperature controller, a vacuum device and an electric stirrer in a 1L four-port separation round bottom reactor, Add 700g of glycerol diglycidyl ether epoxy resin ((DGEBA), epoxy equivalent EEW = 187g / eq, provided by Nanya Plastics, Commodity -13- This paper is in accordance with China National Standard (CNS) A4 specifications (210X297 mm) ------------ Approval of clothes -------- ΐτ ------ i (Please read the precautions on the back before filling in this page) 4 3 88 3 3 Printed by A7 B7, Shellfish Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs 5. Description of the Invention (11) Name L-128E) Heated to 110 ° C with a heating bag, while stirring and vacuuming (< 100mmHg) for about 30 minutes, In order to remove a trace of moisture in the epoxy resin, return the reactor to normal pressure and pass in dry nitrogen. Increase the temperature to After 30 ° C, 5 2.5 g of 9,10-dihydro-9-oxy-10-phosphophenanthrene 10-oxide (9,10-dihydro-9-oxa-l O-phosphaphenanthrene -1 O-oxide (Referred to as DOPO, purchased by TCI)) After melting and stirring, the reaction temperature is increased to 160 ° C, and the reaction is performed at 160 ° C for 5 hours. After cooling, a solid epoxy resin Π! Is obtained, and its epoxy equivalent is 215 g / eq (the theoretical equivalent of epoxy equivalent is 2 16 g / eq) 〇 Example 2-3: Epoxy resin semi-cured product IIP2 (phosphorus content 2% by weight) and ΙΡ3 (phosphorus content 3% by weight) According to the reaction conditions of Example 1, 113.5 g and 185 g of DOPO and 700 g of DGEBA were prepared, and a solid epoxy resin Π 2 (ring containing 2% by weight of phosphorus and 2S2 g / eq of epoxy equivalent) was prepared. The theoretical equivalent of oxygen equivalent is 252 g / eq), and the solid epoxy resin Π3 with phosphorus content of 3% by weight and epoxy equivalent of 308 g / eq (theoretical equivalent of epoxy equivalent is 306 g / eq). Example 4: Cresol formaldehyde novolac epoxy reacts with DOPO to form epoxy semi-cured product C! 2P2 (phosphorus content 2% by weight) Preparation of a condenser with a calcium chloride drying tube ,nitrogen Into a 1L four-port split-bottom reactor with a thermoelectric radon temperature controller, a vacuum pump, and an electric stirrer, add 400 g of cresol aldehyde epoxy resin (cresol -14- I ^ ^ ^ I ^ Order III-III Travel {Please read the Note $ on the back before filling in this purchase) This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) 83.3.10,000 438833 A7 B7 V. Description of the invention (12) formaldehyde novolac epoxy (referred to as CNE) (number of functional groups 12, epoxy equivalent EEW = 205 g / eq, supplied by Nanya Plastics, trade name NPCN-704), heated to n0 ° C in a heating bag * while stirring and vacuuming (< 100mmHg) for about 30 minutes, in order to remove a trace of moisture in the epoxy resin, return the reactor to normal pressure and pass in dry nitrogen. After the temperature was raised to 130 ° C, 68 g of DOPO was added and melted and stirred, and then the reaction temperature was increased to 160 ° C, and the reaction was performed at 160 ° C for 2.5 hours. After cooling, a solid epoxy resin was obtained, with an epoxy equivalent of 275 g / eq (theoretical equivalent of epoxy equivalent was 285 g / eq). Example 5: Preparation of epoxy resin semi-cured product Ci2P4 (phosphorus content 4% by weight) DOPO with different dosages (155 g) and 400 g CNE were prepared according to the reaction conditions of Example 4 to obtain a phosphorus content 4 Solid epoxy resin C12P4 (wt.%) And epoxy equivalent 485 g / eq (the theoretical equivalent of epoxy equivalent is 464 g / eq). --------- Meal ------ ΐτ ------ ^ (Please read the note on the back before filling out this page} Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy ¾ 15- # Zhang; Ot applies Chinese national kneading rate {CMS) A4 specification (210X297 mm) 83. 3.] 0, 〇〇〇4 3 88 λ 3 A7 B7 V. Description of the invention (13) The reaction of Examples 4 and 5 is as follows Equation V

+

0 < m < 12 X = A or B r; 〇1 at least one of B A = eight -CH2- € H-CH;

OH

B = -C

H2— (ihM

CH factory E; where E is

---------- ^ ------ Order ------- ^ (Please read the notes on the back before filling out this page) II. Complete curing of the semi-cured epoxy resin The semi-cured epoxy resin of Examples 1 to 5 and dGEBA and CNE as a control were added. The equivalent of diamin〇 {jiphenyl sulfone 'is abbreviated as DDS. ), Phenol-formaldehyde novolac 'Η equivalent 105 g / eq (PN for short) or dicyandiamide -16- This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 438833 A7 B7 V. Description of the invention (14) (dicyandiamide, abbreviated as DICY) is a hardener. It is first honed into a powder and then heated to 150 ° C to be in a molten state. After stirring evenly, it enters a hot aluminum mold and solidifies in an oven. Example of using PN as a hardener 'Before being heated, 0.2% by weight of triphenylphosphine is