KR20160036562A - Curable compositions - Google Patents

Abstract

Embodiments of the present invention include a curable composition comprising an epoxy resin and a curing agent component comprising a polymer having a first constituent unit, a second constituent unit and a third constituent unit, wherein the epoxy group to the second constituent unit The molar ratio is in the range of 0.5: 1 to 5: 1. Embodiments of the present invention include a reinforcing element and a prepreg comprising the curable composition and an electrical laminate formed of the curable composition.

Description

CURABLE COMPOSITIONS [0001]

Embodiments of the present invention are directed to a curable composition, in particular a curable composition comprising a polymer, and a method of producing the curable composition.

The curable composition is a composition comprising a thermosetting monomer that can be crosslinked. Crosslinking, also referred to as curing, converts the curable composition into a crosslinked polymer (i.e., a cured product) useful in a variety of applications, such as in the field of composites, electrical laminates and coatings. Some properties of the curable composition and crosslinked polymer that may be considered for a particular application include mechanical properties, thermal properties, electrical properties, optical properties, and processing properties among other physical properties.

For example, the glass transition temperature, dielectric constant, and dissipation factor may be properties that can be regarded as highly relevant to the curable composition used in the electro laminates. For example, having a sufficiently high glass transition temperature for an electrical laminate can be very important to ensure that the electrical laminate is effectively used in a high temperature environment. Likewise, by reducing the dielectric constant and dissipation factor of the electrical laminate, it can help separate the energized area from other areas.

In order to achieve the desired changes in glass transition temperature (T _g ), dielectric constant (D _k ) and dissipation factor (D _f ), previous approaches have added various materials to the curable composition. For example, materials have been added to the curable composition to reduce dielectric constant and dissipation factor. By adding these materials to the curable composition, the dielectric constant and dissipation factor can be reduced, which is desirable, but these materials can negatively alter other properties, such as reducing the glass transition temperature, which is undesirable.

Thus, additional materials are added to increase the glass transition temperature. For example, previous approaches have added poly (styrene-co-maleic anhydride) (SMA) to reduce D _k and D _f . However, this results in a value that is less than ideal Df and T _g, and, as a result, other materials and reduces the Df further is required to increase the T _g. Examples of these materials include cyanates. However, cyanates are expensive and can increase production costs for electrical laminates. Thus, an electric laminate of suitable price with desirable thermal and electrical properties will be advantageous.

summary

In one embodiment of the present invention, an epoxy resin; And a curing agent compound for curing with the epoxy resin, wherein the curing agent composition comprises or consist essentially of a first constituent unit having the formula:

　

　

A second constituent unit having the formula:

　

　

And a third constituent unit having the formula selected from the group consisting of:

,

, 및

,

, And

≪ / RTI >

In the formula,

m, n and r are each independently a real number representing the mole fraction of each constituent unit in the polymer, and each R is independently hydrogen, a halogen, an aromatic group or an aliphatic group, M ⁺ and M ⁺ And the molar ratio of the epoxy group to the second structural unit is in the range of 0.5: 1 to 5: 1.

Embodiments of the present invention provide curable compositions. For various embodiments, the curable compositions of the present invention have a curing agent component comprising a polymer. The curable compositions of the present invention provide a cured product having desirable thermal and electrical properties. The preferred thermal properties may include glass transition temperature and decomposition temperature, and preferred electrical properties may include dielectric constant and dissipation factor. The cured products of the curable compositions of the present invention may be useful in electrical encapsulants, composites, electrical laminates, adhesives, prepregs and / or powder coatings.

As used herein, the term "structural units" refers to the smallest structural unit (a group of atoms comprising a part of the essential structure of a macromolecule) or monomer, which is a repeating unit constituting a macromolecule such as a polymer.

As used herein, "work," "one," "the," "at least one," and "one or more" are used interchangeably. The term "and / or" means one, more than one, or all of the listed items. The description of a numerical range by an endpoint includes all numbers contained within that range (e.g., 1 to 5 include 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

For one or more embodiments, the curable compositions comprise an epoxy resin. The epoxy group is a carbon chain or a group having an oxygen atom attached directly to two adjacent or non-adjacent carbon atoms of the ring system. The epoxy resin may be selected from the group consisting of aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, and combinations thereof.

For one or more embodiments, the curable compositions comprise an aromatic epoxy resin. Examples of aromatic epoxy resins are: hydroquinone, resorcinol, bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, phenol novolak, cresol novolac, trisphenol (tris- (4- hydroxyphenyl) Methane), 1,1,2,2-tetra (4-hydroxyphenyl) ethane, tetrabromobisphenol A, 2,2-bis (4-hydroxyphenyl) But are not limited to, glycidyl ether compounds of polyphenols such as 3-hexafluoropropane, 1,6-dihydroxynaphthalene, and combinations thereof.

