KR102499841B1 - Thermosetting resin composition and cured product of the same - Google Patents

Abstract

The present invention uses a maleimide-reactive furan-based novolak resin to form a cured structure uniformly distributed in both bismaleimide and epoxy resin, and has a thermosetting property capable of realizing high heat resistance and excellent flame retardancy without halogen-based or phosphorus-based structures. A resin composition and a cured product thereof are provided.

Description

Thermosetting resin composition and cured product thereof {THERMOSETTING RESIN COMPOSITION AND CURED PRODUCT OF THE SAME}

The present invention relates to a thermosetting resin composition comprising a maleimide-reactive furan-based novolak resin and a cured product thereof.

Recently, in the field of electronic devices, there is an increasing demand for materials that exhibit excellent mechanical properties while having optical properties, and further have various morphological properties.

In particular, as the demand for high heat resistance and low dielectric materials increases with the recent growth of the 5G market, high heat resistance such as bismaleimide (BMI) is used in the epoxy system used in the existing copper clad laminate (CCL) application field. A composition into which the material is introduced is being utilized. However, in the case of such bismaleimide, compatibility with the epoxy curing system is not good, and a high temperature curing temperature of 250 ° C or higher is required to realize complete curing properties, so that the maximum performance cannot be expressed in a general CCL curing system of 200 ° C or lower. Allylated BPA, Amino Triazine Novolac (ATN), etc. are being developed to solve this problem, but a high temperature of 200 ℃ or more is still required during curing to realize the entire physical properties of BMI. Therefore, it is necessary to develop a new concept CCL curing agent that has good compatibility with bismaleimide and can be cured at 200 ° C or lower.

On the other hand, due to such low compatibility and high-temperature curing characteristics, the cured product of the existing resin system into which BMI was introduced has a structure in which an epoxy-curing agent cured product and a BMI self-cured product are mixed, and a cured structure in which the epoxy resin and BMI are uniform cannot form. Due to this, there is a possibility of raising a problem with reliability due to problems such as microgelation during curing or double Tg of the cured product.

Therefore, when manufacturing a high heat resistance and low dielectric material, there is a further need to develop a resin composition and a CCL curing system that forms a curing structure in which bismaleimide and epoxy are uniformly distributed and improves curing properties and reliability.

An object of the present invention is to provide a thermosetting resin composition containing a maleimide-reactive furan-based novolak resin and a cured product thereof.

According to one embodiment of the invention, one or more epoxy resins are included,

In addition to the epoxy resin, at least one novolac resin represented by Formula 1 below; and at least one bismaleimide represented by the following formula (2), or a cycloaddition reaction product of the novolak resin and the bismaleimide,

A thermosetting resin composition is provided.

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently hydrogen, hydroxy, a substituted or unsubstituted C1 to C30 alkyl, or a substituted or unsubstituted C6 to C60 aryl group,

a and b are each independently an integer from 0 to 4;

n is an integer between 1 and 10;

[Formula 2]

In Formula 2,

R ₃ is a divalent organic group derived from a hydrocarbon having 1 to 40 carbon atoms.

In addition, the present invention may increase the curing efficiency by further including a thermosetting catalyst, a solvent, a radical initiator, or a mixture thereof in the thermosetting resin.

In addition, the present invention provides a method for producing the thermosetting resin composition described above.

In addition, the present invention provides a cured product of the thermosetting resin composition described above.

In addition, the present invention is a substrate; and a resin layer disposed on one side or both sides of the substrate, wherein the resin layer is formed from the thermosetting resin composition as described above.

According to the present invention, a resin composition capable of curing bismaleimide-curing agent-epoxy and a curing system applying the same can be provided.

In the present invention, terms such as first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.

In addition, terms used in this specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as "comprise", "comprise" or "having" are intended to indicate that there is an embodied feature, number, step, component, or combination thereof, but one or more other features or It should be understood that the presence or addition of numbers, steps, components, or combinations thereof is not precluded.

As used throughout this specification, the terms "about," "substantially," and the like are used at or approximating that value when manufacturing and material tolerances inherent in the stated meaning are given, and do not convey the understanding of this application. Accurate or absolute figures are used to help prevent exploitation by unscrupulous infringers of the disclosed disclosure.

In addition, the term "step of (doing) ..." or "step of ..." as used throughout the specification does not mean "step for ...".

In addition, in the present specification, (meth)acrylate is meant to include both acrylate and methacrylate.

Also, in the present invention, (co)polymer is meant to include both homo-polymer and co-polymer.

Unless otherwise defined herein, “copolymerization” may mean block copolymerization, random copolymerization, graft copolymerization, or alternating copolymerization, and “copolymer” means block copolymer, random copolymer, graft copolymer, or alternating copolymer. can mean synthesis.

In this specification, the term "combination of these" included in the expression of the Markush form means a mixture or combination of one or more selected from the group consisting of the components described in the expression of the Markush form, It means including one or more selected from the group consisting of.

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

means a bond connected to another substituent.

Unless otherwise defined, "substitution" in the present specification, at least one hydrogen of the compound is C _1-30 Alkyl; C _2-30 alkenyl, C _2-30 alkynyl, C _1-10 alkylsilyl; C _3-30 cycloalkyl; C _6-30 aryl; C _6-30 alkylaryl; C _6-30 arylalkyl; C _5-30 heteroaryl; C _1-10 alkoxy; silane; alkylsilane; alkoxysilane; hydroxy; amine; alkylamines; arylamine; It means substituted with an ethyleneoxyl or halogen group.

In the present specification, "hetero" means an atom selected from the group consisting of N, O, S, and P, unless otherwise defined.

In the present specification, unless otherwise defined, "alkyl" is a "saturated alkyl group" that does not contain any alkenyl or alkynyl; or "unsaturated alkyl" containing at least one alkenyl or alkynyl. "Alkenyl" means a substituent in which at least two carbon atoms form at least one carbon-carbon double bond, and "alkyne" means a substituent in which at least two carbon atoms form at least one carbon-carbon triple bond. do.

The alkyl may be straight chain or branched chain alkyl. Specifically, the C _1-30 alkyl is C _1-30 straight chain alkyl; C _1-20 straight chain alkyl; C _1-10 straight chain alkyl; C _1-5 straight chain alkyl; C _3-30 branched chain alkyl; C _3-20 branched chain alkyl; C _3-15 branched chain alkyl; or C _3-10 branched chain alkyl. In addition, the alkyl may be C _1-6 lower alkyl, C _7-10 intermediate alkyl, or C _11-30 higher alkyl. More specifically, C _1-30 alkyl is methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, or iso-pentyl group, etc. There is, but is not limited to. Meanwhile, in the present specification, "iPr" means an iso-propyl group.

For example, C _1-4 alkyl means that there are 1 to 4 carbon atoms in the alkyl chain, which is methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t-butyl. Indicates that it is selected from the group consisting of.

In the present specification, "cycloalkyl" may be cyclic alkyl, and specifically, the C _3-20 cycloalkyl is C _3-20 cyclic alkyl; C _3-15 cyclic alkyl; or C _3-10 cyclic alkyl. More specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto. Meanwhile, "Cy" in the present specification means a cycloalkyl having 3 to 6 carbon atoms.

As used herein, “alkenyl” may be straight-chain, branched-chain, or cyclic alkenyl. Specifically, the C _2-20 alkenyl is C _2-20 straight-chain alkenyl, C _2-10 straight-chain alkenyl, C _2-5 straight-chain alkenyl, C _3-20 branched-chain alkenyl, C _3-15 branched-chain alkenyl, C _3-10 branched chain alkenyl, C _5-20 cyclic alkenyl or C _5-10 cyclic alkenyl. More specifically, C _2-20 alkenyl may be ethenyl, propenyl, butenyl, pentenyl or cyclohexenyl and the like.

As used herein, "alkoxy" is a functional group in which the above-described alkyl is bonded to an oxy group, that is, an oxygen atom, and specifically includes methoxy, ethoxy, isopropoxy, n-butoxy, tert-butoxy, phenyloxy, and cyclohexyl. A siloxy group etc. are mentioned.

In this specification, "aromatic group" means a substituent in which all elements of a cyclic substituent have p-orbitals, and these p-orbitals form conjugation. Specific examples include aryl and heteroaryl.

As used herein, "aryl" includes a single ring or a fused ring, that is, a plurality of ring substituents that divide adjacent pairs of carbon atoms. In one example, the aryl includes a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. According to one embodiment of the present invention, the aryl is C _6-60 aryl; C _6-40 aryl; C _6-30 aryl; C _6-20 aryl; C _6-18 aryl; Or it may be C _6-12 aryl, specifically phenyl, naphthyl, anthracenyl, dimethylanilinyl, anisolyl, etc., but is not limited thereto.

