JP5996750B2 - Electrical laminate structure containing reaction product of curable composition - Google Patents

Description

Embodiments of the present disclosure relate to a curable composition, particularly a curable composition comprising a non-halogen flame retardant, and a method of making the curable composition.

A curable composition is a composition comprising a thermosetting monomer that can be crosslinked. Curing
Crosslinking, also referred to as linking, allows curable compositions to be used in various fields, such as composites, electrical laminates, among others, due to their chemical resistance, mechanical strength, and electrical properties, among others.
And converted to a crosslinked polymer (ie, cured product) useful in coatings. For example, the curable composition can be used in electronic devices as a protective film, an adhesive material, and / or an insulating material (such as an interlayer insulating film).

In order to be useful for these applications, the cured product of the curable composition should provide ease of handling and certain necessary physical, thermal, electrical insulation, and moisture resistance properties. is there. For example, a curable composition having a low dielectric constant, high solubility, and low hygroscopicity, and a high glass transition temperature (T _g ) may be a desirable combination of properties for electrical applications.

The use of curable compositions in electronic equipment applications can also affect the electrical signals generated in electronic equipment. Increasing the electrical signal frequency in an electronics system (eg, a computer system) allows data to be processed at a faster rate. However, curable compositions in the vicinity of such electrical signals can have a significant impact on the transmission loss of electrical signals in such high frequency circuits. In order to minimize this effect, curable compositions having a low dielectric constant and low dissipation factor in addition to other properties discussed herein are desirable.

However, the curable composition can be flammable. Therefore, various techniques have been performed to impart flame retardancy to the cured product of the curable composition. Two main approaches have been taken to impart flame retardancy. The first is a “Green” approach in which a halogen-free compound is used. The second method uses a halogen compound. Halogenated compounds have been used for decades in the electronics industry to impart flame retardancy to electrical and electronic assemblies. For example, tetrabromobisphenol-A (TBBA) has been a flame retardant that has contributed significantly in electrical laminates for many years. However, halogenated compounds are now being rigorously investigated by environmental protection groups because of the possibility of dioxin formation during incineration of electronic components at the end of their useful life. In many developed countries, combustion of parts is regulated and controlled, but in developing countries, combustion is often not regulated, increasing the possibility of brominated dioxin emissions into the atmosphere.

According to embodiments of the present disclosure, a curable composition comprising an epoxy resin, a non-halogen flame retardant comprising at least two aryl-cyanato groups and at least two phosphorus groups, and a copolymer of styrene and maleic anhydride. Is provided. For various embodiments, the non-halogen flame retardant is of formula (I):

（式中、ｍは、１から２０の整数であり；ｎは、０から２０の整数であり、但し、ｎが０
である場合、ｍは、２から２０の整数であることを条件とし；式中、Ｘは、硫黄、酸素、
孤立電子対、およびそれらの組合せからなる群から選択され；式中、それぞれのＲ^１およ
びＲ^２は、独立して、水素、１から２０個の炭素原子を有する脂肪族部分、６から２０個
の炭素原子を有する芳香族炭化水素部分であり（ここで、脂肪族部分および芳香族炭化水
素部分は、結合して環状構造を形成することができる）；式中、Ｒ^３は、水素、１から２
０個の炭素原子を有する脂肪族部分、６から２０個の炭素原子を有する芳香族炭化水素部
分、Ｒ^４Ｒ^５Ｐ（＝Ｘ）ＣＨ_２−、およびＲＯＣＨ_２−（ここで、Ｒは、１から２０個の
炭素原子を有する脂肪族部分である）からなる群から選択され；式中、それぞれのＲ^４お
よびＲ^５は、独立して、１から２０個の炭素原子を有する脂肪族部分、６から２０個の炭
素原子を有する芳香族炭化水素部分（ここで、脂肪族部分および芳香族炭化水素部分は、
結合して環状構造ＲＸ−を形成することができる）であるか、またはＲ^４およびＲ^５は一
緒になって、Ａｒ^２Ｘ−であり；式中、それぞれのＡｒ^１およびＡｒ^２は、独立して、ベ
ンゼン、ナフタレン、またはビフェニルである）
の化合物で表され得る。

(Wherein m is an integer from 1 to 20; n is an integer from 0 to 20, provided that n is 0.
Where m is an integer from 2 to 20; where X is sulfur, oxygen,
Selected from the group consisting of lone pairs, and combinations thereof; wherein each R ¹ and R ² is independently hydrogen, an aliphatic moiety having 1 to 20 carbon atoms, 6 to 20 Wherein the aliphatic and aromatic hydrocarbon moieties can be combined to form a cyclic structure; wherein R ³ is hydrogen, 1 To 2
An aliphatic moiety having 0 carbon atoms, an aromatic hydrocarbon moiety having 6 to 20 carbon atoms, R ⁴ R ⁵ P (═X) CH ₂ —, and ROCH ₂ — (where R is Wherein each R ⁴ and R ⁵ is independently an aliphatic moiety having from 1 to 20 carbon atoms, which is an aliphatic moiety having from 1 to 20 carbon atoms; , Aromatic hydrocarbon moieties having 6 to 20 carbon atoms, where the aliphatic and aromatic hydrocarbon moieties are
R ⁴ and R ^{5 taken} together are Ar ² X—; wherein each Ar ¹ and Ar ² are independently Benzene, naphthalene, or biphenyl)
It can be represented by

For the various embodiments, the method of preparing the curable composition comprises preparing an epoxy resin, and reacting the epoxy resin with a non-halogen flame retardant and a copolymer of styrene and maleic anhydride, The non-halogen flame retardant comprises at least two aryl-cyanato groups and at least two phosphorus groups.

The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The description that follows illustrates specific embodiments in more detail.
In several places throughout the application, guidance is provided through lists of examples, which examples can be used in various combinations. In each case, the enumerated list serves only as a representative group and should not be interpreted as an exclusive list.

FIG. 1 provides a positive electrospray ionization mass spectrum from a DOP-BN polycyanate (CE-DOP-BN) sample of the present disclosure. FIG. 2 provides an expanded positive electrospray ionization mass spectrum from a DOP-BN polycyanate (CE-DOP-BN) sample of the present disclosure. FIG. 3 provides Fourier transform infrared (FTIR) spectra from DOP-BN and DOP-BN polycyanate (CE-DOP-BN). FIG. 4a provides a distortionless enhancement by polarization transfer (DEPT) nuclear magnetic resonance (NMR) spectrum from DOP-BN polycyanate (CE-DOP-BN). FIG. 4b gives quantitative ¹³ C NMR from DOP-BN-polycyanate (CE-DOP-BN). FIG. 5 gives a quantitative ³¹ P NMR spectrum from DOP-BN-polycyanate (CE-DOP-BN).

According to embodiments of the present disclosure, a curable composition comprising an epoxy resin, a non-halogen flame retardant comprising at least two aryl-cyanato groups and at least two phosphorus groups, and a copolymer of styrene and maleic anhydride. included. For various embodiments, the non-halogen flame retardant can be a cyanate derivative of a phosphorus-substituted polyphenol formed by condensing an active phosphorus compound (HP (= X) R ⁴ R ⁵ ) with an etherified resole. The etherified resole is from bisphenol A and the active phosphorus compound is H-DOP (9,10
In the specific case of -dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) the phosphorus-substituted polyphenol is called DOP-BN and the polycyanate (ie non-halogen flame retardant) is "DOP -BN Polycyanate "and" CE-DOP-
Referenced synonymously with “BN”. The non-halogen flame retardant of the present disclosure is then DOP-BN,
A non-halogen flame retardant (CE-DOP-BN) is reacted with a compound such as cyanogen halide (for example, cyanogen bromide) that reacts with a hydroxy group on DOP-BN to form a cyanate group.
) Can be obtained.

For various embodiments, the non-halogen flame retardants of the present disclosure can be used as self-curing compounds, curing agents, and / or as components in curing agent compositions for curable compositions, among others. The non-halogen flame retardants of the present disclosure can also be used as reactive starting materials for reacting with other polymers. For example, the aryl-cyanato group of the non-halogen flame retardant may be reacted with an epoxy resin. In this embodiment, the non-halogen flame retardant acts as a crosslinker, curing agent, and / or hardener for the epoxy resin.

The non-halogen flame retardant of the curable composition of the present disclosure also acts as a flame retardant for the cured product of the curable composition, while providing the advantage of containing no halogen. Such cured products, including curable compositions, may also have suitable thermal and electrical properties that are useful as protective films, adhesive materials, and / or insulating materials in various electronic device applications.

Further, the curable composition of the present disclosure includes a copolymer of styrene and maleic anhydride.
Copolymers of styrene and maleic anhydride can provide an acceptable combination of properties in curable compositions, such as epoxy systems that can include low dielectric constants and / or high glass transition temperatures.

