TW201226543A - Dopo-derived flame retardant and synthetic hydrogarnets for epoxy resin compositions - Google Patents

Abstract

This invention relates to synthetic hydrogarnets and 9, 10-Dihydro-9-Oxa-10-Phosphaphenantrene-10-oxide derived additive flame-retardants, which are useful in epoxy resin compositions. The epoxy resin compositions may be used in making prepregs or laminates for printed wiring boards and composite materials.

Description

201226543 VI. Description of the invention: [Technical field to which the invention pertains] Bennomin is involved in the synthesis of garnet and 9,10-dihydro-9-oxa-10-disphenanthrene,-oxide, which can be used as a composition of 9 eq. Derived flame retardant added. The oxy-resin composition can be used to prepare prepreg tapes or laminates for printed wiring boards and composite materials. [Prior Art] The % oxygen resin is used in various applications such as electronic components 'electrical equipment, automobile parts, and sports equipment' because the epoxy resin has desired properties such as adhesion, heat resistance, and film forming property. Flame retardants, particularly brominated % oxy-resin compounds, are used in copper clad laminates and sealants for use in electronic components and electrical equipment. However, γ-containing compounds raise concerns about environmental and human safety, and therefore a more environmentally friendly flame retardant is desired. More environmentally friendly flame retardant types are known to include organophosphorus flame retardants. In the field of epoxy resins and laminates, organophosphorus flame retardants have reactive groups, for example derived from 9,1 fluorene-dihydro-9-oxaxanium-phosphaphenanthrene-oxide ( Those of DOPO), which are typically used in epoxy resin formulations, react with epoxy groups to form a modified epoxy resin. Techniques for preparing modified epoxy resins and their use, including their use in forming prepreg tapes, laminates, and copper clad laminates, are well known in the art. See, for example, U.S. Patent No. 5,036,135; 5,376,453; 5,587,243; 5,759,690; 5,8 1 7,736^ 6,291,626 Bl, 6,291,627 Bl; 6,2 96,940 Bl; 6,353,080 B1; 6,403,220

Bl ’ 6, 403, 690 B1; 6, 486, 242 B1; and w〇 01/42359 A1 (also published in the UK on June 14, 2001). The typical ground phosphorus resistance and the efficiency of the ruler (ATH) are used to burn some of the electrical and electrical solutions. This is the 201226543 required for the hole, and: Γ β “additional” organic phosphorus resistance without reactive groups. In the case of epoxy formulations, it is believed that the covalent bonding between the epoxy resin and the reaction: needs to provide higher vitrification stability. Commonly used mineral flame retardants for polymers such as oxyhydroxide, hydrazine emulsified magnesium (MDH) and oxidized stone have 2 $ it in oxyresin - some mineral flame retardants require higher loading for testing. In some cases, the monthly burn test is too demanding for the mechanical, thermal, and rheological properties of the final product, even at the highest load. For example ATH is around 200. Open Limits apply to epoxy resins that are processed at low temperatures. The same very wear resistant material and fast passivation of the drill bit required on the printed circuit board. If found to provide the new properties of the following flame retardants At month ti, ^fl

This would be tolerable in the art: the flame retardant has an A rate and also meets the more demanding thermal, rheological or electrical properties required for epoxy applications. < SUMMARY OF THE INVENTION The present invention relates to a flame-retardant epoxy composition comprising: (1) an epoxy compound; (ii) a di-d〇p〇 compound having the following structure: when the flammability is limited to a temperature-defining aluminum , learning or beginning, oxygen drilling, fuel efficiency, 201226543

R'r2' R3 and R4 are independently hydrogen, Cl_Cl5 alkyl, c6-c12, KVC 5 aralkyl or eve"alkaryl; or can be raised in R1 and R2 or R3 and R4 Forming a saturated or unsaturated cyclic ring wherein the saturated or unsaturated cyclic ring may be optionally substituted by Ci-c6 alkyl; each m is independently 1, 2, 3 or 4, each R5 and R6 are independently hydrogen or Cl-C6 alkyl; each η is independently 0, 1, 2, 3, 4 or 5; provided that Α is an aryl or direct bond, ^ cannot be 〇; and (iii) has the following empirical formula Synthetic water weight: (8) PCT 113]^1112(011)12_43{(8104); 1' where 1^11 is a 11-member metal atom' M111 is a Group IIIA metal atom, and X is about 〇.〇5 to Approximately 1.5 & or (B), where Μπ and M111 are as defined in (A), and y is a number from about 0.05 to about 1.5; or (C) Mn3Mni2〇y(0H)12-5y-4x (P04 y(Si04)x, wherein M11 201226543 and ΜΙΠ as defined in (A), wherein the cross is as defined in (A), and wherein (B) is defined, provided that the sum of X + y is from about 0.05 to about i 5 ; or (D) ΜΠ 3 ΜΠΙ 2 (0 Η) 12, where M11 and M111 such as (eight Defined. Synthetic water stone In particular, this application provides a synthetic garnet flame retardant comprising a synthetic garnet optionally modified by the introduction of citrate and/or phosphate in its crystal structure. One embodiment of the present invention is a synthetic water stone having the formula: Μη3ΜΙΠ2(〇Η)丨2. Another embodiment of the present invention is a synthetic garnet characterized by: (1) having an empirical formula wherein Mu is an alkaline earth metal or a mixture of more than one alkaline earth metal, preferably Ca; and X and y are from 0 to about a number of 1.5, wherein x + y is from 〇 to about 1.5, preferably from about 〇·〇5 to about 丨.5; more preferably from about 〇丨 to about ;5; even more preferably from about 〇〇5 to about 1 2. Synthetic garnet may also have the following properties: a) Median granules d50 'which is about 〇! to about 1 〇卩, or 〇25 to about, or oh to about 2 〇μηι, or 〇25 to about 〖祚泔, which is determined by a laser diffraction method; b) a surface area of from about 5 to about 3 〇m 2 /g, which is preferably from about 1 to about 30 m 2 /g as determined by BET, preferably It is from about 5 to about 5 and from about m to about 15 m2/g', even more preferably from about 1 to about ι〇 or from about 2 to about 1 〇 m2/g; or c) at 1 〇C/min The rate of acceleration and the pre-drying at 201226543 105 °C over a period of 4 hours, the TGA temperature of 2% water loss > 230 ° C, preferably > 240 ° C 'better > 250 °C. Synthetic garnet may also be characterized by a surface water content of <0.7 weight%' preferably < 5% by weight, which is at 1 〇5. The infrared moisture balance of C was measured and the sodium oxide content < 〇 5% by weight, which was determined by flame spectroscopy. As described above, the synthetic garnet can be represented by the following general formula (1): MII3MIII2〇y(〇H)12.5y.4x(p〇4)y(Si〇4)x (1) wherein Μ11 is ΠA a metal atom of a group, typically ca, Sr or Ba, or a mixture of at least two of these, or a mixture of any one or more of these and minor amounts (i.e., less than about 50% by weight); M疋111A a metal atom, particularly aluminum, but which may be mixed with a small amount (e.g., less than about 20% by weight) of 3' Ga, a ratio or a butyl group, or a mixture of any two or more of these; and wherein y is from about 〇 to about The number of 15 wherein X + y is from 0 to about 1.5, preferably from about 〇〇5 to about 丨5, more preferably from about 〇1 to about 1.5, even more preferably from about 〇5 to about 12. There may be trace amounts of other metal atoms 'a hai metal atom does not adversely affect the flame retardant and the flame retardant heat stabilizer aa. When the product is not used in the synthetic product or the source is broken, the product can be Μ 3Μιπ2(〇η)ι2 is expressed as the sum of Μ1 as in the above formula (1). When phosphorus is not used in the synthesis product, the 'water garnet can be expressed by the following general empirical formula: ', M 3MI, i^〇h) i2.4x(Si〇4)x 〇a) where M and M 1 is as in the above formula (1), and X is about 〇, 〇5 to about 1 _ 5, preferably about 〇, .1 to about ^, more preferably from about 0.05 to about 1.2 0. When the product is not used in the original, the synthetic water weight can be expressed by the following 201226543 total empirical formula: M1I3MIII2〇y(〇H)12.5y(P〇4)y (1B) where Μ11 and Mm are as in the above formula (η In that case, Yi and y are from about 〇·〇5 to about 1.5', preferably from about 〇丨 to about 丨$, more preferably from about 0.05 to about 1.2. Another consistent scheme is synthetic water plum, which is The following general empirical formula (2) is used to indicate:

Mn3Al2Oy(〇H)12.5y.4x(P〇4)y(Si〇4)x (2) wherein Mn is a Group A metal atom, typically Ca, Sr or Ba, or a mixture of at least two of these, Or a mixture of any one or more of these and a trace amount (i.e., 'less than about 5 weight percent) of Mg; wherein X and y are from 〇 to a number of about 1.25, wherein X + y is from 〇 to about 15 , preferably It is preferably about 〇5 to about 15' (m to about 丨.5, even more preferably about 〇.〇5 to about 1.2. Here again, there may be traces of other metal atoms, the metal atom It does not adversely affect the flame retardant and the heat stabilizer of the flame retardant. When a source of ruthenium or phosphorus is not used in the synthesis product, the product can be represented by the formula Αΐ 3Αΐ2(〇Η) 2, where μ11 is As in the above formula (2), when a phosphorus source is not used in the synthesized product, the synthetic garnet can be expressed by the following general empirical formula:

Mn3Al2(0H)12.4x(Si04)x (2A) wherein Μπ is as in the above formula (2), and χ is from about 〇〇5 to about u' is preferably from about 0.1 to about 1.5, more preferably about 0. 〇s to about 丨2. When the product is not used in the synthesis of the product, the synthetic garnet can be expressed by the following general formula:

Mu3Al2Oy(〇H)12.5y(P〇4)y (2B) wherein Μ11 is as in the above formula (2), and y is from about 〇.〇5 to about 201226543 1.5, preferably about 〇.丨 to about 丨5, more preferably about 5 to about 丨 2. Another consistent solution is synthetic garnet, which can be represented by the following general empirical formula (3):

Ca3Al2〇y(〇H)12..5y.4x(p〇4)y(Si〇4)x , where X and y are numbers from 0 to about 1_5, wherein X + y is from 〇 to about 1.5, Preferably, it is from about 5 to about 1.5, more preferably from about 1.5 to about 0.5 and from about 0 to about 1.2. As described above, there may be traces of other metal atoms which do not adversely affect the flame retardant and the heat stabilizer of the flame retardant. When no ruthenium or phosphorus source is used in the synthesis product, the product can be represented by the formula CasAldOHh2. When a phosphorus source is not used in the synthesis product, the synthetic garnet can be represented by the following general empirical formula:

Ca3Al2(〇H)12.4x(Si〇4)x (3A) wherein x is from about 0.05 to about 1.5, preferably from about 〇1 to about 丨5, more preferably from about 0.001 to about 1.25. When no helium source is used in the synthesis product, the synthetic water weight can be represented by the following general empirical formula:

Ca3Al2Oy(〇H)12.5y(P〇4)y (3B) wherein y is from about 0.05 to about i.5, preferably from about 1 to about 15, more preferably from about 0.05 to about 1.2. Synthetic garnet of the present invention (the above formula (1), (1A), (ib), (2), (2A) '(2B) '(3), (3A) or (3B) synthetic garnet It is an effective flame retardant and is further characterized by enhanced thermal stability. Furthermore, it is believed that by virtue of the introduction of salts and salts in the crystal structure, the resulting a 垆 method of synthesizing garnet can be advantageously applied to the shirt. Suitably, it can have a beneficial effect on the postpartum of various plumes of synthetic garnet. In this regard, . ' (for example purely this and 3 in the special synthesis 201226543 water garnet of the present invention (the above formula (1), (1A), (1B), (2), (2A), (2B Or, (3A) or (3B) a flame retardant), at least about 98% by weight, and at least about 98% by weight of the mu is A1.土 Α &amp; ^ n ~ Wanfa can be found in WO 20 10/059508 published on May 27, 2001. 33. Each person 丄, usually, synthetic garnet can be obtained in the following ways To prepare a mixture of: (1) a Group IIIA source of metal (especially an aluminum source), (2) a source of a lanthanum metal (especially an alkaline earth metal source), (3) an optional Shi Xiyuan (Special 3 • <Payment of an aqueous solution of citrate, such as (i) for example

One or more solutions of NaSA or NajbO7, such as amorphous or crystalline in the form of a powder sold as "water glass" and/or (1)): oxidized or () an optional source of phosphorus (especially an aqueous solution of a chemistry, such as squaric acid, Metal or money stone bismuth, Kun team - such as Na3P04, Na2HP04, NaH2P 〇 4, metal or recorded broken brew - urgent, ,, r a fly = 〇 such as Na4P207, and / or metal into ammonium polyphosphate ), &lt; eight pounds over (1) (2), (3) and / or (4) independently and / or their respective X. The mixture is in solid form or in aqueous solution ' and (5) ruthenium metal hydroxide, and the stirred mixture is heated at a temperature of from about 50 to about 1 〇〇〇c with &gt;9, y*'; The reaction product or the reaction product is allowed to cool; and the product is obtained; "The method is also characterized by the formation of a source of a lanthanum metal in the mixture and the ratio of the source of the xg and κ metals of the group: the lanthanum metal and the lanthanum metal -10- 201226543 The molar ratio is from about 1:1 to about 2:1. When there is a Japanese temple, the stone cherries used in the formation of the mixture are supplied with a salt of about GG5 to about 15 moles. Salt/mol prepared modified synthetic inorganic garnet, and/or when present, forms a phosphate source for use in the mixture to provide phosphate in an amount from about 〇μ to about 1.5 moles of phosphate per A modified synthetic inorganic water-weighted stone prepared by Mohr. A preferred ratio of the source of lanthanum used in forming the mixture and/or the source of phosphorus used in forming the mixture provides ruthenate and/or phosphate in an amount of about 〇3 Modified synthetic inorganic garnet prepared to about 1 _5 mole/mole, preferably Modified synthetic inorganic garnet prepared from about 0.05 to about 2 moles of citrate and/or phosphate/mole. Typically, each ruthenium atom from a ruthenium source is in a modified synthetic garnet. A citrate ion is formed, and each phosphorus atom from the phosphorus source forms a phosphate ion in the modified synthetic garnet. 1 A preferred method of preparing a synthetic water boulder according to the present invention involves introducing a suitable amount of comminuted An acid salt and/or a phosphate salt. The method comprises: mixing a mixture of the following materials: an aluminum source, a calcium source, water, a hydrazine and/or a lining source, and an alkali metal hydroxide; and 'at about 5 Torr to Heating the dialling mixture at a temperature of about 1 〇0.c; the aluminum source is (1) aluminum hydroxide, boehmite, pseudoboehmite, alumina or a mixture of any two or more of the foregoing, and i 〇 powder form, the calcium source is (i) an inorganic salt 'calcium hydroxide or oxidation word, including its hydrate, and (ii) a powder form; optionally cooling the reaction product or allowing the reaction product to cool; and recovering the resulting product; The method is also characterized by forming a mixture The ratio of the aluminum source to the calcium source used provides a molar ratio of C a: A1 of from about 1:1 to about 2:1, and the amount of lanthanum used in the formation of the mixed -11 - 201226543 compound provides the amount of bismuth citrate. For the preparation of the synthetic flame retardant per mole, from about 5 to about 1.25 m, preferably from about 1 to about 15 m, more preferably from about 〇.05 to about 丨.2 Mo The eric acid salt of the ear, and/or the phosphorus source used in forming the mixture, provides a phosphate, a synthetic flame retardant in an amount of from about 至5 to about 1.5 moles, preferably about 01. To about 1.5 moles, more preferably about 〇5 to about 1.2 moles of sulphate. As described above, a variety of materials can be used in the preparation of the synthetic garnet of the present invention. Non-limiting examples of 11A and 11A red materials, and preferred embodiments and processing conditions for preparing synthetic water stones can be found in W 0 20 10/059508. Di-dopo compounds The present application also provides bis-dp having the following structure. Compound:

Such as 6 Bu

Wherein A is a direct bond, Cd pen 瑷 瑷 某, 1 middle well, +, 丨 2 square, 匸3-〇: 12 cycloalkyl or c3-c12 soil ', Cyclohexyl or cyclo ..rc .夂Τ3ΐ Long postal base can be optionally replaced by C--C6 pit base, each Ri ' , r3 rr ^ A ^ r is hydrogen, C1-C15 alkyl, C6-C丨2 square , C7-Cl5^ - its ten r bauxite or CrC丨5 alkylaryl; or together with -12- 201226543 Ri and R2 or 尺 3 and R4 for about ^, f about * —, b form saturating or An unsaturated cyclic ring wherein the cyclization ring may be optionally substituted by a C丨-C6 alkyl group, each Π1 being independently 1,9 Ρ ^ ^ ^ , 3 or 4 ; each of R 5 and R 6 is independently hydrogen Or L 1 -C 6 alkyl; and the oxime condition is when hydrazine is aryl bis. When 1, 2'3, 5... 4 direct keys, η cannot be 〇. In one aspect, η-ρ.谇上-士二下& is 1 or 2 and Α is a direct bond. The other η subscripts are 1 and μ Τ) 1 „ 2 . 疋 C6-Ci2 square. On the other hand ' R ' R , R3 and R4 are independent 妯 θ &amp; P 5 _&lt; _,6 疋虱Or Cl - C6 alkyl. In another aspect, each is independently hydrogen or methyl. The specific compound of formula 1 which can be used in the present invention is 6H-ibenz[c,e]H2]oxalate Phosphine benzene; 6,6-(Μ-ethanediyl) bis-,6,6,-dioxybis, benzene[(^][1,2]oxaphosphorane, 6,6 ,-(1,4-butanediyl) ",6,6-monooxide; or 611_diphenyl[c,e][l,2]oxaphosphorane, ♦diphenylene diphenyl ) bis, M, - dioxide. The term "alkyl" as used herein, unless otherwise indicated, includes hydrazine, a saturated monovalent hydrocarbon radical having a straight or branched moiety. Examples of alkyl groups include, but are not limited to, methyl, T 丞 ethyl, propyl, isopropyl, butyl, isobutyl, u butyl, pentyl and hexyl. As used herein, unless otherwise indicated, the term "aryl" refers to an organic group derived from an aromatic hydrocarbon, such as a strepinyl, anthracenyl and an anthracenyl group. "Aryl" includes fused ring groups. At least one of the rings is aromatic. As used herein, the term "aralkyl represents a non-limiting example of an aryl-alkyl-aryl aryl group which is benzyl (C6H5CH2_) and a methyl group (CH3C6H4CH2-). Soil-13-201226543 as used herein The term "alkaryl" means "alkyl-aryl". Non-limiting examples of calcined aryl groups are methylphenyl-, dinonylphenyl-, ethylphenyl-propylphenyl isopropylphenyl-, butylphenyl-, isobutylphenyl- And t-butylphenyl-. The term "alkenyl" as used herein, unless otherwise indicated, includes alkyl moieties having at least one carbon-carbon double bond, wherein alkyl is as defined above. Examples of alkenyl groups include, but are not limited to, ethenyl and propenyl. The term "cycloalkyl" as used herein, unless otherwise indicated, includes a non-aromatic saturated cyclic alkyl moiety, wherein alkyl is as defined above. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. Unless otherwise indicated, examples of beans include, but are not limited to, cyclopropylcyclohexenyl and cycloheptenyl, as described herein, including non-aromatic cyclic dilute moieties. The term "cycloalkenyl" as used in the package includes alkenyl as defined above. Cycloalkenyl, cyclobutenyl, cyclopentyl, unless otherwise stated, all of the above groups derived from a hydrocarbon may have up to about 丨 to about 20 carbon atoms (eg, Ci_C 2 decyl, c 6 _ c 2 G aryl, C7-C2 decane square, CVC2. aralkyl) or} to about 12 carbon atoms (eg cvc12 alkyl, c6-c12 aryl 'c7_Ci2 aryl, C7_Ci2 aralkyl) or 1 to about 8 A carbon atom or from 1 to about 6 carbon atoms. The law can be applied at the PCT. The method comprises the preparation of a bis-d〇p〇 compound prepared by the preparation of a di-d〇po compound of the formula I, PCT/US 1 0/35359 and PCT/usl/35354, having the following structure: -14- 201226543