In the present specification, “heteroaryl” refers to an aryl substituent including a heteroatom selected from the group consisting of N, O, S, and P in the aryl substituent. When the heteroaryl substituent is a fused ring, each ring may contain 1 to 3 hetero atoms.

Also, “halogen” in the present specification may be fluoro (F), chloro (Cl), bromo (Br) or iodo (I).

Meanwhile, in the present specification, "hydrocarbyl group" means a monovalent hydrocarbon compound, and includes alkyl, alkenyl, alkynyl, aryl, aralkyl group, aralkenyl, aralkynyl, alkylaryl, alkenylaryl and alkynylaryl; and the like. As an example, hydrocarbyl can be straight chain, branched chain or cyclic alkyl. More specifically, the hydrocarbyl group having 1 to 40 carbon atoms is methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, cyclo straight-chain, branched-chain or cyclic alkyl such as hexyl; or an aryl group such as phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, or fluorenyl. It may also be an alkyl aryl such as methylphenyl, ethylphenyl, methylbiphenyl, or methylnaphthyl, or an arylalkyl such as phenylmethyl, phenylethyl, biphenylmethyl, or naphthylmethyl. It may also be alkenyl such as allyl, ethenyl, propenyl, butenyl, and pentenyl.

In this specification, "hydrocarbylene group" means a divalent hydrocarbon compound, and includes alkylene, alkenylene, alkynylene, arylene, aralkylene, aralkenylene, aralkynylene, alkyl arylene, alkenylarylene and alkynylarylene; and the like. As an example, hydrocarbylene can be a straight-chain, branched-chain or cyclic alkylene. More specifically, hydrocarbylene having 1 to 40 carbon atoms is methylene, ethylene, n-propylene, iso-propylene, n-butylene, iso-butylene, tert-butylene, n-pentylene, n-hexylene, straight-chain, branched-chain or cyclic alkylene such as n-heptylene and cyclohexylene; or arylene such as phenylene, biphenylene, naphthylene, anthracenylene, phenanthrenylene, or fluorenylene. In addition, it may be an alkylarylene such as methylphenylene, ethylphenylene, methylbiphenylene, or methylnaphthylene, or an arylalkylene such as phenylmethylene, phenylethylene, biphenylmethylene, or naphthylmethylene.

Unless otherwise defined herein, “copolymerization” may mean block copolymerization, random copolymerization, graft copolymerization, or alternating copolymerization, and “copolymer” means block copolymer, random copolymer, graft copolymer, or alternating copolymer. can mean synthesis.

In addition, in this specification, when each layer or element is referred to as being formed “on” or “on” each layer or element, it means that each layer or element is formed directly on each layer or element, This means that another layer or element may be additionally formed on the object or substrate between each layer.

Since the present invention can have various changes and various forms, specific embodiments will be exemplified and described in detail below. However, it should be understood that this is not intended to limit the present invention to the specific disclosed form, and includes all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

Based on the above definition, embodiments of the present invention will be described in detail. However, these are presented as examples, and thereby the present invention is not limited and the present invention is only defined by the scope of the claims to be described later.

As a result of continuous experiments by the present inventors, a cured structure uniformly distributed in both bismaleimide and epoxy resin is formed using a furan-based novolak resin having a specific structure, and high heat resistance and excellent flame retardancy without halogen-based or phosphorus-based structures It was confirmed that a thermosetting resin composition and a cured product thereof capable of implementing a can be provided and the invention was completed.

Hereinafter, the present invention will be described in more detail.

Thermosetting resin composition

According to one embodiment of the present invention, a thermosetting resin composition comprising at least one furan-based novolak resin having maleimide reactivity, at least one bismaleimide, and at least one epoxy resin is provided.

Specifically, the thermosetting resin composition includes at least one epoxy resin, and together with the epoxy resin, at least one novolak resin represented by the following formula (1), and at least one bismaleimide represented by the following formula (2) contains or; or a cycloaddition reaction product of the novolak resin and the bismaleimide.

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently hydrogen, hydroxy, substituted or unsubstituted C _1-30 alkyl, or substituted or unsubstituted C _6-60 aryl;

a and b are each independently an integer from 0 to 4;

n is an integer between 1 and 10;

[Formula 2]

In Formula 2,

R ₃ is a divalent organic group derived from a hydrocarbon having 1 to 40 carbon atoms.

In particular, as shown in Chemical Formula 1, the novolak resin contains a phenol ring together with a furan ring, so that it is possible to bond with maleimide in bismaleimide through a cycloaddition reaction, and at the same time, it is possible to reduce the hydroxyl of the phenol ring. Through this, it has the characteristic that curing reaction with epoxy resin is possible. In particular, when the range of n is greater than 10, an excessively large structure is formed during the cycloaddition reaction, so that a non-uniform cured product may be formed due to the microgelation reaction.

As an example, the cycloaddition reaction between the novolak ring and bismaleimide may include a Diels-Alder reaction (hereinafter referred to as DA reaction).

For example, in Formula 1, R ₁ and R ₂ are each hydrogen, hydroxy, or methyl, or o-Cresol, phenol, 2,6-xylenol (2,6- Xylenol), catechol, resorcinol, bisphenol A, bisphenol F, or a substituent derived from furfuryl alcohol. Preferably, R ₁ and R ₂ may each be hydroxy, or methyl, or a substituent derived from o-Cresol, or 2,6-Xylenol. .

Specifically, R ₁ and R ₂ in Formula 1 may each be hydrogen, hydroxy, methyl, or phenyl, wherein methyl or phenyl is further hydroxy, methyl, ethyl, propyl, butyl, pentyl, hexyl, or may be further substituted with one or more of the phenyl.

Meanwhile, the thermosetting resin composition according to one embodiment of the present invention may secure excellent heat resistance by introducing the bismaleimide of Chemical Formula 2.

For example, in the bismaleimide, in Chemical Formula 2, R ₃ may include any one of the following divalent organic groups:

.

.

Preferably, R ₃ may include any one of the following divalent organic groups:

.

.

The novolac resin of Chemical Formula 1 and the bismaleimide of Chemical Formula 2 may be used as a single compound, or may be thermally polymerized before mixing with an epoxy resin to be used as a cycloaddition reaction product.

In addition, the cycloaddition reaction product of the novolak resin of Chemical Formula 1 and the bismaleimide of Chemical Formula 2 may be further subjected to thermal polymerization to produce an irreversible polycyclic structure compound, which may be mixed with an epoxy resin.

Meanwhile, the thermosetting resin composition according to one embodiment of the present invention includes an epoxy resin together with the novolak resin and bismaleimide.

Specifically, the epoxy resin may be represented by Formula 3 below.

[Formula 3]

In Formula 3,

R ₄ is substituted or unsubstituted C _1-30 alkyl or substituted or unsubstituted C _6-60 aryl.

Specifically, in Chemical Formula 3, the substituent R ₄ is a substituent derived from the epoxy resin, and is preferably a novolac skeleton-containing epoxy resin or a dicyclopentadiene skeleton-containing epoxy resin. epoxy resins, bisphenol skeleton-containing epoxy resins, diphenyl alkylene skeleton-containing epoxy resins, triazine skeleton-containing epoxy resins, fluorene-based epoxies fluorene skeleton-containing epoxy resins, triphenol alkylene skeleton-containing epoxy resins, biphenyl skeleton-containing epoxy resins, xylene skeleton-containing epoxy resins. resins), biphenyl aralkyl skeleton-containing epoxy resins, naphthalene skeleton-containing epoxy resins, alicyclic skeleton-containing epoxy resins, or pura It may be a substituent derived from furanyl skeleton-containing epoxy resins.

For example, in Formula 3, R ₄ is substituted or unsubstituted C _1-20 alkyl, C _1-15 alkyl, C _1-12 alkyl, or C _1-6 alkyl, or substituted or unsubstituted C 1-15 alkyl. _6-40 aryl, or C _6-30 aryl, or C _6-24 aryl, or C _6-20 aryl, or C _6-18 aryl, or substituted or unsubstituted C _3-40 heteroaryl, or C _{3 -30} heteroaryl, or C _3-20 heteroaryl, or C _3-15 heteroaryl, or C _3-12 heteroaryl. Preferably, in Formula 4, R ₄ may be phenyl, biphenyl, diphenylethyl, triazinyl, fluorenyl, triphenol methyl, xylenyl, naphthyl, cyclohexyl, or furanyl.

For example, the epoxy resin may include novolac skeleton-containing epoxy resins, dicyclopentadiene skeleton-containing epoxy resins, and bisphenol skeleton-containing epoxy resins. , diphenyl alkylene skeleton-containing epoxy resins, triazine skeleton-containing epoxy resins, fluorene skeleton-containing epoxy resins, triphenol alkylene-based epoxy resins (triphenol alkylene skeleton-containing epoxy resins), biphenyl skeleton-containing epoxy resins, xylene skeleton-containing epoxy resins, biphenyl aralkyl skeleton-containing epoxy resins epoxy resins, naphthalene skeleton-containing epoxy resins, alicyclic skeleton-containing epoxy resins, and furanyl skeleton-containing epoxy resins It may be one or more species.