For one or more embodiments, the curable compositions comprise alicyclic epoxy resins. Examples of alicyclic epoxy resins include polyglycidyl ethers of polyols having at least one alicyclic ring or cyclohexene oxides obtained by epoxidizing compounds containing cyclohexene rings or cyclopentene rings with an oxidizing agent or cyclopentene But are not limited to, oxides. Some specific examples thereof include hydrogenated bisphenol A diglycidyl ether; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate; 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate; 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate; 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate; 3,4-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; ≪ / RTI > and combinations thereof.

For one or more embodiments, the curable compositions comprise an aliphatic epoxy resin. Examples of aliphatic epoxy resins include polyglycidyl ethers of aliphatic polyols or alkylene-oxide adducts thereof, polyglycidyl esters of aliphatic long chain polybasic acids, glycidyl acrylates or glycidyl methacrylates with vinyl- But are not limited to, homopolymers synthesized by polymerization, and copolymers synthesized by vinyl-polymerizing glycidyl acrylate or glycidyl methacrylate and other vinyl monomers. Some specific examples are glycidyl ethers of polyols, such as 1,4-butanediol diglycidyl ether; 1,6-hexanediol diglycidyl ether; Triglycidyl ether of glycerin; Triglycidyl ether of trimethylol propane; Tetraglycidyl ether of sorbitol; Hexaglycidyl ether of dipentaerythritol; Diglycidyl ether of polyethylene glycol; And diglycidyl ether of polypropylene glycol; Polyglycidyl ethers of polyether polyols obtained by adding one type or two or more types of alkylene oxides to aliphatic polyols such as propylene glycol, trimethylol propane, and glycerin; Diglycidyl esters of aliphatic long chain dibasic acids; ≪ / RTI > and combinations thereof.

For various embodiments, the curing agent compound is a first structural unit of formula (I) as shown below:

　

　

A second constituent unit of the formula (II) shown below:

　

　

A third constituent unit selected from the group consisting of formulas (III), (IV), and (V) as shown below:

　

　

Lt; RTI ID = 0.0 >

m, n and r are each independently a real number representing the mole fraction of each constituent unit in the polymer, and each R is independently hydrogen, a halogen, an aromatic group or an aliphatic group, Is in the range of 0.5: 1 to 5: 1. In various embodiments, each R is hydrogen. M ⁺ and M ²⁺ represent metal ions. M ⁺ has an oxidation state of +1 and M ²⁺ has an oxidation state of +2.

For various embodiments, the second constituent unit comprises from 4% to 49% by weight of the polymer. In some embodiments, the second structural unit is present in an amount ranging from 10% to 25% by weight of the polymer.

For various embodiments, the third constituent unit comprises 0.0056% to 9.3% by weight of the polymer. In some embodiments, the third building block constitutes 0.17% by weight of the polymer.

Styrene-based compounds as used herein include, unless otherwise specified, compound styrene having the formula C ₆ H ₅ CH = CH ₂ and compounds derived therefrom (e.g., styrene derivatives). The maleic anhydride, which may be referred to as cis-butenedioic anhydride, tosylic anhydride, or dihydro-2,5-dioxofuran, has the formula: C ₂ H ₂ (CO) ₂ O. In one embodiment, the first and second structural units are styrene and maleic anhydride copolymers.

The styrene and maleic anhydride copolymers discussed herein have been used in curable compositions. Commercial examples of such styrene and maleic anhydride copolymers include SMA® 1000, SMA® 2000, SMA® 3000, SMA® EF-30, SMA® EF-40, SMA® EF-60, and SMA® EF-80 But are not limited to these, all of which are available from Cray Valley.

For various embodiments, the styrene and maleic anhydride copolymers may have a weight average molecular weight of from 2,000 to 20,000; For example, the copolymer may have a weight average molecular weight of from 3,000 to 11,500. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

For various embodiments, the styrene and maleic anhydride copolymer may have a molecular weight distribution of 1.1 to 6.1; For example, the copolymer may have a molecular weight distribution of 1.2 to 4.0.

For various embodiments, the styrene and maleic anhydride copolymer may have an acid value of 100 milligrams per gram of potassium hydroxide (mg KOH / g) to 480 mg KOH / g; For example, the copolymer may have an acid value of 120 mg KOH / g to 285 mg KOH / g, or 156 mg KOH / g to 215 mg KOH / g.

In one embodiment, the polymer comprises a fourth constituent unit of formula (VI) as shown below:

　(VI),

(VI),

, ≪ / RTI >

p is a real number representing the molar fraction of the fourth constituent unit in the polymer, and Ar is an aromatic group.

For various embodiments, examples of such aromatic groups include, but are not limited to, phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl, and substituted naphthyl. In one embodiment, the aromatic group is a phenyl group.

In one embodiment, the styrene and maleic anhydride copolymer is modified to include aromatic amine compounds such as aniline. The aromatic amine compound (e.g., aniline) may be used to react with a portion of the maleic anhydride groups in the styrene and maleic anhydride copolymer. This may result in the fourth structural unit as described above present in the polymer.