further uniformly mixed as a hardening accelerator. DGEBA epoxy resin is cured at 160 ° C for one hour and then 180 ° C for four hours. CNE is cured at 160 ° C for one hour, 180 ° C for two hours, and 2001 for two hours. The pure CNE epoxy resin that contains no phosphorus has been cured for an additional 2201 hours. The cured sample was slowly cooled to room temperature to avoid cracks in the rabbit. Table 1 shows the dynamic mechanical (DMA) properties of the hardened samples obtained from the semi-cured material of Examples 1-3. Table 2 shows the thermal cracking analysis of the hardened samples. Table 3 shows the results of the UL-94 flame resistance test of the hardened samples. . ----: ----- ^ — < Please read the note on the back first and then write this page) 'ΐτ Printed by the Central Laboratories of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives__ Dynamic mechanical properties Sample glass transition temperature (Tg, t) The elastic modulus is 50. . , 10 * Pa DGEBA / DDS 190 18.8 IIPi / DDS 188 19.2 IIP2 / DDS 155 20.4 IIP3 / DDS 124 18.1 DGEBA / PN 15 1 16.4 ΙΙΡ, / PN 134 18.4 ιιρ2 / ρν 129 21.3 ιιρ3 / ρν 117 17.7 -17- 83, 3.10,000 This paper size is in accordance with Chinese national standard (CNS> Α4 size (210 × 297 mm)) Printed by the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4 3 88 3 3 A7 B7,15, V. Description of the invention () Table 2 Thermal cracking hall ^ Analysis sample loss 5%. C at n2 5% loss ° C in air at 70 (TC, N2 residual ash content (%) at 700 ° C, air residual ash content (%) DGEBA / DDS 405 379 15.1 0 IIPi / DDS 388 375 15.93 4 IIP2 / DDS 386 363 17.64 11.3 IIP3 / DDS 375 356 20 18.7 DGEBA / PN 423 417 19.1 0 ΙΙΡι / ΡΝ 396 386 22.5 15.9 IIP2 / PN 371 383 25 19.5 IIP3 / PN 366 364 26.9 20.7 Table 3 UL-94 flame resistance test and LOI (limiting oxygen index) measurement results Phosphorus content Burning time (seconds) UL-94 Sample% Ist combustion 2nd combustion level LOI DGEBA / DDS 0 > 60 V-2 22 ΙΙΡ , / DDS 0.78 9.5 5.3 V-1 25 IIP2 / DDS 1.60 6.3 3.1 V-0 28 iip3 / dds 2. 49 2.1 0.9 V-0 30 DGEBA / PN 0 > 80 Smoke 21 IIPj / PN 0.67 53 V-2 23 IIP2 / PN 1.41 19.2 4.5 V-1 25 IIP3 / PN 2.23 2.1 1.1 V-0 27 -18- I ~ ^ ^ nn IIII — Line (Please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 83.3.10,000 438833 A7 _B7__ V. Description of the invention (16 ) Table 4 shows the dynamic mechanical (DMA) properties of the hardened samples obtained from the semi-cured material of Example 4-5, Table 5 shows the thermal cracking analysis of the hardened samples, and Table 6 shows the UL-94 flame resistance test of the hardened samples. result. „T In I ^ (Please read the notes on the back ^ before filling out this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives Table 4 Dynamic mechanical properties Sample glass transition temperature (Tg, t) Elasticity 50t, 108pa CNE / DDS 255 1.02 Cl2P2 / DDS 228 1.06 C12P4 / DDS 178 1.05 CNE / PN 216 2.12 C12P2 / PN 178 2.89 C12P4 / PN 155 2.37 CNE / DICY 248 1.23 CI2P2 / DICY 213 1.78 C12P4 / DICY 169 1.25 -19-83. 3.10,000 This paper uses the Chinese National Standard (CNS) A4 size (210X297 mm) 43 88 3 3 A7 B7 V. Description of the invention (17 Table 5 Pyrolysis analysis sample 5% loss ° C at n2 5% loss ° C in air at 700 ° C, N2 residual ash content (%) at 700QC, air residual ash content (%) C, 2 / DDS 407 416 29.9 CnPi / DDS 386 387 42.3 25 c12p4 / dds 371 374 43.6 29.5 C, 2 / PN 407 408 40.1 0 c12p2 / pn 391 394 47.6 35 c12p4 / pn 376 378 46.7 41 Cn / DICY 373 380 29.3 2.2 Ci2P2 / DICY 363 370 33.7 21.4 C12P4 / DICY 364 370 35.0 27.9 Central government standard Printed by the Bureau of Shellfish Consumer Cooperatives *. Table 6 UL-94 flame resistance test and LOI (limiting oxygen index) Measured results: Phosphorus content of the sample, Drip smoke level LOI C, 2 / DDS 0 with fm *. jm: V-2 23 C12P2 / DDS 1.69 e j »w e / w v-0 27 C12P4 / DDS 3.63 te 4ttt IIH? V-0 33 C12 / PN 0 with M Jl, V-2 21 c] 2p2 / pn 1.45 Μ JiW far. ΤΙΓΓ .ytw V-0 26 C12P4 / PN 3.29 Μ 4ml τγγγ y \ \\ V-0 28 C12 / DICY 0 Yes 4ττΐ Ull- V-2 24 C12P2 / DICY 1.86 Sister J \\\ te / ΙΛΛ V-0 34 c12p4 / dicy 3.83 fit Attt iHiT V-0 38 -20- Applicable to this paper size China National Standard (CNS) A4 specification (210X297 mm) 83. 