Specifically, the epoxy resin is novolac epoxy resin, dicyclopentadiene epoxy resin (DCPD epoxy resin, dicyclopentadiene epoxy resin), bisphenol epoxy resin, diphenylethylene epoxy resin ( diphenylethylene epoxy resin, triazine epoxy resin, dimethyl fluorene epoxy resin, diphenyl fluorene epoxy resin, triphenol methane epoxy resin ), biphenyl epoxy resin, xylylene epoxy resin, biphenyl phenyl methyl epoxy resin, naphthyl epoxy resin, 3,4- It may be at least one selected from the group consisting of epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate resin and furanyl epoxy resin. . Preferably, the epoxy resin may be novolac epoxy resin or bisphenol epoxy resin.

In one embodiment, the novolak resin of Formula 1 is in an amount of 50 to 200 mol% based on 100 mol% of the epoxy equivalent of the above-mentioned epoxy resin, and the bismaleimide of Formula 2 is the novolac resin In an amount of 50 to 200 mol% based on 100 mol% of the hydroxyl equivalent of the epoxy resin, the epoxy resin may be used in an amount of 50 to 200 mol% based on 100 mol% of the hydroxyl equivalent of the novolac resin. .

Meanwhile, in the present specification, equivalent (eq.) means molar equivalent.

As described above, the cured product thermally cured from the blended composition forms a cured structure in which the novolak resin is uniformly distributed in both the bismaleimide and the epoxy resin, and has high heat resistance without halogen-based and phosphorus-based structures. And it can be implemented with a material having excellent flame retardancy.

Although detailed evaluation methods for each physical property will be described later, when the mixing of the novolak resin and the bismaleimide and the epoxy resin is specifically controlled within the above range, the cured product can realize various physical properties.

For example, when the novolak resin, bismaleimide, and epoxy resin are blended at 1 wt% to 40 wt%, respectively, based on the mixing ratio, the cured product can be implemented as an excellent material that balances heat resistance and adhesiveness. At this time, the total of the novolak resin, bismaleimide, and epoxy resin does not exceed 100% by weight. As the mixing ratio of bismaleimide increases, thermal characteristics are excellent but adhesiveness may rather decrease, and as the mixing ratio of epoxy resin increases, adhesiveness is excellent but thermal characteristics may decrease.

Specifically, the novolak resin may be included in an amount of 1% to 40% by weight based on the total weight of the thermosetting resin composition, preferably 5% by weight or more, or 8% by weight or more, or 10% by weight or more, or 15 wt% or more, or 18 wt% or more, or 20 wt% or more, and 38 wt% or less, or 35 wt% or less, or 32 wt% or less, or 30 wt% or less, or 29 wt% or less, or 25 wt% or less % or less.

In addition, the bismaleimide may be included in an amount of 1% to 40% by weight based on the total weight of the thermosetting resin composition, preferably 2% by weight or more, or 2.5% by weight or more, or 3% by weight or more, or 3.5% by weight or more 30% or less, or 25% or less, or 20% or less, or 15% or less, or 13% or less, or 11% or less, by weight % or more, or 3.8% or more, or 4% or more, by weight may be below.

Meanwhile, when the cycloaddition reaction product of the novolak resin and the bismaleimide is used, the above-described mixing ratio may be used as a standard.

Preferably, the cycloaddition reaction product of the novolac resin and the bismaleimide may be included in an amount of 5% to 50% by weight based on the total weight of the thermosetting resin composition, more preferably 6% by weight or more, or 8% or more, or 10% or more, or 12% or more, or 15% or more, or 18% or more, or 20% or more, or 24% or more, and up to 45%, or 42 or less than or equal to 40%, or less than or equal to 38%, or less than or equal to 35%, or less than or equal to 32%, or less than or equal to 30% by weight.

In addition, the epoxy resin may be included in an amount of 1% to 40% by weight based on the total weight of the thermosetting resin composition, preferably 5% by weight or more, or 8% by weight or more, or 10% by weight or more, or 12% by weight or more. % or more, or 14 wt% or more, or 15 wt% or more, and may be 39 wt% or less, or 38 wt% or less, or 37 wt% or less, or 36 wt% or less, or 35 wt% or less.

For reference, in the present specification, "part by weight" means a relative concept expressed as a ratio of the weight of the remaining material based on the weight of a certain material. For example, in a mixture in which the weight of substance A is 50 g, the weight of substance B is 20 g, and the weight of substance C is 30 g, the amounts of substance B and substance C based on 100 parts by weight of substance A are 40, respectively. parts by weight and 60 parts by weight.

On the other hand, "% by weight" means an absolute concept expressed as a percentage of the weight of the weight of a certain material out of the total weight. In the above example mixture, the contents of substance A, substance B, and substance C are 50% by weight, 20% by weight, and 30% by weight, respectively, based on 100% of the total weight of the mixture.

In the thermosetting resin composition of the present invention, the epoxy resin may be included in a molar ratio of 0.7 to 1.3, preferably 0.8 to 1.2, based on the molar content of hydroxyl groups contained in the novolac resin.

Meanwhile, the thermosetting resin composition may further include a thermosetting catalyst, a radical initiator, a solvent, or a mixture thereof generally known in the art.

For example, the thermal curing catalyst may be any one selected from the group consisting of an imidazole compound, a phosphine compound, a phosphonium salt, and a tertiary amine, or a mixture of two or more thereof.

The thermosetting catalyst may be used in an amount of 0.1 part by weight or less or 0.0001 to 0.1 part by weight based on 100 parts by weight of the epoxy resin, preferably 0.08 part by weight or less, or 0.06 part by weight or less, or 0.05 part by weight or less, Alternatively, 0.045 parts by weight or less, or 0.035 parts by weight or less may be used. In addition, for the catalysis, the thermosetting catalyst may be used in an amount of 0.001 parts by weight or more, or 0.0015 parts by weight or more, or 0.002 parts by weight or more, or 0.0025 parts by weight or more, or 0.0028 parts by weight or more.

In addition, the thermosetting resin composition may further include a radical initiator. In this case, the radical initiator may be any one selected from the group including an azo-based compound and a peroxide-based compound, or a mixture of two or more of them.

The radical initiator may be used in an amount of 1.0 parts by weight or less or 0 to 1.0 parts by weight based on 100 parts by weight of the epoxy resin, preferably 0.8 parts by weight or less, 0.6 parts by weight or less, or 0.5 parts by weight or less, or 0.48 parts by weight or less. It can be used in parts by weight or less, or 0.45 parts by weight or less, or 0.4 parts by weight or less. In addition, the radical initiator may be used in an amount of 0.01 parts by weight or more, or 0.02 parts by weight or more, or 0.05 parts by weight or more, or 0.08 parts by weight or more, or 0.1 parts by weight or more, or 0.12 parts by weight or more, or 0.15 parts by weight or more. .

For example, the solvent may be any one selected from the group consisting of ketone-based solvents, acetate-based solvents, carbitol-based solvents, aromatic hydrocarbon-based solvents, and amide-based solvents, or a mixture of two or more thereof.

Examples of the ketone-based solvent include methyl ethyl ketone and cyclohexanone. Examples of the acetate-based solvent include ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl ether acetate. Examples of the carbitol-based solvent include methyl cellosolve, butyl carbitol, etc., examples of the aromatic hydrocarbon-based solvent include toluene, xylene, etc., examples of the amide-based solvent include dimethyl formamide, dimethyl acetamide, N-methylphy Rolidone, etc.

Specifically, the solvent in the thermosetting resin composition may be included in a residual amount excluding the novolac resin, bismaleimide, epoxy resin, thermosetting catalyst, radical initiator, and the like. That is, the total amount of novolak resin, bismaleimide, epoxy resin, thermosetting catalyst, radical initiator, etc., and solvent does not exceed 100% by weight. For example, the solvent may be included in 10% to 85% by weight based on the total weight of the thermosetting resin composition, preferably 15% by weight or more, or 18% by weight or more, or 20% by weight or more, or 25% by weight or more % or more, or more than 28%, or more than 33%, but less than or equal to 70%, or less than or equal to 68%, or less than or equal to 65%, or less than or equal to 60%, or less than or equal to 58%, or less than or equal to 56% by weight can

Meanwhile, the thermosetting resin composition is a reaction between at least one epoxy resin, at least one novolak resin represented by Formula 1, and at least one bismaleimide represented by Formula 2, or a reaction with one or more epoxy resins It may contain the resin obtained by the reaction of the above-mentioned novolac resin and the cycloaddition reaction product of the said bismaleimide.