The modified polymer can be obtained through a chemical reaction, for example, by reacting a styrene and maleic anhydride copolymer with an amine compound to combine the copolymer with a monomer. In addition, the polymer can be obtained by combining two or more species of monomers through chemical reactions (e.g., reaction of styrene-based compounds, maleic anhydride, and maleic acid compounds). In one embodiment, the process of modifying styrene and maleic anhydride may include imidization. In other embodiments, the styrene and maleic anhydride may be modified with an amide acid. The reacted monomers and / or copolymers form constituent units of the polymer.

For various embodiments, the mole fraction m is greater than or equal to 0.50 and the mole fraction (n + p + r) is less than or equal to 0.50, where (m + n + p + r) = 1.00. For various embodiments, the molar ratio of said first building block to said other building blocks is in the range of 1: 1 to 20: 1. In one embodiment, the molar ratio of the first structural unit to the second structural unit is in the range of from 3: 1 to 6: 1. The molar ratio of r / (n + p + r) is in the range of 0.001 to 0.1. In one embodiment, the molar ratio of r / (n + p + r) is 0.007.

For various embodiments, the second constituent unit comprises from 5% to 40% by weight of the polymer. In some embodiments, the second constituent unit comprises 10% to 20% by weight of the polymer.

For various embodiments, the third building block constitutes from 0.03% to 5% by weight of the polymer. In some embodiments, the third building block constitutes 0.37% by weight of the polymer.

For various embodiments, the fourth constituent unit comprises from 8% to 9% by weight of the polymer.

For various embodiments, the curable compositions of the present invention have a molar ratio of epoxy groups of the polymer to the second structural units in the range of 0.5: 1 to 5: 1; 1.0 to 2.7: 1.0 in other embodiments, 0.7: 1.0 to 2.7: 1.0 in another embodiment, 0.9: 1.0 to 1.9: 1.0 in yet another embodiment, and the molar ratio of the epoxy group to the second constituent unit And in other embodiments within the range of 1.0: 1.0 to 1.7: 1.0.

For various embodiments, the curable composition may comprise a solvent. The solvent may be selected from the group consisting of methyl ethyl ketone (MEK), toluene, xylene, 4-methyl-2-pentanone, N, N-dimethylformamide (DMF), propylene glycol methyl ether (PM), cyclohexanone, Acetate (DOWANOL (TM) PMA), and mixtures thereof. For various embodiments, the solvent may be used in an amount of from 30% to 60% by weight, based on the total weight of the curable composition.

For various embodiments, the curable composition may comprise a catalyst. Examples of the catalyst include 2-methylimidazole (2MI), 2-phenylimidazole (2PI), 2-ethyl-4-methylimidazole (2E4MI), 1-benzyl- But are not limited to, boric acid, triphenylphosphine (TPP), tetraphenylphosphonium-tetraphenylborate (TPP-k), and combinations thereof. For various embodiments, the catalyst (10 wt% solution) may be used in an amount of 0.01 wt% to 2.0 wt%, based on the weight of the solid component in the curable composition.

For various embodiments, the curable compositions may include a co-curing agent. The phenolicizing agent may be reactive with the epoxide of the epoxy compounds. The tackifier may be selected from the group consisting of novolaks, amines, anhydrides, carboxylic acids, phenols, thiols, and combinations thereof. For various embodiments, the curing agent may be used in an amount of from 1% to 90% by weight, based on the weight of the polymer.

For one or more embodiments, the curable composition comprises an additive. The additives may be selected from the group consisting of dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, flow modifier drip retarders, flame retardants, anti-blocking agents, release agents, toughening agents, ≪ / RTI > water. The additive may be used in an effective amount for a particular use as understood by those of ordinary skill in the art. For different uses, the effective amount may have a different value. The curable compositions of the present invention do not contain a cyanate group.

The flame retardant may be an additive to the curable composition as described above. Examples of flame retardants include, but are not limited to, halogenated and non-halogenated flame retardants, including brominated and non-brominated flame retardants. Specific examples of brominated additives include tetrabromobisphenol A (TBBA) and materials derived therefrom: TBBA-diglycidyl ether, bisphenol A or the reaction product of TBBA and TBBA-diglycidyl ether, and bisphenol A diglycidyl ether Lt; / RTI > ether and TBBA.

The non-brominated flame retardant is DOP (9,10-dihydro-9-oxa-10-phosphapenanthrene 10-oxide), such as DOP-hydroquinone (10- (2 ', 5'-dihydroxy Phenyl) -9,10-dihydro-9-oxa-10-phosphapenanthrene 10-oxide), condensation products of DOP with glycidyl ether derivatives of novolak and inorganic flame retardants such as aluminum trihydrate , Aluminum hydroxide (boehmite) and aluminum phosphinite. When an inorganic flame retardant filler is used, a silane treated grade is preferred.