3.10,000 I-^ --- ^ ----- sai ------ ir ------ ^ (Please read first Please fill in this page on the back of the page) 438833 V. Description of the Invention (is) -1-Correction 89. V. 1 ^ Corrected in July 2000) (Please read the notes on the back before filling this page) From Table 1 to It can be seen from the results in Table VI that the cured product of the phosphorus-containing epoxy resin of the present invention not only has high heat resistance, mechanical properties, and a high glass transition point temperature, but also has excellent flame resistance, no dripping and blackness during combustion. The phenomenon of smoke is very suitable as a circuit board material, semiconductor Packaging materials and other engineering applications. Example 6: Cresol formaldehyde novolac epoxy reacts with DOPO to form a semi-cured epoxy resin C8P (1% by weight of phosphorus), C8P2 (2% by weight of phosphorus) C8P3 (containing Phosphorus content 3% by weight) except for cresol formaldehyde novolac epoxy (CNE) under the trade name NPCN-703 (functional group number 8, epoxy equivalent EEW = 220 g / eq, provided by Nanya Plastics) ) Instead of NPCN-704 and using different amounts of DOPO, repeat the procedure of Example 4 to prepare the epoxy resin semi-cured product CsPJ containing 1% by weight of phosphorus), CSPZ (2% by weight of phosphorus) 〇8 卩 3 (3% by weight of dish). The epoxy equivalent weights (EEW) of C8Pi, CsPi and CgP3 were 235.44, 291.6 and 361.57 g / eq, respectively. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the semi-cured epoxy resin of Example 6 and CNE as a control by adding an equivalent amount of hardener and 0.1 parts by weight (per 100 parts by weight of semi-cured epoxy resin). Triphenylphosphine is used as a hardening accelerator. The hardener is selected from a phenol-formaldehyde novolac 'OH equivalent 105 g / eq (abbreviated as PN) or a melamine-phenol novolac (abbreviated as MPN-1) having the following formula: MPN-2): 21-This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm)

Of which 438833 n / m N m AHEW * MPN-1 2.83 3.31 1.87 88 MPN-2 1.7 1.87 2.26 82 * AHEW: active hydrogen equivalent The mixture is first honed into a powder and then heated to 13 ° C in a molten state. After stirring evenly , Into the hot aluminum mold and cured in an oven. It is pre-cured for one hour at 60 t, then cured for two hours at 1, and post-cured at 220 ° C for two hours. The pure CNE epoxy resin containing no phosphorus is further cured by 220 " C for two hours. The cured sample was slowly cooled to room temperature to avoid cracks in the rabbit. Table 7 shows the thermal cracking (TGA) analysis of the hardened samples obtained from the semi-cured material of Example 6, and Table 8 shows the results of the UL · 94 flame retardancy test of the hardened samples. -22- The size of this paper applies to China National Standard (CNS) A4 (2) 0 X 297 mm) τ ------ ^ ----------------- line (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by 4388 3 3 Lost temperature, c Residual ash content at 700 ° C (%) Epoxy resin equivalent Tg (° C) P (%) N (%) N2 Air n2 Air C8 / PN 178.16 0 0 448.3 449.2 29.04 1.36 C8P1 / PN 159.82 0.69 0 443,7 443.4 30.64 14.98 C8F2 / PN 149.65 1.47 0 433.1 437.7 31.36 22.47 C8P3 / PN 137.73 2.32 0 423.5 428.2 36.7 30.13 C8 / MPN-1 197.21 0 5.71 425.6 428.7 31.06 1.79 C8P1 / MPN-1 179.66 0.73 5.43 421 423.9 32.82 17.51 C8P2 / MPN-1 169.33 1.54 4.64 412.4 415.7 33.13 24.22 C8P3 / MPN-1 156.52 2.41 3.91 401.6 411.2 39.84 32.7 C8 / MPN-2 205.82 0 7.33 407.9 426.1 33.29 1.946 C8P1 / MPN-2 183.06 0.74 6.97 406.8 415.1 33.95 19.57 C8P2 / MPN-2 171.26 1.56 5.92 391.6 413.1 34.03 27.68 C8P3 / MPN-2 162.91 2.44 4.97 382.5 403.8 41.31 35.69 < Please read the precautions on the back before filling this page) Installation ------------ Order: -------- line -23-A7 B7 r positive 1 V. Description of the invention (2G) Survey and correction in July of the year) ...... 1 _-... This paper size is applicable to China Standard (CNS) A4 specification (210 X 297 mm) 4388 3 3 r__ A7 Date of amendment / ------ I— _ Humble 7 supplement._ 5. Description of the invention (21) (Amended in July 2000) Table 8 UL-94 flame retardance test and LOI (Limit oxygen index) epoxy resin purpose Hue uniform! ί Ρ (%) Ν (%) Visible smoke UL-94 level LOI C8 / PN 0 0 Severe V-2 21 C8P1 / PN 0.69 0 Slight V-1 23 C8P2 / PN 1.47 0 / \ w ^ ΤΤΓ No V-0 25 C8P3 / PN 2.32 0 Μ and V-0 27 C8 / MPN-1 0 5.71 Severely severe V-2 23 C8P1 / MPN-1 0.73 5.43 New Zealand ΕΕ V-0 26 C8P2 / MPN-1 1.54 4.64 ft Μ / ,,, V-0 30 C8P3 / MPN-1 2.41 3.91 Μ Tttil V-0 34 C8 / MPN-2 0 7.33 Slightly severe V-2 24 C8P1 / MPN-2 0.74 6.97 jM New Zealand / \\\ V- 0 27 C8P2 / MPN-2 1.56 5.92 Input J \\\ and V-0 32 C8P3 / MPN-2 2.44 4.97 μy \\\ MS, V-0 36 The nitrogen-phosphorus group can be seen from Tables 7 and 8. The cured epoxy resin (CsIVMPN) has the same flame retardant effect because it requires a smaller amount of phosphorus than the cured epoxy resin containing phosphorus group (c8px / pn) due to the combined effect of nitrogen and phosphorus. However, compared with the conventional epoxy resin cured products (C8 / PN, C8 / MPN), the phosphorus-containing group and nitrogen-phosphorus group-containing epoxy resin cured product of the present invention are not suitable for black smoke. For semiconductor packaging materials. The present invention G is described in conjunction with the above specific embodiments. Those skilled in the art will be able to make various changes based on the above description. The scope of the invention includes such changes as are defined within the scope of the following patent applications and their spirit. This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) (please read the precautions on the back before filling this page) -Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Claims (1)

