JP2022529361A - Epoxy resin, a method for producing the same, and an epoxy resin composition containing the same. - Google Patents

Abstract

The present invention is a non-crystalline fluorene epoxy that has improved workability, storage stability, fluidity and smoothness while ensuring excellent heat resistance, high flexibility, low coefficient of thermal expansion, and high refractive index. Provided are a resin and a method for effectively producing the resin.

Description

The present invention provides workability, storage stability, fluidity and smoothness while ensuring excellent heat resistance and high flexibility (low modulus at high epoxy), low coefficient of thermal expansion (low CTE), and high refractive index. The present invention relates to a non-crystalline fluorene-based epoxy resin and a method for producing the same, an epoxy resin composition and the method for producing the same, a laminated board and a method for producing the same.

Epoxy resins are applied in various fields such as package substrates (IC substrate) on which silicon chips are mounted, EMC encapsulants, underfills, die bonding materials that bond chips and substrates, solder resists, conductive pastes, and PCBs. It is a core organic material for semiconductor packaging, and is still widely used today due to its excellent heat resistance, insulation properties, chemical resistance, and mechanical properties.

However, in recent years, with the rapid development of semiconductor packaging technology, there is increasing interest in the development of new epoxy materials for next-generation packaging, recognizing the limitations of existing epoxy materials. Further, with the miniaturization, weight reduction, and high performance of electronic products, semiconductor chips have become thinner, and problems that cannot be solved by conventional epoxy resin compositions have arisen due to the increase in high integration or surface mountability. In particular, in the case of packaging in which a plurality of thin chips are laminated for thinning and high functionality, the demand for the development of a new epoxy material continues. For example, as semiconductor packaging technology focusing on the protection and coupling functions of semiconductor integrated circuits (ICs) advances toward system integration, it is necessary to develop materials that can efficiently reduce the generation of stress applied to substrates. Therefore, epoxy material technology with higher performance is required in terms of mounting reliability (CTE, stress, mechanical properties).

Generally, as an epoxy resin, a bisphenol A type epoxy resin is widely known, and as a solid epoxy resin, a bisphenol A type epoxy resin whose molecular weight is increased by a condensation reaction is used. High molecular weight epoxies may cause blocking. For this reason, novolak-type solid epoxy resins are widely used, but such high molecular weight resins have the disadvantages of high viscosity and poor fluidity and smoothness. In addition, tetramethylbiphenol diglycidyl ether, triglycidyl isocyanurate, etc. have been proposed, but all of them have excellent storage stability, but have a high elastic modulus of the cured product and lack flexibility.

On the other hand, it is known that the bisphenol fluorene type phenol resin exhibits excellent properties such as heat resistance. Such 9,9-bis (4-hydroxyphenyl) fluorene (9,9-Bis (4-hydroxyphenyl) fluorene), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (9,9) -Compounds such as Bis [4- (2-hydroxyethoxy) phenyl] fluorene) are also known to be used in epoxy resins. The epoxy resin having a fluorene structure can improve properties such as heat resistance and flexibility as compared with the conventional bisphenol type epoxy resin. However, since it has crystallization properties, there are problems such as a decrease in solubility in a solvent and precipitation to decrease storage stability, or a decrease in workability due to a high melting point. Most of the crystalline polymer materials have a spherulite structure in which thin layers of lamellar structures are gathered inside, and the fine structure inside the lamellar differs depending on the chain structure of each polymer substance. These crystal structures are densely arranged because the molecules have the smallest volume, and because they are physically strongly bonded, they have high strength from the aspect of physical characteristics, high melting temperature, and are poorly soluble in the solvent. Due to its non-tough physical properties, its application is very limited and it is common for workability and storage stability to be very poor. In addition, due to the shrinkage phenomenon that accompanies the formation process of the crystal structure, warpage of the appearance may occur when molding a thin product, so improvement is required.

Further, when the fluorene compound simply exists as a dimer, there is a problem that the viscosity is too high and the fluidity and smoothness are lowered. An epoxy compound was introduced into the dimer structure of such a fluorene-based compound, but the epoxy compound having such a dimer structure has a problem that it is difficult to mold a resin and easily causes defects, and compatibility and workability are limited. There are disadvantages.

On the other hand, when a fluorene-based epoxy resin composition having a high glass transition temperature is used, there is a problem that the elastic modulus is greatly increased and the elastic modulus becomes vulnerable to external stress due to heat or external impact. Therefore, a non-fluorene-based epoxy compound was mixed and used. In this case, although the balance between shrinkage rate, elastic modulus and moldability was improved, the fluorene-based epoxy resin had high flexibility, high refraction, and high heat resistance. There is a problem that the unique characteristics of fluorene are deteriorated.

Therefore, in order to ensure the processability and reliability of electronic parts during the manufacture of epoxy resins used for polymer materials, the polymer crystallinity is adjusted to the optimum point to provide excellent thermal stability as well as high flexibility and low. There is a further need for the development of epoxy resins that have the advantages of physical properties such as the coefficient of thermal expansion and that have good workability, storage stability, and fluidity.

The present invention has a three-dimensional and bulky cardo structure, ensuring excellent heat resistance and high flexibility (low volumeus at high temperature), low coefficient of thermal expansion (low CTE), and high refractive index. However, a non-crystalline fluorene-based epoxy resin having improved workability, storage stability, fluidity and smoothness, and a method for producing the same are provided.

The present invention also provides an epoxy resin composition containing the amorphous fluorene-based epoxy resin and a method for producing the same.

The present invention also provides a laminated board including a resin layer made of the epoxy resin composition and a method for manufacturing the laminated board.

前記化学式１中、
Ｒ_１およびＲ_２はそれぞれ独立して、水素、置換または非置換の炭素数１～１０のアルコキシ基、置換または非置換の炭素数１～１０のアルキル基、置換または非置換の炭素数３～２０のシクロアルキル基、または置換または非置換の炭素数６～３０のアリール基であり、

前記繰り返し単位１中、
ｎは２≦ｎ≦１０の範囲を満たす値であり、
Ｒ_３およびＲ_４はそれぞれ独立して、水素、置換または非置換の炭素数１～１０のアルコキシ基、置換または非置換の炭素数１～１０のアルキル基、置換または非置換の炭素数３～２０のシクロアルキル基、または置換または非置換の炭素数６～３０のアリール基である。 According to one embodiment of the present invention, a novolac-type fluorene-based epoxy compound containing a fluorene-based epoxy compound represented by the following chemical formula 1 and a novolac-type fluorene-based epoxy compound containing the following repeating unit 1 and containing the following repeating unit 1 is included. A non-crystalline fluorene epoxy resin containing 3% to 80% of a compound based on the total weight is provided.

In the chemical formula 1,
R ₁ and R ₂ are independently hydrogen, an alkoxy group having 1 to 10 carbon atoms substituted or unsubstituted, an alkyl group having 1 to 10 carbon atoms substituted or unsubstituted, and 3 to 10 carbon atoms substituted or unsubstituted. 20 cycloalkyl groups, or substituted or unsubstituted aryl groups having 6 to 30 carbon atoms.

In the repeating unit 1,
n is a value that satisfies the range of 2 ≦ n ≦ 10.
R ₃ and R ₄ are independently hydrogen, an alkoxy group having 1 to 10 carbon atoms substituted or unsubstituted, an alkyl group having 1 to 10 carbon atoms substituted or unsubstituted, and 3 to 10 carbon atoms substituted or unsubstituted. It is a cycloalkyl group of 20 or an aryl group having 6 to 30 carbon atoms which is substituted or unsubstituted.

The present invention also provides the above-mentioned method for producing an amorphous fluorene-based epoxy resin.

The present invention also provides an epoxy resin composition containing the non-crystalline fluorene-based epoxy resin composition, a curing agent, a curing catalyst, and a solvent.

The present invention also includes a substrate and a resin layer located on one or both sides of the substrate, the resin layer providing a laminated board made of the epoxy resin composition as described above.

According to the present invention, a non-crystalline fluorene having improved workability, storage stability, fluidity and smoothness while ensuring excellent heat resistance, high flexibility, low coefficient of thermal expansion, and high refractive index. A system epoxy resin is provided.

It is a figure which shows the analysis graph of the differential scanning calorimetry (DSC) with respect to the fluorene-based biphenol resin of Example 1-1 produced by the Embodiment of this invention. It is a figure which shows the analysis graph of the differential scanning calorimetry (DSC) with respect to the 4,4'-(9-fluorenylidene) diphenol compound of the conventionally known comparative example 1-1. It is a figure which shows the analysis graph of the gel permeation chromatography (GPC) for the fluorene-based biphenol resin of Example 1-1 produced by one Embodiment of this invention. It is a figure which shows the analysis graph of the gel permeation chromatography (GPC) with respect to the 4,4'-(9-fluorenylidene) diphenol compound of the conventionally known comparative example 1-1.

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.

Also, the terms used herein are used solely to describe a particular embodiment and are not intended to limit the invention. Singular expressions include multiple expressions unless they mean that they are explicitly different in context. As used herein, terms such as "include", "provide" or "have" are intended to specify the existence of the described features, numbers, stages, components or combinations thereof. It must be understood that it does not preclude the possibility of existence or addition of one or more other features, numbers, stages, components, or combinations thereof.

The terms "about", "substantially", etc. to the extent used herein are, or are close to, the numerical values, where the manufacturing and material tolerances inherent in the referred meaning are presented. It is used as a meaning to prevent unscrupulous infringers from unfairly using disclosures that are appropriate or numerically mentioned to aid in the understanding of the invention.

Also, the term "... stage" or "... stage" as used herein does not mean "stage for ...".

As used herein, the term "these combinations" as used in a Markush-style representation means one or more mixtures or combinations selected from the group of components described in the Markush-style representation. It means that it contains one or more selected from the group consisting of the above-mentioned components.

および

は、他の置換基に連結される結合を意味する。 In the present specification.

and

Means a bond linked to another substituent.

As used herein, "substitution" means that, unless otherwise defined, at least one hydrogen of the compound is an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms and 2 to 30 carbon atoms. Alkinyl group, alkylsilyl group with 1 to 10 carbon atoms; cycloalkyl group with 3 to 30 carbon atoms; 6 to 30 aryl groups with carbon atoms; heteroaryl group with 1 to 30 carbon atoms; alkoxy group with 1 to 10 carbon atoms; Silane group; alkylsilane group; alkoxysilane group; amine group; alkylamine group; arylamine group; means substituted with ethyleneoxyl group or halogen group.

As used herein, "hetero" means an atom selected from the group consisting of N, O, S and P, unless otherwise defined.

As used herein, an "alkyl group" is a "saturated alcohol group"; or at least one, which does not contain any alkenyl or alkynyl group, unless otherwise defined. It is meant to include all "unsaturated alkyl groups" containing one alkenyl group or alkynyl group. The "alkenyl group" means a substituent in which at least two carbon atoms form at least one carbon-carbon double bond, and the "alkyne group" means a substituent in which at least two carbon atoms form at least one carbon. -It means a substituent having a carbon triple bond. The alkyl group can be branched, linear or cyclic.

The alkyl group is a linear or branched alkyl group having 1 to 20 carbon atoms, specifically, a lower alkyl group having 1 to 6 carbon atoms, an intermediate alkyl group having 7 to 10 carbon atoms, and a carbon number of carbon atoms. It can be an 11-20 higher alkyl group.

For example, an alkyl group having 1 to 4 carbon atoms means that there are 1 to 4 carbon atoms in the alkyl chain, which are methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, and so on. It is selected from the group consisting of sec-butyl and t-butyl.

Typical alkyl groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, an ethenyl group, a propenyl group, a butenyl group and the like.

The "cycloalkyl group" is a cyclic alkyl group, and specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

The "alkoxy group" is an oxy group in which the above-mentioned alkyl group is bonded to an oxygen atom, and specifically, a methoxy group, an ethoxy, an isopropoxy, an n-butoxy, a tert-butoxy, a phenyloxy, and the like. Cyclohexyloxy groups and the like can be mentioned.

"Aromatic group" means a substituent in which all elements of the cyclic substituent have p-orbitals and these p-orbitals form a conjugation. Specific examples include aryl and heteroaryl groups.

An "aryl group" comprises a single ring or a fused ring, i.e., a substituent of multiple rings sharing adjacent pairs of carbon atoms.

"Heteroallyl group" means an aryl group containing a heteroatom selected from the group consisting of N, O, S and P in the aryl group. When the heteroaryl group is a fused ring, each ring may contain 1 to 3 heteroatoms.

Unless otherwise defined herein, "copolymer" means block copolymer, random copolymer, graft copolymer or alternate copolymer, and "copolymer" means block copolymer. It means a random copolymer, a graft copolymer or an alternate copolymer.

Also, as used herein, when it is referred to that each layer or element is formed "on" each layer or element, does it mean that each layer or element is formed directly on each layer or element? It means that other layers or elements can be further formed on the object, substrate between each layer.

Since the present invention can be modified in various ways and can have various forms, specific examples will be illustrated below in detail. However, this is not intended to limit the invention to any particular form of disclosure, unless it is understood to include all modifications, equivalents or alternatives contained within the ideas and technical scope of the invention. It doesn't become.

Embodiments of the present invention will be described in detail based on the above definitions. However, this is merely an example, and the present invention is not limited thereto, and is defined only within the scope of the claims described later.

As a result of continuous experiments by the present inventors, the molecular weight distribution of the polymer is reduced in order to reduce the crystal irregularity and crystallinity of the amorphous compound substituted with the −OH group by the production method described later. By adjusting the physical state with the minimum deformation, it has the advantages of physical properties such as high flexibility and low thermal expansion coefficient as well as excellent thermal stability, and workability and storage stability. The invention was completed after confirming that a non-crystalline fluorene epoxy resin having good fluidity could be provided.

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

Epoxy Resin According to one embodiment of the invention, workability, storage stability, fluidity and smoothness have been improved while ensuring excellent heat resistance and high flexibility, a low coefficient of thermal expansion, and a high refractive index. Non-crystalline fluorene epoxy resins are provided.

Specifically, in the epoxy resin, the heat resistance of the epoxy resin is increased by introducing a fluorene structure into the main chain of the epoxy resin as a cardo-based unit that is rigid and has excellent heat resistance and processability. Further, at the same time as the cardo-based unit having an out-of-plane structure is introduced, the crystallinity is reduced by adjusting the molar ratio by the novolak reaction, so that the processability of the material, for example, solubility is improved. improves. In addition, such crystallinity adjustment can realize high flexibility and refractive index as well as excellent thermal stability, and can be applied to various fields such as electronic materials that require high functionality.

In particular, the epoxy resin of the present invention is a non-crystalline solid containing a fluorene-based epoxy compound and a dimer or a polymer having a dimer or a dimer in which a part of the compound is produced by a novolak reaction in an optimum range. Is shown.

前記化学式１中、
Ｒ_１およびＲ_２はそれぞれ独立して、水素、置換または非置換の炭素数１～１０のアルコキシ基、置換または非置換の炭素数１～１０のアルキル基、置換または非置換の炭素数３～２０のシクロアルキル基、または置換または非置換の炭素数６～３０のアリール基であり、

前記繰り返し単位１中、
ｎは２≦ｎ≦１０の範囲を満たす値、つまり、ｎは２以上～１０以下の範囲を満たす値であり、
Ｒ_３およびＲ_４はそれぞれ独立して、水素、置換または非置換の炭素数１～１０のアルコキシ基、置換または非置換の炭素数１～１０のアルキル基、置換または非置換の炭素数３～２０のシクロアルキル基、または置換または非置換の炭素数６～３０のアリール基である。
特に、前記繰り返し単位１中、ｎは２以上～１０以下の範囲の値であり、具体的には、ｎは２以上～６以下の範囲を満たす値である。特に、ｎは樹脂の成形の改善および相溶性と作業性を改善する側面から２以上または３以上であり得、熱安定性と共に高い柔軟性と低い熱膨張係数などを確保する側面から１０以下であり得る。 More specifically, the non-crystalline fluorene-based epoxy resin provided in one embodiment of the present invention is a novolac-type fluorene-based epoxy compound containing the fluorene-based epoxy compound represented by the following chemical formula 1 and the following repeating unit 1. Contains 3% to 80% of a novolak-type fluorene-based epoxy compound containing the following repeating unit 1 based on the total weight.

In the chemical formula 1,
R ₁ and R ₂ are independently hydrogen, an alkoxy group having 1 to 10 carbon atoms substituted or unsubstituted, an alkyl group having 1 to 10 carbon atoms substituted or unsubstituted, and 3 to 10 carbon atoms substituted or unsubstituted. 20 cycloalkyl groups, or substituted or unsubstituted aryl groups having 6 to 30 carbon atoms.

In the repeating unit 1,
n is a value that satisfies the range of 2 ≦ n ≦ 10, that is, n is a value that satisfies the range of 2 or more and 10 or less.
R ₃ and R ₄ are independently hydrogen, an alkoxy group having 1 to 10 carbon atoms substituted or unsubstituted, an alkyl group having 1 to 10 carbon atoms substituted or unsubstituted, and 3 to 10 carbon atoms substituted or unsubstituted. It is a cycloalkyl group of 20 or an aryl group having 6 to 30 carbon atoms which is substituted or unsubstituted.
In particular, in the repeating unit 1, n is a value in the range of 2 or more and 10 or less, and specifically, n is a value satisfying the range of 2 or more and 6 or less. In particular, n can be 2 or more or 3 or more from the aspect of improving the molding of the resin and improving compatibility and workability, and 10 or less from the aspect of ensuring high flexibility and a low coefficient of thermal expansion as well as thermal stability. could be.

前記化学式１ａ中、Ｒ_１およびＲ_２は前記化学式１で定義した通りである。
前記化学式１中、Ｒ_１およびＲ_２はそれぞれ独立して、水素、炭素数１～４のアルキル基、または炭素数６～１２のアリール基であり、好ましくは、Ｒ_１およびＲ_２は水素であり得る。ただし、これは一例に過ぎず、本発明の一実施形態はこれに限定されない。 Preferably, the fluorene-based epoxy compound represented by the chemical formula 1 contains the following chemical formula 1a.

In the chemical formula 1a, _R1 and _R2 are as defined in the chemical formula 1.
In the above chemical formula 1, R ₁ and R ₂ are independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and R ₁ and R ₂ are preferably hydrogen. could be. However, this is only an example, and one embodiment of the present invention is not limited to this.

前記繰り返し単位１ａ中、ｎ、Ｒ_３およびＲ_４は前記繰り返し単位１で定義した通りである。 Preferably, the novolak type fluorene epoxy compound containing the repeating unit 1 contains the following repeating unit 1a.

In the repeating unit 1a, n, R ₃ and R ₄ are as defined in the repeating unit 1.

The novolak-type fluorene-based epoxy compound containing the repeating unit 1 has a three-dimensional and bulky cardo structure, and secures excellent heat resistance and high flexibility, a low coefficient of thermal expansion, and a high refractive index. Also, workability and storage stability and fluidity and smoothness can be improved.

In the non-crystalline fluorene-based epoxy resin of the present invention, the novolac-type fluorene-based epoxy compound containing the repeating unit 1 is based on the total weight, that is, the fluorene-based epoxy compound represented by the chemical formula 1 and the repeating unit. 3% to 80% based on the total weight of the novolak type fluorene epoxy compound containing 1, specifically 10% to 75%, or 10% to 70%, or 10% to 60%, or 10 It is characterized by containing% to 30% or 15% to 30%. The content of the novolak-type fluorene-based epoxy compound containing the repeating unit 1 can be 80% or less from the aspect of being applied to an epoxy intermediate having a low softening point and a low melt viscosity and high fluidity and smoothness, and is a solvent. It is 3% or more from the aspect for synthesizing a resin that exists in an amorphous state without problems such as a decrease in solubility and precipitation and a decrease in storage stability, or a decrease in workability due to a high melting point. obtain.

As an example, the fluorene-based epoxy compound represented by the chemical formula 1 and the novolac-type fluorene-based epoxy compound containing the repeating unit 1 are contained in a weight ratio of 97: 3 to 20:80, specifically 90:10 to 25. : 75, or 90:10 to 30:70, or 90:10 to 40:60, or 90:10 to 70:30, or 85:15 to 70:30. The molar ratio of the fluorene-based compound represented by the chemical formula 1 to the novolak-type fluorene-based epoxy compound containing the repeating unit 1 is to be applied to an epoxy intermediate having a low softening point and a low melt viscosity and high fluidity and smoothness. It can be a weight ratio of 20:80 or more from the side of the above, and in a non-crystalline state without problems such as a decrease in solubility in a solvent and precipitation to decrease storage stability, or a decrease in workability due to a high melting point. It can be less than or equal to the weight ratio of 97: 3 from the side for synthesizing the existing resin.

Specifically, in the repeating unit 1, R ₃ and R ₄ are independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and R ₅ is preferable. And R ₆ can be hydrogen. However, this is only an example, and one embodiment of the present invention is not limited to this.

On the other hand, in the non-crystalline fluorene-based epoxy resin of the present invention, after reacting the fluorene-based compound with formaldehyde at a specific molar ratio (step 1) as described later, all the hydroxyl groups of the phenol group are epoxidized. (Step 2), finally obtained.

前記繰り返し単位Ａ中、
ｌは１≦ｌ≦１０の範囲を満たす値、つまり、ｌは１以上～１０以下の範囲を満たす値であり、
Ｒ’およびＲ’’はそれぞれ独立して、水素、置換または非置換の炭素数１～１０のアルコキシ基、置換または非置換の炭素数１～１０のアルキル基、置換または非置換の炭素数３～２０のシクロアルキル基、または置換または非置換の炭素数６～３０のアリール基である。
具体的には、前記繰り返し単位Ａ中、ｌは１≦ｌ≦６の範囲を満たす値、つまり、ｌは１以上～６以下の範囲を満たす値であり得る。
また、Ｒ’およびＲ’’はそれぞれ独立して、水素、炭素数１～４のアルキル基、または炭素数６～１２のアリール基であり、好ましくは、Ｒ’およびＲ’’は水素であり得る。ただし、これは一例に過ぎず、本発明の一実施形態はこれに限定されない。 However, in the step 2, all the hydroxy groups of the fluorene-based biphenol resin may not be epoxidized. Thus, the final copolymer may include, but is not limited to, the following repeating unit A:

In the repeating unit A,
l is a value satisfying the range of 1 ≦ l ≦ 10, that is, l is a value satisfying the range of 1 or more and 10 or less.
R'and R'' are independently hydrogen, substituted or unsubstituted alkoxy groups having 1 to 10 carbon atoms, substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, and substituted or unsubstituted carbon atoms having 3 carbon atoms. It is a cycloalkyl group of up to 20 or an aryl group having 6 to 30 carbon atoms which is substituted or unsubstituted.
Specifically, in the repeating unit A, l may be a value satisfying the range of 1 ≦ l ≦ 6, that is, l may be a value satisfying the range of 1 or more and 6 or less.
Further, R'and R'' are independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and preferably R'and R'' are hydrogen. obtain. However, this is only an example, and one embodiment of the present invention is not limited to this.

On the other hand, the epoxy equivalent (EEW, epoxyy equivalent weight) of the amorphous fluorene-based epoxy resin may be 200 g / eq to 500 g / eq or 230 g / eq to 480 g / eq. Here, the epoxy equivalent is a value obtained by dividing the number average molecular weight (g / mol) of the resin by the epoxy equivalent number (eq / mol). The epoxy group in the copolymer is the site where the hydroxy of phenol was epoxidized in the above-mentioned step 3, and that the content thereof satisfies the above range is high flexibility and refraction as well as excellent thermal stability. It means that the rate can be achieved.

The non-crystalline fluorene epoxy resin may have a number average molecular weight (Mn) of 200 g / mol to 2000 g / mol and a weight average molecular weight (Mw) of 300 g / mol to 2000 g / mol. Specifically, the number average molecular weight (Mn) of the non-crystalline fluorene-based epoxy resin is 250 g / mol to 2000 g / mol, 300 g / mol to 2000 g / mol, or 325 g / mol to 1500 g / mol, or 350 g. It can be from / mol to 1250 g / mol or 400 g / mol to 1000 g / mol. The weight average molecular weight (Mw) of the non-crystalline fluorene epoxy resin is 300 g / mol to 2000 g / mol, 350 g / mol to 2000 g / mol, or 350 g / mol to 1500 g / mol, or 360 g / mol or more. It can be 1250 g / mol, or 420 g / mol to 950 g / mol. Further, the molecular weight distribution (Mw / Mn) determined by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the fluorene-based biphenol resin is 0.8 to 4.0, or 0. It can be 9.9 to 2.0, or 0.95 to 1.8, or 1.03 to 1.4.

As an example, the number average molecular weight and the weight average molecular weight of the non-crystalline fluorene-based epoxy resin are measured by gel permeation chromatography (GPC), and the obtained measured values are converted into polystyrene. could be. As a specific measurement method, a usual method applicable to a fluorene-based epoxy resin can be applied.

Further, the amorphous fluorene epoxy resin is amorphous and has a melting point (Tm) of 30 ° C. to 120 ° C., or 30 ° C. to 100 ° C., or 30 ° C. to 80 ° C. or 60 ° C. to 68 ° C. .. This is due to a step added to reduce crystallization, and the melting point of the amorphous fluorene epoxy resin is 140 ° C to 170 ° C (Tm) of the existing crystalline fluorene epoxy resin. In comparison, it is considered to be significantly lower.

The non-crystalline fluorene epoxy resin is an epoxy resin containing a bifunctional or higher novolak polymer of 3% to 97% based on the total weight, and is a phenol-based curing agent and a glass transition temperature at the time of curing. Since (Tg) realizes a high glass transition temperature of 180 ° C. or higher, 180 ° C. to 250 ° C., or 183 ° C. to 200 ° C., it is characterized in that a high glass transition temperature and high flexibility can be realized at the same time.

As an example, the melting point (Tm) and glass transition temperature (Tg) of the non-crystalline fluorene epoxy resin can be measured using a differential scanning calorimetry (DSC). Specifically, the temperature of the resin sample is increased from a temperature below room temperature at a rate of 10 ° C./min, and a changing part of Heat Flow appears on the DSC (manufactured by Mettler) curve where heat absorption appears at a constant inclination. The intermediate value between the temperature at which the Heat Flow begins to change and the temperature at which the change ends is defined as the glass transition temperature (Tg), and the temperature corresponding to the peak of the heat absorption peak (peak) corresponding to the bottom of the DSC curve is the melting point. (Tm).

Further, the amorphous fluorene-based epoxy resin is amorphous and has a characteristic that a softening point appears even at a temperature other than a low melting temperature. Specifically, the softening point (Ts) of the amorphous fluorene epoxy resin can be 70 ° C. to 120 ° C., or 80 ° C. to 110 ° C., or 85 ° C. to 105 ° C., or 88 ° C. to 98 ° C. Here, the softening point of the amorphous fluorene-based epoxy resin can be measured by the ASTM E28 standard using the Ring and Ball method.

Further, the amorphous fluorene epoxy resin may have a melt viscosity of 290 cps to 500 cps, or 320 cps to 400 cps, or 350 cps to 397 cps. As an example, the melt viscosity is a value measured at 150 ° C. using a rotary viscometer manufactured by Brookfield.

Further, the amorphous fluorene-based epoxy resin was measured by dissolving a resin sample in a cyclohexanone solvent at a weight ratio of 1: 1 and then crystallizing and precipitating at room temperature (RT, 23 ° C to 25 ° C). At times, crystals do not precipitate and have very good storage stability.

The amorphous fluorene epoxy resin has a refractive index (RI) of 1.61 to 1.639, or 1.62 to 1.629, 1.625 to 1.629, 1.6264 to 1. It can be .6289. As an example, the refractive index (RI) was measured at a wavelength of 404 nm by joining to a prism and changing the incident angle of light.

Method for Producing Epoxy Resin In still another embodiment of the present invention, a method for producing the above-mentioned amorphous fluorene-based epoxy resin is provided.

In particular, according to the present invention, it has a three-dimensional and bulky cardo structure, and while ensuring excellent heat resistance and high flexibility, a low coefficient of thermal expansion, and a high refractive index, workability and storage stability are ensured. A method for effectively producing an amorphous fluorene-based epoxy resin having improved properties, fluidity and smoothness is provided.

Specifically, in the present invention, the molar ratio of the reactant is optimized in a predetermined range by the Novolac reaction in which a fluorene compound and formaldehyde are polycondensed, and excellent heat is obtained while adjusting the crystallinity of the final epoxy resin. It has high flexibility and refractive index as well as stability, and can exhibit good properties of workability, storage stability, fluidity and smoothness.

前記化学式２中、
Ｒ_５およびＲ_６はそれぞれ独立して、水素、置換または非置換の炭素数１～１０のアルコキシ基、置換または非置換の炭素数１～１０のアルキル基、置換または非置換の炭素数３～２０のシクロアルキル基、または置換または非置換の炭素数６～３０のアリール基であり、

前記繰り返し単位２中、
ｍは２≦ｍ≦１０の範囲を満たす値、つまり、ｍは３以上～１０以下の範囲を満たす値であり、
Ｒ_７およびＲ_８はそれぞれ独立して、水素、置換または非置換の炭素数１～１０のアルコキシ基、置換または非置換の炭素数１～１０のアルキル基、置換または非置換の炭素数３～２０のシクロアルキル基、または置換または非置換の炭素数６～３０のアリール基である。
特に、前記繰り返し単位２中、ｍは２以上～１０以下の範囲の値であり、具体的には、ｍは２以上～６以下の範囲を満たす値である。特に、ｍは樹脂の成形改善および相溶性と作業性を改善する側面から２以上または３以上であり得、熱安定性と共に高い柔軟性と低い熱膨張係数などを確保する側面から１０以下であり得る。 More specifically, in the presence of an acid catalyst, a fluorene-based biphenol compound represented by the following chemical formula 2 is reacted with formaldehyde at a molar ratio of 2: 1 to 10: 1, and a novolak type containing the following repeating unit 2. A step of producing a fluorene-based biphenol resin containing a fluorene-based biphenol compound (step 1), and a step of reacting the fluorene-based biphenol resin with epihalohydrin in the presence of a hydroxide salt (step 2). The above-mentioned method for producing a non-crystalline fluorene-based epoxy resin, which comprises the above-mentioned.

In the chemical formula 2,
R ₅ and R ₆ are independently hydrogen, an alkoxy group having 1 to 10 carbon atoms substituted or unsubstituted, an alkyl group having 1 to 10 carbon atoms substituted or unsubstituted, and 3 to 10 carbon atoms substituted or unsubstituted. 20 cycloalkyl groups, or substituted or unsubstituted aryl groups having 6 to 30 carbon atoms.

In the repeating unit 2,
m is a value that satisfies the range of 2 ≦ m ≦ 10, that is, m is a value that satisfies the range of 3 or more and 10 or less.
R ₇ and R ₈ are independently hydrogen, an alkoxy group having 1 to 10 carbon atoms substituted or unsubstituted, an alkyl group having 1 to 10 carbon atoms substituted or unsubstituted, and 3 to 10 carbon atoms substituted or unsubstituted. It is a cycloalkyl group of 20 or an aryl group having 6 to 30 carbon atoms which is substituted or unsubstituted.
In particular, in the repeating unit 2, m is a value in the range of 2 or more and 10 or less, and specifically, m is a value satisfying the range of 2 or more and 6 or less. In particular, m may be 2 or more or 3 or more from the aspect of improving the molding of the resin and improving compatibility and workability, and 10 or less from the aspect of ensuring high flexibility and a low coefficient of thermal expansion as well as thermal stability. obtain.

前記化学式２ａ中、Ｒ_５およびＲ_６は前記化学式２で定義した通りである。 Preferably, the fluorene-based compound represented by the chemical formula 2 contains the following chemical formula 2a.

_In the chemical formula 2a, R5 and R6 are as defined in the chemical formula ₂ .

In the above chemical formula 2, R ₅ and R ₆ are independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and preferably R ₅ and R ₆ are hydrogen. could be. However, this is only an example, and one embodiment of the present invention is not limited to this.

In particular, in the method for producing a non-crystalline fluorene-based epoxy resin, the fluorene-based biphenol compound represented by the chemical formula 2 and formaldehyde have a molar ratio of 2: 1 to 10: 1, specifically 2.5: 1. Reactioning at a molar ratio of ~ 10: 1, or 3: 1 ~ 10: 1, or 4.5: 1 ~ 10: 1, or 6: 1 ~ 10: 1, or 6: 1 ~ 8: 1. It is a feature. The reaction molar ratio of the fluorene-based biphenol compound represented by the chemical formula 2 to formaldehyde is a molar ratio of 2: 1 from the aspect of being applied to an epoxy intermediate having a low softening point and a low melt viscosity and high fluidity and smoothness. Aspects for synthesizing a resin that exists in a non-crystalline state without problems such as a decrease in solubility in a solvent and precipitation due to a decrease in storage stability, or a decrease in workability due to a high melting point. To 10: 1 molar ratio or less.

In step 1, the step of reacting formaldehyde with the fluorene-based biphenol compound represented by the chemical formula 2 is a solid-phase non-crystalline resin linked by a methylene group as an addition condensate by a novolak reaction in the presence of an acid catalyst. It is characterized by manufacturing.

Specifically, the step of reacting the fluorene-based biphenol compound represented by the chemical formula 2 with formaldehyde is carried out under the conditions of 750 Torr to 770 Torr or 755 Torr to 765 Torr at 100 ° C. to 140 ° C. or 115 ° C. to 125 ° C. Can be done. As an example, the novolak reaction of step 1 can be carried out for 1 hour to 10 hours, or 2 hours to 6 hours under the conditions as described above.

Further, in the step 1, the acid catalyst is one or more selected from the group consisting of oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, paratoluene sulfonic acid, methyl sulfonic acid, and acetic acid, and oxalic acid is preferably used. can do. However, this is only an example, and one embodiment of the present invention is not limited to this.

The acid catalyst is 0.01 mol to 10 mol parts, specifically 0.05 mol to 8 mol parts, or 0.1 mol, based on 100 mol of the fluorene-based biphenol compound represented by the chemical formula 2. It can be used in a content of 5 mol parts to 5 mol parts or 0.5 mol part to 4 mol parts.

On the other hand, the fluorene-based compound obtained by the novolak reaction is a non-crystalline fluorene-based biphenol resin (novolak-type phenol resin) containing a novolak-type fluorene-based biphenol compound containing the repeating unit 2.

前記繰り返し単位２ａ中、ｍ、Ｒ_７およびＲ_８は前記繰り返し単位２で定義した通りである。
具体的には、前記繰り返し単位２中、Ｒ_７およびＲ_８はそれぞれ独立して、水素、炭素数１～４のアルキル基、または炭素数６～１２のアリール基であり、好ましくは、Ｒ_７およびＲ_８は水素であり得る。ただし、これは一例に過ぎず、本発明の一実施形態はこれに限定されない。 Preferably, the novolak-type fluorene-based biphenol compound containing the repeating unit 2 contains the following repeating unit 2a.

In the repeating unit 2a, m, R ₇ and R ₈ are as defined in the repeating unit 2.
Specifically, in the repeating unit 2, R ₇ and R ₈ are independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and R ₇ is preferable. And R ₈ can be hydrogen. However, this is only an example, and one embodiment of the present invention is not limited to this.

The fluorene-based biphenol resin may have a number average molecular weight (Mn) of 200 g / mol to 2000 g / mol and a weight average molecular weight (Mw) of 200 g / mol to 2000 g / mol. Specifically, the number average molecular weight (Mn) of the fluorene-based biphenol resin is larger than the number average molecular weight of the crystalline monomer represented by the chemical formula 1, and more specifically, 300 g / mol to 2000 g / mol, or It can be 400 g / mol to 2000 g / mol, or 420 g / mol to 1500 g / mol, or 425 g / mol to 1250 g / mol, or 425 g / mol to 800 g / mol. The weight average molecular weight (Mw) of the fluorene-based biphenol resin is larger than the weight average molecular weight of the crystalline monomer represented by the chemical formula 1, and more specifically, 300 g / mol to 2000 g / mol or 400 g / mol. It can be from 2000 g / mol, or 420 g / mol to 1500 g / mol, or 425 g / mol to 1250 g / mol, or 450 g / mol to 950 g / mol. Further, the molecular weight distribution (Mw / Mn) determined by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the fluorene-based biphenol resin is 0.5 to 4.0 or 0. It can be .8 to 2.0, or 0.9 to 1.5, or 1.05 to 1.2.

As an example, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the fluorene-based biphenol resin were measured by gel permeation chromatography (GPC), and the obtained measured values were converted into polystyrene. Can be the value. As a specific measurement method, a usual method applicable to a fluorene-based biphenol resin can be applied.

Specifically, the fluorene-based biphenol resin may have a hydroxyl group equivalent of 175 g / eq to 250 g / eq, or 180 g / eq to 200 g / eq, or 185 g / eq to 190 g / eq. Here, the hydroxyl group equivalent (OHEW, hydroxy equivalent weight) is a value obtained by dividing the number average molecular weight (g / mol) of the resin by the hydroxyl group equivalent number (eq / mol). The fact that the hydroxyl group equivalent in the resin satisfies the above range means that high flexibility and a high refractive index can be realized with excellent thermal stability in the subsequent epoxidation step.

Further, the fluorene-based biphenol resin may not have a melting point (Tm), or may have a melting point (Tm) of 150 ° C. to 230 ° C., 160 ° C. to 225 ° C., or 170 ° C. to 222 ° C. As an example, the melting point (Tm) of the fluorene-based biphenol resin can be measured using a differential scanning calorimetry (DSC). Specifically, the temperature of the resin sample is increased from a temperature below room temperature at a rate of 10 ° C./min, and the temperature corresponding to the apex of the heat absorption peak (peak) corresponding to the bottom of the DSC (Mettler) curve is set to the melting point. (Tm).

Further, the fluorene-based biphenol resin may have no softening point (Ts), or the softening point (Ts) may be 110 ° C. to 180 ° C., 120 ° C. to 165 ° C., or 125 ° C. to 150 ° C. Here, the softening point of the fluorene-based biphenol resin can be measured by the ASTM E28 standard using the Ring and Ball method.

On the other hand, the non-crystalline fluorene-based biphenol resin (novolak-type phenol resin) obtained by the novolak reaction is reacted with epihalohydrin in the presence of a hydroxide salt (step 2), and the final substance is a non-crystalline fluorene-based biphenol resin. Manufacture epoxy resin.

Specifically, the step of reacting the fluorene-based biphenol resin with epihalohydrin is 25 ° C. to 120 ° C., or 30 at a pressure condition of 100 Torr to 300 Torr, or 120 Torr to 200 Torr, or 140 Torr to 180 Torr in the presence of a hydroxide salt. It can be carried out at ° C. to 120 ° C. or 30 ° C. to 80 ° C. As an example, the epoxidation reaction of the step 2 can be carried out for 0.5 hours to 10 hours, or 2 hours to 6 hours, or 3 hours to 5 hours under the above-mentioned conditions.

In step 2, the amount of epihalohydrin used may be 1 to 20 times the molar amount, specifically 4 to 8 times the molar amount of the hydroxyl group of the fluorene-based biphenol resin.

Further, the epihalohydrin may be one or more selected from the group consisting of epifluorohydrin, epichlorohydrin, epibromohydrin, epiiodohydrin, and β-methylepichlorohydrin, and may be specific. Epichlorohydrin can be used for.

In the step 2, the amount of the hydroxide salt used may be 0.85 to 1.2 times the molar amount of the hydroxyl group of the phenol resin.

Further, the hydroxide salt can be a hydroxide of an alkali metal or an alkaline earth metal, and is selected from the group consisting of NaOH, KOH, CsOH, Ca (OH) ₂ and Mg (OH) ₂ as an example. Can be one or more species. Specifically, NaOH, KOH and the like can be used. However, this is only an example, and one embodiment of the present invention is not limited to this.

The hydroxide salt can be used in a solid state or an aqueous solution dissolved in water, and specifically, at 25 ° C. to 120 ° C. or 30 ° C. to 120 ° C. under pressure conditions of 100 Torr to 300 Torr or 120 Torr to 200 Torr. It can be added in small portions over 0.5 hours to 6 hours or 2 hours to 5 hours, or can be added by a dropping method to cause a reaction.

Hereinafter, each step of the above-mentioned method will be described with reference to a specific example of the above-mentioned method for producing an amorphous fluorene-based epoxy resin.

ここで、ｎ’は０≦ｎ’≦１０の範囲を満たす値、つまり、ｎ’は０以上～１０以下、または０以上～６以下、または０以上～５以下の範囲を満たす値である。 The crystalline compound 4,4'-(9-fluorenylidene) diphenol (4,4'-(9-Fluorenylidene) diphenyl) was combined with formaldehyde (Formalin) and novolac in the presence of oxalic acid. By the reaction of the above, a solid polymer resin represented by the following chemical formula A can be produced. At this time, the reactivity of 4,4'-(9-fluorenylidene) diphenol can be adjusted by changing the molar ratio of the novolak reaction, and the molecular weight distribution is confirmed by gel permeation chromatography (GPC) analysis. Then, the softening point (Ts, softening point) of the product was measured by Ring and Ball method. Therefore, the crystalline / amorphous property can be controlled by adjusting the n'= 0 (monomer) content in the following, and the intermediate resin suitable for the synthesis of the epoxy resin is represented by the following chemical formula A. 4,4'-(9-Fluorenylidene) diphenyl-novolac resin can be produced. At this time, the range of the preferable molar ratio of the novolak reaction, the process conditions, and the like are as described above.

Here, n'is a value satisfying the range of 0 ≦ n'≦ 10, that is, n'is a value satisfying the range of 0 or more and 10 or less, 0 or more and 6 or less, or 0 or more and 5 or less.

ここで、ｎ’は０≦ｎ’≦１０の範囲を満たす値であり、ｍ’は０≦ｍ’≦１０の範囲を満たす値であり、ＯＧはグリシジルエーテル（ｇｌｙｃｉｄｙｌ ｅｔｈｅｒ）基である。 The 4,4'-(9-fluorenylidene) diphenol-novolac resin (4,4'-(9-Fluorenylidene) diphenol-novolac resin) represented by the chemical formula A is converted into excess epichlorohydrin. It can be melted and epoxidized by reaction with NaOH under reduced pressure conditions to produce the final product, a non-crystalline fluorene-based epoxy resin represented by the following chemical formula B.

Here, n'is a value satisfying the range of 0≤n'≤10, m'is a value satisfying the range of 0≤m'≤10, and OG is a glycidyl ether group.

As an example, a fluorene-based phenol resin produced by the above synthetic method is prepared by adding 1 to 20 times the excess mole of epichlorohydrin, preferably 3 to 8 times the mole of epichlorohydrin to the hydroxyl group of the phenol resin. Is dissolved and sodium hydroxide is further reacted with a solid or aqueous solution at a reaction temperature of 30 ° C. to 120 ° C. under reduced pressure for 0.5 hours to 10 hours. At this time, the reason for carrying out the reaction under reduced pressure is to remove the water generated by the reaction with sodium hydroxide or potassium hydroxide or the water used for the reaction, and by removing the water and carrying out the reaction. Epoxidation can be performed by suppressing side reactions.

Epoxy resin composition and cured product In still another embodiment of the present invention, there is provided an epoxy resin composition containing the above-mentioned non-crystalline fluorene-based epoxy resin, and an epoxy resin cured product formed from the epoxy resin composition.

In particular, the epoxy resin composition may be an epoxy resin curable composition containing a curing agent or the like together with the above-mentioned non-crystalline fluorene-based epoxy resin.

前記化学式１中、
Ｒ_１およびＲ_２はそれぞれ独立して、水素、置換または非置換の炭素数１～１０のアルコキシ基、置換または非置換の炭素数１～１０のアルキル基、置換または非置換の炭素数３～２０のシクロアルキル基、または置換または非置換の炭素数６～３０のアリール基であり、

前記繰り返し単位１中、
ｎは２≦ｎ≦１０の範囲を満たす値であり、
Ｒ_３およびＲ_４はそれぞれ独立して、水素、置換または非置換の炭素数１～１０のアルコキシ基、置換または非置換の炭素数１～１０のアルキル基、置換または非置換の炭素数３～２０のシクロアルキル基、または置換または非置換の炭素数６～３０のアリール基である。 Specifically, the novolac-type fluorene-based epoxy compound represented by the following chemical formula 1 and the novolac-type fluorene-based epoxy compound containing the following repeating unit 1 are included, and the total weight of the novolac-type fluorene-based epoxy compound containing the following repeating unit 1 is increased. Provided is an epoxy resin curable composition, which is a varnish composition containing a non-crystalline fluorene epoxy resin, a curing agent, a curing catalyst and a solvent, which contains 3% to 80% as a reference.

In the chemical formula 1,
R ₁ and R ₂ are independently hydrogen, an alkoxy group having 1 to 10 carbon atoms substituted or unsubstituted, an alkyl group having 1 to 10 carbon atoms substituted or unsubstituted, and 3 to 10 carbon atoms substituted or unsubstituted. 20 cycloalkyl groups, or substituted or unsubstituted aryl groups having 6 to 30 carbon atoms.

In the repeating unit 1,
n is a value that satisfies the range of 2 ≦ n ≦ 10.
R ₃ and R ₄ are independently hydrogen, an alkoxy group having 1 to 10 carbon atoms substituted or unsubstituted, an alkyl group having 1 to 10 carbon atoms substituted or unsubstituted, and 3 to 10 carbon atoms substituted or unsubstituted. It is a cycloalkyl group of 20 or an aryl group having 6 to 30 carbon atoms which is substituted or unsubstituted.

Since the detailed description of the chemical formula 1 and the repeating unit 1 is as described above, the detailed description thereof will be omitted here.

By containing the above-mentioned non-crystalline epoxy resin, the epoxy resin composition ensures workability and storage stability while achieving high flexibility and refractive index as well as excellent thermal stability. A laminated board for semiconductor packages, a laminated board for high-frequency transmission, and a copper-clad laminated board (CCL) that solves the problems of fluidity and smoothness deterioration that occur during novolacization by adjusting the crystallinity to the optimum point. ), Flexible display substrate (Flexible display substrate), and suitable for application to laminated plates such as insulating plates.

As the component other than the epoxy resin, those generally known in the art can be selected.

Further, the epoxy resin may further contain a non-fluorene-based epoxy compound that does not contain a fluorene structure, if necessary, in order to adjust the physical properties.

As an example, the non-Fluorene epoxy compound is bisphenol A, bisphenol F, 3,3', 5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl. Sulfur, 4,4'-dihydroxydiphenylketone, 4,4'-biphenol, 3,3', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, resorcinol, catechol, hydroquinone, dihydroxynaphthalene, etc. Or is it an allylated product of the compound or a divalent phenol such as an allylated bisphenol A, an allylated bisphenol F, an allylated novolak resin; or a biphenol A novolak, o-cresol novolak, m-cresol novolak, p- Whether it is a trivalent or higher valence phenol such as cresol novolak, xylenol novolak, phenol aralkyl resin, naphthol aralkyl resin, dicyclopentadiene resin; or halogenated bisphenols such as tetrabromobisphenol A, or select from these. It can be a glycidyl ether compound derived from one of the mixtures to be made.

The non-crystalline fluorene epoxy resin of the present invention and the non-fluorene epoxy compound are used in a weight ratio of 1: 3 to 3: 1 or 1: 2 to 2: 1 in terms of shrinkage, elastic modulus and moldability. It is possible to achieve the unique characteristics of high flexibility, high refraction, and high heat resistance with excellent balance.

Further, the curing agent may contain any one selected from the group containing a phenol novolac resin, a cresol novolak resin, a dicyclopentadiene resin, and a dicyandiamide, or a mixture of two or more of them. For example, the phenol novolac resin has two or more hydroxyl groups, and the hydroxyl group equivalent (OHEW, hydroxy equivalent weight) can be 80 g / eq to 200 g / eq. Here, the hydroxyl group equivalent is a value obtained by dividing the number average molecular weight (g / mol) of the resin by the hydroxyl group equivalent number (eq / mol).

In the epoxy resin composition, the composition ratio of the epoxy resin to the curing agent is the number of epoxy groups in the epoxy resin with respect to the hydroxyl group in the curing agent, or the epoxy in the epoxy resin with respect to the amine active hydrogen group in the curing agent. The molar ratio of the number of groups is preferably 0.8 to 1.2 (epoxy group / (hydroxyl group or amine active hydrogen group)).

Further, the solvent is any one selected from the group containing a ketone solvent, an acetate solvent, a carbitol solvent, an aromatic hydrocarbon solvent, and an amide solvent, or two or more of them. It can be a mixture.

Examples of the ketone solvent include methyl ethyl ketone and cyclohexanone, examples of the acetate solvent include ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and examples of the carbitol solvent include ethyl acetate, butyl acetate and cellosolve acetate. Examples of the aromatic hydrocarbon solvent include toluene and xylene, and examples of the amide solvent include dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. ..

On the other hand, the epoxy resin composition may further contain a curing catalyst. At this time, the curing catalyst may be any one selected from the group containing an imidazole compound, a phosphine compound, a phosphonium salt, and a tertiary amine, or a mixture of two or more of these.

In still another embodiment of the present invention, there is provided an epoxy resin cured product formed from the epoxy resin composition described above.

Specifically, the epoxy resin cured product may be a completely cured state or a semi-cured state of the epoxy resin composition depending on the intended use and function. Since the description of the epoxy resin composition is as described above, the description thereof is omitted here.

Further, the cured epoxy resin may be in the form of a prepreg formed by drying glass fibers or the like impregnated with the epoxy resin composition.

Laminated Plate In still another embodiment of the present invention, a laminated plate to which the epoxy resin composition is applied is provided.

Specifically, the present invention provides a laminated board including a substrate and a resin layer located on one or both sides of the substrate, and the resin layer is formed from the above-mentioned epoxy resin composition.

The resin layer may be a cured or semi-cured state of the epoxy resin composition depending on the intended use and function. Since the description of the epoxy resin composition is as described above, the description thereof is omitted here.

On the other hand, the substrate may be any one substrate selected from the group including the semiconductor substrate, the copper foil plate, and the insulating plate. For example, as in Example 1-1 and the evaluation example described later, a copper foil plate can be used for the substrate, and the laminated plate can be realized by CCL (Copper Clad Laminate). However, this is only an example, and one embodiment of the present invention is not limited to this.

Method for Producing Laminated Plate In still another embodiment of the present invention, there is a step of impregnating the glass fiber with the composition and a step of drying the glass fiber impregnated with the composition to obtain a prepreg. Provided is a method for manufacturing a laminated board, which comprises a step of laminating the prepreg on a substrate and then crimping the prepreg to obtain a laminated board.

This is one of several methods for manufacturing the laminates described above. It is possible to use only one prepreg, or to manufacture and use a plurality of prepregs.

Further, it is possible to use only one substrate, and it is also possible to use a plurality of the substrates. When a plurality of the substrates are used, at the stage of laminating the prepreg on the substrate and then crimping to obtain a laminated board, the prepreg is positioned between two different substrates and then crimped.

Regardless of the number of the prepreg and the laminated board, in the step of laminating the prepreg on the substrate and then crimping to obtain the laminated board, the crimping pressure, temperature, time and the like follow those generally known in the art.

Hereinafter, preferred embodiments will be presented to aid in the understanding of the present invention. However, the following examples are provided only for easier understanding of the present invention, which does not limit the content of the present invention.

前記反応式１中、ｘは０≦ｘ≦１０の範囲を満たす値、つまり、ｘは０以上～１０以下、または０以上～６以下、または０以上～５以下の範囲を満たす値である。特に、ｘ＝０である場合、反応物であるモノマーを示す。 (I) Primary reaction (step 1): Production of fluorene-based biphenol resin by novolak reaction As represented by the following reaction formula 1, 4,4'-(9-fluorenylidene) diphenol (4) which is a crystalline compound. , 4'-(9-fluorenylidene) diphenyl) was produced as a solid polymer resin containing a polymer produced by the reaction of formaldehyde with novolac in the presence of an acid catalyst.

In the reaction formula 1, x is a value satisfying the range of 0 ≦ x ≦ 10, that is, x is a value satisfying the range of 0 or more and 10 or less, 0 or more and 6 or less, or 0 or more and 5 or less. In particular, when x = 0, it indicates a monomer that is a reactant.

Example 1-1
First, 100 g (0.285 mol) of 4,4'-(9-fluorenylidene) diphenol and 1 g (0.011 mol) of oxalic acid dihydrate as an acid catalyst were added to a 1 L volume reaction vessel with methyl cellosolve. , 2-methoxyethanol) was added to 200 g and dissolved at 80 ° C. Then, 3.9 g (0.048 mol) of 37% (w / v) formaldehyde was added, the temperature was raised to 120 ° C., and then the reaction was carried out for 4 hours. At this time, the 4,4'-(9-fluorenylidene) diphenol compound was reacted with formaldehyde at a molar ratio of 6: 1, and oxalic acid was 100 mol of the 4,4'-(9-fluorenilidene) diphenol compound. Was reacted at 3.86 mol based on the above. Methyl cellosolve was recovered at normal pressure (25 ° C.) while raising the temperature to 180 ° C., and further reduced pressure recovery was advanced to 20 torr or less. The resin for which the solvent recovery was completed was solidified at room temperature, and the softening point of Example 1-1 was 135 ° C.

Example 2-1
100 g (0.285 mol) of 4,4'-(9-fluorenylidene) diphenol (4,4'-(9-Fluorenylidene) diphenyl) and 1 g (0) of oxalic acid as an acid catalyst in a 1 L volume reaction vessel. .011 mol) was added to 200 g of methyl cellosolve (2-methoxyethanol) and dissolved at 80 ° C. Then, 2.9 g (0.036 mol) of 37% formaldehyde was added, the temperature was raised to 120 ° C., and then the reaction was carried out for 4 hours. At this time, the 4,4'-(9-fluorenylidene) diphenol compound was reacted with formaldehyde in a molar ratio of 8: 1, and oxalic acid was 100 mol of the 4,4'-(9-fluorenylidene) diphenol compound. Was reacted at 3.86 mol based on the above. After completion of the reaction, the methyl cellosolve was recovered at normal pressure (25 ° C.) while raising the temperature to 180 ° C., and the vacuum recovery was further advanced to 20 torr or less. The resin for which the solvent recovery was completed was solidified at room temperature, and the softening point of Example 2-1 was 127 ° C.

Comparative Example 1-1
Crystallization characteristics were evaluated using a monomer (monomer) having a purity of 99.9% that does not proceed with the novolak reaction to the 4,4'-(9-fluorenylidene) diphenol compound as a comparative group.

Comparative Example 2-1
The molar ratio of 4,4'-(9-fluorenylidene) diphenol compound to formaldehyde is 0.55: 1, and oxalic acid is based on 100 mol of the 4,4'-(9-fluorenilidene) diphenol compound. The process proceeded under the same conditions as in Example 1 except that the reaction was carried out at 9.8 mol. The produced resin exhibited amorphous properties at room temperature, and the softening point was 197 ° C.

4,4'-(9-fluorenylidene) diphenol-novolak resin (4,4'-(9-Fluorenylidene) of Examples 1-1 to 2-1 and Comparative Examples 1-1 to 2-1. ) Diphenyl-novolac resin), the specific reaction molar ratio conditions and the results of physical property measurement for the resin are shown in Table 1 below.

In particular, in the crystallinity evaluation of the resin, the melting point (Tm, ° C.), the hydroxyl group equivalent (OHEW, g / eq), and the softening point (° C.) were measured, and the number average molecular weight (Mn, g / mol) was determined by GPC analysis. And the weight average molecular weight (Mw, g / mol), the molecular weight distribution (Mn / Mw), the content of the monomer compound represented by the chemical formula 1 (monomer content of n = 1,%) and the repeating unit 1. The novolak polymer (polymer content of n = 2 or more,%) was measured. At this time, it is a value measured based on the total weight of the novolak polymer (n = 2 or more polymer content,%) containing the monomer compound represented by the chemical formula 1 and the repeating unit 1.

At this time, the physical properties are measured by using a differential scanning calorimetry (DSC) and gel permeation chromatography (GPC), respectively, and the specific measurement method is as described above.

On the other hand, the analysis graphs of the differential scanning calorimetry (DSC) for the fluorene-based biphenol resin of Example 1-1 and the 4,4'-(9-fluorenylidene) diphenol compound of Comparative Example 1-1 are shown respectively. 1 and FIG. 2 are shown.

In particular, as shown in FIG. 1, in the DSC curve of Example 1-1, it is produced of a fluorene-based biphenol resin containing a novolak-type compound formed by a compound bond having a large molecular weight by binding a monomer, and as a non-crystalline solid. The melting point did not appear, and as shown in FIG. 2, the melting point was 232 ° C. as a characteristic of the crystalline resin having a monomer structure in the DSC curve of Comparative Example 1-1.

In addition, the analysis graphs of gel permeation chromatography (GPC) for the fluorene-based biphenol resin of Example 1-1 and the 4,4'-(9-fluorenylidene) diphenol compound of Comparative Example 1-1 are shown respectively. 3 and FIG.

In particular, as shown in FIG. 3, in the GPC curve of Example 1-1, the molecular weight distribution diagram of the fluorene-based biphenol resin containing a compound having a novolak-type structure having n = 2 or 3 or more repeating units is confirmed. As shown in FIG. 4, in the GPC curve of Comparative Example 1-1, the 4,4'-(9-fluorenylidene) diphenol compound as a monomer or monomer structure having a repeating unit n = 1 can be obtained. It was confirmed that it appeared as a single peak of.

On the other hand, as shown in Table 1, as a result of confirming the molecular weight distributions of Example 1-1, Example 2-1 and Comparative Example 2-1 it is confirmed that a polymer larger than the dimer was synthesized. It was possible to measure the melting point (Tm) with a differential scanning calorimetry (DSC), and it was confirmed that the crystallinity was sufficiently controlled.

(II) Secondary reaction (step 2): Production of final substance by epoxidation reaction As represented by the following reaction formula 2, 4,4'-(9-fluorenylidene) diphenol-novolak resin (4) produced above. , 4'-(9-Fluorenylidene) diphenyl-novolac resin) was reacted with epihalohydrin in the presence of a hydroxide to prepare a non-crystalline fluorene epoxy resin as a final substance.

In the reaction formula 2, x is a value satisfying the range of 0 ≦ x ≦ 10, y is a value satisfying the range of 0 ≦ y ≦ 10, and OG is a glycidyl ether. Specifically, x and y are values that satisfy the range of 0 or more and 10 or less, 0 or more and 6 or less, or 0 or more and 5 or less, respectively. In particular, when x = 0 and y = 0, the monomers corresponding to the respective reactants are shown.

Example 1-2
To a 1 L volume reaction vessel, 100 g (0.53 mol) of 4,4'-(9-fluorenylidene) diphenol-novolak resin of Example 1-1 was added to 296 g (3.2 mol) of epichlorohydrin. And dissolved at 65 ° C. Then, 42 g (0.525 mol) of 50% NaOH was added dropwise at 30 ° C. to 80 ° C. for 4 hours under a reduced pressure of 180 torr for reaction. At this time, the epichlorohydrin was reacted with the hydroxyl group of the 4,4'-(9-fluorenylidene) diphenol-novolak resin at a molar content of 3 to 8 times, and NaOH was 0.85 times. The reaction was carried out with a molar content of ~ 1.2 times. The pressure was maintained at 180 torr, the reaction proceeded at 30 ° C to 120 ° C, and the reaction proceeded by continuously removing water in order to suppress side reactions caused by water during the reaction process. After the reaction was completed, the generated salts and by-reactants were removed using methyl isobutyl ketone (MIBK, methyl isobutyl ketone), toluene and distilled water. The epoxy equivalent of the amorphous fluorene-based epoxy resin thus produced was 250 g / eq.

As a result of confirming the molecular weight distribution of the product of Example 1-2 thus produced by GPC analysis, a polymer larger than the dimer was synthesized, and the secondary reaction product in which the epoxidation reaction proceeded was Ball and Ring. The softening point was measured by the method.

Example 2-2
The epoxidation reaction proceeded in the same manner as in the secondary reaction conditions of Example 1-2, except that 100 g of 4,4'-(9-fluorenylidene) diphenol-novolak resin of Example 2-1 was used. did.

As a result of confirming the molecular weight distribution of the product of Example 2-2 thus produced by GPC analysis, a polymer larger than the dimer was synthesized, and the secondary reaction product in which the epoxidation reaction proceeded was Ball and Ring. The softening point was measured by the method.

Comparative Example 1-2
An epoxy resin was produced in the same manner as in Example 1-1, except that a 4,4'-(9-fluorenylidene) diphenol compound having a purity of 99.9% in Comparative Example 1-1 was used.

Comparative Example 2-2
100 g (0.52 mol) of 4,4'-(9-fluorenylidene) diphenol-novolak resin of Comparative Example 2-1 was added to 296 g (3.2 mol) of epichlorohydrin and dissolved at 65 ° C. rice field. Then, 42 g (0.525 mol) of 50% NaOH was added dropwise at 30 ° C. to 80 ° C. for 4 hours under a reduced pressure of 180 torr to react, and after the reaction was completed, methyl isobutyl ketone (MIBK, methyl isobutyl ketone), Toluene and distilled water were used to remove the generated salts and by-reactants.

As a result of confirming the molecular weight distribution of the product of Comparative Example 2-2 thus produced by GPC analysis, a polymer larger than the dimer was synthesized, and the secondary reaction product in which the epoxidation reaction proceeded was Ball and Ring. The softening point was measured by the method.

前記構造式中、ｚは１≦ｚ≦１０の範囲を満たす値である。 Comparative Example 3-2
Using a commercially available phenol novolac epoxy resin (trade name: YDPN-638EK80, manufactured by Kokuto Kagaku Co., Ltd., EEW179.7 g / eq, viscosity 370 cps @ 25 ° C.), the structural formula of the epoxy resin (YDPN-638EK80) is as follows. be.

In the structural formula, z is a value that satisfies the range of 1 ≦ z ≦ 10.

The melting point (Tm, ° C.) measured for the evaluation of the crystallinity of the fluorene epoxy resins of Examples 1-2 to 2-2 and Comparative Examples 1-2 to 2-2, and Epoxy equivalent (EEW, g / eq), softening point (Ts, ° C), number average molecular weight (Mn, g / mol) by GPC analysis, weight average molecular weight (Mw, g / mol), molecular weight distribution (Mn / Mw) ), Melt viscosity (cps @ 150 ° C.), storage stability (cyclohexanone 50% dilute), and refractive index (RI) are as shown in Table 2 below.

At this time, the physical properties are measured by using a differential scanning calorimetry (DSC) and gel permeation chromatography (GPC), respectively, and the specific measurement method is as described above.

However, the melt viscosity of the fluorene-based epoxy resin is measured at 150 ° C. using a rotary viscometer manufactured by Brookfield, and the storage stability is obtained by dissolving the sample in a cyclohexanone solvent at a weight ratio of 1: 1. After that, the phenomenon of crystallizing and precipitating at room temperature (RT, 23 ° C to 25 ° C) was measured, and the refractive index (RI) was measured at a wavelength of 404 nm by joining to a prism and changing the incident angle of light. It was measured.

As shown in Table 2 above, the amorphous fluorene epoxy resins of Examples 1-2 and 2-2 have a softening point and a melt viscosity of Comparative Example 2-2 while lowering the crystallinity. It was lower than epoxy resin. This is a solidified resin that can be applied to various fields such as electronic materials that require high functionality while maintaining the unique characteristics of the fluorene structure such as high refractive index with minimal deformation. Manufactured.

<Test example>
Copper-clad laminates (CCL: Copper) were applied to the epoxy resins of Examples 1-2 to Example 2-2, Comparative Example 1-2, Comparative Example 2-2, and Comparative Example 3-2 by the following methods. The physical property evaluation at the time of manufacturing the copper laminate) was measured, and the measurement results are as shown in Table 3 below.

1) Production of test pieces for CCL evaluation The epoxy resins of Examples and Comparative Examples, the curing agent, and the curing catalyst are mixed in a composition of 32% by weight and 0.02% by weight, respectively, based on the total weight of solid content. Then, methyl ethyl ketone (MEK, methyl ethyl ketone) was used as a solvent to prepare varnish solutions having a solid content of 70% by weight. Here, as the curing agent, a phenol novolac curing agent having a softening point of 95.2 ° C. was used, and as a catalyst, 2-methylimidazole (2MI, 2-methylimidazole) was used. The solution viscosity of the varnish solution thus produced was measured at 25 ° C. using a rotary viscometer manufactured by Brookfield, and the measurement results are as shown in Table 3 below.

After impregnating 2116 type E-glass glass fibers with each of the varnish solutions thus produced, the prepreg was produced by placing it in an oven at 175 ° C. and drying it for 2 minutes.

Eight pieces of each prepreg were placed between two 1 ounce (oz) copper foils and then hot pressed at a temperature of 180 ° C. and a pressure of 200 psi for 1 hour and 30 minutes, respectively. A test piece for evaluating CCL physical properties was obtained.

2) Glass transition temperature (Tg)
The glass transition temperature (Tg) was set to IPC TM-650 2.4.25 using a differential scanning calorimeter (DSC) after the resin compositions of each Example and Comparative Example were maintained at 180 ° C. for 6 hours and cured. Measured according to the standard of.

3) Coefficient of thermal expansion (CTE)
The coefficient of thermal expansion (CTE) was measured according to the IPC TM-650 2.4.24 standard after the resin compositions of each Example and Comparative Example were maintained at 180 ° C. for 6 hours and cured.

4) Flexural modulus
The bending elasticity is determined by adhering the resin compositions of the Examples and Comparative Examples to the metal foils to produce each metal leaf with resin, and facing the resin surface with respect to each of the two metal foils with resin. By overlapping, double-sided copper-clad laminates were manufactured. After etching the entire surface of the copper-clad laminates on both sides, the copper-clad laminates were cut into a width of 5 mm and a length of 30 mm, and calculated using DMA (Dynamic Mechanical Analysis).

Claims (14)

The novolac-type fluorene-based epoxy compound represented by the following chemical formula 1 and the novolac-type fluorene-based epoxy compound containing the following repeating unit 1 are contained, and the novolac-type fluorene-based epoxy compound containing the following repeating unit 1 is 3% based on the total weight. Non-crystalline fluorene epoxy resin containing -80%:

In the chemical formula 1,
R ₁ and R ₂ are independently hydrogen, an alkoxy group having 1 to 10 carbon atoms substituted or unsubstituted, an alkyl group having 1 to 10 carbon atoms substituted or unsubstituted, and 3 to 10 carbon atoms substituted or unsubstituted. 20 cycloalkyl groups, or substituted or unsubstituted aryl groups having 6 to 30 carbon atoms.

In the repeating unit 1,
n is a value that satisfies the range of 2 ≦ n ≦ 10.
R ₃ and R ₄ are independently hydrogen, an alkoxy group having 1 to 10 carbon atoms substituted or unsubstituted, an alkyl group having 1 to 10 carbon atoms substituted or unsubstituted, and 3 to 10 carbon atoms substituted or unsubstituted. It is a cycloalkyl group of 20 or an aryl group having 6 to 30 carbon atoms which is substituted or unsubstituted. The non-crystalline fluorene according to claim 1, wherein the fluorene-based epoxy compound represented by the chemical formula 1 and the novolak-type fluorene-based epoxy compound containing the repeating unit 1 are contained in a weight ratio of 90:10 to 30:70. Epoxy resin. The non-crystalline fluorene system according to claim 1, wherein R ₁ and R ₂ in the chemical formula 1 are independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Epoxy resin manufacturing method. The number average molecular weight is 200 g / mol to 2000 g / mol.
The amorphous fluorene-based epoxy resin according to claim 1, wherein the epoxy equivalent is 200 g / eq to 500 g / eq. In the presence of an acid catalyst, the fluorene-based biphenol compound represented by the following chemical formula 2 is reacted with formaldehyde at a molar ratio of 2: 1 to 10: 1, and the novolac-type fluorene-based biphenol compound containing the following repeating unit 2 is contained. At the stage of manufacturing fluorene-based biphenol resin,
A method for producing a non-crystalline fluorene-based epoxy resin, which comprises a step of reacting the fluorene-based biphenol resin with epihalohydrin in the presence of a hydroxide salt.

In the chemical formula 2,
R ₅ and R ₆ are independently hydrogen, an alkoxy group having 1 to 10 carbon atoms substituted or unsubstituted, an alkyl group having 1 to 10 carbon atoms substituted or unsubstituted, and 3 to 10 carbon atoms substituted or unsubstituted. 20 cycloalkyl groups, or substituted or unsubstituted aryl groups having 6 to 30 carbon atoms.

In the repeating unit 2,
m is a value that satisfies the range of 2 ≦ m ≦ 10.
R ₇ and R ₈ are independently hydrogen, an alkoxy group having 1 to 10 carbon atoms substituted or unsubstituted, an alkyl group having 1 to 10 carbon atoms substituted or unsubstituted, and 3 to 10 carbon atoms substituted or unsubstituted. It is a cycloalkyl group of 20 or an aryl group having 6 to 30 carbon atoms which is substituted or unsubstituted. The method for producing a non-crystalline fluorene-based epoxy resin according to claim 5, wherein the fluorene-based biphenol compound represented by the chemical formula 2 and formaldehyde are reacted at a molar ratio of 3: 1 to 9: 1. The method for producing an amorphous fluorene-based epoxy resin according to claim 5, wherein the step of reacting the fluorene-based biphenol compound represented by the chemical formula 2 with formaldehyde is carried out at 100 ° C. to 140 ° C. under the conditions of 750 Torr to 770 Torr. .. The non-crystalline fluorene system according to claim 5, wherein R ₅ and R ₆ in the chemical formula 2 are independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Epoxy resin manufacturing method. The non-crystalline fluorene-based epoxy according to claim 5, wherein the acid catalyst is at least one selected from the group consisting of oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, p-toluenesulfonic acid, methylsulfonic acid, and acetic acid. Resin manufacturing method. The non-crystalline fluorene epoxy according to claim 5, wherein the acid catalyst is used in a content of 0.01 mol to 10 mol parts based on 100 mol of the fluorene-based biphenol compound represented by the chemical formula 2. Resin manufacturing method. The method for producing a non-crystalline fluorene-based epoxy resin according to claim 5, wherein the fluorene-based biphenol resin has a number average molecular weight of 200 g / mol to 2000 g / mol and a hydroxyl group equivalent of 175 g / eq to 250 g / eq. .. The step of reacting the fluorene-based biphenol resin with epihalohydrin is carried out at 25 ° C. to 120 ° C. under a pressure condition of 100 Torr to 300 Torr in the presence of a hydroxide salt to produce the amorphous fluorene epoxy resin according to claim 5. Method. An epoxy resin composition comprising the non-crystalline fluorene-based epoxy resin according to claim 1, a curing agent, a curing catalyst, and a solvent. With the board
Includes a resin layer located on one or both sides of the substrate.
The resin layer is a laminated board formed from the epoxy resin composition according to claim 13.

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