For example, the thermosetting resin composition may include a resin including a repeating unit represented by Chemical Formula 4 below.

[Formula 4]

In Formula 4,

R ₁ and R ₂ are each independently hydrogen, hydroxy, substituted or unsubstituted C _1-30 alkyl, or substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _3-60 heteroaryl; ,

a and b are each independently an integer from 0 to 4;

R ₃ is a divalent organic group derived from a hydrocarbon having 1 to 40 carbon atoms;

R ₄ is substituted or unsubstituted C _1-30 alkyl or substituted or unsubstituted C _6-60 aryl;

n is an integer between 1 and 10;

n' is an integer between 1 and 9;

m is an integer from 1 to 10;

In Formula 4, the substituents R ₁ , R ₂ , R ₃ , R ₄ , a, b, and n are as described above in relation to Formulas 1, 2, and 3, and thus further descriptions are omitted. do.

Method for producing thermosetting resin composition

In another embodiment of the invention, a step of preparing a furan-based novolak resin having maleimide reactivity by reacting a phenolic compound with a furan-based compound, and at least one novolac resin, at least one bismaleimide, and A method for producing a thermosetting resin composition comprising the step of obtaining a thermosetting resin composition by mixing at least one epoxy resin is provided.

In one embodiment, the method for preparing the thermosetting resin composition comprises the steps of reacting at least one phenolic compound represented by Formula A with furfural to produce a novolac resin represented by Formula 1 below; and

A step of mixing at least one kind of novolak resin thus produced, at least one kind of bismaleimide represented by the following formula (2), and at least one kind of epoxy resin.

[Formula A]

In Formula A,

R is independently hydrogen, hydroxy, substituted or unsubstituted C1 to C30 alkyl, or substituted or unsubstituted C6 to C60 aryl group,

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently hydrogen, hydroxy, substituted or unsubstituted C _1-30 alkyl, or substituted or unsubstituted C _6-60 aryl;

a and b are each independently an integer from 0 to 4;

n is an integer between 1 and 10;

[Formula 2]

In Formula 2,

R ₃ is a divalent organic group derived from a hydrocarbon having 1 to 40 carbon atoms.

In another embodiment, the method for preparing the thermosetting resin composition comprises the steps of reacting at least one phenolic compound represented by Formula A with furfural to produce a novolac resin represented by Formula 1 below;

reacting at least one novolak resin thus produced with at least one bismaleimide represented by the following formula (2) at 100° C. or lower to produce a cycloaddition product of the novolac resin and the bismaleimide; and

and mixing the novolak resin thus produced, the cycloaddition reaction product of the bismaleimide, and at least one epoxy resin.

[Formula A]

In Formula A,

each R is independently hydrogen, hydroxy, substituted or unsubstituted C _1-30 alkyl, or substituted or unsubstituted C _6-60 aryl;

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently hydrogen, hydroxy, substituted or unsubstituted C _1-30 alkyl, or substituted or unsubstituted C _6-60 aryl;

a and b are each independently an integer from 0 to 4;

n is an integer between 1 and 10;

[Formula 2]

In Formula 2,

R ₃ is a divalent organic group derived from a hydrocarbon having 1 to 40 carbon atoms.

In the step of preparing the maleimide-reactive furan-based novolak resin, the phenol-based compound reacting with the furan-based compound is specifically o-cresol, phenol, 2,6-xyle It may be at least one selected from the group consisting of 2,6-xylenol, catechol, resorcinol, bisphenol A, and bisphenol F. Preferably, the phenolic compound may be o-cresol, phenol, 2,6-xylenol, and catechol.

In addition, in the step of preparing the furan-based novolak resin having maleimide reactivity, the furfural is present in a molar ratio (furfural: phenolic compound) of 0.1:1 to 2.0:1 based on the total amount of the phenolic compound. It can be reacted, preferably, it can be reacted in a molar ratio of 0.5: 1 to 2.0: 1.

Meanwhile, descriptions of the novolak resin of Chemical Formula 1, the bismaleimide of Chemical Formula 2, and the epoxy resin produced by reacting the phenolic compound with furfural are omitted as described above.

On the other hand, no special method is required for the step of mixing the novolak resin, bismaleimide, and epoxy resin. That is, by simply mixing the novolak resin, bismaleimide, and an epoxy resin, a resin composition that can be produced as a cured product by thermal curing can be obtained.

However, the novolac resin of Chemical Formula 1 and the bismaleimide of Chemical Formula 2 may be used as a single compound or may be used as a cycloaddition reaction product by performing a Diels-Alder reaction before mixing with an epoxy resin.

The Diels-Alder reaction process is performed at 100 °C or less or 15 °C to 100 °C. Preferably, the Diels-Alder reaction process may be carried out at 98 ° C or less, or 95 ° C or less, or 90 ° C or less, or 85 ° C or less, or 80 ° C or less, and in terms of improving reaction efficiency, 20 ° C. or more, or 25 °C or higher, or 30 °C or higher, or 35 °C or higher, or 40 °C or higher.

In addition, the cycloaddition reaction product of the novolak resin of Chemical Formula 1 and the bismaleimide of Chemical Formula 2 may generate an irreversible polycyclic structure compound through an additional chain polymerization reaction. At this time, the chain polymerization reaction may be further accelerated by adding a radical initiator. Preferably, a peroxide-based radical initiator such as benzoyl peroxide (BPO) or dicumyl peroxide (DCP) may be added.

Meanwhile, depending on the characteristics of the desired cured product, the mixing ratio of the novolak resin, bismaleimide, and epoxy resin may be varied, and the mixing ratio is as described above.

For example, in the thermosetting resin composition of the present invention, the novolak resin of Formula 1 is prepared by the method shown in Scheme 1 below, and at least one novolac resin and at least one bismaleimide represented by Formula 2 are prepared, and It can be prepared by mixing one or more types of epoxy resins. The preparation method may be more specific in synthesis examples and examples to be described later.

[Scheme 1]

In Reaction Scheme 1, R is as defined in Formula A above, and R ₁ , R ₂ , a, b, and n are as defined in Formula 1 above.

Specifically, in Reaction Scheme 1, at least one phenolic compound represented by Chemical Formula A is reacted with furfural to prepare a novolac resin represented by Chemical Formula 1, and one kind of novolak resin thus produced It can be prepared by mixing at least one bismaleimide represented by the following formula (2) and at least one epoxy resin. By using it together with the novolac resin represented by Formula 1, in the thermosetting resin composition of the present invention, bismaleimide, a highly heat-resistant material, is uniformly distributed in the epoxy curing system, and even if the curing temperature is lowered to less than 250 ° C. Perfect curing properties can be realized.

As another example, the thermosetting resin composition of the present invention generates a novolak resin of Formula 1 by the method shown in Scheme 2 below, and reacts it with bismaleimide represented by Formula 2 to prepare a cycloaddition reaction, The cycloaddition reactant may be prepared by mixing one or more epoxy resins. The preparation method may be more specific in synthesis examples and examples to be described later.

[Scheme 2]

STEP 1

STEP 2

In Reaction Scheme 2, R is as defined in Formula A above, R ₁ , R ₂ , a, b, n are as defined in Formula 1 above, and R ₃ is as defined in Formula 2 above. , and n' is an integer between 1 and 9.

Specifically, in Reaction Scheme 2, at least one phenolic compound represented by Chemical Formula A is reacted with furfural to prepare a novolac resin represented by Chemical Formula 1 (Step 1), and the resulting furnace It can be prepared by reacting the rockfish resin with the bismaleimide represented by Formula 2 to prepare a cycloaddition reactant (Step 2), and mixing the thus produced cycloaddition reactant with at least one epoxy resin. In this way, by using the cycloaddition reaction product of the novolak resin of Chemical Formula 1 and the bismaleimide of Chemical Formula 2, the thermosetting resin composition of the present invention provides uniformity of bismaleimide, a highly heat-resistant material, in an epoxy curing system. Even if the curing temperature is lowered to less than 250 ° C.

Cured products and materials containing them

In still other embodiments of the invention, a cured product of the above-described thermosetting resin composition and a material including the same are provided. The above-described thermosetting resin composition may be thermally cured by a thermal curing method and conditions generally known in the art, and the thermally cured product may be implemented with various materials.

In particular, the thermosetting composition of the present invention includes at least one epoxy resin, a novolac resin of Formula 1 and a bismaleimide of Formula 2 as a single compound, or as a cycloaddition reaction product thereof. , Bismaleimide, a highly heat-resistant material, can be uniformly distributed in the epoxy curing system.