For various embodiments, the curable composition includes a non-halogen flame retardant, a copolymer of styrene and maleic anhydride, and an epoxy resin. For various embodiments, the molar ratio of epoxy groups of the epoxy resin to maleic anhydride groups of the copolymer of styrene and maleic anhydride is in the range of 1.0: 1.0 to 2.6: 1.0. obtain. Further, the phosphorus content of the curable composition may range from 0.1 weight percent (wt%) to 3 based on the total weight of the curable composition.
. It can be in the range of 5 wt%. For the various embodiments, the molar ratio of epoxy groups to maleic anhydride groups and the phosphorus content of the curable composition is determined by curing the curable composition without CE-DOP-BN and a copolymer of styrene and maleic anhydride. Provides improved thermomechanical and electrical properties compared to the product. For example, the thermomechanical and electrical properties include, but are not limited to, non-halogen flame retardants, copolymers of styrene and maleic anhydride, and glass of cured products of curable compositions having epoxy resins. There may be mentioned transition temperature, dielectric constant, and dissipation factor. In addition to flame retardancy, the curable compositions of the present disclosure may also provide other desirable physical properties such as heat resistance and processability (including solvent solubility).

For various embodiments, the curable composition comprises an epoxy resin. An epoxy resin is a compound having an epoxy group, in which an oxygen atom is directly bonded to two adjacent or non-adjacent carbon atoms of a carbon chain or ring system. The epoxy resin can be selected from the group consisting of aromatic epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, and combinations thereof.

For the various embodiments, the curable composition comprises an aromatic epoxy compound. Examples of aromatic epoxy compounds include, but are not limited to, glycidyl ether compounds of polyphenols such as hydroquinone, resorcinol, bisphenol A, bisphenol F, 4,4′-dihydroxybiphenyl, phenol novolac, cresol novolac, tris. Phenol (tris- (4-hydroxyphenyl) methane), 1,1,2,2
-Tetra (4-hydroxyphenyl) ethane, tetrabromobisphenol A, 2,2-
Bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane,
1,6-dihydroxynaphthalene, and combinations thereof.

For various embodiments, the curable composition includes an alicyclic epoxy compound. Examples of alicyclic epoxy compounds include, but are not limited to, epoxidizing a polyglycidyl ether of a polyol having at least one alicyclic ring or a compound containing a cyclohexene ring or a cyclopentene ring with an oxidizing agent. And a compound containing cyclohexene oxide or cyclopentene oxide obtained by the above method. Some specific examples include, but are not limited to, hydrogenated bisphenol A diglycidyl ether;
Epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate; 3
, 4-Epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate; 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3
3,4-epoxycyclohexanecarboxylate; 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate;
4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate; bis (3,4-epoxycyclohexylmethyl) adipate; methylene-bis (3,4-epoxycyclohexane); 2,2 -Bis (3,4-epoxycyclohexyl) propane; dicyclopentadiene diepoxide; ethylene-bis (3
, 4-epoxycyclohexanecarboxylate); dioctyl epoxy hexahydrophthalate; di-2-ethylhexyl epoxy hexahydrophthalate; and combinations thereof.

For various embodiments, the curable composition comprises an aliphatic epoxy compound. Examples of aliphatic epoxy compounds include, but are not limited to, polyglycidyl ethers of aliphatic polyols or alkylene-oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, vinyl of glycidyl acrylate or glycidyl methacrylate. Homopolymers synthesized by polymerization, and copolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate and other vinyl monomers.
Some specific examples include, but are not limited to, glycidyl ethers of polyols, such as 1,4-butanediol diglycidyl ether; 1,6-hexanediol diglycidyl ether; triglycidyl ether of glycerin. Triglycidyl ether of trimethylolpropane; tetraglycidyl ether of sorbitol; hexaglycidyl ether of dipentaerythritol; diglycidyl ether of polyethylene glycol;
And diglycidyl ethers of polypropylene glycol; polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyols (such as propylene glycol, trimethylolpropane, and glycerin); Diglycidyl esters of chain dibasic acids; and combinations thereof.

For the various embodiments, the epoxy resin is 1 wt based on the total weight of the curable composition.
For example, the epoxy resin can be used in an amount of 20 wt% to 90 wt%, preferably 20 wt% to 60 wt%, based on the total weight of the curable composition.
% Can be used.

For various embodiments, the curable composition includes a non-halogen flame retardant that includes at least two aryl-cyanato groups and at least two phosphorus groups. As used herein,
The aryl-cyanato group can be a monocyclic or polycyclic aromatic hydrocarbon group that includes at least one cyanato group (—OCN) attached thereto. In addition, the phosphorus group
It may be a monocyclic or polycyclic aromatic hydrocarbon group containing at least one phosphorus atom bonded thereto.

  For various embodiments, such non-halogen flame retardants have the formula (I):

（式中、ｍは、１から２０の整数であり；式中、ｎは、０から２０の整数であり、但し、
ｎが０である場合、ｍは、２から２０の整数であることを条件とし；式中、Ｘは、硫黄、
酸素、孤立電子対、およびそれらの組合せからなる群から選択され；式中、それぞれのＲ
^１およびＲ^２は、独立して、水素、１から２０個の炭素原子を有する脂肪族部分、６から
２０個の炭素原子を有する芳香族炭化水素部分（ここで、脂肪族部分および芳香族炭化水
素部分は、結合して環状構造を形成することができる）であり；式中、Ｒ^３は、水素、１
から２０個の炭素原子を有する脂肪族部分、６から２０個の炭素原子を有する芳香族炭化
水素部分、Ｒ^４Ｒ^５Ｐ（＝Ｘ）ＣＨ_２−、およびＲＯＣＨ_２−（ここで、Ｒは、１から２
０個の炭素原子を有する脂肪族部分である）からなる群から選択され；式中、それぞれの
Ｒ^４およびＲ^５は、独立して、１から２０個の炭素原子を有する脂肪族部分、６から２０
個の炭素原子を有する芳香族炭化水素部分（ここで、脂肪族部分および芳香族炭化水素部
分は、結合して環状構造ＲＸ−を形成することができる）であるか、または式中、Ｒ^４お
よびＲ^５は一緒になって、Ａｒ^２Ｘ−であり；ならびに式中、それぞれのＡｒ^１およびＡ
ｒ^２は、独立して、ベンゼン、ナフタレン、またはビフェニルである）
の化合物で表され得る。

(Wherein m is an integer from 1 to 20; where n is an integer from 0 to 20, provided that
When n is 0, m is an integer from 2 to 20; where X is sulfur,
Selected from the group consisting of oxygen, lone pair, and combinations thereof; wherein each R
¹ and R ² are independently hydrogen, an aliphatic moiety having 1 to 20 carbon atoms, an aromatic hydrocarbon moiety having 6 to 20 carbon atoms, wherein the aliphatic moiety and aromatic carbon The hydrogen moieties can be joined to form a cyclic structure); wherein R ³ is hydrogen, 1
Aliphatic moieties having from 20 to 20 carbon atoms, aromatic hydrocarbon moieties having from 6 to 20 carbon atoms, R ⁴ R ⁵ P (═X) CH ₂ —, and ROCH ₂ — (where R is 1 to 2
Wherein each R ⁴ and R ⁵ is independently an aliphatic moiety having 1 to 20 carbon atoms, 6 being an aliphatic moiety having 0 carbon atoms; To 20
An aromatic hydrocarbon moiety having 1 carbon atom, wherein the aliphatic and aromatic hydrocarbon moieties can be combined to form the cyclic structure RX-, or wherein R ⁴ And R ^{5 taken} together are Ar ² X—; and wherein each Ar ¹ and A
r ² is independently benzene, naphthalene, or biphenyl)
It can be represented by

As used herein, an aliphatic moiety includes a saturated or unsaturated linear or branched hydrocarbon group. This term is used to encompass alkyl, alkenyl, and alkynyl groups, for example. As used herein, an aromatic hydrocarbon moiety includes mono- or polynuclear aromatic hydrocarbon groups.

As discussed herein, the non-halogen flame retardants of the present disclosure then react with DOP-BN and a hydroxy group on DOP-BN to produce a cyanate group (eg, bromide bromide). A non-halogen flame retardant (CE-DOP-B)
N) can be obtained from forming. For various embodiments, CE-DOP-BN is
It may have a conversion rate of hydroxyl group to cyanate group in the range of 20% to 100%, preferably in the range of 40% to 100%, more preferably in the range of 50% to 100%.