For one or more embodiments, the curable composition may have a gel time of from 200 seconds (s) to 400 seconds at 171 DEG C, including all individual values and / or subranges therein; For example, the curable composition may have a gel time of from 205 s to 395 s at 171 캜, or from 210 s to 390 s at 171 캜.

The gel time can represent the reactivity (e.g., at a specific temperature) of the curable compositions and can be expressed in seconds up to the gel point. Gel point refers to the point of initial polymer network formation where the structure is substantially branched such that each unit of network is essentially connected to each other unit of the network. When the curable composition reaches the gel point, the remaining solvent is trapped by the substantially branched structure. When the trapped solvent reaches its boiling point, bubbles can form in the structure (e.g., a prepreg resulting in an undesirable product).

For one or more embodiments, as discussed herein, the curable composition has a gel time of from 200 to 400 seconds at 171 < 0 > C. In some cases, the curable composition having a gel time of greater than 400 seconds at 171 DEG C is used to adjust the gel time from 200 seconds to 400 seconds at 171 DEG C, from 200 seconds to 375 seconds at 171 DEG C, or from 200 seconds to 350 seconds at 171 DEG C For example, by adding catalysts and / or additives as discussed herein. For some applications, curable compositions having a gel time of less than 200 seconds at < RTI ID = 0.0 > 171 C < / RTI > can be regarded as being too reactive relative to the equipment throughput rate.

Embodiments of the present invention provide a prepreg comprising a reinforcing element and a curable composition as discussed herein. The prepreg can be obtained by a process comprising impregnating the matrix component into the reinforcing element. The matrix component surrounds / surrounds or supports the reinforcing element. The curable compositions disclosed can be used for matrix components. The matrix component and the reinforcing element of the prepreg provide a synergistic effect. This synergism defines that the product obtained by curing the prepreg and / or the prepreg has mechanical and / or physical properties that are not obtainable with the individual components alone.

The reinforcing element may 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 fibers may be coated. Examples of fibrous coating materials include, but are not limited to, boron.

Examples of glass fibers include, but are not limited to, A-glass fiber, E-glass fiber, C-glass fiber, R-glass fiber, S-glass fiber, T-glass fiber and combinations thereof. An aramid is an organic polymer, examples of which include, but are not limited to, Kevlar (R), Twaron (R), 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. Examples of biomass fibers include, but are not limited to, fibers formed from wood, non-wood, and combinations thereof.

The reinforcing element may be a fabric. The fabric may be formed from fibers as discussed herein. Examples of fabrics include, but are not limited to, stitched fabrics, woven fabrics, and combinations thereof. The fabric may be unidirectional, multiaxial, and combinations thereof. The reinforcing element may be a combination of the fibers and the fabric.

The prepreg can be obtained by impregnating the matrix component into the reinforcing element. The step of impregnating the matrix component into the reinforcing element may be performed by various processes. The prepreg can be formed by contacting the matrix element with the reinforcing element through rolling, dipping, spraying, or other such procedures. After the prepreg reinforcing element contacts the prepreg matrix component, the solvent may be removed by volatilization. During and / or after the solvent is volatilized, the prepreg matrix component can be cured and, for example, can be partially cured. Such volatilization and / or partial cure of the solvent may be referred to as B-staging. The product of the B-stage may be referred to as a prepreg.

For some applications, B-staging may occur through exposure to a temperature of 60 ° C to 250 ° C; For example, B-staging may occur through exposure to a temperature of 65 ° C to 240 ° C, or 70 ° C to 230 ° C. For some applications, B-staging may occur for a period of one minute (min) to 60 minutes; For example, B-staging may occur for a period of 2 to 50 minutes, or 5 to 40 minutes. However, for some applications the B-staging may occur at different temperatures and / or at different times.

One or more of the prepregs can be cured (e.g., more fully cured) to obtain a cured product. The prepreg may be laminated before it is further cured and / or may be formed into a single shape. For some applications (e.g., when an electrical laminate is being produced), the layers of the prepreg can be alternated with layers of conductive material. Examples of the conductive material include, but are not limited to, copper foil. The prepreg layers may then be exposed to conditions that allow the matrix component to be more fully cured.

One example of a process for obtaining a more fully cured product is pressurization. One or more prepregs can be placed into a press in which it is subjected to a curing force for a predetermined curing time period to obtain a more fully cured product. The press may have a curing temperature of 80 ° C to 250 ° C; For example, the press may have a curing temperature of from 85 캜 to 240 캜, or from 90 캜 to 230 캜. For one or more embodiments, the press has a curing temperature that ramps from a lower cure temperature to a higher cure temperature over a lamp time period.

During said pressing, said one or more prepregs may be subjected to a curing force through said press. The curing force may have a value from 10 kilopascals (kPa) to 350 kPa; For example, the curing force may have a value of 20 kPa to 300 kPa, or 30 kPa to 275 kPa. The predetermined curing time period may have a value of from 5 s to 500 s; For example, the predetermined curing time period may have a value of 25 s to 540 s, or 45 s to 520 s. Other curing temperatures, curing force values, and / or predetermined curing time periods are possible for other processes to obtain the cured product. Additionally, the process may be repeated to further cure the prepreg and to obtain the cured product.

