TW201841977A - Non-migratory, high-melting/softening polymeric phosphorus-containing flame retardant for printed wiring boards - Google Patents

Abstract

There is provided herein a flame retardant composition comprising: (a) a compound having the general formula (I): (I) which has a weight average molecular weight of from about 1,000 to about 700,000, and (b) a polyphenylene ether and/or an oligomer thereof. There is also provided an article comprising the flame retardant composition, and a method of making the article.

Description

Non-moving high melting point/softening point polymeric phosphorus-containing flame retardant for printed wiring boards

The present disclosure relates to halogen-free flame retardant compositions and prepregs, metal clad laminates, and printed wiring boards containing the same.

In recent years, electrical equipment has made advances in the high capacity of signals, which require advanced dielectric characteristics, such as lower specific permittivity and lower dielectric loss tangent, for high-speed communication in applications such as semiconductor substrates. It is necessary. At present, the motor and electronics industry is rapidly developing. The development direction of electronic devices is lightweight, high performance, high reliability, and environmental protection. The specific requirements for laminates for printed circuits are expressed by high heat resistance, low coefficient of thermal expansion, high heat and humidity resistance, environmental affinity, good flame retardancy, low dielectric constant and dielectric loss, and high modulus of elasticity. Conventional epoxy resins have not fully met the development requirements of printed circuit laminates, and have been contained in poly(alkylene ether) compositions having high thermal stability, low dielectric constant and dielectric loss, and excellent toughness. Replace. Furthermore, the presence of poly(aryl ether) improves flammability but is not sufficient to pass the required flammability test. Due to the high circuit density and the potential for the large amount of heat generated therefrom, good flame retardancy is particularly important in such demanding applications. Conventional poly(aryl ether) resins are thermoplastic materials having a high molecular weight. High melt viscosity results in poor flow and poor solubility, making conventional poly(aryl ether) very difficult to process. In printed circuit laminate applications, high molecular weight poly(aryl ethers) are replaced by low molecular weight, modified polyphenylene ether (PPE) having specific end groups. For example, in CN101796132A, a modified PPE having a number average molecular weight of less than 5,000 is used in combination with a cyanate ester compound. The copper-clad laminate made of the resin composition has a low dielectric constant and dielectric loss, preferable heat resistance, and low water absorption. However, in CN101796132A, the reactive group of the low molecular weight PPE resin is insufficiently reactive and hardly participates in the crosslinking reaction of the cyanate ester. The cured product consists of a semi-interpenetrating network (semi-IPN). The PPE resin in the semi-IPN itself cannot be crosslinked, but can only be dispersed in the free network in the crosslinked network structure. Adding a reactive flame retardant will only make this problem worse. The PPE modification with end groups containing unsaturated double bonds has been very successful. For example, such a non-saturated PPE can be widely used in the field of thermosetting resins, as described in U.S. Patent No. 5,071,922, to the name of U.S. Patent Nos. 6,352,752 and 6,627,704. In CN102807658, a butadiene-containing polyolefin resin having a relatively large molecular weight is used as a crosslinking agent, and blended with a component of a functionalized PPE resin and a starter to obtain a laminate for a printed circuit. Resin composition. The composition has very good dielectric properties and heat resistance and is suitable for use in high frequency electronic circuit boards. Laminates prepared for use in printed circuit boards are known to be flammable and generally require the addition of a halogenated flame retardant. However, halogenated flame retardants are undesirable for many applications. Furthermore, small molecule flame retardants often result in reduced mechanical properties and deterioration of the material. At the same time, the mobility and volatility problems cause performance degradation and flame retardant effects are not ideal. Therefore, in the thermosetting resin composition, an organic phosphorus-containing flame retardant has been successively substituted for the halogenated flame retardant, such as EP A 0384939, EP A 0384940, EP A 0408990, DE A 4308184, DE A 4308185, DE A 4308187 , as described in WO A 96/07685, and WO A 96/07686. However, many such organic phosphorus-containing flame retardants may also suffer from mobility problems and may require the presence of specific reactive groups, such as epoxy resins, to chemically bond to the resin. It is therefore highly desirable to have a non-mobile flame retardant and have a melting point/softening point sufficient to withstand the soldering process without participating in the cross-linking process. In addition, for laminates in printed circuit boards, current environmental standards require lead-free processes due to increasing environmental awareness. Therefore, the process performance requirements of the substrate are particularly strict, such as glass transition temperature (Tg) and heat resistance in the solder bath, which have become important issues to be overcome.