Wherein A is a direct bond, a C6-C12 aryl group, (: 3-(:12 cycloalkyl or C3-C12 cycloalkenyl, wherein the cycloalkyl or cycloalkenyl group may be optionally C! C6 alkyl substituted; each R1, R2, R3 and R4 are independently hydrogen, CrCu alkyl, C6-C12 aryl, C7-C15 aralkyl or (:7-(:15 alkaryl; or together) R1 and R2 or R3 and R4 are capable of forming a saturated or unsaturated cyclic ring, wherein the saturated or unsaturated cyclic ring may be optionally substituted by a C 1 -C 6 alkyl group; each m is independently 1,2, 3 or 4; each of R5 and R6 is independently hydrogen or CVC6 alkyl; and each η is independently 0, 1, 2, 3, 4 or 5; provided that when hydrazine is an aryl group or a direct bond, η cannot Is 0; includes a compound of the formula

Wherein R3, R4 and m are as defined above; and the compound of formula B is reacted in the presence of the test -15-201226543

Hal—(CR5CR6)-A~(CR5R6)rHal

SB wherein R5' R6 and n are as defined above and Hal is halogen (e.g., F, Cl' I or Br); provided that when A is an aryl group or a direct bond, η cannot be zero. One type of test that can be used is a metal test, such as a metal alkoxide test and a metal amide. The alkali metal of the base includes lithium, sodium and a clock. Examples of tests that may be used include, but are not limited to, potassium decoxide, sodium decoxide, lithium methoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide, potassium t-butoxide, sodium t-butoxide, lithium diisopropyl guanamine, and mixture. Potassium tert-butoxide and sodium methoxide are preferred. Any suitable amount of base can be used in the process of the invention. These suitable amounts include from about 1 to about 1 equivalent or from about 0.5 to about 5 equivalents based on the amount of the hydrazine-based compound. The process may also contain an optional solvent. Examples of such solvents may include, but are not limited to, heptane, hexane, petroleum ether, methylcyclohexane; toluene, toluene, ethylbenzene 'tetrahydrofuran, dimercaptosulfoxide (DMS), 1 &gt; 4_ No. burning 'dimercaptodecylamine (DMF), dimercaptoacetamide (DMAc) 'acetonitrile, ethylene glycol, dimethyl ether, ethylene glycol diethyl ether, geqi' / 3⁄4 compound. The process can be carried out at a temperature of from about 10 ° C to about 75 ° C. Another method that can be used to prepare the subsinging bridging compounds of Formula I, from the United States in March 31, 2010 and November 5, 2010, respectively, in the main Tb ° ° A No. 6 1 Found in /3 1 9580 and 61/410,694, they are called "process for the preparation of DOPO-Derived -16 - 201226543

Compounds&quot;&apos; and all incorporated herein by reference. In this method, DOPO and compounds of formula C

H〇-(CH2)n-〇H Formula C is carried out in the presence of a catalyst at a temperature of from about 100 ° C to about 25 ° C. The catalyst which can be used is any suitable catalyst for the dehydration and/or Arbuz〇v reaction. Generally suitable catalysts are alkyl halides, metal ii compounds, soil metal halides, transition metals and their halides, or acid catalysts such as decyl p-toluene sulphuric acid, ethyl p-toluene sulphonate . Arbuzov reaction catalysts are particularly suitable. The process may optionally employ a solvent, preferably a high boiling solvent, and optionally an entrainer. Preferably, the compound of formula I should have a purity greater than about 95% or about 98% or about 99% when combined with an epoxide. The purity level can be determined by using NMR spectroscopy. One skilled in the art of NMR spectroscopy can develop methods to measure the purity of a compound of formula I, and one method can be found in PCT/US1 0/35359. Preferably, the compound of formula I is spheronized or ground prior to the combined polymer. The d5 〇 particle size after spheronization or grinding may be less than about 15 μm or less than 1 〇 μηι or less than about 5 μηι or less than about 3 μηι or less than about 2 μηι. The d5 〇 particle size can even be +1 μηη, for example about 100 nm to 800 nm. The d50 particle size is the median particle size, with half of the particles above this value and half of the particles below this value. Any suitable grinding or spheronization technique can be used, such as jet milling. It is also preferred that when the d5Q particle size is greater than about 2 μηι, the single mode particle size distribution of the compound of formula I is preferably such that the compound can more uniformly mix the polymer. -17- 201226543 To determine the median particle size, use a Coulter LS-230 counter with a smaller bulk modulus or equivalent. Follow the manufacturer's instructions. Alternatively, a Horiba laser scattering device (e.g., Η〇ι^& LA900 Model 799 1) or equivalent can be used. The method includes: weighing a sample. (typically in an amount of from about 1 gram to about 0.015 grams) and placed in a clean dry:: the aluminum cup has been washed with deionized water prior to use. The device autosampler uses a 1% Trit〇n®·ι〇〇 surfactant and sonication to disperse the 0.05 § sample in water. The suspension is looped by measuring the element and is measured The powder particles in the component scatter the laser beam. The detector in the device measures the intensity of the scattered light. The computer in the device calculates the mean particle size 'average particle size and particle size distribution from the tamper measurement. The compound is essentially or completely free of organic tests, because the machine test can adversely affect its use as a flame retardant, especially when used in epoxidation. Substantially free of organic tests means less than about ' 〇 ppm or less than about 100 () ppm or less than about 1 〇〇 or lower than the fpm species to make the compound of formula I substantially or completely free of organic base ',: do not use any organic base in the reaction To prepare a compound, if the method of measuring the amount of the organic base is a method of spectroscopy. The organic base is an organic compound as a base. The organic base is usually but not a proton acceptor. They usually contain a nitrogen atom, Easy proton = and nitrogen-containing The compounds are typically (iv). Examples include but not only virgin, dinonylamine, triethylamine, tripropylamine, base, di: _N•ethylmorpholine, imidazole 'benzimidazole' histamine 'phosphorus A carbonate or hydroxide of some organic cations. Fortunately, the compound of formula 1 is substantially free of unreacted DOPO, -18-201226543 because DOPO can adversely affect its use as a flame retardant. Containing DOPO means a lower than DOO of less than about 50,000 ppm or less than about 2 Torr, a paw or less than about 10,000 ppm or less than about 10,000 ppm or less than about ι〇〇ppn^ A preferred method is to wash the product before and/or after the reduction using water or a water miscible solvent such as an alcohol (e.g., isopropanol), an aldehyde or a ketone (e.g., acetone). The DOPO content can be measured using nmr spectroscopy. Preferably, the solvent remaining in the compound of formula I after purification should be less than about 100 ppm or less than about 1 ppm or less than about 5 ppm. The amount of solvent can be determined using NMR spectroscopy. One method of reducing the amount of solvent in a compound of formula I is about 1 Torr. &lt;3C to 1 70 ° C under vacuum or nitrogen purge for about 2 to about 24 hours. If the compound is rounded or ground 'preferably at a temperature above room temperature, such as by hot air jet milling To reduce only volatile materials. Epoxy Resins Any suitable epoxy resin that can be used in the art can be used as an epoxy compound in the present invention. Representative epoxy resins suitable for use in the present invention are shown in Clayton A. May Edited by Epoxy Resins Chemistry and Technology, Second Edition (Marcel Dekker, Inc. New York' 1988), B. Ellis, Editor and Technology of

Epoxy Resins (Blackie Academic &amp; Professional »