Preferred non-halogen flame retardants of formula (I) are those wherein X is oxygen, n is 1, m is 1, each R ¹ and R ² is a methyl group (Me), and R ³ is R ⁴ R ⁵ P (= X)
CH ₂ —, R ⁴ and R ^{5 taken} together to form Ar ² X (where Ar ² is R ⁴ R
⁵ P (= X) - is represented by the formula (II):

の化合物で表されるようなビフェニルである）であるものを含む。式（Ｉ）のさらなる好
ましい非ハロゲン難燃剤は、Ｘが酸素であり、ｎが０であり、ｍが２または３であり、Ｒ
^３がＲ^４Ｒ^５Ｐ（＝Ｘ）ＣＨ_２−であり、Ｒ^４およびＲ^５が一緒になって、Ａｒ^２Ｘ（こ
こで、Ａｒ^２は、Ｒ^４Ｒ^５Ｐ（＝Ｘ）−が式（ＩＩ）の化合物で表されるようなビフェニ
ルである）であるものを含む。式（Ｉ）のさらなる好ましい非ハロゲン難燃剤は、Ｒ^４Ｒ
^５Ｐ（＝Ｘ）ＣＨ_２−が、（Ｃ_２Ｈ_５Ｏ）_２Ｐ（＝Ｏ）−、（ＰｈＯ）_２Ｐ（＝Ｏ）−、
Ｐｈ（ＭｅＯ）Ｐ＝（Ｏ）−、およびＰｈ_２Ｐ（＝Ｏ）−であるものであり、ここで、Ｐ
ｈは、フェニル基（Ｃ_６Ｈ_５−）である。好ましくは、Ａｒ^１は、ベンゼンである。Ｒ^４
Ｒ^５Ｐ（＝Ｘ）−のさらなる構造は、

And biphenyl as represented by the above compound). Further preferred non-halogen flame retardants of formula (I) are those wherein X is oxygen, n is 0, m is 2 or 3, and R
³ is R ⁴ R ⁵ P (═X) CH ₂ —, R ⁴ and R ⁵ are taken together to form Ar ² X (where Ar ² is R ⁴ R ⁵ P (═X) — That is biphenyl as represented by the compound of formula (II). Further preferred non-halogen flame retardants of formula (I) are R ⁴ R
_{^{5 P (= X) CH 2}} - _{is, (C 2 H 5 O)} 2 P (= O) -, (PhO) 2 P (= O) -,
Ph (MeO) P = (O)-, and Ph ₂ P (= O)-, where P
h is a phenyl group (C ₆ H ₅ —). Preferably Ar ¹ is benzene. R ⁴
A further structure of R ⁵ P (═X) —

を含む。

including.

As used herein, at least two phosphorus groups for non-halogen flame retardants are (
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) (
H-DOP).

Ｈ−ＤＯＰは、日本国の三光株式会社から「Ｓａｎｋｏ−ＨＣＡ」という商品名で市販さ
れているか、または独国のＳｔｒｕｋｔｏｌ（登録商標）から市販されている「Ｐｏｌｙ
ｄｉｓ（登録商標）ＰＤ３７１０」である。

H-DOP is commercially available under the trade name “Sanko-HCA” from Sanko Co., Ltd. in Japan, or “Poly” available from Struktol (registered trademark) in Germany.
dis (registered trademark) PD3710 ".

For various embodiments, H-DOP can be reacted with an etherified resole. Examples of suitable etherified resoles include butyl ether bisphenol-A resole made with bisphenol A, formaldehyde and n-butanol. Etherified resoles are typically a mixture of monomeric, dimeric and oligomeric structures. Examples of commercially available etherified resoles include SANTOLINK ™ EP 560, a butyl etherified phenol formaldehyde condensation product, and a cresol mixture where the manufacturer has a weight average molecular weight of 4000 to 6000 and a polydispersity of 2 to 3. PHENODUR ™ VPR 1785/50, a butoxymethylated phenol novolak characterized as a highly butyl etherified resole based on
Both of these products are UCB Group (headquartered in Brussels, Belgium) and its branch office UCB GmbH & Co. It is available from KG (corporate company in Germany). Other resole compounds available from UCB include, for example, PHENODUR ™ PR401, PHENODUR ™ PR411, PHENODUR ™ PR
515, PHENODUR ™ PR711, PHENODUR ™ PR612,
PHENODUR (TM) PR722, PHENODUR (TM) PR733, PHEN
ODUR ™ PR565 and PHENODUR ™ VPR1775.

  An example of butyl ether bisphenol-A resole is shown below:

（ここで、Ｂｕは、ブチル基であり、ｍは、１から１０の整数であり得る）。本明細書で
検討されるように、ブチルエーテルビスフェノール−Ａレゾールは、ブチルエーテルビス
フェノール−Ａレゾールの単量体、二量体および／またはオリゴマーの組合せとして存在
してもよい。さらに、ブチルエーテルビスフェノール−Ａレゾールにおけるオルト位の１
個または複数のブチルエーテル基（−ＣＨ_２ＯＢｕ）は、他の基、例えば、−Ｈ、および
−ＣＨ_２ＯＨで置き換えられ得る。上記の構造は、実際の構造を単純化したものである。
当技術分野でよく知られているように、架橋基（bridging groups）の一部は、メチレン
架橋（bridges）よりはむしろ−ＣＨ_２ＯＣＨ_２−であり得る。これは、レゾールを製造
するために使用される工程パラメータ（とりわけ、触媒型、ｐＨ、アルコール濃度、およ
び温度）によって調節され得る。

(Where Bu is a butyl group and m can be an integer from 1 to 10). As discussed herein, butyl ether bisphenol-A resole may exist as a combination of butyl ether bisphenol-A resole monomers, dimers and / or oligomers. Furthermore, 1 of the ortho position in butyl ether bisphenol-A resole
One or more butyl ether groups (—CH ₂ OBu) may be replaced with other groups, eg, —H, and —CH ₂ OH. The above structure is a simplification of the actual structure.
As is well known in the art, some of the bridging groups may be —CH ₂ OCH ₂ — rather than methylene bridges. This can be adjusted by the process parameters used to produce the resole, especially the catalyst type, pH, alcohol concentration, and temperature.

For various embodiments, active phosphorus compounds (such as H-DOP) can be reacted with etherified resoles by blending or mixing them together to form a reactive composition. The reactive composition can be heated to initiate the reaction of the two components to form an alcohol and form a phosphorus polyphenol intermediate. For various embodiments, the reaction temperature is preferably less than the decomposition temperature of the starting material. Generally, the reaction temperature is 100 degrees Celsius (° C.
), Preferably above 120 ° C, more preferably above 150 ° C. The reaction is preferably performed by converting the HP moiety of H-DOP to -OB of butyl ether bisphenol-A resole.
Sufficient time is allowed to react with the u moiety. The reaction time is typically 60 minutes to 1
It is 2 hours, preferably 2 to 6 hours, more preferably 2 to 4 hours.

For various embodiments, the reaction is preferably in the absence of water (in general, water is less than 5 wt%, more preferably less than 3 wt%, as water may tend to react with H-DOP).
Most preferably, it is present at less than 1 wt%). Removal of the alcohol co-product generally helps to complete the reaction. Accordingly, the pressure in the reaction vessel is preferably reduced to a pressure below atmospheric pressure, for example, below 0.1 bar, to help drive off alcohol or by-products at temperatures below the above-mentioned minimum decomposition temperature. . The reaction vessel may optionally be purged with a gas or volatile organic liquid to further assist in the removal of byproduct (s). The gas or volatile organic liquid is preferably inert to the contents of the reaction vessel. An example of such an inert gas includes, but is not limited to, nitrogen gas.

Butyl ether bisphenol-A resole is usually an organic solvent such as butanol, xylene, or Dowanol ™ PM (The Dow Chemical
A portion of the solvent can be removed either by heating or applying a vacuum to the solution prior to the addition of H-DOP. H-DOP and etherified resole
Preferably, based on the total solids of the composition, the range is 10: 1 to 1:10, preferably 5: 1 to 1: 5, more preferably 2: 1 to 1: 2, most preferably 1.1. : 1 to 1:
Mixed at a weight ratio (H-DOP: etherified resole) in the range of 1.1. If necessary, other materials such as catalysts or solvents may be added to the reaction mixture of H-DOP and etherified resole.

For various embodiments, the reaction product of H-DOP and butyl ether bisphenol-A resole replaces most (but not necessarily all) of the butyl ether groups present on the butyl ether bisphenol-A resole. In this specification, DOP-B
The resulting compound, referred to as N, is shown below.

In general, the DOP-BN reaction product from the reaction of H-DOP with etherified resole is
It is a mixture of oligomers (m = 1 to 20). The number average degree of polymerization of the phosphorus polyphenol product is related to the molecular weight of the etherified resole starting material.