For example, the thermosetting resin composition of the present invention is obtained by mixing a novolac resin of Formula 1, a bismaleimide of Formula 2, and at least one epoxy resin in the same manner as in Scheme 3 below, and performing a thermal curing reaction, A thermal curing product can be prepared. The preparation method may be more specific in synthesis examples and examples to be described later.

[Scheme 3]

In Reaction Scheme 3, R ₁ , R ₂ , a, b, n are as defined in Formula 1 above, R ₃ are as defined in Formula 2 above, and R ₄ are as defined in Formula 3 above. The same, m' is an integer between 1 and 10, n' is an integer between 1 and 9.

As another example, the thermosetting resin composition of the present invention is obtained by mixing a novolac resin of Formula 1 and a cycloaddition reaction product of bismaleimide of Formula 2 with one or more epoxy resins in the same manner as in Scheme 4 below, followed by a thermal curing reaction By performing, it is possible to prepare a thermally cured product. The preparation method may be more specific in synthesis examples and examples to be described later.

[Scheme 4]

In Reaction Scheme 4, R ₁ , R ₂ , a, b, n are as defined in Formula 1 above, R ₃ are as defined in Formula 2 above, and R ₄ are as defined in Formula 3 above. The same, m' is an integer between 1 and 10, n' is an integer between 1 and 9.

In particular, as shown in Reaction Schemes 3 and 4, another feature of the curing reaction of the resin composition according to the present invention is that the cycloaddition reaction product of novolak resin and bismaleimide, which is a product of the Diels-Alder reaction, which is a reversible reaction, is generated If possible, the cycloaddition reactant is stabilized by carrying out and fixing the ene reaction through thermal polymerization at 120 ° C or higher. In addition, after mixing the cycloaddition reactant, which is a product of the Diels-Alder reaction, with an epoxy resin, through thermal polymerization, not only the ene reaction between the cycloaddition reactants but also the curing reaction may proceed together. Through this reaction, it is possible to improve the uniformity of the cured product in the curing reaction, and further prevent phase separation between the remaining raw material and the cured product during the curing process. For example, in Schemes 3 and 4, peroxide-based radical initiators such as benzoyl peroxide (BPO) and dicumyl peroxide (DCP) are added to the composition in order to effectively implement a thermal polymerization reaction with epoxy. can be introduced

In addition, in the thermal curing process of Schemes 3 and 4, bismaleimide, which is a highly heat-resistant material, is improved, and even when the curing temperature is lowered to less than 250 ° C. Specifically, the thermal curing process may be performed at a temperature of 100 °C to 220 °C. Preferably, the thermal curing process temperature is 120 °C or higher, or 135 °C or higher, or 150 °C or higher, or 165 °C or higher, or 180 °C or higher, and 210 °C or lower, or 205 °C or lower, or 200 °C or lower, or 195 °C or lower, or 190 °C or lower.

In addition, the thermal curing process may be performed in the above-described temperature range for about 1 hour to about 10 hours, about 1.5 hours to about 8 hours, or about 2 hours to about 6 hours.

On the other hand, as described above, the cured product of the thermosetting resin composition described above may have various physical properties depending on the mixing ratio of the raw materials.

In particular, the curing density of the thermosetting resin composition of the present invention increases according to the dual curing characteristics, and it is possible to realize a low coefficient of thermal expansion (CTE).

In addition, as shown in Schemes 3 and 4 above, a polycyclic structure is stably formed through continuous curing, so that the uniformity and adhesiveness of the cured product can be improved.

As an example, the present invention provides a cured epoxy resin material formed from the thermosetting resin composition described above.

Specifically, the cured epoxy resin material may be formed in a fully cured state or a semi-cured state of the thermosetting resin composition, depending on a desired use or function. Description of the thermosetting resin composition is omitted as described above.

In some cases, the cured epoxy resin material may be in the form of a prepreg formed by drying glass fibers impregnated with the thermosetting resin composition.

Laminate

In another embodiment of the present invention, a laminate to which the thermosetting resin composition is applied is provided.

Specifically, a substrate; and a resin layer disposed on one side or both sides of the substrate, wherein the resin layer is formed from the thermosetting resin composition described above.

The resin layer may be formed by curing or semi-curing the thermosetting resin composition according to a desired use or function. Description of the thermosetting resin composition is omitted as described above.

Meanwhile, the substrate may be any one substrate selected from the group consisting of a semiconductor substrate, a copper foil, and an insulating plate. For example, as in the embodiments and evaluation examples described later, the laminate may be implemented as CCL (Copper Clad Laminate) using a copper plate as the substrate. However, this is only an example, and one embodiment of the present invention is not limited by this example.

Manufacturing method of laminated board

In another embodiment of the present invention, impregnating the glass fiber with the composition; drying the glass fibers impregnated with the composition to obtain a prepreg; It provides a method for manufacturing a laminated plate comprising: laminating the prepreg on a substrate and then compressing the prepreg to obtain a laminated board.

This is one of several methods of manufacturing the aforementioned laminated board. It is possible to use only one sheet of the prepreg, and it is also possible to manufacture and use several sheets.

In addition, it is also possible to use only one sheet of the substrate, and it is also possible to use several sheets. In the case of using multiple substrates, the step of laminating the prepreg on the substrate and then compressing the prepreg to obtain a laminated board; may include placing the prepreg between two different substrates and then compressing the prepreg.

Regardless of the number of the prepregs and the laminated plates, in the step of laminating the prepregs on a substrate and then compressing them to obtain a laminated plate, the pressing pressure, temperature, time, etc. may be according to what is generally known in the art. there is.

Hereinafter, a preferred embodiment is presented to aid understanding of the present invention. However, the following examples are only provided to more easily understand the present invention, and the content of the present invention is not limited thereby.

<Synthesis of novolac resin>

Synthesis Example 1: Furan-based novolak resin synthesis (OCFN small molecule)

300 g of ortho-Cresol, 18 g of 50% NaOH aqueous solution, and 21 g of purified water (PW) were put in a flask equipped with a stirrer and a cooler, and the mixture was dissolved by raising the temperature to 95 °C. 133.3 g of furfural was added dropwise over 2 hours at 95°C. It was made to react further for 4 hours after completion|finish of dripping. Immediately after the reaction was completed, the resin was dissolved with 1225 g of methyl isobutyl ketone, and then neutralized to pH 7.0 by adding 150 g of purified water and phosphoric acid. After neutralization, the solvent was recovered to synthesize low-molecular-weight OCFN (O-Cresol Furanyl Novolac, Mn/Mw: 590/733) having a hydroxy equivalent weight (OHEW) of 174 g/eq and a softening point of 77.4 °C of Formula 1a below.

[Formula 1a]

In Formula 1a, n1 is 3.4.

In addition, the low molecular weight OCFN resin obtained according to Synthesis Example 1 was dissolved in tetrahydrofuran (THF, Tetrahydrofuran) at 2.5 wt%, and GPC instrumental analysis (Shimadzu, Gel Permeation Chromatography Systems; Shodex, KF-801, 802, 803, 805 Columns ) was done. The analysis temperature was 40 ^o C and the mobile phase was Tetrahydrofuran (HPLC grade) flowed at 1 mL/min. Through the GPC data measured in this way, it was confirmed that the furan-based novolak resin according to Synthesis Example 1 had a weight average molecular weight (Mw) of 733 g/mol, and the average repeating unit of the novolak resin was 3.4 (n1 = 3.4). .

Synthesis Example 2: Synthesis of furan-based novolac resin (OCFN medium molecule)

300 g of o-Cresol, 18 g of 50% NaOH aqueous solution, and 21 g of purified water were added to a flask equipped with a stirrer and a cooler, and the mixture was heated up to 95 °C to dissolve. At 95 ° C., 156.8 g of Furfural was added dropwise over 2 hours. It was made to react further for 4 hours after completion|finish of dripping. Immediately after the reaction was completed, the resin was dissolved with 1225 g of methyl isobutyl ketone, and then neutralized to pH 7.0 by adding 150 g of purified water and phosphoric acid. After neutralization, the solvent was recovered to synthesize a medium molecule OCFN (Mn/Mw: 741/971) having 160.1 g/eq of OHEW and a softening point of 102.4 °C of Formula 1b below.

[Formula 1b]

In Chemical Formula 1b, n2 is 4.6.

In addition, the low molecular weight OCFN resin obtained according to Synthesis Example 2 was dissolved in THF at 2.5 wt% and subjected to GPC instrumental analysis (Shimadzu, Gel Permeation Chromatography Systems; Shodex, KF-801, 802, 803, 805 Columns). The analysis temperature was 40 ^o C and the mobile phase was Tetrahydrofuran (HPLC grade) flowed at 1 mL/min. Through the GPC data measured in this way, it was confirmed that the furan-based novolak resin according to Synthesis Example 3 had a weight average molecular weight (Mw) of 971 g/mol, and the average repeating unit of the novolac resin was 4.6 (n2 = 4.6). .

Synthesis Example 3: Synthesis of furan-based novolac resin (OCFN polymer)

300 g of o-Cresol, 18 g of 50% NaOH aqueous solution, and 21 g of purified water were added to a flask equipped with a stirrer and a cooler, and the mixture was dissolved by raising the temperature to 95 °C. 222.2 g of Furfural was added dropwise over 2 hours at 95 °C. After completion of the dropwise addition, the temperature was raised to 115° C., followed by further reaction for 4 hours. Immediately after the reaction was completed, the resin was dissolved with 1225 g of methyl isobutyl ketone, and then neutralized to pH 7.0 by adding 150 g of purified water and phosphoric acid. After neutralization, the solvent was recovered to synthesize OCFN (Mn/Mw: 1095/1627, about 0.673), a polymer having 279.6 g/eq of OHEW and a softening point of 125 °C of Formula 1c.

[Formula 1c]

In Chemical Formula 1c, n3 is 8.2.

In addition, the low molecular weight OCFN resin obtained according to Synthesis Example 3 was dissolved in THF at 2.5 wt% and subjected to GPC instrumental analysis (Shimadzu, Gel Permeation Chromatography Systems; Shodex, KF-801, 802, 803, 805 Columns). The analysis temperature was 40 ^o C and the mobile phase was Tetrahydrofuran (HPLC grade) flowed at 1 mL/min.

Through the GPC data measured in this way, it was confirmed that the furan-based novolac resin according to Synthesis Example 3 had a weight average molecular weight (Mw) of 1627 g/mol, and the average repeating unit of the novolak resin was 8.2 (n3 = 8.2).

Synthesis Example 4: Synthesis of furan-based novolak resin (XYFN)

244.3 g of 2,6-xylenol, 13.6 g of 50% NaOH aqueous solution, and 16 g of purified water were added to a flask equipped with a stirrer and a cooler, and the mixture was heated to 95 °C to dissolve. 96.1 g of Furfural was added dropwise over 2 hours at 95 °C. After completion of the dropwise addition, the temperature was raised to 115° C. and further reacted for 4 hours. Immediately after the reaction was completed, the resin was dissolved with 1225 g of methyl isobutyl ketone, and then neutralized to pH 7.0 by adding 150 g of purified water and phosphoric acid. After neutralization, the solvent was recovered to synthesize XYFN (Xylenol Furanyl Novolac) of Formula 1d below.

[Formula 1d]

In Chemical Formula 1d, n4 is 1.6.

In addition, the XYFN resin obtained according to Synthesis Example 4 was dissolved in THF at 2.5 wt% and subjected to GPC instrumental analysis (Shimadzu, Gel Permeation Chromatography Systems; Shodex, KF-801, 802, 803, 805 Columns). The analysis temperature was 40 ^o C and the mobile phase was Tetrahydrofuran (HPLC grade) flowed at 1 mL/min.

Through the GPC data measured in this way, it was confirmed that the furan-based novolac resin according to Synthesis Example 4 had a weight average molecular weight (Mw) of 447 g/mol, and the average repeating unit of the novolak resin was 1.6 (n4 = 1.6).

Synthesis Example 5: Furan-based novolak resin synthesis (BPAFN)

282.3 g of Bisphenol A, 15.2 g of 50% NaOH aqueous solution, 20 g of purified water, and 846.9 g of n-Butanol were added to a flask equipped with a stirrer and a cooler, and the mixture was dissolved by heating to 95 °C. 96.1 g of Furfural was added dropwise over 2 hours at 95 °C. After completion of the dropwise addition, the temperature was raised to 115° C., followed by further reaction for 4 hours. After the reaction was completed, 150 g of purified water and phosphoric acid were added to neutralize the pH to 7.0. After neutralization, the solvent was recovered to synthesize BPAFN (Bisphenol A Furanyl Novolac) of Formula 1e below.

[Formula 1e]

In Chemical Formula 1e, n5 is 5.7.

In addition, the BPAFN resin obtained according to Synthesis Example 5 was dissolved in THF at 2.5 wt% and subjected to GPC instrumental analysis (Shimadzu, Gel Permeation Chromatography Systems; Shodex, KF-801, 802, 803, 805 Columns). The analysis temperature was 40 ^o C and the mobile phase was Tetrahydrofuran (HPLC grade) flowed at 1 mL/min.

Through the GPC data measured in this way, it was confirmed that the furan-based novolac resin according to Synthesis Example 5 had a weight average molecular weight (Mw) of 1979 g/mol, and the average repeating unit of the novolac resin was 5.7 (n5 = 5.7). .

<Synthesis of Cycloaddition Reaction Product>

Synthesis Example 6: Synthesis of cycloaddition reaction product of novolak resin (DA reaction of OCFN + BMI)

In a flask equipped with a stirrer and a cooler, 200 g of novolak resin (OCFN) synthesized in Synthesis Example 2 and 400 g of methyl ethyl ketone (MEK) were added, stirred at 250 rpm, and heated to 50 ° C. to dissolve make it Then, while maintaining stirring, 90 g of 1,1-(methylenedi-4,1-phenylene)bismaleimide (BMI, 1,1-(Methylenedi-4,1-phenylene)bismaleimide) was divided into three parts (each 30 g) was divided and introduced at intervals of 1 hour.

After the raw materials were added, the aging reaction was carried out for 2 hours, and unreacted substances were removed by filtration, and then dried in an oven at 100 ° C. for 5 hours to recover the novolak resin cycloaddition reaction product (OCFN + BMI).

As a result of GPC instrumental analysis of the cycloaddition reaction product (DA reaction of OCFN + BMI) of novolak resin obtained according to Synthesis Example 6, the RT of the n = 0 peak of OCFN before the reaction is about 2.0 min shift (main component peak RT = 36.5 to RT = 34.5), it was confirmed that the molecular weight increase due to the binding of BMI (MW. 358.4) was reflected. In addition, as a result of FT-IR analysis of the cycloaddition reaction product of the novolac resin (DA reaction of OCFN + BMI), a peak shift change was observed (derived from BMI: 827 cm - ¹ , 3097 cm ^{- 1} , 3474 cm ⁻¹ and derived from furan: 1010 cm ⁻¹ ), and it was confirmed that a cycloaddition reaction product of a novolak resin of the following formula 1g was obtained.

[Formula 1g]

In Chemical Formula 1g, n2 is 4.6.

According to Synthesis Example 6, it can be seen that the cycloaddition reaction between BMI and Furan Novolac occurs well at low temperature, and through this, a uniform composition can be formed. In addition, high-density curing is possible during subsequent epoxy curing, so thermal properties can be increased, and the Double Tg phenomenon that occurs during epoxy-BMI curing according to the existing method can be solved.

Measurement of curing reactivity for cycloaddition reaction products of novolac resin (autopolymerization of DA reactant of OCFN + BMI by single heat treatment)

The self-curing reactivity of the novolak resin obtained according to Synthesis Example 6 was measured by ene-reaction for the cycloaddition reaction product (DA reaction of OCFN+BMI).

The cycloaddition reaction product forms a polycyclic structure by ene-reaction when heated at a high temperature to prevent the reverse reaction (rDA) of the cycloaddition reaction and enhances heat resistance. When the cycloaddition product was exposed to an oven at 210° C. for 3 hours, it was confirmed that a cured structure was formed by self-polymerization. As a result of FT-IR analysis before and after the ene-reaction, a peak shift change was observed, and the Alkene CH in the 850 cm ^-1 ~ 1000 cm ^-1 section decreased. This is due to the reduction of the alkene structure through ene-reaction, and the production of a cured product of Formula 1h below was confirmed by the target reaction.

[Formula 1h]

In Chemical Formula 1h, n2 is 4.6 and m1 is an integer from 1 to 10.

Measurement of curing reactivity for cycloaddition reaction products of novolac resin when adding radical initiator (autopolymerization of DA reactant of OCFN+BMI by radical catalyst)

Mixing the cycloaddition reaction product (DA reaction of OCFN + BMI) of the novolac resin obtained according to Synthesis Example 6 with 1% by weight of dicumyl peroxide (DCP), the same method as in the previous curing reactivity measurement As a result, the self-curing reactivity by the ene-reaction by the radical catalyst was measured.

The cycloaddition reaction product forms a polycyclic structure by ene-reaction when heated at a high temperature to prevent the reverse reaction (rDA) of the cycloaddition reaction and enhances heat resistance. When the cycloaddition product was exposed to an oven at 170° C. for 3 hours, it was confirmed that a poorly solvent-soluble cured product was formed by self-polymerization. As a result of FT-IR analysis before and after the ene-reaction, a peak shift change was observed, and the Alkene CH in the 850 cm ^-1 ~ 1000 cm ^-1 section decreased. This is due to the reduction of the alkene structure through the ene-reaction, and it was confirmed that the cured product was produced by the target reaction at 200 ℃ or less by introducing the DCP catalyst.

<Preparation of Epoxy Resin Composition>

Example 1: Preparation of furan novolac epoxy resin composition

As an epoxy resin, 10 g of phenol novolac type epoxy resin YDPN-638 sold by Kukdo Chemical, 15.55 g of novolac resin (OCFN) synthesized in Synthesis Example 2 as a curing agent, and 1,1-(methylene as bismaleimide) 2.57 g of di-4,1-phenylene)bismaleimide (BMI, 1,1-(methylenedi-4,1-phenylene)bismaleimide) and 2-methyl imidazole (2MI, 2-methyl imidazole) as a catalyst. The epoxy resin composition of Example 1 was prepared by mixing 2 mg, 0.1 g of dicumyl peroxide (DCP) as a radical initiator, and 35 g of methylethylketone (MEK) as a solvent.

In this case, the 2-methyl imidazole (2MI) and dicumyl peroxide (DCP) were used in amounts of 0.002 parts by weight and 0.01 parts by weight, respectively, based on the weight of the epoxy resin.

Here, the epoxy resin YDPN-638 is a phenol novolak-type epoxy resin, and is a resin obtained by epoxidizing phenolic hydroxyl groups of intermediates made of phenol and formalin as raw materials.

Example 2: Preparation of furan novolac epoxy resin composition

An epoxy resin composition was prepared in the same manner as in Example 1, but the epoxy resin composition of Example 2 was prepared without using dicumyl peroxide (DCP) as a radical initiator.

Example 3: Preparation of furan novolac epoxy resin composition

As an epoxy resin, a novolac resin (15.55 g) synthesized by Synthesis Example 2 in the same manner as in Synthesis Example 6 and 1,1 -(methylenedi-4,1-phenylene)bismaleimide (BMI, 1,1-(methylenedi-4,1-phenylene)bismaleimide); 2.57 g), that is, 18.12 g of the cycloaddition reaction of novolac resin and bismaleimide was used as a curing agent, 2 mg of 2-methyl imidazole (2MI) as a catalyst, and methylethyl as a solvent. The epoxy resin composition of Example 3 was prepared by mixing 35 g of ketone (MEK).

Here, the epoxy resin YDPN-638 is a phenol novolak-type epoxy resin, and is a resin obtained by epoxidizing phenolic hydroxyl groups of intermediates made of phenol and formalin as raw materials.

Comparative Example 1: Preparation of Novolac Epoxy Resin Composition

An epoxy resin composition was prepared in the same manner as in Example 1, except that 7.78 g of Amino Triazine Novolac (ATN) was used as a curing agent, the BMI content was changed to 1.69 g, and 2-methyl imidazole (2MI, The epoxy resin composition of Comparative Example 1 was prepared without using both 2-methyl Imidazole) and dicumyl peroxide (DCP) as a radical initiator.

Example 4: Preparation of furan novolac epoxy resin composition

As an epoxy resin, 344 g of Modified biphenyl type epoxy resin KSE-3060H sold by Kukdo Chemical, 200 g of novolak resin synthesized in Synthesis Example 2 as a curing agent, 1,1-(methylenedi-4, 106 g of 1-phenylene)bismaleimide (BMI, 1,1-(methylenedi-4,1-phenylene)bismaleimide), 0.4 g of 2-methyl imidazole (2MI, 2-methyl Imidazole) as a catalyst, radical initiator The epoxy resin composition of Example 4 was prepared by mixing 3.84 g of dicumyl peroxide (DCP) as a solvent and 330 g of methyl ethyl ketone (MEK) as a solvent.

Here, the epoxy resin KSE-3060H is a modified biphenyl type epoxy resin, and is a resin obtained by epoxidizing a phenolic hydroxyl group of a biphenyl type intermediate.

Comparative Example 2: Preparation of Novolac Epoxy Resin Composition

Epoxy of Comparative Example 2 by mixing 420 g of Modified biphenyl type epoxy resin KSE-3060H sold by Kukdo Chemical as an epoxy resin, 180 g of Amino Triazine Novolac (ATN) as a curing agent, and 330 g of methyl ethyl ketone (MEK) as a solvent. A resin composition was prepared.

Here, the epoxy resin KSE-3060H is a modified biphenyl type epoxy resin, and is a resin obtained by epoxidizing a phenolic hydroxyl group of a biphenyl type intermediate.

Comparative Example 3: Preparation of Novolac Epoxy Resin Composition

As an epoxy resin, 420 g of the modified biphenyl type epoxy resin KSE-3060H sold by Kukdo Chemical, 250 g of the novolak resin synthesized in Synthesis Example 2 as a curing agent, and 2-methyl imidazole (2MI, 2-methyl Imidazole as a catalyst) ) 0.4 g, and 330 g of methyl ethyl ketone (MEK) as a solvent were mixed to prepare an epoxy resin composition of Comparative Example 3.

Here, the epoxy resin KSE-3060H is a modified biphenyl type epoxy resin, and is a resin obtained by epoxidizing a phenolic hydroxyl group of a biphenyl type intermediate.

<Test Example 1>

For the epoxy resin compositions of Examples 1 to 3 and Comparative Example 1, physical properties were evaluated in the following manner, and the measurement results are shown in Table 1 below.

1) Heat resistance evaluation (Tg measurement)

The epoxy resin compositions of Examples 1 to 3 and Comparative Example 1 were cured by holding at 180 ° C. for 2 hours, then cured by holding at 190 ° C. for 4 hours, and then, using differential scanning calorimetry (DSC) to cure IPC. The glass transition temperature (Tg , ℃) was measured according to the TM-650 2.4.25 standard.

2) Thermal decomposition evaluation (measurement of Td and ash content)

The epoxy resin compositions of Examples 1 to 3 and Comparative Example 1 were maintained at 180 ° C. for 2 hours, cured at 190 ° C. for 4 hours, and then thermal decomposition temperature was determined according to IPC TM-650 2.4.24.6 standard using thermal analysis (TGA). (Td, ℃) and ash content (%) were measured.

Specifically, the epoxy resin composition was maintained at 180 ° C. for 2 hours and cured at 190 ° C. for 4 hours, and then TGA (thermaogravimetry analysis) was measured and the temperature was raised from 50 ° C. to 700 ° C. , It was maintained at 700 ° C for 60 minutes, and the temperature (Td_5%, ° C) when 5% by weight was reduced to 95% by weight and the content (%) of charcoal powder (Char) at 700 ° C were measured.

Example 1 Example 2 Example 3 Comparative Example 1 Td (5%, ℃) 368.6 368.6 368.6 352.6 Carbon content (%, 700 ℃) 32.3 49.15 49.15 27.83

As shown in Table 1, the epoxy resin compositions of Examples 1 to 3 using the maleimide-reactive furan-based novolak resin according to the present invention have higher thermal decomposition compared to Comparative Example 1 using DOPO-BPA and ATN as curing agents, respectively. It showed the temperature Td (5%), the ash content was also high at 700 ° C, and it was confirmed that the thermal decomposition stability was very good.

In addition, according to Example 2, the resin composition and the cured product were formed by reacting the epoxy resin, the novolak resin of Formula 1, and BMI, respectively, and the resin composition by reacting the epoxy resin and the cycloaddition reactant according to Example 3 And when forming a cured product, it can be seen that excellent thermal decomposition stability can be secured.

<Test Example 2>

The epoxy resin compositions of Example 4 and Comparative Examples 2 to 3, and physical property evaluation were measured when manufacturing a copper clad laminate (CCL) as follows using the same, and the measurement results are shown in Table 2 below.

Specimen manufacturing method for CCL evaluation

After impregnating 2116 type E-glass glass fiber with the epoxy resin compositions of Example 4 and Comparative Examples 2 to 3 as a varnish solution (50% by weight of solid content), put in an oven at 170 ° C. and dry for 2 minutes, respectively. A prepreg was prepared.

Four sheets of each prepreg were placed between two sheets of 1 oz. copper foil, and then hot-rolled at a temperature of 190 ° C. and a pressure of 200 psi for 1 hour and 30 minutes, and each specimen for evaluating CCL properties was prepared. obtained.

1) Evaluation of curing reactivity (G/T measurement)

To evaluate the reactivity to the epoxy resin compositions of Example 4 and Comparative Examples 2 to 3, gelation time (G/T, Varnish Gel time) was measured.

Specifically, 100 mg of the epoxy resin composition was placed on a hot plate at 170 ° C., stirred with a toothpick and lifted, and the time (seconds, sec) until the resin did not hang like a thread was measured.

