TWI306861B - Phosphorus containing flame retardant resins and flame retardant resin compositions - Google Patents

Description

1306861 " Trends in the development of agents and flame retardant resins. The production of printed circuit boards often gives the epoxy resin flame retardancy with the four deserts, and with the global demand for non-toothing of electronic and electrical products, and the communication products tend to be light, thin, short, and small, as printing. The surface of the board for the use of the board, in addition to no secrets, the connection, the nature, the ion migration and other younger generations to raise the tree, is the subject of an urgent bribe. U.S. Patent No. 5,456,978 discloses the use of an epoxy oleic acid vinegar, a nitrogen-containing epoxy resin, and a metal composite hardener to form a composition. The disadvantage is that the phosphoric acid is easily hydrolyzed to produce a copper box, and the metal complex has a metal ion migration problem, which affects the dielectric constant. [Republic of China Patent No. 583258] discloses the use of an epoxy resin, a dihydrophenylhydrazine wicking compound, a second well ring resin, a condensed dish vinegar, and an epoxidized polybutanide. The disadvantage is that the condensation of phosphoric acid will produce water emulsifiers and salts which are easily released, and epoxidized at high temperature: ^ easy =. • The Republic of China Patent No. 555827 and the Republic of China Patent No. 572983 disclose the use of a bromine-based epoxy resin or an acid-terminated acrylonitrile/butadiene rubber, which is disadvantageous in that the synthetic rubber has problems such as high temperature deterioration and ion migration. The Republic of China Patent No. 342410 discloses an adhesive for a flexible printed circuit board. The composition of the adhesive includes: an epoxy resin, an acid-end acrylonitrile/diuretic rubber, and an antioxidant fresh component to solve the ion migration problem. However, in fact, the antioxidant can only prevent the high temperature deterioration of the rubber, and can not effectively solve the ion migration problem of the rubber towel emulsifier and salt. [1301] [Embodiment] The present invention provides a phosphorus-containing flame retardant resin having a structure represented by the formula (I): (I)

Where R1 is selected from:

1306861 R2 is selected from:

—o-c Η

CH,

I —〇CH„ — C —CH2〇 ——

I ch3 CH3

I 〇— CH2— c —CH—ο— CH3 CH—CH, i ch3 10 1306861 01 6 R Ίο 6 R Io OMnc CMno // Γ \\ 3 \A/ OMnc cnHO /N\ 〇I 6 RIT N, one Ο——R6—Ο

Ο—R6 Ο—m one or more of the group consisting of; R3 is selected from: R4 R6 0=C C=〇

11 1306861

12 1306861 The acid bond of 嫦 之 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行 进行Containing a miscible epoxy tree-forming agent, reacting with epoxy tree m to form a dish-containing flame retardant epoxy resin. The invention is characterized in that the compound of the present invention is refractory, and the olefinic group or the olefinic group containing the olefinic bond includes: a tetrahydrophthalic anhydride at a position, a tetrahydrophthalic anhydride at a position of 2, a tetradecanophthalic acid at a position of 3 Formic anhydride, 4-tetrahydrophthalic anhydride, methyltetrachlorophthalic anhydride, nadic anhydride, methyl nadic anhydride, di-s-butene-addition, methyl-diene-shun Butadiene dianhydride addenda, dodecenyl succinic acid field, dicyclopentadiene-cis succinic anhydride dianhydride addenda, H fine (tetra) butyl dicarboxylic acid rider, Yishui methyl 2 substituted butenylw hydrogen benzene Methacrylic anhydride, anhydrous end-alkyl alkene tetrahydrophthalic anhydride, cis-dianhydride, methyl cis-succinic anhydride, itaconic anhydride, m-tetra- phthalic acid, 2-position tetrahydrophthalic acid , 3 tetrahydrophthalic acid, shirt tetraphthalic acid, methyl tetrahydrophthalic acid, nadic acid 1 kinadic acid, ene- maleic acid addenda, Jiaxian II Alkene-maleic acid addenda, decyl-butanyl-amp; dicyclopenta-succinyl-butanic acid addenda, dingqing·__cis-butan-acid add-on, anhydrous methyl 2 substituted butenyl Tetrahydrobenzene Acid, anhydrous terminal alkyl alkene tetrahydro fresh dicarboxylic acid, cis-dicarboxylic acid, f-based cis-diacid, itaconic acid, anti-butyric acid, methyl fumaric acid, hexadiene diacid , dihydrohexadiureate, and the like. "The synthesis of the present invention contains a flammable resin, and the use of the dibasic acid anhydride includes: a ruthenium tetrazinc phenanthrene acid group, a 2-position tetrahydrophthalic anhydride, a 3-position tetrahydrophthalic phthalate, 4 14 1306861 Dicarboxylic acid dimethoate, methyl tetra gas phthalic anhydride, Nadick acid field, alumina, gas anhydride, decadiene-maleic anhydride addenda, methyl hydrazine-ene dicarboxylic acid _ addition Twelve dilute two _, double _ fine-cis-butyl,,, ^. Fork from a maleic anhydride with a urpinen-cis-butanol dianhydride add-on, anhydrous

Tetrahydrobenzoic acid_, anhydrous thiefene ton fresh-manic anhydride methyl cis-butanic anhydride, itaconic acid, tetrachlorophthalic acid, 2 tetrahydrophthalic acid, 3 digits Hydrogen phthalic acid, 4-position tetrahydrophthalic acid, methyltetrahydrophthalic acid, nadic acid, fluorenamic acid n-butadiac diacid adduct, Jiaxian diene-shun Butene diacid addenda, dodecenyl succinic acid, dicyclopentadiene, read di-addition, ___ pre-diacid addendum ^ water methyl 2 substituted bute_ fresh two cap, thief-based olefin Tetrahydrophthalic acid, maleic acid, methyl cis-butanic acid, itaconic acid, transbutanic acid, methyl-butenic acid, hexadienedioic acid, dihydrohexadiene Diacid, hexahydrophthalic anhydride, methyl hexahydro fresh diacetic anhydride, qiaoya f-based hexahydro fresh dicarboxylic acid, methyl bridge methylene hexaphthalic anhydride, phthalic anhydride, Terephthalic acid, isophthalic anhydride, α-nonylated maleic anhydride, glutaric anhydride, sebacic anhydride, α-phellandric acid-maleic anhydride addenda, sebacic anhydride, twelve Alkyl succinic anhydride, hexahydroortho Dicapric acid, methyl hexahydrophthalic acid, sulfhydryl/, phthalic acid, methyl benzyl hexahydrophthalic acid, phthalic acid, terephthalic acid, isophthalic acid Dicarboxylic acid, α-nonenylated maleic acid, glutaric acid, azelaic acid, sebacic acid, a-phellandricacid-maleic acid addenda, dodecyl

15 1306861 —*Acid, D0P0-R1 addenda, etc. The invention comprises a synthesis of a flammable resin, and the diol comprises: hydrogenation double _, gasification benzene second test, U dimethanol cyclohexane, U, 6,6 tetramethylhexadiene diol, U, 4, 4 Methyl butanol propanol, monopropylene glycol, polypropylene glycol, U butanediol, 2,3 butanol, 1,4-butane, dibutylene glycol, polytetramethylene glycol, neopentyl glycol, &amp;&amp; 4 trimethyl], 3 pentanediol, bis-indenyl dialkyl alcohol, double ethoxylate and the like. The invention has the advantages of synthesizing phosphorus-containing materials, and the advantages of the invention include: Shuangqing epoxy resin, fine epoxy resin, clear epoxy resin, hydrogenated double residual epoxy resin, __oxygen, and methyl epoxide Resin, double-pass epoxy resin, four-base g-glycerol, sulphur-burning, triphenyl glycidyl sulphide, triglycidyl-amino-amino, glycidyl-trimeric, tetraglycidyl Aminodiphenylmethane, tetraglycidyl xylene diamine, tetraglycidyl ^ 3 - bisaminomethylcyclohexanol bis (2, 3 -epoxycyclopentyl) 3, 4_epoxy 6-methyl-dry hexylcarboxylic acid 3,4,-epoxy 6, hexylmethylcyclohexyl acetal, vinyl cyclohexane diepoxide, 3, 4-epoxycyclohexyl decanoic acid 3, , 4, epoxy cyclohexyl methyl ketone, diisodecadiene diepoxide, adipic acid bis (3, 4 epoxide knee methylcyclohexyl ketone, bicyclo fluorene di-baked diepoxide, n-Butyl condensed water _, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Acid glycidyl ester, tertiary acid shrinkage Picking, condensing water (4), polyethylene glycol shrinking water _, polypropylene 2 16 1306861 alcohol condensed water _, butanediol glycidyl ether, polybutylene glycol glycidol, diglycidyl ether aniline, trimethylolpropane Triglycidyl ether, glycerol triglycidyl ether, glycerin epoxy resin, diglycidyl phthalate _, endo-indenyltetrahydrophthalic acid diglycidyl phthalate, phthalic acid condensed water甘制, tetrachlorophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, 4,5 epoxy cyclohexane 1,2-didecanoic acid diglycidyl §, phthalic acid The present invention will be further illustrated by the following examples and comparative examples, without limiting the scope of the invention. Example 1: Synthesis of A epoxy resin 30.4 g (0.2 m〇le) of tetrahydrophthalic anhydride, hydrogenated bisphenol A 23. 6 g (0. lmole), D0P043·2g (〇. 2mole), two Toluene 8〇g, triphenyl dish 0·%, put into the four-glass reaction with mechanical mixing, condensation tube, nitrogen reaction, The temperature was raised to 150 ° C, the reaction was carried out for 10 hours, and the dehydration esterification reaction was carried out. After the completion of the reaction, the temperature was lowered to 120 ° C, and HP-7200 L epoxy resin 100·5 g (Japan ink/epoxy equivalent = 245) was added to maintain 140. The reaction of the epoxy resin is 943g/mole, and the content of the epoxy resin is 3. 3%. 〇. 2m〇ie), ι, 4 dimethanol cyclohexane 17 1306861 14. 4g (0. lmole), d〇P〇43. 2g (〇. 2mole), xylene 80g, triphenylphosphonium. 2g , put into a four-port glass reactor equipped with mechanical stirring, condensing tube, nitrogen, raise the temperature to 150 ° C, react for 10 hours, carry out dehydration esterification reaction, after the reaction is completed, cool down to 120C 'Add CY-179 epoxy resin 51.7 g (Xu Ciba/epoxy equivalent = 126), maintained at 140 C, reacted for 4 hours, and the solvent was removed under reduced pressure and then cooled, and the epoxide equivalent weight was 692 g/mole and the oxime content was 3.1%. 6克(0. lmole), D0P043 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 2g (0. 2mole), xylene 8〇g, triphenylphosphine 0. 2g, put into a four-glass reaction with mechanical mixing, condensation tube, nitrogen gas, heat up to 150 ° C, reaction 1〇 After the completion of the dehydration esterification reaction, after the completion of the reaction, the temperature is lowered to 120 ° C, CY-175 epoxy resin is added 54.5 g (Xu Ciba / epoxy equivalent = i33), maintained at 140 ° C, the reaction for 4 hours, minus 3%。 The epoxy group was 693g/mole, and the phosphorus content was 4.3%. Example 2: Synthesis of D-Epoxy Resin 2. 4g (〇·2mole), 1,6-hexanediol 11·8g (〇. lm〇le), D0P043. 2g (0. 2mole) 2 g of xylene, 3 phenyl hydrazine. 2 g, put into a four-neck glass reactor equipped with mechanical stirring, a condenser, and nitrogen, and the temperature was raised to 15 Torr.匚, reaction 4 small 18 1306861 'to carry out dehydration and vinegarization reaction' after completion of the reaction to cool down, add CY_192 epoxy resin 57. 8g (Xu Ciba / epoxy equivalent = 141), maintain 14 (rc, reaction for 4 hours After decompression and dewatering, the cooling is divided into (4) oxy equivalents and squama content of 4.6 %. Example 5: Synthesis of E epoxy resin Dicyclopentadiene-maleic anhydride addenda 4 〇. 8g(〇. 2m〇le), neopentyl glycol 10. 4g (0. lmole), D0P043· 2g (0.2mole), diphenylbenzene 80g, triphenylphosphonium·2g, technically equipped with mechanical disturbance Mixing, condensing tube, nitrogen four-glass reaction dad, heating to 150 ° C, reaction for 10 hours 'dehydration esterification reaction, after the reaction is completed, cool down to 120 ° C, add DY-022 epoxy resin 41.4g (asahi 6%。 Ciba / epoxide equivalent = 1 〇 1), maintained at 140 ° C, the reaction was carried out for 4 hours, the solvent was removed under reduced pressure and then cooled, the analysis of the epoxy equivalent of 647 g / mole, the lining content of 4.6%. 5g(0. lmole), D0P043· 2g The synthesis of the F-epoxy resin is 3-5. (g. 2mole), 2, 2, 4 trimethyl-1,3 pentanediol 14. 7g (0. lmole), D0P043 · 2g (0. 2mole), diphenyl benzene 80g, triphenyl oxime. 2g Put into a four-glass reaction with mechanical stirrer, condenser tube and nitrogen gas, heat up to 150 C, react for 10 hours, carry out dehydration esterification reaction, and cool down to 12 (TC after adding 705 epoxy resin). The 5% of the epoxy resin equivalent of 19 1306861 was 836 g/mole, and the dish content was 3.5%. The solvent was removed and the solvent was removed under reduced pressure for 4 hours. Example 7: Synthesis of G epoxy resin 22.4 g (〇. 2 mole), dipropylene glycol 13.4 g (〇. lm〇ie), D0P043. 2g (0.2 mole), xylene 80 g, three Phenol was filled in. 2 g, put into a four-port glass reactor equipped with mechanical stirring, a condenser, and nitrogen, and the temperature was raised to 15 ° C, and the reaction was carried out for 4 hours to carry out dehydration esterification reaction, and after the completion of the reaction, the temperature was lowered to 12 Torr. (:, adding 139.4 g of EXA-4850-1000 epoxy resin (Daichi ink/epoxy equivalent = 34 〇), maintaining at 140 ° C, reacting for 4 hours, removing the solvent under reduced pressure, cooling, and analyzing the epoxy equivalent </ RTI> 835 g / mole, phosphorus content of 3. 5%. Example 8: Synthesis of bismuth epoxy vinegar 30.4 g (0.2 mole) of tetrahydrobenzene phthalic anhydride Propylene 34.4g (0. lmole), D0P043 · 2g (0. 2mole), xylene 8〇g, triphenyl dish 0·2g, put into a four-glass reaction with mechanical mixing, condensation tube, nitrogen reaction dad 6克(大日本墨/环氧体积量 = = = = = = = = = = = = = = = = = = = = = 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Example 9·· Synthesis of I epoxy resin

20 1306861 Di-anhydrous acid B-4400 (Daichi ink / molecular weight 264) 26.4 g (0. lmole), xylene 7 〇 g, dimethyl acetamide 5 〇 g, put into mechanical stirring, condensation Tube, nitrogen four-glass reaction dad, temperature control in 5 ~ 1 〇 (3c, stirring state '1 hour drop added to complete a single reliance 24 4g continuous Linyi hour, add sulfuric acid 0.5g, warm up to 120~15 4克(〇. T. g. g. g. g. g. g. 2mole), ruthenium diol intermediate 35g (〇. lmole), D0P043· 2g (〇. 2mole)' diphenyl benzene 80g, triphenylphosphonium 2g, put into mechanical stirring, condensing tube, nitrogen In the four-glass reactor, the temperature is raised to i5〇°c, and the reaction is ίο, the dehydration esterification reaction is carried out. After the reaction is completed, the temperature is lowered to 12 ° C, and DY-022 epoxy resin is added to 41.4 g (Daily ink/ring Oxygen equivalent = 1 〇 1), maintained at 140 ° C, and reacted for 4 hours. The solvent was removed under reduced pressure and then cooled, and the epoxide equivalents were 714 g/niole and the lining content was 4.1%. Og. 2g (0. 3mole), D0P043. 2g. 2g (0. 3mole), D0P043. 2g (0. 2inole), hexadiene dianhydride 24. 8g (0. 2mole) 'diphenylbenzene 80g, tetrabutoxy titanium ruthenium. 2g, the pen has mechanical stirring, condensation tube, nitrogen four-glass reaction The temperature was raised to the reaction for 4 hours, and the dehydration esterification reaction was carried out, and the solvent was removed under reduced pressure, followed by cooling, and the acid amount was analyzed to be 759 g/mole and the squamous content was 4.1%.

21 1306861 Example 11: Synthesis of K polyester. Itaconic anhydride 58. 2g (0. 52mole), propylene glycol 76. lg (l. Omole), D0P0112 · 3g (0. 52mole), maleic anhydride 49. 0g (0. 5mole), xylene lOOg, tetrabutoxy titanium ruthenium. 2g, put into a four-glass reaction with mechanical stirring, condensing tube, nitrogen, dad, heat to 150 ° C, reaction for 4 hours, dehydration The esterification reaction, the solvent is removed under reduced pressure, and the acid base equivalent is 1389 (^/111 〇16, the phosphorus content is 5.8%. Example 12: Synthesis of L polyester will be tetrapholine phthalic anhydride 76. 0g (〇.52mole), propylene glycol lg (l. Omole), D0P0112. 3g (0.52 mole), maleic anhydride complex Og (〇 · 5mole), diterpene benzene i〇〇g, tetrabutoxy titanium 〇· 2g, put into a four-port glass anti-nucleus equipped with mechanical lining, condensation tube, nitrogen, and raise the temperature to (10). c, react 4 small 3 inches, carry out dehydration esterification reaction, remove solvent after vacuum distillation, cool, analyze acid The base equivalent is UWSg/moie and the phosphorus content is 6_. Comparative Example 1 The epoxy resin legs of A~I epoxy resin and 188 (double age A type epoxy resin, epoxy equivalent (10), Changchun) , 4, a Diam In〇__ gift (four), J polyester resin 'mixed epoxy epoxy resin than hardener active hydrogen 1:1 ratio, \ 22 1306861 with or without acid end propyl cyanide / butyl rubber (CTBN), further added with 0.1% 2-ethyl 4-mercaptoimidazole' to form an epoxy resin varnish. It was applied to a copper foil with a film thickness of 15 μm and dried by i〇〇〇c for 60 minutes. After curing at °C for 10 minutes, the polyimide film was heat-bonded to the surface of 'the surface was further aged at 16 (TC for 30 minutes, and the peel strength (Kg/cm) was measured after cooling, and the flame retardancy was measured by the method of UL-94'. The results are shown in Table 1. Table 1 Oxygen Resin DDM (g) (g)

CTBN(g) J Polyester (g) P°/〇UL94 22.8 22.8 22.822.8 22.822.8 7.0 22.8 3.2 3.2 4.0 4.3 4.3 3.3 3.3 3.7 4.00.02.1 V-0 V-0 V-0 V-0 V- 0 V-0 V-0 V-0 V-0 Combustion peel strength (Kg/cm) 1.8 1.6 2.4 1.9 2.5 2.3 1.71.2 0.4 0.6 23 $ 1306861 Comparative Example 2 K~L polyester resin and TC at room temperature -141 (unsaturated polyester resin, manufactured by Lida Chemical Co., Ltd.) was mixed with styrene, cobalt octoate and ethyl ketone peroxide to form a test piece, and the flame retardancy was measured by the method of dish-94. The results are shown in the table. The second is shown.

Table 2 Polyester Resin (g) Styrene octanoic acid ruthenium peroxide----- (g) (g) Acetylene (g) K 296 300 4.5 ~~ ' h*----- 18 L 313 300 — ----— 4.5 —-—~__ 18 TC-141 ----- 200 300 ----— 4,5 —*^ 18 P°/〇_____ UL94 ----— 2.8 V-1 3.1 V-1 0.0 burning

24 1306861 [Simple description of the diagram] [Main component symbol description]

Claims (1)

1306861 X. Patent application scope: 1. A scaly flame retardant resin having a structure as shown in the general formula (I): Formula (I) Where R1 is selected from: R2 is selected from the following: 26 1306861 Chi ?h2 O— C — R6 — C — 〇 — CH, CH, CH. OCH2—C—CH2〇 CH. 1306861 ο ο R6—〇 ”m Ο——R6--Ο— .m Γ - C. C ' R6—〇- — • - / \ / \ - *- m 一~0—R6· -N Ar N— R6-0- , - m \ / \^ / One or more of the groups formed; R3 is selected from: 28 1306861 One or more of the group consisting of; R4 is selected from: H, C1~C3 alkyl; 29