For various embodiments, the non-halogen flame retardant of formula (I) provided herein is a DO
P-BN can be prepared by reacting with a compound that reacts with a hydroxy group to form a cyanate group. Examples of such compounds include cyanogen halides such as cyanogen bromide and cyanogen chloride. The reaction is carried out in the presence of a base which may include alkali metal hydroxides and / or aliphatic amines such as triethylamine and / or sodium hydroxide.

For various embodiments, considering the exothermic nature of the reaction and the volatility of the cyanogen halide,
The reaction can be carried out at a low temperature. For example, the reaction temperature is −40 ° C. to 40 ° C., preferably −2 ° C.
It can be from 0 ° C to 10 ° C. Inert organic solvents can be used, where such inert organic solvents include, but are not limited to, aromatic hydrocarbons such as benzene, toluene or xylene; ethers such as diethyl. Ethers or tetrahydrofuran; halogenated aliphatic or aromatic hydrocarbons such as methylene chloride or chlorobenzene; and / or ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone.

For various embodiments, the curable composition of the present disclosure has at least 0.1 wt% to 3.
For example, the curable composition of the present disclosure has a phosphorus content of at least 2.2 wt% to 3.0 wt%, based on the total weight of the curable composition. Can do.

For various embodiments, the non-halogen flame retardant is 1 based on the total weight of the curable composition.
It is used in an amount in the range of wt% to 90 wt%, preferably in the range of 10 wt% to 60 wt%, and even more preferably in the range of 20 wt% to 50 wt%.

For various embodiments, the curable composition may also include a copolymer of styrene and maleic anhydride. A copolymer of styrene and maleic anhydride is a polymer formed by monomers of styrene and maleic anhydride. For various embodiments, the copolymer of styrene and maleic anhydride has the formula (III):

の第１の構成単位、式（ＩＶ）：

The first structural unit of formula (IV):

の第２の構成単位を有し、ここで、それぞれのｍおよびｎは、独立して、スチレンと無水
マレイン酸とのコポリマー中のそれぞれの構成単位のモル分率を表す実数であり、それぞ
れのＲは、独立して、水素、芳香族基または脂肪族基である。本明細書で使用される場合
、「構成単位」は、その繰り返しが巨大分子、例えば、ポリマーを構成する最小構成単位
（巨大分子の本質的な構造の一部を構成する原子の群）またはモノマーを指す。

Wherein each m and n is independently a real number representing the mole fraction of each constituent unit in the copolymer of styrene and maleic anhydride, R is independently hydrogen, an aromatic group or an aliphatic group. As used herein, “building block” refers to the smallest building block (group of atoms that forms part of the macromolecular's essential structure) or monomer whose repeats constitute a macromolecule, eg, a polymer. Point to.

For various embodiments, the mole fraction m is in the range of 0.50 to 0.89 and the mole fraction n is in the range of 0.11 to 0.50, where (m + n) = 1.00. For this embodiment, m and n are each greater than zero. For each R group, examples of aromatic groups include, but are not limited to, phenyl, biphenyl, naphthyl, substituted phenyl or biphenyl, and naphthyl. Examples of aliphatic groups include, but are not limited to alkyl and alicyclic alkyl.

Copolymers of styrene and maleic anhydride used in this disclosure are in the range of 1.0: 1.0 to 8.0: 1.0, preferably 1.0: 1.0 to 6.0: 1. Having a molar ratio of styrene to maleic anhydride within the range of 0.0 and 50,000 grams per mole (g / mo
l), preferably less than 20,000 g / mol, even more preferably 10,000
It may be selected from a copolymer of styrene and maleic anhydride or a mixture of copolymers of styrene and maleic anhydride having a weight average molecular weight (Mw) that is less than g / mol. The weight average molecular weight can be determined by gel permeation chromatography (GPC).

For various embodiments, the curable composition comprises a copolymer of styrene and maleic anhydride in the range of 10 wt% to 90 wt%, preferably 20 wt% to 80 wt%, based on the total weight of the curable composition. It was used in an amount within the range, more preferably within the range of 20 wt% to 60 wt%. For various embodiments, the curable composition is 1.0: 1
. Within the range of 0 to 2.6: 1.0, preferably within the range of 1.3: 1.0 to 1.8: 1.0, most preferably 1.3: 1.0 to 1.4: 1 Having a molar ratio of epoxy groups to maleic anhydride groups in the range of 0.0.

Commercial examples of such copolymers of styrene and maleic anhydride include, but are not limited to, SMA® EF-40, SMA® EF-60, S
MA <(R)> EF-80, and SMA <(R)> 1000, all of which are available from Sartomer Company, Inc.

In a further embodiment, the copolymer of styrene and maleic anhydride can be modified to include an aniline compound. Aniline compounds can be used to react with some of the maleic anhydride groups in the copolymer of styrene and maleic anhydride. A copolymer of modified styrene and maleic anhydride (also referred to herein as a “terpolymer”) may be incorporated into the curable composition to provide the desired thermal and electrical properties. The modified styrene and maleic anhydride copolymer can be incorporated into the curable composition to provide the desired thermal and electrical properties. The formation of a copolymer of modified styrene and maleic anhydride has been investigated in International Patent Application No. //, The Dow Chemical Company Docket No. 70069 entitled “CURABLE COMPOSITIONS” The disclosure of which is incorporated herein by reference.

For various embodiments, the modified styrene and maleic anhydride polymer can be represented by the formula (
III):

の第１の構成単位、式（ＩＶ）：

The first structural unit of formula (IV):

の第２の構成単位、式（Ｖ）：

A second structural unit of formula (V):

の第３の構成単位を有するターポリマーであることができ、ここで、それぞれのｍ、ｎお
よびｒは、独立して、ターポリマー中のそれぞれの構成単位のモル分率を表す実数であり
、それぞれのＲは、独立して、水素、芳香族基または脂肪族基であり、Ａｒは、芳香族基
であり、ここで、エポキシ基対第２の構成単位は、１．０：１．０から２．７：１．０の
範囲のモル比を有する。種々の実施形態について、それぞれのＲは、水素であり、Ａｒは
、フェニル基である。

Wherein each m, n and r is independently a real number representing the mole fraction of each constituent unit in the terpolymer, Each R is independently hydrogen, an aromatic group or an aliphatic group, and Ar is an aromatic group, where the epoxy group versus the second building block is 1.0: 1.0 To a molar ratio in the range of 2.7: 1.0. For various embodiments, each R is hydrogen and Ar is a phenyl group.

For various embodiments, the mole fraction m is 0.50 or more, and the mole fractions n and r are each independently 0.45 to 0.05, where (m + n + r) = 1 .00
It is. For various embodiments, the first building block versus the second building block ranges from 1: 1 to 20
For example, the molar ratio of the first building block to the second building block is 3:
It can have a range of 1 to 15: 1.

For the various embodiments, the second building block is based on the total weight of the terpolymer of 0.
It constitutes 10 wt% to 41 wt%. In one embodiment, the second building block comprises 5.0 wt% to 20 wt%, based on the total weight of the terpolymer. For various embodiments, the third building block is 0.10 wt% to 62, based on the total weight of the terpolymer.
. It constitutes 69 wt%. In one embodiment, the third building block comprises 0.50 wt% to 50 wt%, based on the total weight of the terpolymer.

For various embodiments, the copolymer of styrene and maleic anhydride is modified with an aromatic amine compound. Specific examples of the aromatic amine compound include, but are not limited to, aniline, substituted aniline, naphthalene amine, substituted naphthalene amine, and combinations thereof.

For embodiments incorporating a copolymer of modified styrene and maleic anhydride, the copolymer of modified styrene and maleic acid is within the range of 10 wt% to 90 wt%, based on the total weight of the curable composition. , Preferably in the range of 20 wt% to 80 wt%, more preferably in the range of 20 wt% to 60 wt%. Further, for embodiments incorporating a copolymer of modified styrene and maleic anhydride, the curable composition is within the range of 1.0: 1.0 to 2.6: 1.0, preferably 1. Copolymer of epoxy groups to styrene and maleic anhydride in the range of 3: 1.0 to 1.8: 1.0, most preferably in the range of 1.3: 1.0 to 1.4: 1.0 Can have a molar ratio of

Embodiments of the present disclosure may also be useful in other applications requiring flame retardant materials, including semiconductor packaging applications, electrical and electronic applications, and composite applications. Furthermore, non-halogen flame retardants are substantially free of both bromine and halogen atoms (eg, fluorine, chlorine, iodine, and astatine).

The curable compositions of the present disclosure described above may also optionally utilize curing catalysts, fillers, solvents, and combinations thereof. Examples of suitable curing catalysts include, but are not limited to, zinc (II) 2-ethylhexanoate, or other transition metal cations and mixtures thereof, 2-methylimidazole, 2-phenylimidazole, 2- Ethyl-4-
Examples include methylimidazole, 1-benzyl-2-phenylimidazole, boric acid, triphenylphosphine, tetraphenylphosphonium-tetraphenylborate, and mixtures thereof. The curing catalyst is in the range of 0.01 wt% to 10 wt%, preferably 0.05 wt% to 5.0 wt%, even more preferably 0.05 wt% to 2.0 wt%, based on the total weight of the curable composition. % Can be used in amounts in the range of%.

Examples of suitable fillers include, but are not limited to, fused silica, aluminum hydroxide, talc powder, mica powder, and the like, and combinations thereof. The filler may be used in an amount in the range of 10 wt% to 80 wt%, preferably in the range of 10 wt% to 75 wt%, and even more preferably in the range of 10 wt% to 50 wt%, based on the total weight of the curable composition. .

Examples of suitable solvents include, but are not limited to, methyl ethyl ketone, dimethylformamide, cyclohexanone, propylene glycol methyl ether acetate, and combinations thereof. The solvent is 20 wt based on the total weight of the curable composition.
% To 80 wt%, preferably 20 wt% to 70 wt%, and even more preferably 30 wt% to 50 wt%.

Due to their unique combination of properties, the curable compositions of the present disclosure can be useful in the preparation of various articles in the manufacturing industry. Accordingly, the present disclosure also provides a shaped article, reinforcing composition, laminate, electrical laminate, as described below, from a prepreg of the above composition, and a cured or partially cured curable composition of the present disclosure, Includes coatings, molded articles, adhesives and composite products. Furthermore, the curable compositions of the present disclosure can be used for various purposes in the form of dry powders, pellets, homogeneous masses, impregnated products and / or compounds.

For various embodiments, curable compositions with non-halogen flame retardants can be used to prepare resin sheets, resin-coated metal foils, prepregs, laminated substrates, or multilayer substrates, among other items. In a further embodiment, the curable composition having the non-halogen flame retardant of the present disclosure can further include a resin such as a bismaleimide-triazine epoxy resin, where the non-halogen flame retardant and resin of the present disclosure include: It can be used to prepare the items described above.

Various additional additives may be added to the compositions of the present disclosure. Examples of these further additives include fiber reinforcements, fillers, pigments, dyes, thickeners, wetting agents, lubricants, flame retardants and the like.

Embodiments of the present disclosure provide a prepreg comprising a reinforcing component and a curable composition, as discussed herein. The prepreg can be obtained by a method including a step of impregnating a matrix component into a reinforcing component. The matrix component surrounds and / or supports the reinforcing component. The disclosed curable composition can be used for matrix components.
The matrix component and the reinforcing component of the prepreg provide a synergistic effect. This synergy defines that the prepreg and / or product obtained by curing the prepreg has mechanical and / or physical properties not achieved with the individual components alone.

The reinforcing component can be a fiber. Examples of fibers include, but are not limited to, glass, aramid, carbon, polyester, polyethylene, quartz, metal, ceramic, biomass, and combinations thereof. The fiber can be coated. An example of a fiber coating includes, but is not limited to boron.

Examples of glass fibers include, but are not limited to, A-glass fibers, E-glass fibers, C-glass fibers, R-glass fibers, S-glass fibers, T-glass fibers, and combinations thereof. Can be mentioned. Aramid is an organic polymer, examples of which include, but are not limited to, Kevlar®, Twaron®, and combinations thereof. Examples of carbon fibers include, but are not limited to, fibers formed from polyacrylonitrile, pitch, rayon, cellulose, and combinations thereof. Examples of metal fibers include, but are not limited to, stainless steel, chromium, nickel, platinum, titanium, copper, aluminum, beryllium, tungsten, and combinations thereof. Examples of ceramic fibers include, but are not limited to, fibers formed from aluminum oxide, silicon dioxide, zirconium dioxide, silicon nitride, silicon carbide, boron carbide, boron nitride, silicon boride, and combinations thereof. Can be mentioned. Examples of biomass fibers include, but are not limited to, wood, non-wood,
And fibers formed from combinations thereof.

The reinforcing component can be a fabric. The fabric may be formed from fibers as discussed herein. Examples of fabrics include, but are not limited to, sutures, wovens, and combinations thereof. The fabric can be unidirectional, multiaxial, and combinations thereof. The reinforcing component can be a combination of fibers and fabrics.

The prepreg can be obtained by impregnating the matrix component into the reinforcing component.
Impregnation of the matrix component into the reinforcing component can be accomplished by various methods. The prepreg may be formed by contacting the reinforcing component and the matrix component by rolling, dipping, spraying, or other such operation. After the prepreg reinforcing component has been contacted with the prepreg matrix component, the solvent can be removed by volatilization. During and / or after the solvent is volatilized, the prepreg matrix component may be cured, eg, partially cured. Solvent volatilization and / or partial curing may be referred to as B-staging. The B-staged product may be referred to as a prepreg.

For some applications, B-staging can occur by exposure to temperatures from 60 ° C to 250 ° C; for example, B-staging is from 65 ° C to 240 ° C, or from 70 ° C to 230 ° C. Can be caused by exposure. For some applications, B-staging can occur over a period of 1 to 60 minutes; for example, B-staging can occur over a period of 2 to 50 minutes, or 5 to 40 minutes. However, for some applications, B-staging can occur at different temperatures and / or different time periods.

One or more prepregs may be cured (eg, more fully cured) to obtain a cured product. The prepreg may be layered and / or formed into a shape before being further cured. For some applications (eg, when an electrical laminate is being manufactured), the layers of prepreg can be alternated with layers of conductive material. An example of the conductive material includes, but is not limited to, copper foil. The prepreg layer can then be exposed to conditions such that the matrix component is more fully cured.

One example of a method for obtaining a more fully cured product is pressing. One or more prepregs can be placed in a press where it undergoes a curing force for a predetermined curing time interval to obtain a more fully cured product. The press can have a curing temperature of 80 ° C to 250 ° C; for example, the press can be 85 ° C to 240 ° C, or 90 ° C to 2 ° C.
It can have a curing temperature of 30 ° C. For one or more embodiments, the press has a cure temperature that is ramped over a ramp time interval from a lower cure temperature to a higher cure temperature.

During pressing, one or more prepregs can be subjected to a curing force by pressing. The curing power may have a value that is from 10 kilopascals (kPa) to 350 kPa; for example, the curing power may have a value that is from 20 kPa to 300 kPa, or from 30 kPa to 275 kPa. The predetermined cure time interval may have a value that is 5 seconds to 500 seconds; for example, the predetermined cure time interval has a value that is 25 seconds to 540 seconds, or 45 seconds to 520 seconds. Also good. Other cure temperatures, cure power values, and / or predetermined cure time intervals are possible for other methods of obtaining a cured product. Further, in this method, the prepreg may be further cured to obtain a cured product.

Embodiments of the curable composition may also include at least one synergist to help improve the flame out ability of the curable composition. Examples of such synergists include, but are not limited to, magnesium hydroxide, zinc borate, metallocene and combinations thereof. In addition, embodiments of this composition also include adhesion promoters such as modified organosilanes (epoxidation, methacryl, amino), acetylacetonate,
Sulfur containing molecules and combinations thereof may also be included. Other additives include, but are not limited to, wetting and dispersing aids such as modified organosilanes, Byk®.
900 series and W9010 (Byk-Chemie GmbH), modified fluorocarbons and combinations thereof; air release additives such as Byk® A530,
Byk (R) A525, Byk (R) A555, and Byk (R)
A560 (Byk-Chemie GmbH); surface modifiers such as slip and brighteners; mold release agents such as waxes; and other functional additives or pre-reaction products that improve polymer properties such as isocyanates, Mention may be made of isocyanurates, cyanate esters, allyl-containing molecules or other ethylenically unsaturated compounds, acrylates and combinations thereof.

The heat required to provide an appropriate cure state can depend on the proportions of the components making up the composition and the nature of the components used. In general, the compositions of the present disclosure vary from 0 ° C. to 400 ° C., depending on the presence or amount of curing catalyst or curing agent, or the type of ingredients in the composition,
Preferably, it can be cured by heating at a temperature in the range of 100 ° C to 250 ° C.
The time required for heating can be from 30 seconds to 10 hours, where the exact time is
The resin composition is applied as a thin coating or as a molded article of relatively large thickness, or as a laminate or as a matrix resin for fiber reinforced composites, especially for electrical and electronic applications (eg applied to electrically non-conductive materials). And then curing the composition)
It depends on whether it is used.

The following examples are presented to illustrate the scope of the invention, but are not intended to limit the scope of the invention.

  material

Tetrahydrofuran, available from Sigma-Aldrich (hereinafter “Aldrich”).

  Anhydrous dichloromethane, available from Aldrich.

XZ92774 (XZ92741, 57 wt% DOP-BN in propylene glycol methyl ether solution), available from The Dow Chemical Company.

9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (
H-DOP, “Sanko-HCA”), available from Sanko, Japan.

EPICLONE HP7200 (trademark) (HP7200, DCPD type epoxy resin)
Available from DIC Corporation.

SMA® EF-40 (SMA 40, a copolymer of styrene and maleic anhydride), Sartomer Company, Inc. Available from SMA 40 is 4:
It has a styrene to maleic anhydride molar ratio of 1 and a weight average molecular weight of 10,500.

SMA® EF-60 (SMA 60, a copolymer of styrene and maleic anhydride), Sartomer Company, Inc. Available from SMA 60 is 6:
It has a styrene to maleic anhydride molar ratio of 1 and a weight average molecular weight of 11,500.

SMA® 1000 (SMA 1000, a copolymer of styrene and maleic anhydride), Sartomer Company, Inc. Available from SMA1000
Has a 1: 1 styrene to maleic anhydride molar ratio and a weight average molecular weight of 5,500.

Butyl ether bisphenol-A resole (SANTOLINK ™ EP 560
, Etherified resole), UCB GmbH & Co. Available from

  Nitrogen, available from Air Products.

  Available from cyanogen bromide, Aldrich.

  Triethylamine, base, available from Aldrich.

  Dichloromethane, available from Aldrich.

  Granular anhydrous sodium sulfate, available from Aldrich.

2-butanone (methyl ethyl ketone (MEK), solvent), The Dow Chemi
Available from the Cal Company.

N-dimethylformamide (DMF, solvent), Sinopharm Chemical
Co. Available from

Zinc (II) 2-ethylhexanoate (Zn catalyst, solution: 10 wt in methyl ethyl ketone
%), Curing catalyst, available from Sigma-Aldrich.

2-methylimidazole (2MI, solution: 10 wt% in methanol, curing catalyst), Si
Available from gma-Aldrich.

  Synthesis of solid DOP-BN

To prepare solid DOP-BN, a 60 gram sample of XZ92741 was placed in a 32 ounce wide-mouthed glass jar and then placed in a vacuum oven set at 100 ° C. for 18 hours,
The solvent was removed. The resulting solid material showed the appearance of fluffy crystals. A 2.661 milligram sample was analyzed by thermogravimetric analysis on a TA Instruments, Q50 TGA under a nitrogen purge of 50 cubic centimeters per minute according to the following procedure: 2
Slope from room temperature to 171 ° C at 0 ° C / min, isothermal at 171 ° C for 45 minutes. Total weight loss was measured at 2.8%.

High pressure liquid chromatography (HPLC) analysis of master blend A (DOP-BN) (UV detection at 254 and 305 nm using a diode array, Prontosil
120-3-C ₁₈ -ace-EPS 3.0 μm, 150 × 4.6 mm column, acetonitrile / water eluent (starting with a 50/50 gradient to 100% acetonitrile, 40 ° C., 1
. 0 mL / min flow rate) is 31.22 area%, 27.11 area% and 11.05 area%
Twenty-one components having three main components constituting Fourier transform infrared spectrophotometric (FTIR) analysis of potassium bromide pellets of DOP-BN (Nicolet FT-I
R spectrophotometer) revealed a sharp strong aromatic band absorbance in 1431.0Cm ^-1 for directly bonded to the phenyl ring in absorbance and phosphorus atom of the hydroxyl group at 3212.8cm ^-1.

DOP-BN by electrospray ionization liquid chromatography mass spectrometry
Analysis of

Solid DOP-BN samples were dissolved in tetrahydrofuran (approximately 10% v / v) and aliquots of these solutions, 5 microliters, were cations (PI) and anions (NI)
Waters Alliance 2690 connected to Micromass QToF2, SN # UC-175, quadrupole / time-of-flight MS / MS system via Micromass Z-spray electrospray (ESI) interface operating in mode
Analyzed by liquid chromatography electrospray ionization mass spectrometry (ESI / LC / MS) on a ternary gradient liquid chromatography system. The following analytical conditions were used:
Column: 150 × 4.6 mm ID × 5 μm, Zorbax SB-C3
Mobile phase: A = DI water w / 0.05% formic acid and B = tetrahydrofuran Gradient program: 80/20 v / v A / B retention 1 min to 21 min Curve 6 5/95
Up to v / vA / B, hold 5 minutes, total operation time = 26 minutes Column temperature: 45 ° C.
Flow rate: 1.0 ml / min (2: 1 separation from interface)
UV detection: diode array 210 to 400 nm
ESI condition: Source Block: 110 ° C. Desolvation: 280 ° C.
Capillary: +/- 2.5kV
Cone: +/- 20V
MS condition: MCP: 2150 V mode: +/− ion scan: 50 to 4000 amu (+) speed: 1.0 sec / scan scan: 50 to 3000 amu (−) speed: 1.0 sec / scan Lockspry Mass Calibrant = (PI / NI) Methanol at a flow rate of 3 microliters / minute (M + H + = 4844.0714, M−H− = 482.055)
8) DE-638 (Penoxsulam ™, Chem. Abs. 219714)
96-2, C16H14F5N5O5S) 12.5 microgram / milliliter solution, one scan taken every 5 seconds.
ESI / LC / MS analysis gave the following proposed structure shown in Table I, where only the components present in excess of 5 area% were considered.

  Synthesis of non-halogen flame retardant (CE-DOP-BN)

To a 250 ml three-necked glass round bottom reactor was added solid DO prepared as described above.
P-BN (4.90 grams, 0.01 hydroxyl equivalent) and anhydrous dichloromethane (5
0 ml, 10.2 ml per gram of DOP-BN). The reactor is further equipped with a condenser (maintained at 0 ° C.), thermometer, overhead nitrogen inlet (
1 liter of nitrogen per minute was used) with magnetic stirring. The solution was stirred and the temperature was brought to 22 ° C.

Cyanogen bromide (1.134 g, 0.0107 mol, 1.07: 1 cyanogen bromide: hydroxyl equivalent ratio) was added to this solution and immediately dissolved therein. A cooling dry ice-acetone bath was placed under the reactor followed by cooling and equilibrating the stirred solution at -7 ° C. Triethylamine (1.03 grams, 0.0102 mol, triethylamine: hydroxyl equivalent ratio 1.02) was added using a syringe in aliquots maintaining the reaction temperature from -7 ° C to -3.5 ° C. The total addition time of triethylamine was 12 minutes. Addition of an initial aliquot of triethylamine resulted in a pale yellow color in the stirred solution, which immediately turned colorless again. Upon further addition, turbidity indicating triethylamine hydrobromide was observed.
After 13 minutes post-reaction at −8 ° C. to −5 ° C., HPLC analysis of sample of reaction product (UV detection at 254 and 305 nm using diode array, Prontosil 120-3-
C ₁₈ -ace-EPS 3.0 μm, 150 × 4.6 mm column, acetonitrile / water eluent (starting with a gradient from 50/50 to 100% acetonitrile, 40 ° C., 1.0 mL / min flow rate) of 31 Clarify the ingredients and every ingredient present is the HPL of DOP-BN
It had a different retention time than that observed in the C analysis. After a cumulative 32 minutes of post-reaction at −8 ° C. to −5 ° C., the product slurry was added to a magnetically stirred deionized water (200 ml) and dichloromethane (50 ml) beaker to obtain a mixture.

After 2 minutes of stirring, the mixture was added to a separatory funnel and allowed to settle, then the dichloromethane layer was collected and the aqueous layer was discarded. Return the dichloromethane solution to the separatory funnel and add fresh deionized water (
100 ml) and extracted three more times. The resulting cloudy dichloromethane solution was dried over granular anhydrous sodium sulfate (5 grams) to give a clear solution which was then supported by a 60 milliliter intermediate fritted glass funnel attached to a branch vacuum flask. A bed of anhydrous sodium sulfate (25 grams) was passed through.

The clear pale yellow colored filtrate was evaporated on a rotary evaporator using a maximum oil bath temperature of 50 ° C. until the vacuum was <1 mmHg. A total of 4.49 grams of white crystalline product was recovered. FTIR analysis of DOP-BN polycyanate potassium bromide pellets revealed the disappearance of hydroxyl group absorbance, the appearance of sharp strong cyanate group absorbance at 2253.7 and 2207.3 cm ⁻¹ , and phenyl bonded directly to the phosphorus atom. 1431 for the ring
. The maintenance of sharp and strong aromatic band absorbance at 0 cm ⁻¹ was demonstrated.

The HPLC / MS data shows the conversion of the phenol moiety to the desired cyanate ester functionality. FIG. 1 includes a cationic ESI mass spectrum obtained by injecting a methanol solution of a sample of DOP-BN polycyanate. Mass 362.19 and 520.
The major ions observed at 14 remain unspecified.
FIG. 2 focused on the higher mass range. The elemental composition of a large number of these ions can be assigned based on the exact mass measurements determined for these ions. The identified ion is a cyanate analog of a phenolic compound observed with the DOP-BN starting material. Both mono- and dicyanates are observed and are shown in Table II. Compound F (Dicyanate) is the target compound for the CE-DOP-BN sample.

  Characterization of non-halogen flame retardants

For the following examples, samples of synthetic non-halogen flame retardant (CE-BOP-BN) are characterized by the following method.

FTIR: A sample of non-halogen flame retardant (CE-DOP-BN) and a sample of DOP-BN raw material were placed on the ATR crystal plane and analyzed directly by FTIR ATR. Smart D
Thermo Nicole with uraSample IR Diamond ATR
A t model 6700 was used. Spectra were collected using Nicolet Omnic 7.3 software. The spectrum is shown in FIG.

As can be seen in FIG. 3, the raw material (DOP-BN) and the non-halogen flame retardant (CE-DOP-
BN) spectrum. In the FTIR spectrum of the raw material (DOP-BN), 32
There is a broad peak around 00 cm ⁻¹ , which represents the hydroxyl group of DOP-BN.
After the reaction and as seen in the non-halogen flame retardant (CE-DOP-BN) spectrum, the peaks are significantly reduced, with two new peaks being 2253 cm ⁻¹ and 2199, respectively.
Appearing at cm ⁻¹ , these represent cyanate groups of non-halogen flame retardants.

NMR: NMR spectrum is Bruker Avance I in Fourier transform mode.
Recorded using an II 400 megahertz NMR spectrometer (Bruker, USA). Chloroform-d was used as a solvent. 4a and 4b show the ¹³ C of CE-DOP-BN.
NMR spectrum is shown. FIG. 4a is a distortion-free sensitivity enhancement (DEPT) by polarization transfer, and FIG. 4b is a quantitative ¹³ C NMR. In FIG. 4b, the peak near 110 parts per million represents C1 of the —OCN group, and the peak at about 40 ppm represents C2. FIG.
According to the integration ratio of these two peaks in b, about 50% of the hydroxyl groups of DOP-BN are converted to -OCN.

FIG. 5 shows the quantitative ³¹ P NMR spectrum of CE-DOP-BN. Triphenyl phosphate (TPP) (99% purity and 9.5 wt% phosphorus content) was used as an internal standard. The integration ratio of the peak for CE-DOP-BN and the peak at −18 ppm for TPP, the phosphorus content in CE-DOP-BN is about 8 wt%.

  Examples 1-4 and Comparative Examples A-D

Examples 1-4 show curable compositions of the present disclosure comprising a non-halogen flame retardant and a copolymer of styrene and maleic anhydride. Comparative Examples A to D are CE-D as non-halogen flame retardants.
The curable composition which uses DOP-BN instead of OP-BN is shown.

  Examples 1-4

CE-DOP-BN, epoxy resin, copolymer of styrene and maleic anhydride, and solvent were mixed together according to the recipe in Table III and shaken to form a homogeneous solution.

  Comparative Examples A to D

DOP-BN, epoxy resin, copolymer of styrene and maleic anhydride, and solvent were mixed together according to the recipe in Table IV and shaken to form a homogeneous solution.

  Analysis of Examples 1 to 4 and Comparative Examples A to D

Curing catalysts were added to the curable compositions of Examples 1-4 and Comparative Examples AD, respectively, according to the formulations in Table III and Table IV. The gelling time of the curable composition was tested on a hot plate maintained at 171 ° C., which is the time that the remaining solvent becomes incorporated into the substantially branched structure. Gelation time indicates the reactivity of the curable composition (eg, at a particular temperature) and can be expressed as the number of seconds to the gel point. The gel point refers to the point of network formation of the initial polymer, where the structure is substantially branched such that each unit of the network is connected to each other unit of the network. ing. When the curable composition reaches the gel point, the remaining solvent becomes incorporated into the substantially branched structure. When the entrapped solvent reaches its boiling point, bubbles can form in the structure (eg, prepreg, resulting in undesirable products). The gel time can be adjusted by the amount of catalyst, which is often adjusted from 200 seconds to 400 seconds. The gel times of Examples 1-4 and Comparative Examples A-D are as shown in Table III and Table IV.

Glass transition temperature: The gelled curable composition was collected from the hot plate surface and post-cured in an oven at 200 ° C. for 3 hours to form a cured product. The glass transition temperature (T _g ) of the cured product was measured with a differential scanning calorimeter (DSC). The results are shown in Table V.

DSC is performed using DSC-Q2000 under flowing nitrogen atmosphere (50 ml / min). Samples (approximately 10.0 mg of the cured product of Examples 1-4 and Comparative Examples AD) were placed in the DSC in the following cycle. Cycle 1: Initial temperature: 40 ° C., final temperature: 250 ° C., and ramp rate = 10 ° C./min. Cycle 2: Initial temperature: 250 ° C., final temperature: 20 ° C., and ramp rate = −20 ° C./min. Cycle 3: Initial temperature: 40 ° C., final temperature: 250 ° C., and ramp rate = 10 ° C./min. Cycle 4: initial temperature: 250 ° C., final temperature 20 ° C., and ramp rate =
−20 ° C./min. Cycle 5: initial temperature: 40 ° C., final temperature: 250 ° C., and ramp rate = 2
0 ° C / min. _Tg was determined from 5 cycles.

Prepreg: The curable compositions of Examples 1 to 4 and Comparative Examples A to D were mixed with glass fiber sheets (
E-glass, Hexcel 7628) was brushed and the glass fiber sheet was placed in a 177 ° C. oven with air flow for 180 seconds to obtain the prepregs of Examples 1-4 and Comparative Examples AD. The prepreg was crushed and the prepreg powders of Examples 1 to 4 and Comparative Examples A to D were collected.

Plaque test: About 3 g of the prepreg powder of Examples 1-4 and Comparative Examples AD was placed on a flat aluminum foil, and then the aluminum foil with the prepreg powder was placed on a metal plate. This assembly was heated to 200 ° C. until the prepreg powder melted. The molten prepreg powder was covered with another aluminum foil sheet, and then a metal plate was placed on the aluminum foil. This assembly was hot pressed at 200 ° C. for 1 hour and then post-cured at 200 ° C. for an additional 3 hours. Bubble-free plaques having a thickness in the range of 0.3 millimeters to 0.5 millimeters were obtained and the dielectric constant / dissipation factor (D _k / D _f ) and glass transition temperature (T _g ) were determined. The glass transition temperature was determined using dynamic mechanical thermal analysis (DMTA). The test is performed using RSA III DMTA (TA instruments). DMTA has a frequency of 6.28 radians / s, an initial temperature of 30 ° C., a final temperature of 250 ° C.,
A ramp rate of 3.0 ° C./min was used.

D _k / D _f is Agilent 4991 with Agilent 16453A test equipment
Analyzed at temperature by A Impedence / Material analyzer. Calibration is performed using Agilent Teflon using D _k / D _f parameters provided by the supplier.
A standard plaque was used. The results are shown in Table V.

As can be seen in Table V, Examples 1-3 (with CE-DOP-BN) show higher glass transition temperatures than the corresponding Comparative Examples A-C (with DOP-BN), while similar D _k
And maintain the D _f value. For example, (having a _D k / _{D f} of 3.10 / 0.011) Example 1 compared to Comparative Example A (with a 3.00 / 0.011 of _D k / _{D f),} Example 2 (
3. Having a D _k / D _f of 10 / 0.009 is comparative example B (D of 3.06 / 0.009)
compared to having a _k / _{D f),} having a _D k / _{D f} of Example 3 (3.13 / 0.008)
Is compared with Comparative Example C (having a D _k / D _f of 3.02 / 0.008). The result is CE
-DOP-BN can increase the glass transition temperature, while similar D _k and D
Indicates that the _f value is maintained. Furthermore, Comparative Examples A and B show two glass transition temperatures, which is undesirable. For example, having two glass transition temperatures indicates that there is a phase separation of the cured resin such that each phase provides a separate glass transition temperature.

Comparison between Example 2 and Example 4 shows that the D _k / D _f value changes when the ratio of the raw materials changes. For example, Example 2 includes 5.0 g CE-DOP-BN and 4.3 g SMA.
While Example 4 has 3.46 g CE-DOP-BN and 4.0 g SMA40. As can be seen in Table V, Example 4 has a lower D _k / D _f than Example 2.
Indicates the value. The lower the D _k / D _f value of Example 4, the more can be attributed to CE-DOP-BN. For example, references to Example 4 and Comparative Example D both have the same amount of SMA 40, but Example 4 incorporates CE-DOP-BN, while Comparative D incorporates DOP-BN. . As can be seen in Table V, Example 4 has a lower D _k / D _f compared to Comparative Example D.
It has a value and a higher _{T g.} Therefore, the low D _k / D _f value of Example 4 is CE-D
It can be attributed to the incorporation of OP-BN. In this way, CE-DOP-BN becomes DOP
Can provide improved properties over BN.

  Examples 5-11 and Comparative Examples E-F

The molar ratio was varied in Examples 5-11 to determine the appropriate molar ratio of epoxy to styrene and maleic anhydride copolymer. For Examples 5-11, phosphorus content vs. CE
The weight ratio of the amount of -DOP-BN was fixed, but the molar ratio of the epoxy (ie epoxy group) to styrene and maleic anhydride copolymer was varied. Comparative Examples EG show curable compositions that do not contain non-halogen flame retardants.

  Examples 5-11

Some CE-DOP-BN, epoxy resin, copolymer of styrene and maleic anhydride, and solvent were mixed together according to the recipe in Table VI and shaken to form a homogeneous solution.

  Comparative Examples EG

Some DOP-BN, epoxy resin, copolymer of styrene and maleic anhydride, and solvent were mixed together according to the recipe in Table VII and shaken to form a homogeneous solution.

  Analysis of Examples 5-11 and Comparative Examples EG

According to the formulations in Table VI and Table VII, the curing catalysts were used in Examples 5-11 and Comparative Examples EG.
In addition to the curable composition, the gelation time of the curable composition was tested on a hot plate maintained at 171 ° C.

Glass transition temperature: The gelled curable composition was collected from the hot plate surface and post-cured in an oven at 200 ° C. for 3 hours to form a cured product. The glass transition temperature (T _g ) of the cured product was measured with a differential scanning calorimeter (DSC). The results are shown in Table VIII.

Prepreg: The curable compositions of Examples 5-11 and Comparative Examples EG were brushed onto a glass fiber sheet (E-glass, Hexcel 7628) and the glass fiber sheet was placed in a 177 ° C. oven with air flow. It put for 180 second and obtained the prepreg of Examples 5-11 and Comparative Examples EG. The prepreg was crushed and the prepreg powders of Examples 5 to 11 and Comparative Examples EG were collected.

Plaque test: About 3 g of the prepreg powder of Examples 5-11 and Comparative Examples EG were placed on a flat aluminum foil, and then the aluminum foil with the prepreg powder was placed on a metal plate. This assembly was heated to 200 ° C. until the prepreg powder melted. The molten prepreg powder was covered with another aluminum foil, and then a metal plate was placed on the aluminum foil. This assembly was hot pressed at 200 ° C. for 1 hour and then post-cured at 200 ° C. for an additional 3 hours. Bubble-free plaques having a thickness of 0.3 millimeters to 0.5 millimeters are obtained, the dielectric constant / dissipation factor (D _k / D _f ) and the glass transition temperature (T _g ).
It was determined. The glass transition temperature was determined using dynamic mechanical thermal analysis (DMTA). The results are shown in Table VIII.

As can be seen in Table VIII, the D _f values for Examples 5-9 and Example 11 are indicated as “0.005-6” as can be seen for Example 5. The D _f test was performed several times, and for some examples (ie, Examples 5-9 and Example 11), the D _f value changed and therefore
The changed D _f value indicated as “0.005 to 6” has a D _f value of 0.005 to 0.00.
It means that the range was up to 6. For the dielectric constant (D _k ) test, a change of 0.1 is
It can result from that test and is considered acceptable. For the dissipation factor (D _f ) test, changes less than 0.001 can result from the test and are considered acceptable.

The molar ratio of HP7200 (epoxy resin) and SMA 40 was 1.1: 1.0 (Example 5).
As changed from 2.6: 1.0 (Example 11), the D _k of the cured resin did not show a significant change (eg, a change of about 0.1, which is considered an acceptable change). ). However, as the molar ratio increased from Example 5 to Example 11 (eg, a change of 0.005, which is greater than an acceptable change), D _f increased. HP7200 and SMA4
When the molar ratio of 0 was 1.3: 1.0 (Example 6) or above, the T _g of the cured resin showed little change. Therefore, a comparison of these results shows that Example 6 and Example 7 give the best _Tg and _Dk / _Df values.

Comparative Examples E to G do not contain CE-DOP-BN. Comparing Examples 5-7 and Comparative Examples EG with the same molar ratio of HP7200 to SMA 40 (ie, Example 5 vs. Comparative Example E; Example 6 vs. Comparative Example F; Example 7 vs. Comparative Example G) Then, SMA40 content of Examples 5-7 is
Although lower than the SMA40 content of the corresponding Comparative Example f-g, Examples 5-7, respectively, than the corresponding Comparative Example E~G provide lower _{D f} value. Furthermore, Example 7 showed a higher T _g as compared with the comparative example G.

Further, a comparison between Example 7 and Example 11 shows that Example 7 and Example 11 have the same molar ratio of HP7200 to SMA EF40, but Example 7 is CE-DOP-
It shows that _Dk / _Df value becomes low, so that the quantity of BN is high. Therefore, CE-DOP-
It can be determined that BN is beneficial to the dielectric properties (D _k / D _f ).

Claims (10)

An electrical laminate structure comprising a reaction product of a curable composition comprising:
The curable composition is
Epoxy resin;
A non-halogen flame retardant; and a copolymer of styrene and maleic anhydride,
The non-halogen flame retardant is represented by the formula (I):

Represented by the compound
m is an integer from 1 to 20;
n is an integer from 0 to 20, provided that when n is 0, m is an integer from 2 to 20;
X is selected from the group consisting of sulfur, oxygen, lone pair, and combinations thereof;
Each of R ¹ and R ² is independently hydrogen, an aliphatic moiety having 1 to 20 carbon atoms, or an aromatic hydrocarbon moiety having 6 to 20 carbon atoms, wherein said aliphatic moiety and The aromatic hydrocarbon moieties can be joined to form a cyclic structure);
R ³ is hydrogen, an aliphatic moiety having 1 to 20 carbon atoms, an aromatic hydrocarbon moiety having 6 to 20 carbon atoms, R ⁴ R ⁵ P (═X) CH ₂ —, and ROCH _2. -Wherein R is an aliphatic moiety having 1 to 20 carbon atoms;
R ⁴ and R ⁵ are each independently an aliphatic moiety having 1 to 20 carbon atoms, an aromatic hydrocarbon moiety having 6 to 20 carbon atoms, wherein the aliphatic moiety and aromatic carbon The hydrogen moieties can combine to form a cyclic structure RX-), or R ⁴ and R ^{5 taken} together are Ar ² X-; and Ar ¹ and Ar ² are each An electrical laminate structure that is independently benzene, naphthalene, or biphenyl. For compounds of formula (I), X is oxygen, n is 1, m is 1, each of R ¹ and R ² is a methyl group, and R ³ is R ⁴ R ⁵ P (= X) CH ₂ —, R ⁴ and R ^{5 taken} together are Ar ² X,
Ar ² is R ⁴ R ⁵ P (═X) — wherein formula (II):

The electrical laminate structure according to claim 1, which is biphenyl as represented by the compound: For compounds of formula (I), X is oxygen, n is 0, m is 2 or 3, R ³ is R ⁴ R ⁵ P (═X) CH ₂ —, R ⁴ and R ⁵ together are Ar ² X,
Ar ² is R ⁴ R ⁵ P (═X) — wherein formula (II):

The electrical laminate structure according to claim 1, which is biphenyl as represented by the compound: The electrical laminate structure according to any one of claims 1 to 3, wherein Ar ¹ is benzene.   The epoxy group of the epoxy resin to the maleic anhydride group of the copolymer of styrene and maleic anhydride has a molar ratio in the range of 1.0: 1.0 to 2.6: 1.0. 5 to 5. The electrical laminate structure according to any one of items 1 to 4.   The epoxy group of the epoxy resin to the maleic anhydride group of the copolymer of styrene and maleic anhydride has a molar ratio in the range of 1.3: 1.0 to 1.4: 1.0. To 5. The electrical laminate structure according to any one of 5 to 5.   7. The curable composition according to any one of claims 1 to 6, wherein the curable composition has a phosphorus content in the range of 0.1 weight percent to 3.5 weight percent, based on the total weight of the curable composition. The electrical laminate structure described in 1.   8. The electrical laminate structure of any one of claims 1 to 7, wherein the copolymer of styrene and maleic anhydride has a molar ratio of styrene to maleic anhydride within the range of 1: 1 to 8: 1. .   The electrical laminate structure of any one of claims 1 to 8, wherein the non-halogen flame retardant is 1 to 90 weight percent of the total weight of the curable composition.   The electrical laminate structure of claim 9, wherein the non-halogen flame retardant is from 10 weight percent to 60 weight percent of the total weight of the curable composition.

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