A8B83D8 6. Scope of patent application Supplementary foot. 7. 〇-1. A phosphorous-containing flame-retardant epoxy semi-cured material having a chemical structure selected from the group consisting of the following formulas (a) to (d): (a) In the formula: the -CH2- group between two benzene rings is 2,2_-; 2,4_- or 4,4-bridge; 0 < m < an integer of 12; Ri =: »or (: 1- (: 4hydrocarbyl; R4 and I are independently hydrogen 'methyl or OCH2d & H2 Ri —ch2- --------------- install i J {Please read the note on the back before filling in this Page) The definition of Rl in the printed consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is the same as above; and X = A or B, and at least one X is B Λ A = -ch2-ch-ch2 OH B = -CH2— (! ; H—CH2—E where E is its midline · -25- This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 438833 A8B8C8D8 axuuu thousand / ηρ · τ) Six, patent application scope (b) XX / N- < P > -Q -〇 ^ ~ N / x X where X has the same definition as above; and Q is 0 —CH— — C— —〇— One S—or one, one, two, |, 11 1 0 (c) where X and Q is as defined above and 1111! Install --------- Order --------- line (Please read the precautions on the back before filling out this page) Member of the Intellectual Property Bureau of the Ministry of Economic Affairs Η Consumption Cooperation Du Printing Standard X The definition is the same as above; and y is-((: 112) "-or phenylene ', where n is an integer from 0 to 6. 2. If the flame-retardant epoxy semi-cured material of item 1 of the scope of patent application, Has the chemical structure of chemical formula (a), and R1 in formula (a) is -CH3 and R4 is hydrogen ° • 26- This paper size applies to Chinese national standard (CNS> A4 present grid (210x297 public love) 4 3 8 8 3 3 A8 B8 C8 D8 rwin 缶 July 绦 TF_) Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 6. Scope of patent application 3. If the flame retardant epoxy semi-cured material of item 2 of the scope of patent application has 1- 30% by weight of phosphorus. 4. If the flame-retardant epoxy resin semi-cured material of item 3 in the scope of patent application has 1 to 5% by weight of phosphorus. The cured product has the chemical structure of chemical formula (c), and Q in the formula (< 0 is -C (CH3) 2- There is 30% by weight of phosphorus. 7. The flame retardant epoxy semi-cured material according to item 6 of the patent application has 1 to 5% by weight of phosphorus. 8. A cured flame retardant epoxy resin containing phosphorus, It is prepared by curing an epoxy resin hardener with a phosphorus-containing flame-retardant epoxy semi-cured material in the first patent application scope. 9. The flame-retardant epoxy resin cured product in the eighth patent application scope, wherein the The hardener is selected from the group consisting of melamine-phenol novolac, phenol-formaldehyde novolac 'dicyandiamide, meihylenedianiline, and diamine Diaminodiphenyl sulfone, phthalic anhydride (phthalic -27- This paper size applies to China National Standard (CNS) A4 specification (21〇x 297 mm), installed ------------ order ---- ----- line (please read the precautions on the back before filling in this page) 438833 A8 B8 C8 D8 (Amended in July 2000) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs on the consumer cooperation. And hexahydrophthaik anhydride Group 10. The flame retardant epoxy resin cured product according to item 8 of the scope of patent application, wherein the same amount of the hardener as the flame retardant epoxy resin semi-cured product is used at a temperature higher than 150 & C. Add to maturity. Π. The flame-retardant epoxy resin cured product according to item 8 of the scope of application for a patent, wherein the flame-retardant epoxy semi-cured product has a chemical structure of the chemical formula (a) 'and R in the formula (a) is -CH3' And R4 is hydrogen. 1 2. The flame retardant epoxy resin cured product according to item 11 of the scope of patent application, wherein the flame retardant epoxy resin semi-cured product has phosphorus content of 1% by weight. 1 3. Flammable epoxy resin cured product 'wherein the flame retardant epoxy semi-cured material has phosphorus content of 2% by weight 14. 14. The flame retardant epoxy resin cured product according to item 8 of the patent application scope' wherein the flame retardant epoxy resin The semi-cured material has the chemical structure of the chemical formula (c), and Q in the formula (0 is -C (CH3) 2-. 