For various embodiments, the cured products formed from the curable compositions of the present invention as discussed herein may have a glass transition temperature of at least 150 < 0 > C.

For various embodiments, the cured products formed from the curable compositions of the present invention as discussed herein may have a thermal decomposition temperature of from 300 DEG C to 500 DEG C; For example, the thermal decomposition temperature may be 359 캜 to 372 캜, or 363 캜 to 368 캜.

For various embodiments, the cured products formed from the curable compositions of the present invention as discussed herein may have a dielectric constant of less than 3.1 at 1 GHz; For example, at 1 GHz the dielectric constant may be 2.9 to 3.0, or 2.8 to 2.9.

For various embodiments, the cured products formed from the curable compositions of the present invention as discussed herein can have a dissipation factor of less than 0.01 at 1 GHz; For example, at 1 GHz, the dissipation factor may be 0.003 to 0.01, or 0.004 to 0.007.

Example

material

SMA® EF30 (SMA 30), SMA® EF40 (SMA 40), and SMA® EF60 (SMA 60), (styrene compound-maleic anhydride copolymer) are available from Cray Valley. SMA 30 has a molar ratio of styrene to maleic anhydride of 3: 1, a weight average molecular weight of 9,500, a number average molecular weight of 3,800, and an acid value of 280 mg KOH / mg. SMA 40 has a molar ratio of styrene to maleic anhydride of 4: 1, a weight average molecular weight of 10,500, a number average molecular weight of 4,500, and an acid value of 215 mg KOH / mg. SMA 60 has a molar ratio of styrene to maleic anhydride of 6: 1, a weight average molecular weight of 11,500, a number average molecular weight of 5,500, and an acid value of 156 mg KOH / mg.

Aniline (amine compound), (greater than 99.0% purity), available from Sigma Aldrich.

Acetic anhydride (analytical grade), available from Sigma Aldrich.

Sodium acetic acid (analytical grade), available from Sinopharm Chemical Company.

Sodium hydroxide (analytical grade), available from Sinopharm Chemical Company.

Sodium carbonate (analytical grade), available from Sinopharm Chemical Company.

Lithium hydroxide (analytical grade), available from Sinopharm Chemical Company.

Potassium hydroxide (analytical grade), available from Sinopharm Chemical Company.

Acetate zinc (analytical grade), available from Sinopharm Chemical Company.

Xylene (solvent), (analytical grade), available from Sinopharm Chemical Company.

Methyl ethyl ketone (solvent), (analytical grade), available from Sinopharm Chemical Company.

2-methylimidazole (catalyst), (analytical grade), available from Sinopharm Chemical Company.

D.E.R. ™ 560 (epoxy resin), available from Dow Chemical Company.

D.E.N. ™ 438 (epoxy novolak resin), Dow Chemical Company.

Tetrabromobisphenol A (greater than 99.0% purity), available from Albemarle.

Aniline-modified SMA polymers were prepared according to the following methods:

Method I (a): In a solution of MEK Reformed SMA

128.28 g of SMA 40 solution (40% in MEK) was loaded into a 250 mL 3-necked flask. The flask was equipped with a magnetic stirrer, a silicone oil bath, a condenser, a nitrogen inlet, and a thermal couple used to monitor the oil bath temperature. The flask was then charged with nitrogen and the flow was kept steady during the reaction.

The heating temperature was set at 80 占 폚. 2.32 g of aniline was then added dropwise via a dropping funnel over a period of 4 minutes. The temperature was maintained at 80 DEG C for 30 minutes.

Then 3.06 g of Ac ₂ O and 6.14 g of NaOAc were added successively to the flask. The heating temperature was set at 90 [deg.] C for 3 hours to maintain gentle reflux. Then, the heating was stopped and the reaction mixture was cooled to room temperature. The excess NaOAc was then removed via vacuum filtration. The filter cake was then washed with a small amount of MEK and all filtrates were combined. The solids content of the filtrate was then tested.

I (b): In toluene solution Reformed SMA

The same procedure was followed as in Method I (a) except that toluene was used as the solvent and refluxed for 6 hours to complete the reaction.

I (c): Sodium acetate  In a toluene solution Reformed SMA

128.30 g of SMA 40 solution (40% in toluene) was loaded into a 250 mL 3-necked flask. The flask was equipped with a magnetic stirrer, a silicone oil bath, a condenser, a nitrogen inlet, and a thermal couple used to monitor the oil bath temperature. The flask was then charged with nitrogen to maintain a steady-state flow during the reaction.

The heating temperature was set at 80 占 폚. 2.33 g of aniline was then added dropwise via a dropping funnel over a period of 1 minute. The solution was heated at 80 < 0 > C for 1 hour. Then, 3.07 g of Ac ₂ O was added to the flask. The heating temperature was set at 120 [deg.] C for 1 hour to maintain gentle reflux. The reaction mixture was then cooled to room temperature. The solids content of the product solution was then tested.