Glasgow, 1 993) Η. E. Lee and K. Neville's Handbook of Epoxy Resins (McGraw Hill, New York, 1967). It is generally advantageous to use an epoxy resin having an average functionality of greater than 1 and preferably at least 1.8, more preferably at least 2 epoxy groups per molecule. In the case of more preferably 19-201226543, the epoxy resin has at least 25 epoxy/molecular, varnish epoxy resins. In another aspect of the invention, the phenolic resin of $ can be any saturated or unsaturated aliphatic, alicyclic &apos;aromatic or heterocyclic human having more than one 丨.2-epoxy group. Heterocyclic epoxidation: σ exemplification is diglycidyl carbazide or trihydration I @l(TGIC) 〇 &amp; disorganized uric acid Suitable epoxy resins are, but not limited to, based on bisphenol and 7 attached (eg Double expectant A, tetradecyl bisphenol A, bisphenol f, bisphenol s, w tetrakisphenylolethane, polybenzopyrene, resorcinol, 4, diphenyl, dihydroxynaphthylene Epoxy resin, and derived from novolac (eg phenol: furfural novolac, cresol: furfural novolac

Hope A novolac, diphenyl-, anthracene _, diphenyl or tridecyl stupid - modified age: formic acid, acid varnish, amino amphibious varnish resin) And a heterocyclic epoxy resin derived from p-aminophenol and cyanuric acid. Further, for example, an aliphatic epoxy resin derived from an M-butylene glycol 'glycerin and a dicyclopentadiene skeleton is suitable. A variety of other suitable epoxy resin systems are available&apos; and can also be suitably identified by those skilled in the art. Epoxy acetal varnish resins (including epoxy cresol novolacs) are commercially available under the following trade names, for example, D.E.Ntm, QUATREX.TM (Dqw)

Trade Company's trademark) ' TactixTM 742 (Ciba's business bar) and Epon (Resolution Performance Products' trademark). Commercial materials typically comprise a mixture of a plurality of glycidoxyphenyl groups and fluorenyl-, ethyl-propyl-phosphooxyphenyl groups. Typically, the amount of the compound of formula I in the flame retardant epoxy composition is from about 〇丨 to about 100 parts by weight or from about 1 to 70 parts by weight per 100 parts by weight of epoxidized human-20-201226543. Alternatively, the amount of the phosphorus i compound in the flame retardant epoxy composition is selected such that the composition will contain from about 0.5% to about 10% by weight, or about 1.2% by weight, based on the total weight of the composition. /〇 to about 7% by weight, or from about 1.5% by weight to about 5% by weight of the constituents. Typically, the amount of synthetic garnet in the flame retardant epoxy composition is from about 0.1 to about 100 parts by weight, or from about 1 to 70 parts by weight per 100 parts by weight of the epoxide. The phosphorus equivalent of the phosphorus-containing flame retardant epoxy composition is typically from about 1 〇〇g/eq to about 1000 g/eq, or from about 100 g/eq to about 800 g/eq, or from about 150 g/eq to about 500 g/eq. Dispersing or wetting agents can also be used in the flame retardant epoxy composition. Dispersants are compounds which are used to suspend or disperse particles in a liquid medium&apos; and are typically polymers or oligomers in nature. The dispersant can be found in Kirl-Othmer Encyclopedia of Chemical

Technology, John Wiley and s〇ns, v〇1 8, 672, 697, 5111, 2004. Any suitable dispersant can be used in the flame retardant epoxy composition. Non-limiting examples of suitable dispersants are alkylammonium salts of polycarboxylic acids, alkylammonium salts of fatty acids; alkanolammonium salts of acidic polymers; propylene glycol methyl ether acetate or polyethylene glycol monomethyl The ether, optionally containing a small amount of polyphosphoric acid or polyphosphate oligomer; or a mixture thereof. In one embodiment, the alkylammonium salt of the polycarboxylic acid can be represented by the formula: N(rM)4+ 0 -C(0)-R12.(C00H)n -21- 201226543 wherein each R 1 is independently *Cl-Cu alkyl, c3_Ci8 cycloalkyl, CVC, 8 aryl or C7-Cis aromatic base; is Ci_c A submethanol group, optionally containing a Junction, and up to about 50. These types of burned quaternary ammonium polybasic compounds are well known in the art. For example, U.S. Patent No. 5, pp. The polybasic acid can be converted to a quaternary salt by the use of a quaternary hydroxide or by an anion exchange with a quaternary ammonium carbonate. In one embodiment, R&quot; is a Ci_Cu alkyl group. In the scheme, R12 is a C2-C20 alkylene group. In the alternative scheme, 2, 3, 4, 5, 6, 7, 8, 9 or 1 〇. ^ 1 Examples of suitable quarter cations include tetramethylethyl-, triethylmethyl...one earth (C^), octyl-, tributyloctyl-, trimethylsulfonyl Examples of the polycarboxylic acid of dimethyltrimethylhexadecyl- and decyltrioctyl-ammonium tetraalkyl include but the anion of X used to form the anionic acid: oxalic acid, the following Substance of polyacid, pimelic acid, suberic acid, 壬 "$ PER acid' glutaric acid, hexanic acid, 癸_dodecanedioic acid, tridecanedioic acid, decanoic acid , hexadecanedioic acid, heptadecanedioic acid, pentadecanedioic acid,

Τ octane di-branched, 丄L eicosane diacid, o-p-dicarboxylic acid, stupid _ untoxidecanedioic acid, hexahydrophthalic acid, citric acid, aconitine, formic acid, stupid Formic acid, trimesic acid or a mixture thereof. ^, propane_i, 2, hydrazine tricarboxylic acid, additional salt to be used in the present invention. It can be represented by the following formula: The oxime is an alkylammonium of a fatty acid '22- 201226543 N(R13)4+ 〇-C(〇)_Rl4 wherein each R13 is independently a Cl-C18 alkyl group, C3_Clpf&lt;alkyl group, C6-c18 aryl or (:7-(:18 arylalkyl; rule 14 is Ci C3 decyl or Ci_c3 〇. The fatty acid can be neutralized by using quaternary ammonium hydroxide or by using a quaternary carbonate anion Exchanged to convert to a quaternary ammonium salt. In one embodiment, the fatty acid anion is derived from an unsaturated fatty acid. Examples of such unsaturated fatty acids include, but are not limited to, myristic acid, hexadecenoic acid, oleic acid, linoleic oil Acid, alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid, sinapic acid, docosahexaenoic acid or mixtures thereof. Suitable examples of (iv) cations include, but are not limited to, tetraalkyl (c丨_c 8) ammonium, such as trimethylethyl triethyl decyl-, tridecyl hexyl ... trimethyl octyl _, three

Butyloctyl-, trimethylsulfonyl-, =methyl I^-methyltetradecyl-, trimethylsulfanyl- and methyltrioctyl-I. The alkanolammonium salt of the acidic polymer used in the present invention is further divided into Le 丨Β 丨Β μ ^ Γ knife. It can be expressed by the following formula: v v J4 L·

Wherein each R15 is independently Cl-C p I 1 L!8 alkyl, (: 3-(: 18 cycloalkyl, C6-C18 aryl, (: 7-(: 18 aryl, c Γ _ L1_C15) Hydroxyalkyl, cc hydroxycycloalkyl CVC, 8-hydroxyaryl, ,, violent C7_C丨8 hydroxyaralkyl; conditionally at least one R contains a hydroxyl group; 2; is a number 垧a a enemy knife straight (Μη) It is a carboxyl group-containing polymer of from 1,000 to 100,000. The alkanolammonium salt of an acidic polymer is known in the field. For example, the patent No. 6,680,266 (by the cited alkylammonium acidic polymer compound) is disclosed. A variety of such cockroaches and how to prepare them. Polymers containing carboxy-23-201226543 can be converted to quaternary ammonium salts by using quaternary ammonium hydroxides or by anion exchange using quaternary ammonium carbonates. Examples include, but are not limited to, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxyhexyl, and hydroxyoctyl. Suitable examples of stanol quaternary cations that may be used include, but are not limited to, dibasic alkyl (C2 - C) s) alkyl (C i - C6) ammonium, such as triethyl hexyl hexyl; trimethyl methethyl ammonium Trihydroxyethyl amyl ammonium; trihydroxydecyl butyl ketone; octadecyl trihydroxyethyl ketone; dialkyl (C8_C18) dihydroxyethyl ammonium salt such as dilauryl dihydroxyethyl ammonium. The polymer has a Μη of about 1, 〇〇〇 to about 1 〇〇, 〇〇〇, or about 3,000 to about 30, 〇〇〇, and ^^ is usually about 1,1 〇〇 to about 15 〇, 〇 〇〇, or about 3,300 to about 4 Å, 〇〇〇. The polymer typically has an acid number of at least about 250, or from about 500 to about 970, or from about 550 to about 900, or from about 700 to One embodiment of the polymer of about 780 ° is a copolymer of an ethylenically unsaturated carboxyl group-containing monomer, or an ethylenically unsaturated carboxyl group-containing monomer, and at least one other polymerizable monomer. Suitable ethylenic bond Monounsaturated tert-containing monomers include, but are not limited to, α,β-unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconol Acid 'methylbutenedioic acid, mesaconic acid, alkylidene malonic acid and cinnamic acid; diterpene tauric acid' such as aconitic acid; dibasic acid anhydride, such as maleic acid needle, Itaconic anhydride and methyl methacrylate; a mono- 3 hydrazine such as maleic acid of the above dicarboxylic acid and monohydric alcohol (for example, alkanol, cellosolve and diethylene glycol monoethyl ether, containing 2 to 16 carbon atoms) Monobutyl acrylate, maleic acid monoethyl diglycol - sigma, etc., corresponding to these maleate fumarate and itaconic acid vinegar; -24-201226543 and two of these monomers Or a combination of various. Another implementation of the acidic polymer is produced from the _-secret 疋 carboxyl-containing polyester. This tree is H-reading acid or acid Xuan and more than 14 compounds ^ Political acid such as phthalic acid:. There are phthalic acid 'terephthalic acid, six gas o-dibenzoic acid, m-dialkyl succinic acid, norbornene diacid, ό s long, ten acid, dimer acid, and these acids in it: :: Diacid '癸 diphthalic acid, isophthalic acid, acid Xu in the presence of J. Preferably, the present dicarboxylic acid, hexahydrophthalic acid, =, 12-decyl-•, maleic acid, norbornene II: they are present in &amp; anhydrides, and their complexes. Polyols reacted with a polybasic acid or acid needle include glycerin, triethyl alcohol, trimethyl alcohol, pentaerythritol, sorbitol 'mannitol' ethylene glycol, diethylene glycol, 23 · butanediol and Oxygenated derivatives. Preferred are pentaerythritol, trimethyl methacrylate, glycerol oxirane derivatives and mixtures thereof. The molar ratio of the two reactants was chosen such that the resulting polyester resin was carboxyl-rich.