2) Heat resistance evaluation (Tg measurement)

Glass transition temperature (Tg, ℃) of CCL specimens using the epoxy resin compositions of Example 4 and Comparative Examples 2 to 3 according to IPC TM-650 2.4.25 standard using differential scanning calorimetry (DSC) was measured.

3) Thermal decomposition evaluation (measurement of Td and ash content)

CCL specimens using the epoxy resin compositions of Example 4 and Comparative Examples 2 to 3 were subjected to thermal analysis (TGA) to determine thermal decomposition temperature (Td, °C) and carbon content (%) according to IPC TM-650 2.4.24.6 standard. measured.

Specifically, the epoxy resin composition was maintained at 180 ° C. for 2 hours and cured at 190 ° C. for 4 hours, and then TGA (thermaogravimetry analysis) was measured and the temperature was raised from 50 ° C. to 700 ° C. , It was maintained at 700 ° C for 60 minutes, and the temperature (Td_5%, ° C) when 5% by weight was reduced to 95% by weight and the content (%) of charcoal powder (Char) at 700 ° C were measured.

4) Coefficients of thermal expansion (CTE)

The thermal expansion coefficient (CTE, ppm/℃) of the CCL specimens using the epoxy resin compositions of Example 4 and Comparative Examples 2 to 3 was measured according to the IPC TM-650 2.4.24 standard using a thermomechanical analysis method (TMA). .

Specifically, the TMA glass transition temperature (TMA_Tg ) and CTE (α1, α2) were analyzed. The CTE value from 25 °C to before the TMA glass transition temperature was measured as α1, and the CTE value from the TMA glass transition temperature to 250 °C was measured as α2.

5) Adhesion evaluation

Adhesion of the CCL specimens using the epoxy resin compositions of Example 4 and Comparative Examples 2 to 3 was measured using a Universal Testing Machine (UTM) according to ASTM D 6862 standard.

Specifically, the measurement was performed using a universal testing machine (UTM). After cutting the CCL specimen into a size of 20mmX100mm, cut the center of the specimen into a width of 10mm, lift the end of the copper foil, and hang it on the jig of the adhesive force measurement device. After that, the peel strength (kgf/cm) when peeled from the copper foil in the direction of 90 degrees at a tensile rate of 50 mm/min with a load cell of 100 N was measured.

Example 4 Comparative Example 2 Comparative Example 3 Gel Time (sec, 170 ℃) 200 160 160 DSC_T _g (℃) ≥200 156.93 161.17 Td5% (℃) 421.27 393.68 408.33 Carbon content (%) 78.94 70.16 67.91 TMA_T _g (℃) 176.5 158.73 156.5 CTE_α1 (ppm/℃) 18.48 22.3 61.32 CTE_α2 (ppm/℃) 146.72 299.49 375.84 90 degree peeling peel strength
(kgf/cm) 1.34 1.37 0.89

As shown in Table 2, the epoxy resin composition of Example 4 using the maleimide-reactive furan-based novolak resin according to the present invention is comparable to Comparative Example 2 using ATN as a curing agent through high-density curing between BMI-Furan-Epoxy or Compared to Comparative Example 3 in which bismaleimide was not used, it exhibited a high glass transition temperature and a high thermal decomposition temperature Td (5%), and showed very good characteristics of carbon dust at 700 ° C. Specifically, in the case of Example 4, as a result of DSC analysis, the glass transition temperature was measured to be 200 ° C or more, and in the case of Comparative Examples 2 and 3, it can be seen that there is a large difference in 156.93 ° C and 161.17 ° C, respectively. In particular, in the case of Example 4, it can be seen that the adhesiveness is significantly improved compared to Comparative Example 3, and it can be seen that the CTE is significantly lower than that of Comparative Examples 2 and 3.

Claims (15)

Including one or more epoxy resins,
In addition to the epoxy resin, at least one novolak resin represented by the following formula (1) and at least one cycloaddition reaction product of bismaleimide represented by the following formula (2) are included,
The cycloaddition reaction product of the novolak resin and the bismaleimide is included in an amount of 20% to 50% by weight based on the total weight of the thermosetting resin composition,
The novolac resin is included in an amount of 50 to 200 mol% based on 100 mol% of the epoxy equivalent of the epoxy resin,
In the cycloaddition reaction product of the novolac resin and the bismaleimide, the bismaleimide is included in an amount of 50 to 200 mol% based on 100 mol% of the hydroxyl equivalent of the novolac resin, and the epoxy resin is Included in an amount of 50 to 200 mol% based on 100 mol% of the hydroxyl equivalent of the novolac resin,
Thermosetting resin composition:
[Formula 1]

In Formula 1,
R ₁ and R ₂ are each independently hydrogen, hydroxy, substituted or unsubstituted C _1-30 alkyl, or substituted or unsubstituted C _6-60 aryl;
a and b are each independently an integer from 0 to 4;
n is an integer between 1 and 10;
[Formula 2]

In Formula 2,
R ₃ is a divalent organic group derived from a hydrocarbon having 1 to 40 carbon atoms.
According to claim 1,
R ₁ and R ₂ are each independently hydrogen, hydroxy, or methyl, or o-cresol, phenol, 2,6-xylenol, catechol (Catechol), resorcinol (Resorcinol), bisphenol A (Bisphenol A), bisphenol F (Bisphenol F), or a substituent derived from furfuryl alcohol (Furfuryl alcohol),
A thermosetting resin composition.
According to claim 1,
R ₃ is to include any one of the following divalent organic groups,
Thermosetting resin composition:

.
According to claim 1,
The epoxy resin is a novolak-based epoxy resin, a dicyclopentadiene-based epoxy resin, a bisphenol-based epoxy resin, a diphenyl alkylene-based epoxy resin, a triazine-based epoxy resin, a fluorene-based epoxy resin, a triphenol alkylene-based epoxy resin, At least one selected from the group consisting of phenyl-based epoxy resins, xylene-based epoxy resins, biphenyl aralkyl-based epoxy resins, naphthalene-based epoxy resins, alicyclic-based epoxy resins, and furanyl-based epoxy resins,
A thermosetting resin composition.
delete delete delete According to claim 1,
The epoxy resin is included in a molar ratio of 0.7 to 1.3 based on the molar content of the hydroxyl group contained in the novolac resin.
A thermosetting resin composition.
According to claim 1,
Further comprising a thermal curing catalyst, a radical initiator, a solvent, or a mixture thereof,
A thermosetting resin composition.
delete Generating a novolac resin represented by the following Chemical Formula 1 by reacting at least one phenolic compound represented by the following Chemical Formula A with furfural;
At least one novolac resin thus produced and at least one bismaleimide represented by Formula 2 are subjected to a Diels-Alder reaction at 20 ° C to 100 ° C to obtain the novolac resin and the bis generating a cycloaddition of maleimide; and
mixing the novolac resin thus produced with the cycloaddition reaction product of the bismaleimide and at least one epoxy resin;
including,
The furfural is reacted in a molar ratio (furfural:phenolic compound) content of 0.5:1 to 2.0:1 based on the total amount of the phenolic compound,
The cycloaddition reaction product of the novolak resin and the bismaleimide is included in an amount of 20% to 50% by weight based on the total weight of the thermosetting resin composition,
The novolac resin is included in an amount of 50 to 200 mol% based on 100 mol% of the epoxy equivalent of the epoxy resin,
In the cycloaddition reaction product of the novolac resin and the bismaleimide, the bismaleimide is included in an amount of 50 to 200 mol% based on 100 mol% of the hydroxyl equivalent of the novolac resin, and the epoxy resin is Included in an amount of 50 to 200 mol% based on 100 mol% of the hydroxyl equivalent of the novolac resin,
Method for producing a thermosetting resin composition.
[Formula A]

In Formula A,
each R is independently hydrogen, hydroxy, substituted or unsubstituted C _1-30 alkyl, or substituted or unsubstituted C _6-60 aryl;
[Formula 1]

In Formula 1,
R ₁ and R ₂ are each independently hydrogen, hydroxy, substituted or unsubstituted C _1-30 alkyl, or substituted or unsubstituted C _6-60 aryl;
a and b are each independently an integer from 0 to 4;
n is an integer between 1 and 10;
[Formula 2]

In Formula 2,
R ₃ is a divalent organic group derived from a hydrocarbon having 1 to 40 carbon atoms.
According to claim 11,
The phenolic compound is o-Cresol, phenol, 2,6-xylenol, catechol, resorcinol, bisphenol A (Bisphenol A), and at least one selected from the group consisting of bisphenol F (Bisphenol F),
Method for producing a thermosetting resin composition.
delete A material comprising a cured product of the thermosetting resin composition according to claim 1.
Board; and
A resin layer located on one side or both sides of the substrate; including,
The resin layer is formed from the thermosetting resin composition of claim 1,
Laminate.