Method II (a): To a solution of Reformed SMA

205.32 g of SMA 40 and 205.23 g of xylene were continuously charged into a 500 mL four-necked flask. The flask was equipped with a magnetic stirrer, a heating mantle, a condenser, a nitrogen inlet, and a thermal couple used to monitor the temperature of the reaction mixture. The flask was then filled with nitrogen and cooling water. During the reaction, the flow was maintained at a steady state and at an appropriate rate.

The heating temperature was set at 135 占 폚 to accelerate the dissolution of SMA40. After a clear solution was formed, the temperature was reduced to 80 占 폚. When the temperature reached 80 占 폚, 9.31 g of aniline was added dropwise via a dropping funnel into the flask within 8 minutes. The flask was then heated at 80 DEG C for 45 minutes.

NaOH aqueous solution (0.168 g of NaOH solids dissolved in 0.58 g of water) was then added dropwise to the flask. The flask was then equipped with a Dean-Stark apparatus. The heating temperature was set at 142 占 폚 to make xylene reflux. Reflux was maintained for 4 hours and water byproducts were separated. The reaction mixture was then cooled to room temperature and the solids content of the product solution tested.

II (b): Any Metal ion additive also  In absent xylene solution Reformed SMA

The procedure of Method II (a) was followed except that azeotropic distillation was maintained for 10 hours without adding any metal ion additive.

The modified SMA polymer synthesized through the above procedures had a maleic anhydride content of 14%.

Varnish  Formulation

Appropriate amounts of SMA polymer, D.E.R.M. 560 and sodium hydroxide were dissolved in MEK. 2-Methyl imidazole was dissolved in methanol to form a 10 wt% solution and finally added. The final wt% of the non-volatile organic material was approximately 50 wt%. The properties of the three formulations and the cured epoxy system are shown in Table 1.

Example 1 of the present invention Comparative Example A Comparative Example B SMA 60 (g) 8.88 8.88 0 SMA 30 (g) 5.01 5.01 10.01 D.E.R.M. 560 (g) 10 10 9.99 NaOH (mg) 6.9 0 0 2-MI (mg) 8.5 7.0 4.0 Gelation time (s) 269 298 297 Curing temperature and time 200 < 0 > C for 1.5 hours,
220 ° C 1.5 hours 200 < 0 > C for 1.5 hours,
220 ° C 1.5 hours 200 < 0 > C for 1.5 hours,
220 ° C 1.5 hours T _g (° C, DSC) 191 145 175 T _g (° C, DMA) 198 163 NA T _d (° C) 358 353 358 D _k (1 GHz) 2.87 2.90 3.00 D _f (1 GHz) 0.0042 0.0049 0.0092

From the results in Table 1, the composition of Comparative Example A has a lower Df than Comparative Example B using only SMA 30. However, the advantage for Df was obtained at the expense of a reduction in T _g . This drawback was improved by the addition of NaOH (500 ppm relative to the weight of SMA). As shown in Example 1 of the present invention, the T _g was raised above 190 ° C while maintaining the same level of D _f

The aniline-modified SMA polymer was used in the thermosetting epoxy composition as a curing agent. Typical varnish formulations are listed in Table 2.

Varnish formulation Solid weight (g) D.E.R. ™ 560 41 D.E.N ™ 438 3 The modified SMA 40 56 2-methylimidazole 0.02

Tables 3 and 4 below show that small amounts of metal ions (ppm levels) can have a significant effect on increasing the T _g of the formulation.

Example 2 3 Comparative Example C 4 5 6 7 Manufacturing method I (a) I (b) I (c) I (c) I (c) I (c) I (c) T _g (° C, DSC) 197 193 140 186 199 182 171 Metal ion additive NaOAc NaOAc none NaOAc NaOAc KCl Zn (OAc) ₂ Metal ion content (ppm.
Varnish resin solid basis) 238 57 ~ 0 56 280 1000 1000

For Examples 2 and 3, metal ions remained from the reaction. In Examples 4 to 7, metal ions were added directly into the varnish.

Examples 2 and 3 showed that the cured resins had a high T _g (> 190 ° C), a T _g much higher than that of conventional FR4 formulations. The different solvents did not have a significant effect on T _g . Comparative Example C showed that if the metal ion was not present in the formulation, the T _g of the cured resin was only 140 ° C. When more sodium salt was added to the varnish, a cured product with higher T _g resulted (as shown in Examples 4 and 5). Examples 6 and 7 showed that the potassium and zinc ions also can increase the T _g by the varnish in a particular load. These results indicated that a significant increase in T _g (30-60 ° C) was observed regardless of where the metal ion originated from the synthesis reaction or from further addition.