Commercially available examples of these dispersants are in the dispersant family, and wetting agents are available from suppliers such as Αν6 (^ Additives and BYK).

Chemie, such as Byk® W90 3 ’ W93 5, W961 and W969. The choice of a particular type of surfactant, wetting agent or dispersant depends on the resin of the laminate or printed wiring board and the desired properties. While the amount of powder or wetting agent can vary, the weight-based amount to be added to the composition, typically based on the total weight of the composition, is from about 0.01% to about 4 weight. /〇 or about 〇丨% by weight to about 2% by weight. The synthetic hydrometma may also be at least partially coated with a decane coating agent. Examples of such decane which can be used are: aminopropyltriethoxydecane, ammonia-25-201226543-ethylethylaminopropyltrimethoxy decane, aminoethylaminopropyltrimethoxy oxime Aminopropyl oxime '3-aminopropyltrimethoxy sulphur' N_(2-aminoethyl)_3_aminopropyltrimethoxy decane, n-(2-aminoethyl)-3-aminopropyl hydrazine Dioxadecane, n_(2-aminoethyl)-3-aminopropyldecyldinonoxydecane, N-cyclohexyl-3aminopropyl-trimethoxydecane, benzylaminoethylamino Propyltrimethoxysulfonium ethylbenzylamino-ethylaminopropyltrimethoxy oxalate, ethylenetrimethoxydecane, vinyltriethoxydecane,vinyldimethoxymethyl Decane, vinyl (tri) methoxy ethoxy) decane, vinyl methoxy methyl decane, vinyl tris(2-methoxyethoxy) decane, vinyl triethoxy decane, A Tris-decyloxydecane, η-hexyltrimethoxy sulphide η octyldiethoxy sulphur, propyltrimethoxy sulphur, propyltriethoxy fluorene , t_butyl trimethoxy decane, isobutyl triethoxy sulfonium propyl dimethoxy zeoxime ' 3 - glycidoxypropyl tridecyloxydecane ' 3-glycoloxy Propyltriethoxydecane, glycoxypropyl-mercaptodiethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, mercaptopropyl-trimethoxydecane, double Triethoxymethyl propyl propyl dithio decane, bis-triethoxy decyl-propyl dithiocarbazite, bis-triethoxymethyl decyl propyl tetrathio decane, four Ethoxylated sulphur, N-cyclohexylaminomethylidene methyldiethoxy decane, n-cyclohexylaminomethyltriethoxy oxime, η-phenylaminomethyltrimethoxy oxime Mercapto propylene oxime oxime) fluorenyl decyloxy decane, fluorenyl propylene methoxymethyl tri methoxy oxime '(mercapto propyl fluorenyl fluorenyl) methyl ethoxy oxime院'Methyl propylene oxymethyl-triethoxy oxysulfan, 3-mercapto propylene methoxy propyl tridecyloxy decane, 3-mercapto propylene oxime -26- 201226543 propyl propyl Mercaptodecane, 3-methyl Benzene oxypropyl triethoxy oxime oxime '(isocyanohydrazino) decyl dimethoxy decane ' 3-isocyanopropyl propyl tridecyloxy decane, 3-trimethoxyl Mercaptoalkylmethyl-nonyl-mercaptocarbamate, n-dimethoxy-(methyl)formamidinylmethyl-0-methyl-aminodecanoate' 3-(triethoxymethyl)矽alkyl)propyl succinic anhydride, methyltrimethoxy decane, decyl triethoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, tridecyl ethoxy decane, different Octyl trimethoxy decane, isooctyl triethoxy decane, hexamethylene trimethoxy decane, (octadecyl) methyl dimethoxy decane, phenyl triethoxy decane, (cyclohexyl) Mercapto-dioxalate, sparkle, dicyclopentyldimethoxy zeoxime and tetraethylphosphonate. The synthetic garnet may be coated with decane by any suitable method. One method is a spray method in which a mixture of equipment from manufacturers such as Loedige, Littleford Day, Hosokawa Alpine and Thyssen Henschel is used to spray decane into a well-mixed synthetic garnet. Commercially available Shi Xixuan An example is the Dynasylan® family of the multi-functional Shishi-singing of Degussa (Evonik Industries AG). The present invention also relates to a cured flame retardant epoxy resin comprising the above flame retardant epoxy resin composition which is reacted with a curing agent or a polymer initiator. The above curing or polymerization initiator is not limited to a specific curing agent or polymerization initiator as long as the agent contributes to polymerization of the epoxy resin in the flame-retardant epoxy composition. Examples of the polymerization initiator are a cationic polymerization initiator such as methanesulfonic acid, aluminum chloride 'vaporized tin' trifluoroborate ethylamine complex, triterpenyl boron-27-201226543 ether complex, etc.; radical polymerization initiator For example, benzophenone, dicumyl peroxide 'oxy-bis-isobutyronitrile, and the like; and an anionic polymerization initiator such as potassium methoxide 'triethylamine' 2 -dimethylaminophenol and the like, and mixtures thereof. The above epoxy curing agent includes any epoxy curing agent known to those skilled in the art. Examples include, but are not limited to, ethylenediamine, trimethylenediamine, tetramethylenediamine 'hexamethylenediamine, m-phenylenediamine, p-phenylenediamine, p-xylenediamine, 4,4' -diaminodiphenylmethane, 4,4,diaminodiphenylpropane, 4,4'-dioxadiphenyl ether, 4,4,-diaminodiphenyl sulfone, 4,4,- Diaminobicyclohexanol 'bis(4-aminophenyl)phenylmethane, i,5-diaminonaphthalene, m-xylylenediamine' p-diphenylene diamine, 1,1-bis(4-amino stupid Base) cyclohexane, dicyanodiamine, phenol/formaldehyde novolac, cresol/formaldehyde novolac, bisphenol A novolac, diphenyl _, fluorene benzene, diterpene benzene or trimethyl benzene - Modified phenol/曱 phenol novolak, aminotriphthol novolac, 曱 / / 甲 / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / The amount of curing agent that can be used is based on the molar equivalent of the curing functional group in the curing agent and the molar equivalent of the unreacted epoxy group in the flame retardant epoxy resin composition. The amount of the curing agent based on the equivalent of the unreacted epoxy group in the phosphorus-containing epoxy resin may be from about 1 to about 丨〇 equivalent, or from about 0.3 equivalent to about 5 equivalents, or about 0.7 equivalents. Up to about 2 equivalents. The polymerization initiator may be added in a concentration of from about 0.01% by weight to about 10% by weight, or from about 0.05% to about 5%, or from about 01% by weight to about 2% by weight based on the total mass of the flame-retardant epoxy resin composition. The curing temperature can generally range from about 25 ° C to about 25 Torr. (:, or about 7〇〇c to about 240 ° C, or about 150 ° C to about 220 ° C. -28- 201226543 In addition, the oxygen curing agent accelerator can also be used to promote flame retardant epoxy, And the curing of the product is usually based on imidazole. Examples of these epoxy curing agent accelerators, such as, for example, but not limited to: 丨 _ methyl Mimi °, 2 -曱基咪 saliva, 1 2 - tiangan, , fluorenyl imidazole ' 1,2,4,5-tetradecylimidazole, 2-ethyl-4-indolyl. Sit, 2-benzyl carbazole , 1-cyanoethyl 2 - stupid