The present inventors have unexpectedly discovered a halogen-free flame retardant composition which is a phosphorus-containing aromatic compound from a modified PPE (polyphenylene ether) and a melting point/softening point higher than 200 ° C and insoluble in the flame retardant composition. Made up of polyester. The flame retardant composition may also contain a thermosetting resin such as an epoxy resin (preferably in a small amount, for example, less than 5% by weight). After curing, the flame retardant composition exhibits a low dielectric constant and a low dielectric loss level, high heat resistance, and excellent flame retardancy. The flame retardant composition shown herein is suitable for use in prepregs, laminates for printed circuits, and the like. This material has not been disclosed in the past as a non-mobile flame retardant for thermosetting resins, especially for thermosetting resins used in PWB applications. Surprisingly, Applicants have discovered that the use of the flame retardant compositions herein can provide sufficient flame retardancy while maintaining high thermal stability, high Tg, and excellent electrical properties. As shown in Fig. 1, the phosphorus-containing aromatic polyester may penetrate each other through a network structure formed of a PPE resin and a crosslinking agent. The phosphorus-containing aromatic polyester can also be combined with the inorganic filler and dispersed in a free state in the crosslinked network structure (Fig. 2). In addition, the active ester group of the phosphorus-containing aromatic polyester can react with the epoxy resin and form a second cross-linked network structure (Fig. 3). The PPE network structure is intertwined with the polyester-epoxy network structure to form an ultra-stable, non-moving structure having excellent thermal and electrical properties.

The expression "non-mobility" as used herein is understood to mean that the composition comprising the flame retardant phosphorus-containing aromatic polyester does not exhibit mobility in the cured thermosetting product. The expression "high melting point/softening point" as used herein is understood to mean that the compound of the formula (I) as used herein has a melting point/softening point higher than 170 ° C and preferably higher than 190 ° C. The expression "insoluble in flame retardant composition" is understood to mean that the flame retardant phosphorus-containing aromatic polyester is insoluble in solvents commonly used in the industry, such as methyl ethyl ketone (MEK), acetone, and others at 25°. A common organic solvent under C. Those of ordinary skill in the art will appreciate that the solubility will vary with the molecular weight of the flame retardant phosphorus-containing aromatic polyester and the structure of the flame retardant phosphorus-containing aromatic polyester. In one embodiment herein, when the flame retardant composition is used in a thermoset composition, it may have a Dk value of less than about 3.2, and preferably less than about 3.0, and/or less than about 0.01, and preferably A Df value of less than about 0.005. In one embodiment, provided herein is a flame retardant composition comprising a compound of formula (I): It has a weight average molecular weight of 1,000 to 700,000, preferably 10,000 to about 100,000, and most preferably 25,000 to about 50,000, and wherein X is a divalent aromatic hydrocarbon group having 6 to about 12 carbon atoms, and it includes benzene stretching Non-limiting examples of radicals, anthranyl, biphenyl, and the like, which may optionally include substituents bonded to an aromatic ring, such as an alkyl or alkoxy group each having up to 6 carbon atoms, Y Is selected from the group consisting of: Wherein Z is a group selected from the group consisting of a covalent bond, -SO ₂ -, -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, and -CH ₂ -; a is an integer from 0 to 2; And b is an integer from 0 to 2, and wherein the wavy line of each structure of Y represents a bond in which Y is bridged with an oxygen atom in the formula (I); R ¹ is selected from the group consisting of H, 1 to about An alkyl group of 4 carbon atoms (such as methyl, ethyl, and propyl), and a phenyl group, a naphthyl group, Wherein R ² is selected from the group consisting of H or -C(=O)R ³ , and wherein R ³ is an alkyl group selected from 1 to 4 carbon atoms (such as methyl, ethyl, and propyl) a phenyl group, a naphthyl group, and an aromatic phenol group selected from the group consisting of a phenol group, an o- cresol group, an m- cresol group, a p- cresol group, an α -naphthol group , and β - naphthol in one of those, and when R ² is H, R ¹ may not be phenyl or naphthyl, and n is ≧ 2, preferably 2 to about 100, and most preferably from 2 to About 50. In one non-limiting embodiment herein, the flame retardant composition described herein may comprise a mixture of different structures of formula (I), for example, the mixture may comprise at least 50% by weight of the structure of formula (I) And preferably, more than 70% by weight of the structure of the formula (I), wherein Y is a moiety selected from the above (i) and (ii), and the remaining different structures of the formula (I) Then, Y is selected from the part (iii) shown above. In one non-limiting embodiment herein, R ¹ in compound (I) is And wherein X is a divalent aromatic hydrocarbon group of 6 to 12 carbon atoms, which is optionally substituted with an alkyl group or alkoxy group of up to 6 carbon atoms. In one embodiment of compound (I), R ¹ is an alkyl group of 1 to 4 carbon atoms, and wherein X is a divalent aromatic hydrocarbon group of 6 to 12 carbon atoms, optionally passing up to 6 carbon atoms Alkyne or alkoxy substituted. In one embodiment of compound (I), X is a divalent aromatic hydrocarbon group of 6 to 12 carbon atoms which is optionally substituted with an alkyl or alkoxy group of up to 6 carbon atoms. Non-limiting examples of some of the compounds of formula (I) include phosphorus-containing aromatic polyesters, such as those described herein, such as 2-(6-oxo bridge-6H-dibenzo[c,e][1, 2] Copolymers of oxaphosphol-6-yl)-1,4-benzenediol and aromatic dicarboxylic acids are commercially available. 1,3-phthalic acid and 2-(6-oxo bridge-6H-dibenzo[c,e][1,2]oxaphosphon-6-yl of CAS Registry No. 102338-15-8 a polymer of -1,4-phenylenediacetate; CAS 1, accession number 102338-14-7, 1,2-phthalic acid and 2-(6-oxo bridge-6H-dibenzo[c, e] a polymer of [1,2]oxyphosphol-6-yl)-1,4-phenylene diacetate; and 1,4-benzene of CAS Registry No. 101842-64-2 Formic acid and 1,1'-[2-(6-oxo bridge-6H-dibenzo[c,e][1,2]oxaphosphon-6-yl)-1,4-phenylene a polymer of diacetate. The flame retardant composition according to the present invention comprises (b) polyphenylene ether (PPE) or an oligomer thereof. The PPE or its oligomer has two or more vinyl groups, allyl groups, or both at both ends of the molecular chain, and is not particularly limited to this structure and can be used. In the present invention, a modified low molecular weight polyphenylene ether resin having a vinyl end group represented by the following general formula (II) is preferred. This is because both sides of the two or more vinyl modifications can satisfy the moisture resistance and dielectric properties due to an increase in glass transition temperature, a low coefficient of thermal expansion, and a decrease in hydroxyl groups. In Formula II, Z ₁ is a compound derived from a divalent moiety, such compounds selected from the group consisting of: bisphenol A, bisphenol F, bisphenol S, naphthalene, anthracene, biphenyl, tetramethyl Biphenyl, phenol novolac, cresol novolac, bisphenol A novolac, DOPO-HQ (10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphine a phenanthrene-10-oxide), and a group consisting of borane compounds, and m ₁ and m ₂ are each independently an integer from 3 to about 20, preferably an integer from about 4 to about 15, Most preferably, it is an integer from about 5 to about 10. The expression "derived from a compound" as used above is understood to mean that the compound has two hydrogen atoms removed from it to provide a valence capable of bridging adjacent portions of the above formula II. In the present invention, it is preferred to use a compound of the formula (II) having at least two vinyl groups at both ends of the molecular chain. However, in addition to vinyl groups, conventional unsaturated double bond moieties known in the art can also be used. Since polyphenylene ether has a high melting point and thus has a high melt viscosity resin composition, it is difficult to manufacture a multilayer board having a conventional polyphenylene ether. Thus, in one embodiment herein, the high molecular weight polyphenylene ether (b) as described herein can be a modified form of the low molecular weight PPE obtained by redistribution of a high molecular weight PPE in one embodiment. In one non-limiting embodiment herein, high molecular weight PPE is understood to be a PPE having a number average molecular weight greater than that described herein for PPE component (b). In one embodiment herein, conventional polyphenylene ethers for copper-clad laminates can be modified by redistribution using polyphenols and radical initiators as catalysts and used as low molecular weights having phenolic groups at both ends. Polyphenylene ether. The structural properties of bisphenol A and the high polarity of the two terminal phenolic groups produced after redistribution previously limited the realization of low dielectric loss characteristics. On the contrary, in the present invention, even after cross-linking, polyphenylene ether can be converted into a PPE containing a vinyl group to thereby produce a PPE having a low polarity, thereby obtaining a polyphenylene ether having a low dielectric loss (b). ). These modified polyphenylene ethers have lower molecular weight and high alkyl group content than conventional polyphenylene-derived compounds, and thus have excellent compatibility with conventional epoxy resins and improved fluidity in the production of laminates, And further improve its dielectric properties. Therefore, a printed circuit board manufactured using the flame retardant composition of the present invention has an advantage of improving physical properties such as moldability, workability, dielectric properties, heat resistance, and adhesion strength. Some non-limiting examples of specific bisphenol compounds having increased alkyl and aromatic content, which may be used herein for redistribution of high molecular weight PPE, except bisphenol A (BPA, 2, 2-double) In addition to (4-hydroxyphenyl)propane, a group selected from the group consisting of bisphenol AP (1,1-bis(4-hydroxyphenyl)-1-phenylethane), bisphenol AF (2,2-bis(4-hydroxyphenyl)butane), bis(4-hydroxyphenyl)diphenylmethane, bis(3-methyl-4-hydroxyphenyl)propane, bis(4-hydroxyl) Phenyl)-2,2-dichloroethylene, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 1,3-bis(4-hydroxyphenyl)anthracene, 5,5'-(1-methylethylidene)-bis[1,1'-(biphenyl)-2-ol]propene, 1,1-bis(4-hydroxyphenyl)-3,3,5-three Methylcyclohexane, 1,1-bis(4-hydroxyphenyl)cyclohexane, mixtures thereof, and the like. The polyphenylene ether resin (b) herein may be modified to have a low molecular weight in the range of 1,000 to 10,000, preferably having a number average molecular weight (Mn) in the range of 1,000 to 5,000, and more preferably 1,000. To the extent of 3,000. In the flame retardant composition according to the present invention, the content of the polyphenylene ether resin or oligomer thereof may be from about 10 to 80% by weight, preferably from about 15 to about 60% by weight based on the total weight of the resin. And preferably from about 20 to about 50% by weight. The crosslinking agent (c) having a carbon-carbon unsaturated double bond may be selected from the group consisting of a hydrocarbon crosslinking agent (1), a crosslinking agent (2) having at least three functional groups, and Block structure of rubber (3). In one embodiment, a hydrocarbon crosslinking agent (1), a crosslinking agent (3) having three or more functional groups, and a rubber (3) having a block structure may be used in combination as a crosslinking curing agent. . The hydrocarbon-based crosslinking agent which can be used in the present invention is not particularly limited as long as it is a hydrocarbon-based crosslinking agent having a double bond or a triple bond, and may preferably be a diene crosslinking agent. Specific examples thereof include butadiene (for example, 1,2-butadiene, 1,3-butadiene, etc.) or a polymer thereof, decadiene (for example, 1,9-decadiene) or a polymer thereof , octadiene or the like or a polymer thereof, vinyl carbazole or the like. These may be used singly or in combination of two or more. According to an example, the polybutadiene represented by the following formula (III) can be used as a hydrocarbon-based crosslinking agent. In the above formula (III), m ₃ is an integer of 10 to 30. The molecular weight (Mw) of the hydrocarbon crosslinking agent may range from 500 to 3,000, preferably from 1,000 to 3,000. Non-limiting examples of crosslinkers containing three or more (preferably three to four) functional groups useful in the present invention include triallyl isocyanurate (TAIC), 1, 2, 4-trivinylcyclohexane (TVCH) or the like. These may be used singly or in combination of two or more. According to an example, triallyl isocyanurate (TAIC) represented by the following formula (IV) can be used as a crosslinking agent containing three or more functional groups. The rubber which can be used in the block structure of the present invention may be in the form of a block copolymer, preferably a butadiene unit, more preferably a butadiene unit and a styrene unit, an acrylonitrile unit, an acrylate unit or the like. Rubber in the form of a block copolymer. Non-limiting examples include styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber, acrylate-butadiene rubber, acrylonitrile-butadiene-styrene rubber, and the like. Random copolymer poly(styrene-co-butadiene) can also be used. These may be used singly or in combination of two or more. According to an example, a styrene-butadiene rubber represented by the following formula (V) can be used as the rubber having a block structure. Wherein m ₄ is an integer of up to 500, and m ₅ is an integer of up to 2100. The styrene-butadiene copolymer has a number average molecular weight of up to 150,000 and includes a 1,2-vinyl group having cross-linking properties. Such a copolymer including a 1,2-vinyl group having cross-linking properties is, for example, a copolymer having a structure represented by Formula VI. The number average molecular weight is equal to or greater than 2,000. The number average molecular weight may range from 2,000 to 150,000, and more preferably from 3,000 to 120,000. In the styrene-butadiene rubber of the present invention, the styrene content is preferably from 20 to 80% by weight, and the butadiene content is preferably from 50 to 80% by weight. The 1,2-vinyl content in the butadiene block is preferably from 40 to 85% by weight. In the thermosetting resin composition of the present invention, the content of the crosslinking agent having a carbon-carbon unsaturated double bond is not particularly limited, but may be in the range of about 5 to 50% by weight based on the total weight of the resin composition. Preferably, it is in the range of about 10 to 45% by weight. When the content of the crosslinkable curing agent falls within the above range, the resin composition has low dielectric properties, curability, moldability, and adhesion. According to one example, when the hydrocarbon crosslinking agent (1) and the crosslinking agent (2) having three or more functional groups are mixed with the PPE crosslinking hardener, the crosslinking agent containing more than one functional group (2) The content is in the range of about 1 to 10% by weight, preferably in the range of about 2 to 5% by weight. If desired, in addition to the above hydrocarbon-based curing agent, a crosslinking agent having three or more functional groups, and a rubber having a block structure, the present invention may additionally include a conventional crosslinking curing agent known in the art. At this time, it is preferred that the crosslinkable curing agent has excellent compatibility with a polyphenylene ether modified with a vinyl group, an allyl group or the like. Non-limiting examples of crosslinking agents having carbon-carbon double bonds that can be used include divinylnaphthalene, divinylbiphenyl, styrene monomer, phenol, triallyl cyanurate (TAC), -(4-vinylbenzyl)ether, and combinations thereof. The initiator is used for the unsaturated portion of the thermosetting resin to induce any compound to generate free radicals at high temperatures. These starters include peroxides and non-peroxide initiators. The peroxide initiator is selected from one or more of bisisophenylpropyl peroxide, butyl perbenzoate, and 2,5-dimethyl-2,5-di(tertiary butylperoxy) a hex-3-yne, a di(tertiary butyl) peroxide, a tertiary butyl isopropenyl propyl peroxide, a di(tertiary butylperoxy-m-isopropyl)benzene, 2, 5-Dimethyl-2,5-di(tertiary butylperoxy)hexane, bis(tertiary butylperoxy)isodecanoic acid, 2,2-di(tertiary butylperoxy) Butane, (benzyl benzyl peroxy) hexane, bis (trimethyl decyl) peroxide. Typically, the non-peroxide initiator is selected from one or more of 2,3-dimethyl-2,3-diphenylbutane and 2,3-trimethyldecyloxy-2,3-diphenyl. Butane. In one embodiment herein, the flame retardant composition can be a non-limiting example of additionally comprising a thermosetting resin, such as an epoxy resin. In one non-limiting embodiment, the epoxy resin may be present in the flame retardant composition in an amount from about 0.1% to about 25% by weight, preferably from about 1 to about 15% by weight, optimally. It is from about 1 to about 5% by weight of the flame retardant composition. The epoxy resins may be selected from, for example, halogen-free epoxy resins, phosphorus-free epoxy resins, and phosphorus-containing epoxy resins, and mixtures thereof, including but not limited to DEN 438, DER 330 Epon 164 (DEN and DER are The Dow Chemical Company's trademark); contains epoxy functional poly a compound of an oxazolidinone; a cycloaliphatic epoxy resin; a GMA/styrene copolymer; and a reaction product of DEN 438 and a DOPO resin; and a combination of any of the foregoing. Most preferred are low Dk and low Df epoxy resins, for example, DCPD (such as EPICLON HP-7200 series) epoxy or epoxidized polybutadiene. The flame retardant composition may optionally contain at least one co-crosslinking agent and/or any one or more curing catalysts, Lewis acids, inhibitors, and benzo-containing compounds. compound of. The flame retardant composition optionally may contain at least one additional crosslinkable epoxy resin or a blend of two or more epoxy resins. The flame retardant composition may also optionally contain at least one curing catalyst and at least one inhibitor. All of the above components may be blended or mixed together in any order to form a flame retardant composition. The flame retardant composition prepared according to the present invention is obtained by using the compound of the formula (I), the PPE resin (b), any epoxy resin, and any other co-crosslinking agent (ie, , a mixture of curing agents; can be used to make prepregs, laminates, and circuit boards for use in the electronics industry, and as a phosphorus-containing flame retardant composition to coat the so-called build-up technology described herein ( Build-up technology) metal foil. The flame retardant composition according to the present invention may optionally contain at least one crosslinking curing agent. The compound (a) of the formula (I) described herein can be used as a filler for the thermosetting epoxy resin composition as described herein, and will vary with the particular epoxy resin and the particular compound used, and There are variations in the art that have specific processing parameters known to those of ordinary skill in the art. The compound of the formula (I) can be used alone as an additive or in combination with other organic or inorganic fillers such as mineral fillers of non-limiting examples, for example, Al(OH) ₃ , Mg(OH) ₂ , cerium oxide, aluminum oxide, titanium dioxide, and the like. Further, the compound (a) of the present invention can be used in combination with other flame retardants as a reactant (such as those described in U.S. Patent No. 8,202,948) or as an additive (such as described in U.S. Patent No. 9,012,546). The entire content of which is incorporated herein by reference in its entirety, in its entirety herein. In one embodiment herein, the amount of filler other than the compound of formula (I) may range from about 1 to about 30 weight percent, from about 3 to about 25 weight percent, and most preferably from about 5 to about 20 weight percent. . In one non-limiting embodiment, the compound of formula (I) described herein can be used in an effective flame retardant amount of from about 20 to about 250 parts by weight per 100 parts of PPE resin component (b), more specifically From about 40 to about 200 parts by weight per 100 parts of the PPE resin component (b), and most specifically from about 60 to about 180 parts by weight per 100 parts of the PPE resin component (b). In order to provide sufficient flame retardancy, the compositions herein will contain from 1% to about 5% phosphorus in the final composition. In one embodiment, the above amount of the compound of formula (I) described herein can be an amount of a compound of formula (I) described herein used in any of the compositions described herein. As described above, by blending a compound of the formula (I), at least one PPE resin (b), any at least one epoxy resin, and any at least one co-crosslinking agent, as described herein, Any of the other optional components to form the flame retardant composition described herein; or in another embodiment, by blending at least one compound of formula (I), at least one PPE resin (b) A phosphorus-containing flame retardant epoxy resin composition is formed from at least one epoxy resin, and at least one co-crosslinking agent, and any other optional components described herein. Any number of co-crosslinkers (i.e., in addition to the compounds of formula (I) described herein) can also be used arbitrarily for any of the above compositions in which an epoxy resin is present. Suitable co-crosslinking agents which may optionally be present in combination with the epoxy compounds according to the invention include, for example, polyfunctional co-crosslinkers known to those of ordinary skill in the art. The co-crosslinking agent includes, for example, a copolymer of styrene and maleic anhydride having a molecular weight (M _w ) in the range of 1,500 to 50,000 and an acid anhydride content of more than 15%. Commercially available examples of these materials include SMA 1000, SMA 2000, SMA 3000, and SMA 4000, available from Elf Atochem SA, having 1:1, 2:1, 3:1, and 4:1 styrene-matrices, respectively. The ratio of anhydride to anhydride is in the range of 6,000 to 15,000. Other less preferred co-crosslinkers for use in the present invention include hydroxyl containing compounds. Other phenolic functional materials may also be used but are not suitable, and they include co-crosslinking agents which upon heating form a phenolic crosslinker having a functionality of at least two. In one embodiment herein, the flame retardant composition can have a low level of phenolic compound, such as from about 0.001 to about 5%, preferably from about 0.01 to about 2%, based on the total weight of the flame retardant composition. And preferably from about 0.01 to about 1% of the phenolic compound. Any of the flame retardant compositions of the present invention described herein may optionally contain a curing catalyst. Examples of suitable curing catalyst materials (catalysts) which can be used in the present invention include compounds containing a moiety of an amine, a phosphine, an ammonium, a ruthenium, an anthracene, or an anthracene, or a mixture thereof. A particularly preferred catalyst is a nitrogen-containing heterocyclic compound. The amount of any curing catalyst used depends on the molecular weight of the catalyst, the activity of the catalyst, and the rate at which the polymerization proceeds. Typically, the curing catalyst is used in an amount of from 0.01 part per 100 parts resin (phr) to about 1.0 phr, more specifically from about 0.01 phr to about 0.5 phr, most specifically from about 0.1 phr to about 0.5 phr. The curable composition of the present invention may optionally be present as boric acid and/or maleic acid as a curing inhibitor. In that case, the curing agent is preferably a polyamine or a polyamine. The amount of curing inhibitor will be known to those of ordinary skill in the art. The flame retardant composition of the present invention may also optionally contain one or more other flame retardant additives including, for example, red phosphorus, coated red phosphorus, or liquid or solid phosphorus-containing compounds (eg, "EXOLIT" from Clariant GmbH. OP 930", EXOLIT OP 910), and ammonium polyphosphate (such as "EXOLIT 700" from Clariant GmbH), phosphites, or phosphazenes; nitrogen-containing flame retardants and/or synergists, for example, melamine , melem, melamine, cyanuric acid, and derivatives of nitrogen-containing compounds; halogenated flame retardants and halogenated epoxy resins (especially brominated epoxy resins); Phosphorus-halogen chemicals or compounds containing organic acid salts; inorganic metal hydrates such as Sb ₂ O ₃ , Sb ₃ O ₅ , aluminum hydroxide, and magnesium hydroxide, such as "ZEROGEN 30" from Martinswerke GmbH, Germany, and More preferred is aluminum hydroxide, such as "MARTINAL TS-610" from Martinswerke GmbH, Germany; boron-containing compounds; cerium-containing compounds; cerium oxide; and combinations thereof. When other flame retardant containing phosphorus is present in the composition of the present invention, the phosphorus-containing flame retardant is preferably present in an amount of from 0.2% by weight to 5% by weight based on the total phosphorus content of the total resin composition. The flame retardant composition of the present invention may optionally contain other generally known types of additives including, for example, stabilizers, other organic or inorganic additives, pigments, wetting agents, flow modifiers, ultraviolet barriers, and fireflies. Photo additive. These additives may be present in an amount of from 0 to 5 weight percent, and are preferably present in an amount of less than 3 weight percent. The flame retardant composition preferably contains no bromine atoms, and more preferably contains no halogen atoms. The invention is particularly useful for the manufacture of B-stage prepregs, laminates, adhesive sheets, and resin coated copper foils using techniques well known in the industry. In one embodiment herein, an article comprising any of the flame retardant compositions described herein is provided. In one embodiment, the articles herein can be used in lead-free soldering applications and electronic devices, such as printed circuit board applications. In particular, the article may be a prepreg and/or a laminate. In a specific embodiment, a laminate and/or prepreg is provided, the laminate and/or prepreg comprising any one or more of the flame retardant compositions described herein. In one other embodiment, a printed circuit board is provided herein, optionally a multilayer printed circuit board comprising one or more prepregs and/or laminates (uncured, partially cured, or fully cured) Where the prepreg and/or laminate comprises any one or more of the flame retardant compositions described herein. In one embodiment, a printed circuit board comprising a prepreg and/or a laminate is provided, wherein the prepreg and/or laminate comprises any of the flame retardant compositions described herein. Partial curing as used herein may include any level of cure (other than full cure) and will vary widely depending on the particular materials and manufacturing conditions and the desired end use application. In a specific embodiment, the article herein may additionally comprise a copper foil. In one embodiment, the article can include a printed circuit board. In one embodiment, an FR-4 laminate is provided, the FR-4 laminate comprising the prepreg and/or laminate of the present invention. In a more specific embodiment, a printed circuit board comprising a FR-4 laminate is provided, wherein the FR-4 laminate comprises a prepreg or laminate of the present invention. In one embodiment herein, a method of making a laminate comprising any of the flame retardant compositions described herein is provided, the method comprising impregnating each composition into a filler material (eg, a fiberglass mat) to form a prepreg The prepreg is then treated at elevated temperature and/or elevated pressure to promote partial cure to stage B, and then two or more of the prepregs are laminated to form the laminate. In one embodiment, the laminate and/or prepreg can be used in the applications described herein, such as a printed circuit board. Provided herein, any of the compositions described herein can be used to make prepregs and/or laminates having a good balance of lamination properties and thermal stability, such as high _Tg (i.e., above 130 °C), _Td 330. °C and above, t ₂₈₈ 5 minutes and above, flame retardant grade V-0, good toughness, good adhesion to copper foil, one or more. In recent years, T _d has become one of the most important parameters, because the industry is converted to lead-free solder, lead-free solder than conventional tin-lead solder which melts at a higher temperature. In one embodiment herein, the flame retardant compositions described herein can be used in other applications depending on the particular application, depending on the desired amount, for example, sealants for electronic components, protective coatings, structural adhesions. Agent, structural and / or decorative composites. Examples: Preparation Example 1 DOPO-HQ- diacetate - isophthalic acyl - Synthesis of Polyester (Compound I) is equipped with a mechanical stirrer, a thermometer, and nitrogen inlet 0.25L four-neck flask, add DOPO- HQ-diacetate (106 g, 0.26 mol) was heated to 170 ° C to completely melt. Isodecanoic acid (43 g, 0.26 mol) and potassium acetate 0.3 g were added, and the reaction mixture was heated at 280 ° C for 2 hours without vacuum and subjected to vacuum at 30 mbar for 1 hour. As the reaction proceeded, the mixture became more viscous. The formed acetic acid is distilled out of the reaction zone throughout the reaction to accelerate the polycondensation reaction. The resulting very viscous hot liquid product was quickly poured onto an aluminum plate to avoid solidification in the flask. The final solid light brown product was obtained in quantitative yield. The product contained 2.8% DOPO-HQ-monoacetate and DOPO-HQ-acetate-isodecanoate, 2.2% unreacted DOPO-HQ-diacetate, and 95% higher molecular weight oligomerization. (HPLC area %). The phosphorus content in the product was 6.1%. GPC analysis in DMF showed Mw of 32610 g/mol and Mn of 13360 g/mol. The product was insoluble in MEK after 3 hours at 60 °C. The intrinsic viscosity of the product in DMF was 0.32 dL/g. 2 DOPO-HQ- diacetate Preparation - terephthalic acyl - Synthesis of Polyester (Compound II) is equipped with a mechanical stirrer, a thermometer, 0.25 L four-neck flask, and nitrogen inlet was added DOPO-HQ- Diacetate (106 g, 0.26 mol) and heated to 170 ° C to completely melt. P-citric acid (43 g, 0.26 mol) and potassium acetate 0.3 g were added, and the reaction mixture was heated at 240 ° C for 2 hours without vacuum and 30 mbar under vacuum for 1 hour. As the reaction proceeded, the mixture began to solidify. The formed acetic acid is distilled out of the reaction zone throughout the reaction to accelerate the polycondensation reaction. The final solid off-white product was obtained in quantitative yield. The phosphorus content in the product was 6.2%. The product is insoluble in organic solvents. Solubility test at 25 ° C: Table 1: Materials Examples 1 to 8: Small-scale resin curing test of the present invention having a flame retardant A sample of (a) Compound I was combined with (b) a PPE resin and (c) a crosslinking agent and cured on a small scale. The composition of the small sample is shown in Table 2. The total P% is 2.1 to 2.3%. The samples were cured at 177-182 °C for 2 hours and post-cured at 190-197 °C for 1 hour. The thermal stability of the samples was studied using DSC and TGA. To prepare varnish castings for Dk and Df measurements, the components in Table 2 were blended in a solvent (acetone or toluene). The mixture was dried under vacuum, then molded and cured at 177-182 °C for 2 hours and post-cured at 190-197 °C for 1 hour. The results are shown in Table 3: Table 2: Composition of the small scale curing experiment Table 3: Results of Tg, TGA, Dk, and Df for small scale curing experiments Discussion: As shown in Table 3, Examples 1 and 2 of the present invention have a very low dielectric constant (Dk) and a loss factor (Df) which are close to Comparative Example 3 without a flame retardant. The presence of the flame retardant aids in passing the flammability test without compromising the excellent dielectric properties of the blend. When the PPE resin was removed from the blend, the thermoset sample failed the flammability test (Comparative Example 4). While the invention has been described with respect to the embodiments of the embodiments of the present invention, it is understood by those of ordinary skill in the art that various changes may be made and equivalents may be substituted by equivalents without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention. Therefore, the present invention is intended to be limited to the embodiments of the invention, and

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagram of phosphorus-containing aromatic polyesters and how they can penetrate each other through a network of PPE resins and crosslinkers. 2 is a diagram of a phosphorus-containing aromatic polyester and how it can be combined with an inorganic filler and dispersed in a free state in a crosslinked network structure. Figure 3 is a graph of active ester groups of a phosphorus-containing aromatic polyester and how they react with an epoxy resin to form a second crosslinked network structure.

Claims (28)

A flame retardant composition comprising: (a) a compound having the following general formula (I): It has a weight average molecular weight of from about 1,000 to about 700,000, and wherein X is a divalent aromatic hydrocarbon group containing from 6 to about 12 carbon atoms, which may optionally be subjected to an alkyl or alkoxy group each having up to about 6 carbon atoms. Base substitution, Y is selected from the group consisting of: Wherein Z is a group selected from the group consisting of a covalent bond, -SO ₂ -, -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, and -CH ₂ -; a is an integer from 0 to 2; b is an integer from 0 to 2, and wherein the wavy line of each structure of Y represents a bond in which Y is bridged with an oxygen atom in the formula (I); R ¹ is selected from the group consisting of H, 1 to about 4 Alkyl, phenyl, naphthyl, or Wherein R ² is selected from the group consisting of H or -C(=O)R ³ , and wherein R ³ is an alkyl group selected from 1 to 4 carbon atoms, a phenyl group, a naphthyl group, and an aromatic phenol group The aromatic phenolic group is one selected from the group consisting of a phenol group, an o- cresol group, an m- cresol group, a p- cresol group, an α -naphthol group, and a β -naphthol group, and when R ² is H, R ¹ is not a phenyl or naphthyl group, and n is ≥2; (b) a polyphenylene ether and / or an oligomer thereof; and, (c) having a carbon - carbon unsaturated double bond post Joint agent. A flame retardant composition as claimed in claim 1 wherein R ¹ is And wherein X is a divalent aromatic hydrocarbon group of 6 to 12 carbon atoms, which may be optionally substituted with an alkyl group or alkoxy group of up to 6 carbon atoms. The flame retardant composition of claim 1, wherein R ¹ is an alkyl group of 1 to about 4 carbon atoms, and wherein X is a divalent aromatic hydrocarbon group of 6 to 12 carbon atoms, which may optionally Substituted by an alkyl or alkoxy group of up to 6 carbon atoms. A flame retardant composition according to claim 1, wherein X is a divalent aromatic hydrocarbon group of 6 to 12 carbon atoms, which may be optionally substituted with an alkyl group or an alkoxy group of up to 6 carbon atoms. A flame retardant composition as claimed in claim 1, wherein n is from 2 to about 100. The flame retardant composition of claim 1, wherein the polyphenylene ether (b) is a linear polyphenylene ether which is independently terminated at each end by a vinyl or allyl group. The flame retardant composition of claim 1, wherein the polyphenylene ether (b) is as shown in the formula (II): Wherein Z ₁ is a divalent moiety derived from a compound selected from the group consisting of bisphenol A, bisphenol F, bisphenol S, naphthalene, anthracene, biphenyl, tetramethylbiphenyl, phenol novolac, A A phenol novolac, a bisphenol A novolac, and a borane compound, and m ₁ and m ₂ are each independently an integer of from about 3 to about 20. The flame retardant composition of claim 1, wherein the polyphenylene ether (b) has an average molecular weight of 1,000 to 10,000. The flame retardant composition of claim 1, wherein the polyphenylene ether (b) has an average molecular weight of 1,000 to 3,000. The flame retardant composition of claim 1, which additionally comprises a thermosetting resin in an amount of from about 1% by weight to about 25% by weight. The flame retardant composition of claim 10, wherein the thermosetting resin is an epoxy resin. The flame retardant composition of claim 10, wherein the thermosetting resin is an epoxy selected from the group consisting of a halogen-free epoxy resin, a phosphorus-free epoxy resin, and a phosphorus-containing epoxy resin and a mixture thereof. Resin. A coating composition, encapsulant, composite, adhesive, molded adhesive sheet, or laminate, which comprises the composition of claim 1 of the patent application. The flame retardant composition of claim 1, wherein the composition is halogen-free. An article comprising the composition of claim 1 of the scope of the patent application. For example, the object of claim 15 can be used for lead-free soldering applications and electronic devices. An article of claim 15 wherein the article further comprises a copper foil. An article of claim 15 wherein the article is a printed circuit board. A prepreg comprising a flame retardant composition as in claim 1 of the patent application. A laminate or adhesive sheet comprising the flame retardant composition of claim 1 of the patent application. A printed wiring board comprising the prepreg according to claim 19 of the patent application. A printed wiring board comprising the laminate of claim 20 of the patent application. A method of producing a laminate comprising the composition of claim 1 of the patent application, comprising impregnating the composition into a filler material to form a prepreg, followed by treating the prepreg at a high temperature to promote partial curing to In the B stage, two or more of the prepregs are then laminated under high pressure and high temperature to form a laminate. A printed circuit board manufactured by the method of claim 23 of the patent application. The flame retardant composition according to claim 1, wherein the crosslinking agent (c) having a carbon-carbon unsaturated double bond is selected from the group consisting of a hydrocarbon crosslinking agent (1), containing At least three functional crosslinkers (2), rubbers having a block or irregular structure (3), and combinations thereof. The flame retardant composition of claim 25, wherein the hydrocarbon crosslinking agent (1) is selected from the group consisting of butadiene, polybutadiene, octadiene, polyoctadiene , decadiene, polydecadiene, vinyl carbazole, and combinations thereof. A flame retardant composition according to claim 25, wherein the crosslinking agent (2) having three or more functional groups is selected from the group consisting of: triallyl isocyanurate 1,2,4-trivinylcyclohexane (TVCH), and combinations thereof. A flame retardant composition according to claim 25, wherein the rubber (3) having a block or irregular structure is selected from the group consisting of styrene-butadiene rubber (SBR), propylene. Nitrile-butadiene rubber, acrylate-butadiene rubber, acrylonitrile-butadiene-styrene rubber, and combinations thereof.