1 5. The flame-retardant epoxy resin cured product according to item 14 of the patent application scope, wherein The flame-retardant epoxy semi-cured material has 1-30% by weight of phosphorus. -28- This paper size is applicable to the national standard (CNS) A4 specification (21〇X 297 mm) -------- ------ install ------- 1 order I -------- line < Please read the note on the back before filling this page) 4388 3 3 A8 B8 C8 D8 οηηη ^ ί Employees' cooperation of Intellectual Property Bureau of the Ministry of Economic Affairs, Du printed. 6. Scope of patent application 1 6. If the scope of patent application No. 15 is a flame retardant epoxy resin cured product, wherein the flame retardant semi-cured material has 1 to 5% by weight of phosphorus. 1 7. The flame retardant epoxy resin cured product according to item 8 of the patent application scope, wherein the curing is in the presence of an epoxy resin curing accelerator and per 100 parts by weight of the difficult The flame retardant epoxy resin semi-cured product is cured by adding 0.01 to 1.0 parts by weight of an epoxy resin curing accelerator. 18. If the flame-retardant epoxy resin cured product of item 17 of the patent application scope, The curing agent for epoxy resin is triphenylphosphine. 19. A method for preparing a phosphorus-containing flame-retardant semi-cured epoxy resin semi-hardened product of the scope of application for patent, comprising the step of adding a phosphorus-containing compound having the following formula (1) Reaction with an epoxy resin material having a chemical structure selected from the group consisting of the following formulae (a,) to (d,) in a molten state or in a common solvent: (a,) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) --------- 1 pack ·! --Order ------ line (please read the precautions on the back before filling this page) 438833 A8 B8 C8 D8 VI. The scope of patent application for the -CH2- group between two benzene rings is 2,2_-; 2 , 4,-or 4,4-bridge: 0 < m < integer of 12; R! = 11 or hydrocarbyl; R4 and Rs are independently hydrogen, methyl or Where R1 has the same definition as above; and X '= -CH2-CHhCH2 (b,) / X, -Q- X' --- Ί ----------------------- --Order,-; -------- line (Please read the precautions on the back before filling this page) x ’\ N The definition of X ’in the printed consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is the same as above; and Q is 9H3 -— —c— —ο 心 3, -CH -S—or— '[1 (C,) χΌ In the formula, X ′ and Q have the same definitions as above; and -30- The paper size is applicable to the national standard (CNS) A4 specification (210 X 297 mm) 4388 3 3 A8 B8 C8 D8 --------- 7 Days Toshima TP) 6. Scope of Patent Application (d,) In the formula, X 'has the same definition as above: and Y is-(CH2) n- or phenylene, wherein n is an integer of 0 to 6. 20. The method according to item 19 in the scope of patent application, wherein the reaction is performed at 100t-200 ° C, and the epoxy group of the epoxy resin material is active hydrogen of a phosphorus-containing compound of formula （(bonded to phosphorus Above), the equivalent ratio is between 2: 1 and 1 Q: 1. 21. The method of claim 19, wherein the reaction is performed in the presence of a catalyst, and the catalyst is 2-phenylimidazole, 2-methylimidazole ), Triphenylphosphine, quaternary phosphonium or quaternary amine compounds. 22. The method according to claim 19, wherein the epoxy resin material M has a chemical structure of a chemical formula (a '), and Rig-CHs and R4 in the formula (a') are hydrogen. 23. If you apply for the method of item 22 of the scope of the patent, the difficulty is -31-The size of this paper is suitable for both China National Standard (CNS) A4 specifications (210 X 297 mm) — -------- ----- Equipment ---------------- line (Please read the note on the back ^ # • item before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives 438833 A8 B8 C8 D8 __r > n⑻ 玍 6. The scope of application for patents The flammable epoxy resin semi-cured material has 1-30% by weight of phosphorus. 24. The method of claim 23 in the scope of patent application, wherein the prepared semi-hardened flame retardant epoxy resin has 1-5% by weight of phosphorus. 25. The method of claim 19, wherein the epoxy resin material has a chemical structure of a chemical formula (c '), and Q in the formula (c') is -C (CH3) 2- = 26. The method of the 25th aspect of the patent, wherein the prepared flame-retardant epoxy semi-cured product has 1 to 30% by weight of phosphorus. 