Oral sitting ' 1-(4,6-diamino-s-r: morphyl 9 I -heptyl-2-ethyl)-2-phenylimidazole or a mixture thereof. When the novolac is used as the curing agent, the epoxy curing agent accelerator may be from about 1% by weight to about 5% by weight, or from about 〇_〇1 to about 3%, or by weight of the curing agent used, or It is added at a concentration of from about 0.1% by weight to about 2% by weight, or from about 15% by weight to about 1% by weight. Higher concentrations of accelerator may be added with different curing agents (e.g., DICY, dicyandiamide), wherein the promoter concentration is more typically from 5 to 25 weight percent of the weight of the curing agent. The inversely cured flame-retardant epoxy resin and/or flame-retardant epoxy resin may contain the &amp; conventional addition, such as heat stabilizer, light agent, ultraviolet absorber, antioxidant, antistatic agent, preservative - a compound containing a coupling agent such as an amine-, vinyl- or alkyl-decane graft; sodium stearate or calcium stearate; metal net:: or minus: tongue Filling, materials, pigments, dyes 'lubricants, mold release agents, hair sprays, plasticizers, processing aids, acid scavengers, nucleating agents, β m ^ ] aerosols, dispersants, synergies Agent, mineral filler, strong #. For example, the strengthening of the fiber on the broken fiber group, fiber, glass, metal fiber such as potassium titanate, Lie n A 日 日 1 1 Fillers and other barriers, sputum, agents and smoke-proofing and mixtures thereof, and he is flame retardant... • 29- 201226543 Other flame retardant additives that can be used include, but are not limited to, ammonium polyphosphate, nitrogen-containing synergists such as polyphosphoric acid Melamine, cerium oxide, cerium oxide, hydrated alumina such as aluminum hydroxide (ATH), boehmite, cerium oxide, molybdenum oxide or this A mixture of a compound and an oxide or a salt of zinc, aluminum and/or magnesium. An inorganic filler can be used in the present invention to affect physical properties and lower the composition. Typically, the filler and the reinforcing agent include a fused cerium oxide powder; Alumina; tantalum nitride; aluminum nitride; boron nitride; magnesium oxide; titanium dioxide; calcium carbonate; magnesium carbonate; calcium citrate; glass fiber; asbestos 'talc' kaolin' bentonite '弼石夕石' glass Fiber, glass fabric, glass mat, ground glass fiber 'glass beads (solid or medium) carbonized stone whiskers and mixtures thereof. Many of these materials are listed in

Encyclopedia of Materials Science and Engineering, Vol. ^ «PP. 1745 1759 « MIT Press^ Cambridge Mass. (1 986), the disclosure of which is incorporated herein by reference. In some embodiments, the combination of fillers is preferred, while in other embodiments the reinforcing agent comprises the compound of the present invention, as in the case of glass fabrics used in prepreg tapes and laminates for printed wiring boards. . Other flame retardants or combinations of different flame retardants may be added to the flame retardant composition. Non-limiting examples of such additional flame retardants are mineral flame retardants such as aluminum hydride, magnesium hydroxide, boehmite, layers Double hydroxide (LDH), organically modified LDH, clay, organically modified nano-clay, sapphire acid's sulphuric acid and sulphur-based tin (iv), desertified flame retardant, phosphorus-containing flame retardant' Nitrogen flame retardant, etc. The above cured flame retardant epoxy resin and/or flame retardant epoxy of the present invention can be used to form prepreg tapes and 7 or laminates. Typical, main, and pre-impregnated strips and laminates used for printing lines -30- 201226543 are included in the following:

A) Epoxy-containing preparations such as a formulation and solvent containing the flame-retardant ring gas composition of the present invention and curing _ $ '' ^ Α cation polymerization agent, and optionally the other ten standard additives described above - Formulation, this formulation is applied to or impregnated into the substrate by rolling, dipping, spraying, other known techniques and/or 。 &amp; 所 speed substrate 疋 inorganic or organic A fortifier, in the form of a cilia, fabric or woven material, such as blood VIII, such as a typically woven or nonwoven fibrous mat, containing, for example, fiberglass or paper. B) The impregnated substrate is "B-" "Step": heating at a temperature sufficient to discharge the solvent in the epoxy formulation, and optionally sufficient to partially cure the epoxy formulation, such that the impregnated substrate cooled to room temperature is dry to the touch and Can be handled easily. The "b_stage" step is usually performed at a temperature of 9 〇 cC to 240 γ for a period of 丨 minute to 15 minutes. The impregnated substrate derived from "Β_阶化" is referred to as "prepreg tape". For composites the temperature is most typically 1 〇〇 Q (:, and for electronic laminates is 130 ° C to 200 ° C. C) If an electronic laminate is required, one or more prepreg plates are in alternating layers The stack is laminated or laminated with one or more sheets of electrically conductive material, such as copper foil. D) The laminated board is extruded at a high temperature and a high pressure for a time sufficient to cure the resin and form a laminate. The temperature of the laminating step is usually from 1 〇〇 &lt; 5C to 240 ° C ' and most usually from 165 ° C to 2 〇 0. The lamination step can also be carried out in two or more stages, for example, first The stage is 1〇〇〇C to 15〇0C and the second stage is 165 (3C to 2〇0. (: The pressure is usually 50 N/cm2 to 500 N/cm2. The lamination step is usually carried out for 1 minute to 2). 〇〇 minutes, most usually -31- 201226543 45 minutes to 12 minutes. The lamination step can optionally be carried out at a higher temperature for a shorter period of time (for example in a continuous lamination process) or at a lower temperature. For a long time (for example in a low-energy pressurization process) 乂 E) The optional resulting laminate, such as a copper-clad laminate, can be post-treated by heating at elevated temperatures and ambient pressure for a certain period of time. It is 12 〇. (: to 250 ° C. The post-treatment is usually carried out for 3 至 to 12 hours. F) Usually conductive printed circuits are used in copper clad laminates. Typically, the epoxy resin used in the above step A The solvent is a ketone such as 2-butanone or mercaptoethyl ketone (MEK). However, it can be used to form these formulations. Any other suitable type of solvent that is conventionally used. Examples of such other refrigerants include, but are not limited to, acetone, mercaptoisobutyl ketone (ΜΙΒκ), 2-methoxyethanol, ι_methoxy-2-propanol, Propylene glycol monomethyl ether, ethyl alcohol monoethyl ether acetate, toluene, N, N-dimethylformamide, and mixtures thereof. EXAMPLES The following examples describe the invention. However, it should be understood that The invention is not intended to be limited by the details of the following examples, which are fully described and claimed in the claims. Example 1 Synthetic garnet (Ca3Ah(OH)1〇8(Si〇4)〇3) In this example 'Initial addition of 4 liters of water to a 20-liter vessel' followed by a 4 kg Solvay solution with a NaOH concentration of 5 〇 wt%, a 11.7" 2% solids slurry of unmilled Ca(OH) 2 , and calculated 680 g of water glass (Na2Si307) sodium citrate solution with a concentration of 〇2 of -32-201226543 27% by weight (available from Riedel-de HaSn). The mixture was stirred at a rate of about 15 ° C/min. The mixture is heated to 95 ° C. When the desired temperature is reached, 1 8 500 grams of finely precipitated trihydrate is added. Aluminium. This provides a theoretical amount of decanoate equivalent of 0.3 mol/mole of synthetic flame retardant to give the product Ca3Al2(〇H)i.8(Si〇4) Ci.3. At the same temperature, stir for 1 hour. The product was then recovered, subjected to a pressure screening procedure to washing, and spray dried to dryness. The d5 〇 particle size of the product was about 3.5 μηι ° Example 2 Synthetic garnet (Ca3Al2 ( OH) 1 (}.8 (SiO4) 0.3) The procedure of Example 1 above was carried out, except that C a (Ο Η) 2 was ground before combining the other components. The d 5 〇 of the final product was about 1 · 1 μ m. Example 3 6H-Diphenyl [c,e][l,2]oxaphosphorane, 6,6'-(1,2-ethanediyl)bis-, 6,6,-dioxide

-33- 201226543 Table 1 Preparation of DIDOPO compound of Example 3 Compound MW (g/mol) mp (°C) bP (°C) Physical state Molk mis Eq. DOPO, CAS # 35948-25-5 TCI America 216.17 119 - Solid 1.96 423 - 2.1 tBuOK, CAS # 865-47-4 &gt; igma-Aldrich &gt; St. Louis &gt; MO 112.21 256-258 - Solid 2.05 230 - 2.2 DMSO &gt; CAS # 67-68-5 » Sigma- Aldrich &gt; St. Louis &gt; MO 78.13 16-19 189 Liquid 21.12 1650 1500 12 Di-ethane ethane CAS #75· 34-3 » Sigma-Aldrich St. Louis, MO 98.96 -35 83 Liquid 0.93 92 73 1.0 The 4-neck 5L half-jacketed reactor was equipped with an addition funnel, thermocouple, mechanical stirrer and nitrogen flow. Potassium tert-butoxide (tBuOK) (230 g '2.05 mol) was added to the reactor and 1.5 L of anhydrous DMSO was added as a solvent. The mixture was stirred at room temperature until it became a homogeneous solution. The solution was cooled to 10 ° C and added to DOPO (423 g, 1.96 m〇i) 9 aliquots while maintaining the reaction temperature below 30 ° C (50 _ 60 g / part of the dichloride in the l25 ml addition funnel Ethane (92 g, 〇_93 mol) was slowly added to the above solution over 1 h. The reaction was heated to 5 (rc lh. The reaction was cooled to 1 〇 ° C and water (3 L) was added. Filtration, and the wet cake was washed with water, acetone and ethyl acetate to give 532 g of crude material. The crude material was in MeCN / ethanol / H2O (5320 ml, v: v: v = 1:1: 〇 5) Flow to the mouth' and slowly cool to 5. 〇. The white solid was passed through a thick fritted funnel; and, in a vacuum oven at 80 C to dry for 8 h to give a dry white powder (260 g, 68 wt% yield, 99.4 wt. Purity, 253-269. (: mp ). -34- 201226543 31P-NMR (162 MHz, CDC13) : δ 36.45, 36.25 ppm and 'H-NMR (400MHz, CI) C13) : δ 7.95 (d, J = 8 Hz, 2H, ArH), 7.88 (d, J = 8 Hz ' 2H, ArH), 7.79 - 7.69 (m, 4H, ArH) ' 7.48 (dd, J = 7.2 Hz, 14.4 Hz, 2H), 7.37 (dd, J = 7.2Hz' 7.2 Hz, 2 H, ArH), 7.29-7.24 (m, 2H, ArH), 7.16 (d, J = 12 Hz, 2H, ArH), 2.31 (m, 4H) ppm. Example 4 6H-diphenyl [c,e][ l, 2I oxaphosphorane, 6,6,-(l,2-ethanediyl)bis-,6,6f-dioxide