Example 8 9 10 Comparative Example D Manufacturing method II (a) II (a) II (a) II (b) T _g (DSC, ° C) 193 191 193 144 Metal ion additive NaOH Na ₂ CO ₃ LiOH none Metal ion content (ppm.
Varnish resin solid basis) 203 224 68 ~ 0

In Examples 8-10, metal ions remained from the reaction.

Comparative Example D showed that if there were no metal ions in the formulation, the T _g was only 144 ° C. When sodium or lithium ions were present in the formulation, the T _g was increased above 190 ° C (Examples 8-10). According to the results of Tables 3 and 4, both methods I and II can produce the preferred modified SMA polymer capable of generating a very high T _g in the cured epoxy resin.

Laminate data

Formulation The
Example 11 The
Example 12 Comparative Example E
(From Megtron 4, Panasonic TDS) ingredient D.E.R. ™ 560 41 36 D.E.N ™ 438 3 6 TBBA 0 4 Modified SMA 56 ^a 54 ^b Filler (megacil 525) 25 0 2-methylimidazole 0.01 0.01 Laminate Evaluation Glass fabric 8 ply @ 7628 8 ply @ 2116 8 ply @ 3313 D _k (1 GHz) 4.05 3.75 3.80 D _f (1 GHz) 0.005 0.006 0.005 T _g (° C, DSC) 192 187 176 T _d (° C, 5 wt% loss) 359 359 360 T288 (min, no clad) 34 > 60 NA Thickness (mm, no clad) 1.61 0.95 0.80 CPS (1 Oz Cu, lb / in) 5.6 6.0 6.9 Water absorption rate (PCT, 2 hours) 0.17% 0.38% 0.14% Solder dip (10s @ 288 ℃, 5 cycles) Passed 100% Passed 100% NA UL-94 rating V-0 V-0 V-0

Note: a) prepared by Method I (b); b) Prepared by Method II (a)

The laminate properties were evaluated based on the formulations listed in Table 5. Megtron 4 of Panasonic, a poly (phenylene ether) compound, was selected as Comparative Example E. Examples 11 and 12 of the present invention exhibited excellent dielectric and thermal performance. The T _g was higher than that of Comparative Example E by at least 10 ° C. The _Dk and _Df values were low enough to meet industrial requirements and were similar to those of Comparative Example E. Other performances, such as T _d , T288, copper peel strength and water absorption, were comparable to those of Comparative Example E.

Test Methods

Gelling  Time test

The resin formulations were evaluated for their gelling time through stroke hardening on a hot plate at 171 캜.

Glass transition temperature ( T _g )

The glass transition temperature was measured by differential scanning calorimetry (DSC) using a Q2000 machine from TA Instruments. Typically, thermal scans range from room temperature to 250 ° C and a heating rate of 10 ° C / min is used. From the second cycle, two heating cycles with curves used for T _g determination by the "mid-inflection point" method were performed.

Alternatively, the glass transition temperature was measured from the tangent delta peak on the RSA III dynamic mechanical thermal analyzer (DMTA). The samples were heated from 20 ° C to 250 ° C at a heating rate of 3 ° C / min. The test frequency was 6.28 rad / s.

Thermal decomposition temperature (T _d )

The cured resin was evaluated on a TA Instruments Q50 machine. The heating rate was 10 ° C / min. T _d is defined as the temperature at 5 wt% loss.

At 288 ° C To peeling  Time (T288)

The time (T288) from 288 ° C to peeling was measured using a thermal mechanical analyzer, TA Instruments Q400. The time to peeling was measured as the elapsed time from when the temperature reached 288 ° C until a sudden significant dimensional change (~ 100 mm) occurred.

Dielectric constant ( D _k ) / Dissipation Factor ( D _f )

Epoxy plaques were used for dielectric measurements. The prepreg powder was placed on a flat aluminum foil, and then the aluminum foil with the powder was placed on a flat metal plate. The assembly was heated to 200 DEG C until the epoxy powder melted. The molten powder was covered with another aluminum foil and then a flat metal plate was placed on the aluminum foil. The assembly was pressurized at 200 < 0 > C for 1 hour and post-cured for 3 hours at 220 < 0 > C. A bubble free epoxy plaque having a thickness of 0.5 to 0.8 mm was obtained.

Laminate samples were used directly for dielectric measurements.

Dielectric constants and dissipation factors were measured by an Agilent E4991A RF Impedance / Material Analyzer equipped with Agilent 16453A test fixture under 1 GHz at 24 ° C in accordance with ASTM D-150.

Copper Peel Strength (CPS)

The copper peel strength was measured using an IMASS SP-2000 slip / peel tester equipped with a variable angle peel fixture capable of maintaining a preferred 90 ° peel angle throughout the test. For copper etching, a 2 "x4" copper clad laminate was cut. Two strips of ¼ "graphite tape were placed longitudinally along the specimen on two opposing sides of the laminate with at least a half space between them. The laminate pieces were then placed in a KeyPro benchtop etcher. Once the samples were removed from the etcher and properly dried, the graphite tape was removed to reveal the copper strip. A razor blade was used to pull up one-half of each copper strip. The laminate was then loaded onto an IMASS tester. The copper strip was clamped and the copper peel test was performed at a pull angle of 2.8 in / min at a 90 angle.

Press Cooking  Test (PCT)

The copper-clad laminate was cut into 4 pieces 2 inches by 3 inches in size. Samples were precisely weighed and then placed in an autoclave (Thermo Electron Corp. 8000-DSE). The samples were treated for 2 hours at 121 ° C water vapor. The surface water was wiped and the samples were accurately weighed again to calculate the average water uptake.

Solder  Dip (Solder dip)

After PCT, the laminate samples were immersed in a solder bath for 5 cycles (10 seconds per cycle) at 288 ° C. The blisters on the sample indicated that the sample failed to pass the test. Results were reported by counting passed samples among the total samples tested.

UL94 Flammability Test

Each of the five specimens (13 cm x 12 mm) was ignited twice in a standard UL94 test chamber (Atlas UL94 Chamber VW-1) for 10 seconds. The time from self-extinguishing to self-extinguishing was recorded as burning time. The UL94 VO rating requires a burn time of less than 10 seconds for each ignition and a total burn time of less than 50 seconds for ten ignitions.

Claims (18)

As the curable composition,
Epoxy resin; And
A curing agent compound for curing with the epoxy resin,
Wherein the curing agent compound is a first constituent unit having the formula:

A second constituent unit having the formula:

And
A third constituent unit having a formula selected from the group consisting of the following formulas:

,

, And

≪ / RTI > wherein the curable composition comprises a polymer.
In the formula,
m, n, and r are independently a real number (real number) represents the mole fraction of each constitutional unit in the polymer, each R is independently a hydrogen, a halogen, an aromatic group or an aliphatic group respectively, M ⁺ and M ^{2 +} Is a metal ion, and the molar ratio of the epoxy group to the second constituent unit is in the range of 0.5: 1 to 5: 1. The method according to claim 1,
A fourth constituent unit having the formula:

≪ / RTI >
In the formula,
p is a real number representing the molar fraction of the fourth constituent unit in the polymer, and Ar is an aromatic group. The curable composition of claim 1, wherein at least a portion of the second structural unit is converted to an imide or amide acid by treatment with an amine-containing compound. The curable composition according to any one of claims 1 to 3, wherein the third constituent unit constitutes from 0.005% to 10% by weight of the polymer. The curable composition according to any one of claims 1 to 4, wherein the ratio of r / (n + r) or r / (n + p + r) is in the range of 0.001 to 0.1. The curable composition according to any one of claims 1 to 5, further comprising a flame retardant. The curable composition according to any one of claims 1 to 6, wherein the first constituent unit is styrene. The curable composition according to any one of claims 1 to 7, wherein the second constituent unit is maleic anhydride. The curable composition according to any one of claims 1 to 8, wherein the metal ion is selected from the group consisting of sodium, potassium, lithium, and zinc. The method according to any one of claims 1 to 9, wherein the metal ion is selected from the group consisting of sodium hydroxide, sodium carbonate, sodium acetate, zinc acetate, lithium hydroxide, potassium carbonate, potassium chloride, , A curable composition. The curable composition according to any one of claims 1 to 10, wherein the cured product of the curable composition has a glass transition temperature of at least 150 ° C. The curable composition according to any one of claims 1 to 11, wherein the molar ratio of the first constituent unit to the second constituent unit is in the range of 1: 1 to 20: 1. The curable composition according to any one of claims 1 to 12, wherein the second constituent unit comprises from 0.1% to 49% by weight of the polymer. The curable composition according to any one of claims 1 to 13, wherein the epoxy resin is selected from the group consisting of aromatic epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, and combinations thereof. 15. A prepreg comprising the reinforcing element and the curable composition of any one of claims 1 to 14. An electro laminate structure comprising the reaction product of the curable composition of any one of claims 1 to 14. A method for producing a curable composition,
Providing an epoxy resin; And
And reacting the epoxy resin with a curing agent compound,
Wherein the curing agent compound is a first constituent unit having the formula:

A second constituent unit having the formula:

And
A third constituent unit having a formula selected from the group consisting of the following formulas:

,

, And

≪ / RTI > wherein the polymer comprises a polymer.
In the formula,
m, n, and r are independently a real number (real number) represents the mole fraction of each constitutional unit in the polymer, each R is independently a hydrogen, a halogen, an aromatic group or an aliphatic group respectively, M ⁺ and M ^{2 +} Is a metal ion, and the molar ratio of the epoxy group to the second constituent unit is in the range of 0.5: 1 to 5: 1. 18. The method of claim 17,
Wherein the curing agent compound is a fourth constituent unit having the formula:

≪ / RTI >
In the formula,
p is a real number representing the mole fraction of the fourth constituent unit in the polymer, and Ar is an aromatic group.