27. The method of claim 26 in the scope of patent application, wherein the semi-hardened flame retardant epoxy resin produced has 1 to 5% by weight of phosphorus. • ϋ I tH / κ 4 · 1 1 n ί I {Please read the notes on the back before filling out this page) -II order. -Line-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -Γ. Moderate! Rule | Sheet of paper A4 s) N (c quasi-standard country 32 | centimeter 97 2 438833 V. Description of the invention (is) -1-Zhengyu 89. V. 1 ^ Corrected in July 2000) (Please read the back of the first (Please note this page, please fill in this page) From the results of Tables 1 to 6, it can be seen that the phosphorus-containing epoxy resin cured product of the present invention not only has high heat resistance, mechanical properties, 'high glass transition point temperature, but also flame resistance. Excellent, no dripping and black smoke generated during combustion, very suitable for circuit board materials, semiconductor packaging materials and other engineering applications. Example 6: Cresol formaldehyde novolac epoxy reacts with DOPO to form a semi-cured epoxy resin C8P (1% by weight of phosphorus), C8P2 (2% by weight of phosphorus) C8P3 (containing Phosphorus content 3% by weight) except for cresol formaldehyde novolac epoxy (CNE) under the trade name NPCN-703 (functional group number 8, epoxy equivalent EEW = 220 g / eq, provided by Nanya Plastics) ) Instead of NPCN-704 and using different amounts of DOPO, repeat the procedure of Example 4 to prepare the epoxy resin semi-cured product CsPJ containing 1% by weight of phosphorus), CSPZ (2% by weight of phosphorus) 〇8 卩 3 (3% by weight of dish). The epoxy equivalent weights (EEW) of C8Pi, CsPi and CgP3 were 235.44, 291.6 and 361.57 g / eq, respectively. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the semi-cured epoxy resin of Example 6 and CNE as a control by adding an equivalent amount of hardener and 0.1 parts by weight (per 100 parts by weight of semi-cured epoxy resin). Triphenylphosphine is used as a hardening accelerator. The hardener is selected from a phenol-formaldehyde novolac 'OH equivalent of 105 g / eq (abbreviated as PN) or a melamine-phenol novolac (abbreviated as MPN-1) having the following formula: MPN-2): 21-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Of which 438833 n / m N m AHEW * MPN-1 2.83 3.31 1.87 88 MPN-2 1.7 1.87 2.26 82 * AHEW: active hydrogen equivalent The mixture is first honed into a powder and then heated to 13 ° C in a molten state. After stirring evenly , Into the hot aluminum mold and cured in an oven. It is pre-cured for one hour at 60 t, then cured for two hours at 1, and post-cured at 220 ° C for two hours. The pure CNE epoxy resin containing no phosphorus is further cured by 220 " C for two hours. The cured sample was slowly cooled to room temperature to avoid cracks in the rabbit. Table 7 shows the thermal cracking (TGA) analysis of the hardened samples obtained from the semi-cured material of Example 6, and Table 8 shows the results of the UL · 94 flame retardancy test of the hardened samples. -22- The size of this paper applies to China National Standard (CNS) A4 (2) 0 X 297 mm) τ ------ ^ ----------------- line (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by 4388 3 3 Lost temperature, c Residual ash content at 700 ° C (%) Epoxy resin equivalent Tg (° C) P (%) N (%) N2 Air n2 Air C8 / PN 178.16 0 0 448.3 449.2 29.04 1.36 C8P1 / PN 159.82 0.69 0 443,7 443.4 30.64 14.98 C8F2 / PN 149.65 1.47 0 433.1 437.7 31.36 22.47 C8P3 / PN 137.73 2.32 0 423.5 428.2 36.7 30.13 C8 / MPN-1 197.21 0 5.71 425.6 428.7 31.06 1.79 C8P1 / MPN-1 179.66 0.73 5.43 421 423.9 32.82 17.51 C8P2 / MPN-1 169.33 1.54 4.64 412.4 415.7 33.13 24.22 C8P3 / MPN-1 156.52 2.41 3.91 401.6 411.2 39.84 32.7 C8 / MPN-2 205.82 0 7.33 407.9 426.1 33.29 1.946 C8P1 / MPN-2 183.06 0.74 6.97 406.8 415.1 33.95 19.57 C8P2 / MPN-2 171.26 1.56 5.92 391.6 413.1 34.03 27.68 C8P3 / MPN-2 162.91 2.44 4.97 382.5 403.8 41.31 35.69 < Please read the precautions on the back before filling this page) Installation ------------ Order: -------- line -23-A7 B7 r positive 1 V. Description of the invention (2G) Survey and correction in July of the year) ...... 1 _-... This paper size is applicable to China Standard (CNS) A4 specification (210 X 297 mm) 4388 3 3 r__ A7 amendment date /- ----- I—_ Humble 7 supplement._ 5. Description of the invention (21) (Amended in July 2000) Table 8 UL-94 flame retardant test and LOI (Limit oxygen index) epoxy resin purpose Hue uniform! ί Ρ (%) Ν (%) Visible smoke UL-94 level LOI C8 / PN 0 0 Severe V-2 21 C8P1 / PN 0.69 0 Slight V-1 23 C8P2 / PN 1.47 0 / \ w ^ ΤΤΓ No V-0 25 C8P3 / PN 2.32 0 Μ and V-0 27 C8 / MPN-1 0 5.71 Severely severe V-2 23 C8P1 / MPN-1 0.73 5.43 New Zealand ΕΕ V-0 26 C8P2 / MPN-1 1.54 4.64 ft Μ / ,,, V-0 30 C8P3 / MPN-1 2.41 3.91 Μ Tttil V-0 34 C8 / MPN-2 0 7.33 Slightly severe V-2 24 C8P1 / MPN-2 0.74 6.97 jM New Zealand / \\\ V- 0 27 C8P2 / MPN-2 1.56 5.92 Input J \\\ and V-0 32 C8P3 / MPN-2 2.44 4.97 μy \\\ MS, V-0 36 The nitrogen-phosphorus group can be seen from Tables 7 and 8. The cured epoxy resin (CsIVMPN) has the same flame retardant effect because it requires a smaller amount of phosphorus than the cured epoxy resin containing phosphorus group (c8px / pn) due to the combined effect of nitrogen and phosphorus. However, compared with the conventional epoxy resin cured products (C8 / PN, C8 / MPN), the phosphorus-containing group and nitrogen-phosphorus group-containing epoxy resin cured product of the present invention are not suitable for black smoke. For semiconductor packaging materials. The present invention G is described in conjunction with the above specific embodiments. Those skilled in the art will be able to make various changes based on the above description. The scope of the invention includes such changes as are defined within the scope of the following patent applications and their spirit. This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) (please read the precautions on the back before filling this page) -Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A8B83D8 6. Scope of patent application Supplementary foot. 7. 〇-1. A phosphorous-containing flame-retardant epoxy semi-cured material having a chemical structure selected from the group consisting of the following formulas (a) to (d): (a) In the formula: the -CH2- group between two benzene rings is 2,2_-; 2,4_- or 4,4-bridge; 0 < m < an integer of 12; Ri =: »or (: 1- (: 4hydrocarbyl; R4 and I are independently hydrogen 'methyl or OCH2d & H2 Ri —ch2- --------------- install i J {Please read the note on the back before filling in this Page) The definition of Rl in the printed consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is the same as above; and X = A or B, and at least one X is B Λ A = -ch2-ch-ch2 OH B = -CH2— (! ; H—CH2—E where E is its midline · -25- This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 438833 A8B8C8D8 axuuu thousand / ηρ · τ) Six, patent application scope (b) XX / N- < P > -Q -〇 ^ ~ N / x X where X has the same definition as above; and Q is 0 —CH— — C— —〇— One S—or one, one, two, |, 11 1 0 (c) where X and Q is as defined above and 1111! Install --------- Order --------- line (Please read the precautions on the back before filling out this page) Member of the Intellectual Property Bureau of the Ministry of Economic Affairs Η Consumption Cooperation Du Printing Standard X The definition is the same as above; and y is-((: 112) "-or phenylene ', where n is an integer from 0 to 6. 2. If the flame-retardant epoxy semi-cured material of item 1 of the scope of patent application, Has the chemical structure of chemical formula (a), and R1 in formula (a) is -CH3 and R4 is hydrogen ° • 26- This paper size applies to Chinese national standard (CNS> A4 present grid (210x297 public love) 4 3 8 8 3 3 A8 B8 C8 D8 rwin 缶 July 绦 TF_) Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 6. Scope of patent application 3. If the flame retardant epoxy semi-cured material of item 2 of the scope of patent application has 1- 30% by weight of phosphorus. 4. If the flame-retardant epoxy resin semi-cured material of item 3 in the scope of patent application has 1 to 5% by weight of phosphorus. The cured product has the chemical structure of chemical formula (c), and Q in the formula (< 0 is -C (CH3) 2- There is 30% by weight of phosphorus. 7. The flame retardant epoxy semi-cured material according to item 6 of the patent application has 1 to 5% by weight of phosphorus. 8. A cured flame retardant epoxy resin containing phosphorus, It is prepared by curing an epoxy resin hardener with a phosphorus-containing flame-retardant epoxy semi-cured material in the first patent application scope. 9. The flame-retardant epoxy resin cured product in the eighth patent application scope, wherein the The hardener is selected from the group consisting of melamine-phenol novolac, phenol-formaldehyde novolac 'dicyandiamide, meihylenedianiline, and diamine Diaminodiphenyl sulfone, phthalic anhydride (phthalic -27- This paper size applies to China National Standard (CNS) A4 specification (21〇x 297 mm), installed ------------ order ---- ----- line (please read the precautions on the back before filling in this page) 438833 A8 B8 C8 D8 (Amended in July 2000) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs on the consumer cooperation. And hexahydrophthaik anhydride Group 10. The flame retardant epoxy resin cured product according to item 8 of the scope of patent application, wherein the same amount of the hardener as the flame retardant epoxy resin semi-cured product is used at a temperature higher than 150 & C. Add to maturity. Π. The flame-retardant epoxy resin cured product according to item 8 of the scope of application for a patent, wherein the flame-retardant epoxy semi-cured product has a chemical structure of the chemical formula (a) 'and R in the formula (a) is -CH3' And R4 is hydrogen. 1 2. The flame retardant epoxy resin cured product according to item 11 of the scope of patent application, wherein the flame retardant epoxy resin semi-cured product has phosphorus content of 1% by weight. 1 3. Flammable epoxy resin cured product 'wherein the flame retardant epoxy semi-cured material has phosphorus content of 2% by weight 14. 14. The flame retardant epoxy resin cured product according to item 8 of the patent application scope' wherein the flame retardant epoxy resin The semi-cured material has the chemical structure of the chemical formula (c), and Q in the formula (0 is -C (CH3) 2-. 1 5. The flame-retardant epoxy resin cured product according to item 14 of the patent application scope, wherein The flame-retardant epoxy semi-cured material has 1-30% by weight of phosphorus. -28- This paper size is applicable to the national standard (CNS) A4 specification (21〇X 297 mm) -------- ------ install ------- 1 order I -------- line < Please read the note on the back before filling this page) 4388 3 3 A8 B8 C8 D8 οηηη ^ ί Employees' cooperation of Intellectual Property Bureau of the Ministry of Economic Affairs, Du printed. 6. Scope of patent application 1 6. If the scope of patent application No. 15 is a flame retardant epoxy resin cured product, wherein the flame retardant semi-cured material has 1 to 5% by weight of phosphorus. 1 7. The flame retardant epoxy resin cured product according to item 8 of the patent application scope, wherein the curing is in the presence of an epoxy resin curing accelerator and per 100 parts by weight of the difficult The flame retardant epoxy resin semi-cured product is cured by adding 0.01 to 1.0 parts by weight of an epoxy resin curing accelerator. 18. If the flame-retardant epoxy resin cured product of item 17 of the patent application scope, The curing agent for epoxy resin is triphenylphosphine. 19. A method for preparing a phosphorus-containing flame-retardant semi-cured epoxy resin semi-hardened product of the scope of application for patent, comprising the step of adding a phosphorus-containing compound having the following formula (1) Reaction with an epoxy resin material having a chemical structure selected from the group consisting of the following formulae (a,) to (d,) in a molten state or in a common solvent: (a,) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) --------- 1 pack ·! --Order ------ line (please read the precautions on the back before filling this page) 438833 A8 B8 C8 D8 VI. The scope of patent application for the -CH2- group between two benzene rings is 2,2_-; 2 , 4,-or 4,4-bridge: 0 < m < integer of 12; R! = 11 or hydrocarbyl; R4 and Rs are independently hydrogen, methyl or Where R1 has the same definition as above; and X '= -CH2-CHhCH2 (b,) / X, -Q- X' --- Ί ----------------------- --Order,-; -------- line (Please read the precautions on the back before filling this page) x ’\ N The definition of X ’in the printed consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is the same as above; and Q is 9H3 -— —c— —ο 心 3, -CH -S—or— '[1 (C,) χΌ In the formula, X ′ and Q have the same definitions as above; and -30- The paper size is applicable to the national standard (CNS) A4 specification (210 X 297 mm) 4388 3 3 A8 B8 C8 D8 --------- 7 Days Toshima TP) 6. Scope of Patent Application (d,) In the formula, X 'has the same definition as above: and Y is-(CH2) n- or phenylene, wherein n is an integer of 0 to 6. 20. The method according to item 19 in the scope of patent application, wherein the reaction is performed at 100t-200 ° C, and the epoxy group of the epoxy resin material is active hydrogen of a phosphorus-containing compound of formula （(bonded to phosphorus Above), the equivalent ratio is between 2: 1 and 1 Q: 1. 21. The method of claim 19, wherein the reaction is performed in the presence of a catalyst, and the catalyst is 2-phenylimidazole, 2-methylimidazole ), Triphenylphosphine, quaternary phosphonium or quaternary amine compounds. 22. The method according to claim 19, wherein the epoxy resin material M has a chemical structure of a chemical formula (a '), and Rig-CHs and R4 in the formula (a') are hydrogen. 23. If you apply for the method of item 22 of the scope of the patent, the difficulty is -31-The size of this paper is suitable for both China National Standard (CNS) A4 specifications (210 X 297 mm) — -------- ----- Equipment ---------------- line (Please read the note on the back ^ # • item before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives 438833 A8 B8 C8 D8 __r > n⑻ 玍 6. The scope of application for patents The flammable epoxy resin semi-cured material has 1-30% by weight of phosphorus. 24. The method of claim 23 in the scope of patent application, wherein the prepared semi-hardened flame retardant epoxy resin has 1-5% by weight of phosphorus. 25. The method of claim 19, wherein the epoxy resin material has a chemical structure of a chemical formula (c '), and Q in the formula (c') is -C (CH3) 2- = 26. The method of the 25th aspect of the patent, wherein the prepared flame-retardant epoxy semi-cured product has 1 to 30% by weight of phosphorus. 27. The method of claim 26 in the scope of patent application, wherein the semi-hardened flame retardant epoxy resin produced has 1 to 5% by weight of phosphorus. • ϋ I tH / κ 4 · 1 1 n ί I {Please read the notes on the back before filling out this page) -II order. -Line-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -Γ. Moderate! Rule | Sheet of paper A4 s) N (c quasi-standard country 32 | centimeter 97 2