2H20 ethylene glycol (EG)

DOPO loads high purity DOPO into the reactor and then pours a given amount of mixed diphenylbenzene into the reactor. A 2.62 wt% NaI/EG solution was prepared and charged to the reactor. The water was then stirred and heated to 1 98 C' in 5-6 hours while maintaining the pressure at 4 〇 41 psig. When the contents reached the reaction temperature, the co-feed containing 260 wt% of Nal/EG and mixed xylene was started. The total feed lasts for a minimum of about 14 hours. The feed rate of diphenylbenzene is llb/min. After the feed 1 was 1.5-hours and held for 2 hours, the reactor became full. It was cooled to 1 90 ° C and a sample of the reactor slurry was collected. The NMR results showed that the conversion of D〇p〇 at this point was about 72%. The reactor was again heated to 197-199 ° C for co-feeding and then held for 2.5 hours. At the end of the second co-feed, the D〇P〇 conversion was about 93%'. The reaction mixture was quenched with IPA, and -35-201226543 was slowly cooled to ~100 °C. After the cold section, the contents of the reactor were filtered and the wet cake was washed three times with fresh 1 person and at 13 Torr. (3 vacuum drying. Example 5-10 6H-dibenzo[c,e]丨]., 2] oxaphosphonium benzene, 66,_(12 ethanediyl) bis-' 6,6'- Dioxide and ChAlHOU) &quot; to training 4). 3 Use in Epoxy Laminates Typically, the raw material solutions of the prior resins, curing agents and accelerators are prepared and stored separately to facilitate the test. A 50% by weight solution of 0-cresol epoxy novolac resin containing 5% by weight of 2-butanone (MEK) (NPCN® 703 ' from Nan Ya Corporation) was prepared. Durite SD-1702 Stearic acid beta paint curing agent was obtained from Hexion Corporation. A novolak resin solution was prepared by dissolving 50% by weight of SD-1702 in 50% by weight of MEK^. In Examples 5-6, a two DOPO flame retardant (6H_dibenzo[c,e][1,2]oxaphosphonium benzene containing Example 3 of 13 wt% p was used, using a jet mill, 6,6'-(1,2-ethanediyl) bis, 6,6ι_dioxide) is spheronized to reduce the particle size dS() of the compound to about 2_4 μηη, after which the polymer is combined. The flame retardant resin mixture contains 3% by weight of solids, ρ, excluding the quality contribution from mineral fillers. Together with the mineral filler (yttria or garnet), the resin mixture contains ρ of 21% by weight of the total solids content. A resin mixture was prepared by mixing 128.8 g of a 50 wt% NPCN 7〇3 solution '62 7 § 5 wt% SD-1 702 solution, 27.4 g of a flame retardant and 〇 83 g 2_phenylimidazole accelerator. An additional 3 g of MEK was added to the mixture. Phenol-36- 201226543 The ratio of 'month/黍 and accelerator was about 378. About 11 5 mL of the resin mixture was added to a thermo-electric plate at about 170-1 72 °C. The tongue depressor is divided in half lengthwise and half of the tongue depressor is used to move the resin on the hot plate until it is noticed that rigidity is generated, and then the resin is lifted by the flat portion of the tongue depressor until the formation of the string is stopped. The gel time was 1 minute and 47 seconds, which was determined by the point where the resin "string" was no longer pulled from the resin mixture and the epoxide became "non-sticky". The resin mixture was thoroughly mixed using a high shear mixer stirred at 5 7 rpm for about 20 minutes. 1 1 X 1 1 square inch woven glass fabric (with 643 polished 7628 glass from BGF Industries) cut from larger rolls to a certain size

Inch' and nailed to the wood support at the top and bottom ends of the fabric (12 inches long, 1 inch wide and 1/16 inch thick). The wood support contains holes at the corners to insert a paper clip on one end for suspending the fabric in a step oven. A-stage or resin varnish is applied to the front and back ends of the fabric. Spread the paper clip and insert it into the two holes of a wood support. The resin-saturated fabric was hung from the aluminum support of the laboratory fume hood and allowed to drip dry for approximately 1 minute, after which it was suspended in pre-heated (to 17 〇. 〇 forced air mueM drying phase (Lab Safety Supply Inc· , General Signal unit) 55 seconds. Remove the edge of the B-stage prepreg tape by reducing the size of the plate to i〇 inches Χίο inches. Cut the plate into four 5 inch χ 5 inch plates and weigh Then, a four-layer prepreg tape is stacked between two layers of pacothane release film (Insulectro corp) and two stainless steel plates (1/8 inch thick, 12 χ 12 square inch size). The laminate is in hot extrusion at 5, Formed within _ hours. The resulting laminate was 〇〇35 inches thick and contained 5% by weight of 37-201226543 resin' and the Π weight % resin was subjected to overflow during extrusion. Five pieces of 0 5 inch wide sample were taken. The diamond was used from the laminate to the cut and the edges of the specimen were sanded. The flammability of the test was screened by ASTM D3801-06 using an Atlas UL-94 combustor, resulting in a total burn time of 2 18 seconds. The burning score is All five samples to two samples were burned. The combustion time from the first combustion process to most of the tests exceeded 30 seconds' and no second combustion was performed. Some compounds burned slowly to the clamp. and Examples 5 - 6 Example 7 was prepared in a similar manner except that a 1:1 wt%:wt% mixture of XP-78 66 and melamine polyphosphate (Melapur 200 (M-200) from BASF Corporation) was used. The resin mixture remained The solid content target 3 · 〇 weight % p, excludes the quality contribution of the mineral filler. Together with the mineral filler, the resin mixture contains a total solids content of 2.1% by weight of p. For all 5 samples, the total burn time of 28 seconds is used. The UL-94 V-0 rating was: two burns. These results were obtained from a 0.038 inch thick laminate containing 51% by weight resin. An example of 13.5 wt% p will be used by Fluid Energy Corporation using a jet mill. 4 flame retardant (6Η·dibenzo[ce][12]oxaphosphorylbenzene 6,6,-(1,2-ethanediyl)bis-, 6,6,-dioxide) Spheronize to reduce the particle size dw of the compound to about 2-4 μηι The polymer was then combined. The flame retardant of Example 4 was used to prepare the laminate of Example 8_丨〇. The laminate of Example 8_j was prepared in a similar manner to the laminate of Example 7 except that The ratio of the varnish to the accelerator was about 7.9. For the laminate of Example 8 'For all 5 samples, the UL-94 V-丨 score was obtained using a total burn time of 79 seconds: two Burning-38- 201226543

burn. These results were obtained from a 0 〇 29 inch thick laminate containing 41% by weight of resin. B. The laminate of Example 9 was prepared in a similar manner to the laminate prepared in Example 9, except that a 重5/o^c^BykCliemie W-903 dispersant was added prior to high shear mixing. For all 5 samples, u L - 9 4 V -1 ping was obtained in 2 with a total burning time of 5 3 seconds divided into two combustions. These results were obtained from a 29 inch thick laminate of 46% by weight resin. The laminate of Example 10 was prepared in a similar manner to the laminate prepared in Example 10 except that 08 weight W-903 dispersant was added prior to high shear mixing. For all 5 samples, the UL_94 v_〇 score was obtained using a total burn time of 43 seconds: two burns. These results were obtained from a 32 inch thick laminate containing 49% by weight resin. The total scale content of the sample 5 - 10 was 2 · 1 wt% p. Comparison of laminates The flame retardancy and thermal properties of the laminates are shown in Table 2 below. The flammability of the laminate (UL-94 score) was screened by ASTM D3801-06 using an Atlas UL-94 combustor (v-0 is the highest possible score). The difference in the Tg measurement of the laminate using a valley similar to that in the IPC method IPC-TM-650 (method 2.4.25c) using a temperature increase rate of 20 ° C /min in N 2 is as follows. For laminates based on DEN-43 8 resin, the isothermal holding temperature was 2 Torr. That is, for the npcN-703-based laminate, the isothermal holding temperature was 22 〇 cC, and for the NPcn_7 〇 3 resin-free flame retardant-free laminate, the isothermal holding temperature was 250 °C. TA device -39- 201226543 The software analyzer is used to determine the glass transition temperature. In some cases, a third scan is performed to determine the 3 Tg between the first, second, and third scans. A hole saw is used to drill a sample laminate tray that is sized to fit inside a standard (four) sc disk. The edges of the sample are gently sanded for mating into the pan, and the entire surface of the laminate is mostly facing the bottom of the pan; The sample weight (~4〇_5〇 mg) was recorded and the lid of the sample tray was added using a plunger press to place and seal the lid onto the tray. An empty sealed disk is added to the reference platform. Thermogravimetric analysis (TGA) was performed on a TA Instruments Q500 TGA device. The TGA connects to the PC, which provides user interface and operational system control. Calibrate the temperature scale using Nickel, Aluminum, and Nickel with reference to the certified Curie temperature. The microbalance is calibrated using the certified reference weight. Perform these calibrations according to the steps recommended by the equipment manufacturer. The sample is from about 1 mg to 12 mg which is heated from room temperature to 500 in i纽c/inin under nitrogen. C. The original data file containing the sample weight and temperature data is saved to the PC hard disk during the measurement. After completing the TGA measurement, the 1%, 2%, and 5% weight loss temperatures of the original data were analyzed. The total content of the sample 5-1 was 2.6% by weight p. • 40- 201226543 Table 2. Characterization of Laminates for Examples 5 to 10

Ex % by weight Two DOPO garnet (% by weight) bismuth oxide (% by weight) M-200 (% by weight) UL-94 total burn time Tg ° C (DSC) TGA 1% loss TGA 2% loss TGA 5% loss 5 15.6 (Example 3) - 30 - V-0 41 159 355 375 408 6 15.6 (Example 3) 30 (Example 1) - - Combustion 218 163 339 360 386 7 7.9 (Example 3) 30 (Example 1) - 7.9 V -0 28 169 327 343 371 8 7.9 (Example 4) 30 (Example 2) - 7.9 V-1 79 175 324 343 381 9 7.9 (Example 4) 30 (Example 2) - 7.9 V-1 53 173 309 332 375 10 7.9 (Example 4) 30 (Example 2) - 7.9 V-0 43 173 310 334 371 The chemical name or chemical formula referred to anywhere in the application or its request is either singular or plural and corresponds to Identification of a chemical name or another substance of a chemical form prior to contact (eg, another component, solvent, etc.). What is important is not, if any, what chemical changes, transformations, and/or reactions occur in the resulting mixture or solution, as such changes, transformations, and/or reactions are natural to the combination of specific materials under the conditions disclosed herein. result. Thus, these components are identified as components that are combined with the desired operation or formation of the desired composition. In addition, even if the appended claims may relate to the current substance, component and/or component ("include", "for", etc.), reference is made to other substances and components in the initial disclosure with one or more of the present disclosure. Contact with ingredients and/or ingredients, -41 - 201226543 Substance, component or ingredient present prior to blending or mixing. In accordance with the present disclosure, one of ordinary skill in the art of chemistry may have lost its initial properties by chemical exchange during contact, blending, or mixing operations, and thus this is not an actual description of the present invention and the claims herein. The scope of the embodiments is to be limited, and thus these examples are intended to describe some aspects of the invention. Any equivalent implementation is within the scope of the invention. In fact, various modifications of the invention are obvious to those skilled in the art from the foregoing description. These modifications are also intended to fall into the accompanying statement [Simple description of the schema] None. [Main component symbol description] None. It is really if, the component or the reaction is turned into concern. The specific implementation of the case is intended to fall within and describe the domain technology. -42-

Claims (1)

201226543 VII. Patent application scope: 1. A flame retardant epoxy composition comprising: (i) an epoxy compound; (Π) a compound having the following structure: C3-C! 2 cycloalkenyl, wherein the cycloalkyl or cycloalkenyl group may be optionally substituted by a C 1 -C 6 alkyl group; each R 1 , R 2 , R 3 and R 4 is independently hydrogen, (: 丨 - (:15 alkyl, C6-C12 aryl, C7-C15 aralkyl or (:7-(:15 alkaryl); or together R1 and R2 or R3 and R4 can form a saturated or unsaturated cyclic ring Wherein said saturated or unsaturated cyclic ring may be optionally substituted by a Ci_C6 alkyl group; each m is independently 1, 2, 3 or 4, and each of R5 and R6 is independently hydrogen or C^-C^alkyl; Each η is independently 0, 1, 2, 3, 4 or 5; the premise is that when Α is an aryl group or a direct bond, η cannot be 0; and -43- 201226543 (iii) Synthetic water having the following empirical formula Garnet: (A) Mu3Mm2(0H)12-4x(si04)x, where the atom ''Μ' is a steroid metal atom, and ν, Χ is a number from about 0.05 to about 1,5; or, J ( B) Mn3Mm2Oy(〇H)12.5y(p〇4)y, where Μπ^μ11ι (A) is defined, and y is a number from about 〇〇5 to about ι_5; (C) M1I3MIII2Oy(〇H)12.5y. 4x(p〇4)y(Si04)x , n is taught as and Μ&quot;1 as defined in (A), where again (A) Where Μ 1 is defined and y is as defined in (Β), the precondition is about 0.05 to about 1.5; or (D) Μπ3Μπι2(〇η)12' where Mi, Mm are as in (A) ~ 2 · as claimed The meaning of the first term, and the η subscript of the rabbit, R3 and R4 are independently gas, wherein the synthetic sink stone wherein the compound of formula I is 2; Α is a direct bond; and wherein Rl, r2 or Or C丨-C6 alkyl. 3. The flame retardant according to item 2 of the patent application has empirical formula (A). 4. The composition of claim 3, ________ 6H-diphenyl [c,e ][1,2] oxaphosphorus heteropoly, M, s, 2 ethane: -6,6,-dioxide. bis) 5. as claimed in the third item. ^ Λ , , θ composition Wherein Μπ is Ca, only Mg or a mixture thereof, and Mln is 仏, to meet the composition of the fifth item as in the scope of application. II. M111 is A1. 疋h and 7. 6项之纽#铷甘士A 义义组成' where X is about 〇? 0.8. .4 主约-44- 201226543 8. The composition of claim 1 wherein the epoxy compound is: Born from bisphenol A, tetramethyl bisphenol a, bisphenol F, bis s, tetrakis phenylolethane, polybenzo quinone, resorcinol 4,4'-diphenyl or two Hydroxynaphthylene-based polyphenol epoxy resin; derived from phenol/furfural novolac, indophenol/furfural novolak, double-fraction A varnish, diphenyl-, anthracene-, diphenyl-- or three Methylbenzene-modified phenol/furfural novolac, or an acid-based triterpene varnish-aged epoxy resin; a heterocyclic epoxy resin derived from p-aminophenol or cyanuric acid; and derived from 1 An aliphatic epoxy resin of 4-butanediol, glycerol or dicyclopentadiene; or a mixture thereof. 9) The composition of claim 1 further comprising a synergist, wherein the synergist is ammonium polyphosphate, melamine, melamine phosphate, melamine cyanurate, melamine pyrophosphate, tripolyamine polyphosphate, hydrazine And piperazine phosphate and cyanurate derivatives, phosphazene compounds, polybenzopyrene, cerium oxide, antimony trioxide, pentoxide, sodium citrate, potassium citrate, iron oxide, zinc borate, or Its mixture. 10. The composition of claim 1 further comprising a dispersing agent or a wetting agent. 11. The composition of claim 1, wherein the dispersing or wetting agent is: an alkylammonium salt of a polycarboxylic acid; an alkyl salt of a fatty acid; an alkanolammonium salt of an acidic polymer; Or a mixture thereof. The composition of the invention of claim </ RTI> wherein the amount of the compound of formula j is from about 0.1 to about 100 parts by weight per 100 parts by weight of the epoxy compound; and the amount of the synthetic garnet is from about 〇 to about 1 〇 〇 Parts by weight / 丨 (10) parts by weight of the epoxy compound. -45- 201226543 1 3. If applying for a patented additive, the additive is selected from the group consisting of at least one kind of additive, antioxidant, antistatic agent, light stabilizer, ultraviolet absorbing filler, pigment, Dyes; '!, preservatives, adhesion promoters, agents, plasticizers, agents, mold release agents, foaming agents, fungicides, =, ::: ', acid scavengers, dyes, pigments, stabilizer fillers , reinforced HT agent, dispersant ' synergist, mine anti-π + β day / shell, inorganic filler, other flame retardant additives, smoke inhibitors or mixtures thereof. A 14. For example, the scope of patent application is cyanamide. And, and the composition, the polytriphosphate polytrimer is included. 15. The composition of the first aspect of the patent application, wherein the compound of the formula: has a particle size of less than about 15 microns, and the synthetic water stone (4). The particle size is from about 〇 5 to about 5 microns. 16. The composition of claim 1 of the patent scope further comprising a decane or fatty acid coating on the synthetic water stone. Ο. For example, please refer to the composition of the 16th patent range, wherein the amine base stone smear; bucket: 3 glycidyl oxypropyl trimethoxy oxalate, 3-aminopropyl ethoxy decane, 3 -Aminopropyltrimethoxydecane, 2-aminoethyl-3-aminopropyltrimethoxyxanthine, bis(3-triethoxycarbamyl)-amine, hydrazine Butyl)-3-aminopropyltrimethoxyxanthene. The pre-and/or ▼-containing organic or inorganic reinforcing material and the flame-retardant epoxy composition as in claim 1 of the patent application. A layer calendar formed by the prepreg band of item No. 16. 2〇. A printing board formed by a laminate as claimed in claim 17 of the patent-46-201226543 circuit board. -47- 201226543 IV. Designation of representative drawings: (1) The representative representative of the case is: No. (2) A brief description of the symbol of the representative figure: Yiyi t *»&gt; 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: