KR20210112306A - Modified epoxy resins, epoxy resin compositions, cured products, and laminates for electric/electronic circuits - Google Patents

Abstract

R¹ 은 치환기를 가지고 있어도 되는 알킬기 또는 치환기를 가지고 있어도 되는 아릴기. R² 는 치환기를 가지고 있어도 되는 아릴기. 그 치환기는 할로겐 원자, 탄소수 1 ∼ 12 의 알킬기, 탄소수 1 ∼ 12 의 알콕시기 및 탄소수 6 ∼ 12 의 아릴기로 이루어지는 군에서 선택되는 기.A modified epoxy resin obtained by reacting an epoxy resin (A) having an average of two or more epoxy groups in one molecule and an ester compound (B) represented by the following formula (1) having one ester structure in one molecule.

R ¹ is an alkyl group which may have a substituent or an aryl group which may have a substituent. R ² is an aryl group which may have a substituent. The substituent is a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

Description

Modified epoxy resins, epoxy resin compositions, cured products, and laminates for electric/electronic circuits

The present invention relates to a modified epoxy resin excellent in heat resistance and low dielectric properties, an epoxy resin composition containing the modified epoxy resin and a curing agent, a cured product thereof, and a laminate for electric/electronic circuits comprising the epoxy resin composition.

Since the epoxy resin is excellent in adhesiveness, water resistance, mechanical strength, and electrical properties, it is used in various fields, such as an adhesive agent, a paint, a material for civil engineering construction, and the insulating material of electric/electronic components. In particular, in the electric/electronic field, it is widely used in an insulating mold, a laminated material, a sealing material, etc. In recent years, multilayer circuit boards used in electrical and electronic devices are being miniaturized, lightweight and highly functional, and additional multilayering, high density, thinness, weight reduction, reliability, and moldability improvement are required.

A low dielectric characteristic is mentioned as an important performance calculated|required of the epoxy resin used as the material of electrical/electronic components, such as a laminated board for electrical/electronic circuits.

In recent years, in order to improve the amount and speed of information transmission, the communication frequency has been increased to a higher frequency. Among them, an increase in the transmission loss α has become a major problem. The lower the value of the transmission loss ?, the less attenuation of the information signal, which means that high reliability of communication can be secured. Since α is proportional to the frequency f, α increases in communication in a high frequency region, leading to a decrease in reliability. As a method of suppressing the transmission loss (α), a method of reducing the dielectric loss tangent (tanδ) in which α is proportional to the frequency f is exemplified. For high-speed transmission of communication signals, a material having a low dielectric loss tangent (tan?), that is, a material having a low dielectric characteristic is required.

Moreover, high reliability is calculated|required of electric/electronic components, such as a laminated board for electric/electronic circuits, and balance with various characteristics, such as heat resistance, in addition to a low dielectric characteristic is calculated|required. In particular, as the amount of information transmitted in the high-frequency region increases in recent years, the load applied to the electronic/electronic circuit laminated board increases as well, and internal heat is generated.

Patent Document 1 discloses a modified epoxy resin formed by reacting an acylated polyphenol compound with an epoxy resin with the object of providing a cured epoxy resin excellent in heat resistance while achieving low viscosity and low water absorption.

Specifically, the modified epoxy resin disclosed in Patent Document 1 is an epoxy resin obtained by reaction of a diacylated phenol compound and a bisphenol-type epoxy resin. Patent document 1 has description to the effect that it is excellent in a low viscosity, low water absorption, and heat resistance. However, the heat resistance of the modified epoxy resin of patent document 1 was not enough.

Moreover, as a result of the examination of the present inventors, from the characteristics requested|required of recent electrical/electronic components, the modified epoxy resin of patent document 1 is a material used in a high frequency area|region, and has a low dielectric property (low dielectric loss tangent (low tan δ)). ) was found to be insufficient.

Japanese Patent Laid-Open No. 8-333437

The object of the present invention is a modified epoxy resin having a good balance between heat resistance and low dielectric properties, an epoxy resin composition containing the modified epoxy resin and a curing agent, a cured product thereof, and a laminate for electrical and electronic circuits comprising the epoxy resin composition is to provide

MEANS TO SOLVE THE PROBLEM This inventor discovered that the said subject could be solved with the epoxy resin which modified|denatured the epoxy resin with the specific monofunctional ester compound.

The gist of the present invention is in the following [1] to [11].

[1] A modified epoxy resin obtained by reacting an epoxy resin (A) having an average of two or more epoxy groups in one molecule and an ester compound (B) represented by the following formula (1) having one ester structure in one molecule.

[Formula 1]

In Formula (1), R<^1> is the alkyl group which may have a substituent, or the aryl group which may have a substituent. R ² is an aryl group which may have a substituent. The substituent is a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

[2] The reaction equivalent ratio of the epoxy resin (A) and the ester compound (B) is 1.6 to 6.0 in the ratio of the number of moles of the epoxy groups of the epoxy resin (A) to the number of moles of the ester group of the ester compound (B), [ 1], the modified epoxy resin described above.

^{[3] The modified epoxy resin according to [1] or [2], wherein R 1} and R ² in the formula (1) are each independently a phenyl group which may have a substituent or a naphthyl group which may have a substituent.

[4] An epoxy resin composition comprising the modified epoxy resin according to any one of [1] to [3] and a curing agent.

[5] The epoxy resin composition according to [4], wherein the curing agent is contained in an amount of 0.1 to 100 parts by weight by solid content, based on 100 parts by weight of the solid content of the modified epoxy resin.

[6] The epoxy resin according to [4] or [5], wherein the modified epoxy resin and another epoxy resin are contained, and the weight ratio of the modified epoxy resin and the solid content of the other epoxy resin is 99/1 to 1/99. composition.

[7] The epoxy resin composition according to [6], wherein the curing agent is contained in an amount of 0.1 to 100 parts by weight as a solid content relative to 100 parts by weight of a total of the solid content of the modified epoxy resin and the other epoxy resins.

[8] The epoxy resin composition according to any one of [4] to [7], wherein the curing agent is at least one selected from the group consisting of phenol curing agents, amide curing agents, imidazoles and active ester curing agents.

[9] A cured product obtained by curing the epoxy resin composition according to any one of [4] to [8].

[10] A laminate for electric/electronic circuits using the epoxy resin composition according to any one of [4] to [8].

[11] A modified epoxy resin comprising a structure represented by the following formula (4).

[Formula 2]

In Formula (4), R<^1> is the alkyl group which may have a substituent, or the aryl group which may have a substituent. R ² is an aryl group which may have a substituent. The substituent is a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

ADVANTAGE OF THE INVENTION According to this invention, the modified epoxy resin which is excellent in the balance of heat resistance and low dielectric characteristic, and an epoxy resin composition, and its hardened|cured material can be provided. For this reason, the modified epoxy resin of this invention and the epoxy resin composition containing it are applicable to various fields, such as an adhesive agent, a paint, a building material for civil engineering, and the insulating material of an electric/electronic component. The modified epoxy resin of the present invention and the epoxy resin composition containing the same are particularly useful as an insulating mold, a laminate material, a sealing material, and the like in the electric/electronic field.

The modified epoxy resin of the present invention and the epoxy resin composition containing the same are multilayer printed wiring boards, laminates for electrical and electronic circuits such as capacitors, adhesives such as film adhesives and liquid adhesives, semiconductor encapsulation materials, underfill materials, 3D- It can be preferably used for interchip fill for LSI, insulating sheet, prepreg, heat dissipation substrate, etc.

EMBODIMENT OF THE INVENTION Embodiment of this invention is described in detail below.

The description given below is an example of embodiment of this invention, and this invention is not limited to the content of description below unless the summary is exceeded.

In this specification, when the expression "-" is used, it shall be used as an expression containing the numerical value or physical property value before and behind it.

[Modified Epoxy Resin]

The modified epoxy resin of the present invention is obtained by reacting an epoxy resin (A) having an average of two or more epoxy groups in one molecule and an ester compound (B) represented by the following formula (1) having one ester structure in one molecule, it will be obtained

[Formula 3]

In Formula (1), R<^1> is the alkyl group which may have a substituent, or the aryl group which may have a substituent. R ² is an aryl group which may have a substituent. The substituent is a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

Moreover, the modified epoxy resin of this invention contains the structure represented by following formula (4).

[Formula 4]

In Formula (4), R<^1> and R<^2> have the same meaning as the thing in said Formula (1).

[mechanism]

The modified epoxy resin of the present invention has a structure in which the ester group of the ester compound (B) is bonded together with the epoxy group of the epoxy resin (A), as shown by the formula (4), resulting from this structure, low dielectric properties this will be good

The reason for this is assumed to be as follows.

As the structure in the ester compound (B), one ester group is present in one molecule, and since the structure contains an alkyl group or an aryl group with low polarity in the structure, a formula formed by reaction with the epoxy group of the epoxy resin (A) The structure of (4) also becomes low polarity, and low dielectric characteristic is expressed. Moreover, the glass transition temperature (Tg) at the time of hardening can also be raised by making the epoxy group derived from an epoxy resin (A) remain suitably in a modified epoxy resin with the structure of Formula (4).

Accordingly, it is considered that an epoxy resin having a good balance between low dielectric properties and heat resistance and excellent, and a cured product thereof can be obtained.

[Epoxy Resin (A)]

The epoxy resin (A) used by this invention is an epoxy resin which has an average of 2 or more epoxy groups in 1 molecule.

As the epoxy resin (A), after the reaction with the ester compound (B), in order to sufficiently express heat resistance, the epoxy equivalent is preferably 400 g/equivalent or less, more preferably 350 g/equivalent or less, and 300 g/equivalent or less. more preferably. From the viewpoint of sufficiently ensuring reactivity with the ester compound (B), the epoxy equivalent of the epoxy resin (A) is preferably 100 g/equivalent or more, more preferably 120 g/equivalent or more, and still more preferably 150 g/equivalent or more. do.

In this invention, "epoxy equivalent" is defined as "the mass of an epoxy resin containing an epoxy group of 1 equivalent", and can measure according to JISK7236.

As an epoxy resin (A), in order to fully express heat resistance, what has an average of 2 or more epoxy groups in 1 molecule is used. From the viewpoint of heat resistance, the epoxy resin (A) preferably has 2.1 or more epoxy groups, more preferably 2.5 or more, and still more preferably 3 or more. On the other hand, from the viewpoint of handleability, the epoxy resin (A) preferably has an average of 12 or less epoxy groups per molecule, more preferably 10 or less, and still more preferably 8 or less.

The number of epoxy groups in one molecule is computable by dividing the number average molecular weight (Mn) measured by the gel permeation chromatography method (GPC method) by the epoxy equivalent. The measurement method by GPC is demonstrated in the Example which publishes a specific example later.

Although an epoxy resin (A) will not be specifically limited if it has an average of 2 or more epoxy groups in 1 molecule, The following are mentioned as the example.

Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, alicyclic epoxy resin having an ester skeleton, bisphenol Z type epoxy resin, anthracene type epoxy resin, naphthalene type epoxy resin, naphthalene tetrafunctional epoxy resin, naphthol type epoxy resin, phenol novolak type epoxy resin, bisphenol A type novolac epoxy resin, cresol novolak type epoxy resin, phenolar Alkyl type epoxy resin, biphenyl type epoxy resin, non-xylenol type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene type epoxy resin.

These epoxy resins (A) may be used alone or as a mixture of two or more.

Among these, naphthalene tetrafunctional epoxy resin, naphthol type epoxy resin, phenol novolac type epoxy resin, bisphenol A type novolak type epoxy resin, cresol novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, non-biphenyl type epoxy resin Ilenol-type epoxy resin, triphenylmethane-type epoxy resin, tetraphenylethane-type epoxy resin, and dicyclopentadiene-type epoxy resin are preferable, phenol novolak-type epoxy resin, bisphenol A-type novolac epoxy resin, cresol novolak-type epoxy Resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, non-xylenol type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, and dicyclopentadiene type epoxy resin are more preferable.

[Ester compound (B)]

The ester compound (B) used by this invention has one ester structure in 1 molecule, and is represented by following formula (1).

[Formula 5]

In Formula (1), R<^1> is the alkyl group which may have a substituent, or the aryl group which may have a substituent. R ² is an aryl group which may have a substituent. The substituent is a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

In Formula (1), a self-polymerizable substituent is not contained in the substituent of ^R<1> and R<^2>.

The ester structure in an ester compound (B) is a substituent which reacts with an epoxy group. The number of ester structures in one molecule of the ester compound (B) is one. Since the ester compound containing two or more ester structures reacts excessively with the epoxy group of the epoxy resin (A), the molecular weight of the modified epoxy resin increases and there is a risk of gelation, the target properties of the modified epoxy resin of the present invention it is difficult to obtain

The ester compound having a self-polymerizable substituent also deteriorates the stability of the compound itself or the epoxy resin after modification, and there is a fear that sufficient curability may not be obtained at the time of reaction with a curing agent.

Here, the "self-polymerizable substituent" refers to polymerization under conditions of room temperature or higher, and examples thereof include a vinyl group, an acryloyl group, and a methacryl group.

^{As R<1>} of said Formula (1), a C1-C12 alkyl group and a C5-C14 aryl group are preferable. Moreover, as R<^2> , a C5-C14 aryl group is preferable.

Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a cyclohexyl group, a heptyl group, an octyl group, A nonyl group, a decyl group, a dodecyl group, a cyclododecyl group, etc. are mentioned. These may have a substituent mentioned later.

As a C5-C14 aryl group, a phenyl group, a biphenyl group, a naphthyl group, anthranyl group, etc. are mentioned. These may have a substituent mentioned later.

^{As R<1>} , R<^2> of said Formula (1), a C5-C14 aryl group is more preferable from a viewpoint of maintaining favorably the reactivity with an epoxy group, heat resistance, and low dielectric loss tangent. A phenyl group, a biphenyl group, a naphthyl group, anthranyl group etc. are mentioned as a C5-C14 aryl group. These may have a substituent mentioned later.

The substituent which the alkyl group or aryl group of R<^{1> , and the aryl group of R<2>} may have is a group selected from a halogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, and a C6-C12 aryl group. These substituents do not impart self-polymerizability to ^{R 1} , R ^{2 .}

Examples of the alkyl group having 1 to 12 carbon atoms as the substituent include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopene Tyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, methylcyclohexyl group, n-octyl group, cyclooctyl group , n-nonyl group, 3,3,5-trimethylcyclohexyl group, n-decyl group, cyclodecyl group, n-undecyl group, n-dodecyl group, cyclododecyl group, benzyl group, methylbenzyl group, dimethylbenzyl group , a trimethylbenzyl group, a naphthylmethyl group, a phenethyl group, a 2-phenylisopropyl group, and the like.

Examples of the alkoxy group having 1 to 12 carbon atoms as the substituent include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group group, isopentoxy group, neopentoxy group, tert-pentoxy group, cyclopentoxy group, n-hexyloxy group, isohexyloxy group, cyclohexyloxy group, n-heptoxy group, cycloheptoxy group, methylcyclohexyloxy group, n-octyloxy group, cyclooctyloxy group, n-nonyloxy group, 3,3,5-trimethylcyclohexyloxy group, n-decyloxy group, cyclodecyloxy group, n-undecyloxy group, n-dodecyloxy group group, cyclododecyloxy group, benzyloxy group, methylbenzyloxy group, dimethylbenzyloxy group, trimethylbenzyloxy group, naphthylmethoxy group, phenethyloxy group, 2-phenylisopropoxy group, and the like.

Examples of the aryl group having 6 to 12 carbon atoms as a substituent include a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, ethylphenyl group, styryl group, xylyl group, n-propylphenyl group, isopropylphenyl group, a mesityl group, an ethynylphenyl group, a naphthyl group, a vinylnaphthyl group, etc. are mentioned.

Among the above-mentioned, ^{as a substituent in R<1>} and R<^2> which you may have, a C1-C4 alkyl group, a halogen atom, etc. are mentioned as a preferable thing, More preferably, it is a methyl group. Particularly preferably, R ¹ and R ² do not have a substituent or have a methyl group as a substituent. This is because, when the substituents are sterically too large, intermolecular aggregation may be hindered and heat resistance may decrease.

It is particularly preferable that the ester compound (B) represented by the formula (1) is a compound represented by the following formula (2) or (3).

[Formula 6]

In formulas (2) and (3), R ³ , R ⁴ , and R ⁵ are each independently a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms. is an arbitrarily selected group. n represents the integer of 0-5, m represents the integer of 0-7.

Specific examples and preferred substituents of R ³ , R ⁴ , and R ⁵ are the same as those described above as substituents which the alkyl group or aryl group of ^{R 1 and the aryl group of R 2 may have.}

It is preferable that the naphthalene ring of Formula (3) has couple|bonded with the oxygen atom of an ester group at 1-position or 2-position, and it is more preferable to couple|bond with it at 2-position.

n is an integer of 0-5, Preferably it is 0-2, More preferably, it is 0-1, Especially preferably, it is 0.

m is an integer of 0-7, Preferably it is 0-3, More preferably, it is 0-1, Especially preferably, it is 0.

These ester compounds (B) may be used alone or as a mixture of two or more.

[Chemical structure of modified epoxy resin]

The modified epoxy resin of this invention contains the structure represented by following formula (4), It can obtain by reacting the epoxy group of the above-mentioned epoxy resin (A) and the ester group of the above-mentioned ester compound (B). As mentioned above, it originates in the structure represented by following formula (4), and the improvement effect of heat resistance and a low dielectric characteristic can be acquired.

[Formula 7]

In Formula (4), R<^1> and R<^2> have the same meaning as the thing in said Formula (1).

[Weight Average Molecular Weight (Mw)]

It is preferable that the range of the weight average molecular weight (Mw) of the modified epoxy resin of this invention is 500-10,000. When Mw is 500 or more, there is no possibility that a dielectric characteristic or a water absorption rate may deteriorate. From a viewpoint of maintaining these characteristics more favorably, Mw of the modified epoxy resin of this invention is more preferable, 600 or more, 700 or more are still more preferable, 1,000 or more are especially preferable. From the viewpoint of properly maintaining the resin viscosity and softening point and making the handleability good, the Mw of the modified epoxy resin of the present invention is preferably 10,000 or less, more preferably 8,000 or less, still more preferably 7,000 or less, and 6,000 or less. is particularly preferred.

Mw can be measured by the gel permeation chromatography method (GPC method). The measurement method by GPC is demonstrated in the Example which publishes a specific example later.

[epoxy equivalent]

It is preferable that the epoxy equivalent of the modified epoxy resin of this invention is the range of 300-1,000 g/equivalent. From the viewpoint of maintaining good heat resistance, the epoxy equivalent of the modified epoxy resin of the present invention is preferably 1,000 g/equivalent or less, more preferably 900 g/equivalent or less, and still more preferably 800 g/equivalent or less. From the viewpoint of maintaining good dielectric properties and water absorption, the epoxy equivalent of the modified epoxy resin of the present invention is preferably 300 g/equivalent or more, more preferably 330 g/equivalent or more, and particularly preferably 360 g/equivalent or more. .

[Softening Point]

It is preferable that the range of the softening point of the modified epoxy resin of this invention in solid form is 60-130 degreeC. As for the softening point of the modified epoxy resin of this invention from a viewpoint of suppressing blocking of resin, 65 degreeC or more is more preferable, 70 degreeC or more is still more preferable, and 75 degreeC or more is especially preferable. In order to sufficiently ensure solvent solubility, the softening point of the modified epoxy resin of the present invention is more preferably 125°C or lower, still more preferably 120°C or lower, and particularly preferably 115°C or lower.

Here, a softening point can be measured according to JISK7234.

Blocking refers to a phenomenon in which the resin pieces of powder are partially melted during storage to form a lump, impairing handleability.

[Method for Producing Modified Epoxy Resin]

The modified epoxy resin of this invention has an epoxy resin (A) which has an average of 2 or more epoxy groups in 1 molecule mentioned above, and the ester compound represented by said Formula (1) which has 1 ester structure in 1 molecule mentioned above. It is obtained by making (B) react.

As a manufacturing method of an epoxy resin (A), the method of condensing a bisphenol type compound and various novolak compounds with epihalohydrin by a well-known method is mentioned, for example. As another method for producing an epoxy resin, a method of introducing an allyl group by an allylation reaction to a phenol or a novolac compound to obtain an allyl compound, and further subjecting the allyl group to an oxidation reaction is exemplified. As the epoxy resin (A), a commercially available one may be used.

The ester compound (B) can be produced by, for example, esterifying an alcohol-based compound or a phenol-based compound by a condensation reaction with an acid chloride or carboxylic acid.

In the production of the modified epoxy resin of the present invention, the reaction equivalent ratio of the epoxy resin (A) and the ester compound (B) is the ratio of the number of moles of the epoxy group of the epoxy resin (A) to the number of moles of the ester group of the ester compound (B) ( Hereinafter, it is preferable to set it as 1.6-6.0 as "molar ratio (epoxy group/ester group)" may be called). When the molar ratio (epoxy group/ester group) is within the above range, the amount of the epoxy group after the modification reaction can be optimally maintained, and properties with good balance of heat resistance and dielectric properties can be expressed. From the viewpoint of further maintaining the balance between heat resistance and dielectric properties, the molar ratio (epoxy group/ester group) is more preferably 1.62 or more, still more preferably 1.63 or more, and particularly preferably 1.65 or more. From the same viewpoint, the molar ratio (epoxy group/ester group) is more preferably 5.5 or less, still more preferably 5.0 or less, and particularly preferably 4.5 or less.

You may use a catalyst for manufacture of the modified epoxy resin of this invention. As a catalyst, any compound may be sufficient as long as it is a compound which has catalytic ability which accelerates|stimulates reaction of an epoxy group and an ester group. Examples of the catalyst include tertiary amines, cyclic amines, imidazoles, organophosphorus compounds, and quaternary ammonium salts.

Specific examples of the tertiary amine include triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, benzyldimethylamine, pyridine, and 4-(dimethylamino)pyridine.

Specific examples of the cyclic amines include 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4,0]undecene-7, 1,5-diazabi Cyclo[4,3,0]nonene-5 etc. are mentioned.

Specific examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole.

Specific examples of the organophosphorus compound include tri-n-propylphosphine, tri-n-butylphosphine, triphenylphosphine, tris(p-tolyl)phosphine, tricyclohexylphosphine, tri(tert-butyl) ) phosphine, tris (p-methoxyphenyl) phosphine, tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetramethylphosphonium hydroxide, tetrabutylphosphonium hydroxide, trimethylcyclohexylphosphonium chloride, Trimethylcyclohexylphosphonium bromide, trimethylbenzylphosphonium chloride, trimethylbenzylphosphonium bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethylphosphonium chloride, triphenyl Ethylphosphonium bromide, triphenylethylphosphonium iodide, triphenylbenzylphosphonium chloride, triphenylbenzylphosphonium bromide, etc. are mentioned.

Among the catalysts listed above, 4-(dimethylamino)pyridine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4,0]undecene-7, 1, 5-diazabicyclo[4,3,0]nonene-5, 2-ethyl-4-methylimidazole, tris(p-tolyl)phosphine, tricyclohexylphosphine, tri(tert-butyl)phosphine , tris(p-methoxyphenyl)phosphine, in particular 4-(dimethylamino)pyridine, 1,8-diazabicyclo[5,4,0]undecene-7, 1,5-diazabicyclo [4,3,0]nonene-5,2-ethyl-4-methylimidazole is preferred.

These catalysts may be used alone or in combination of two or more.

The usage-amount of a catalyst is 0.001 to 1 weight% normally in reaction solid content. When a catalyst is used, a catalyst compound remains as a catalyst residue in the modified|denatured epoxy resin obtained, and when it uses for a printed wiring board, there exists a possibility that the insulation characteristic may deteriorate or the pot life of a composition may be shortened.

Therefore, the nitrogen content derived from the catalyst in the resulting modified epoxy resin is preferably 2000 ppm or less, and the phosphorus content is preferably 2000 ppm or less. More preferably, content of nitrogen in a modified epoxy resin is 1000 ppm or less, and content of phosphorus is 1000 ppm or less. More preferably, the nitrogen content in the modified epoxy resin is 500 ppm or less, and the phosphorus content is 500 ppm or less. Especially preferably, content of nitrogen in a modified epoxy resin is 200 ppm or less, and content of phosphorus is 200 ppm or less. Although the lower limit of content of nitrogen and phosphorus derived from a catalyst is not specifically limited, It is about 1 ppm from the detection limit lower limit of a measuring instrument.

The modified epoxy resin of this invention may use the solvent for reaction in the process of the synthesis reaction at the time of its manufacture. The solvent may be any solvent as long as it dissolves the epoxy resin. Examples of the solvent include an aromatic solvent, a ketone solvent, an amide solvent, and a glycol ether solvent. These solvents may be used only by 1 type, and may be used in combination of 2 or more type.

Specific examples of the aromatic solvent include benzene, toluene, and xylene.

Specific examples of the ketone solvent include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclohexanone, acetylacetone, dioxane, and the like. can

Specific examples of the amide solvent include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, 2-pyrrolidone, N -Methylpyrrolidone etc. are mentioned.

Specific examples of the glycol ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monomethyl Ether acetate etc. are mentioned.

When using a solvent for manufacture of a modified epoxy resin, it is preferable to use so that solid content concentration of a reaction system may become 35 to 95 weight%.

When a highly viscous product is generated during the reaction, the reaction may be continued by additionally adding a solvent.

After completion of the reaction, the solvent may be removed or further added as needed.

In the production of the modified epoxy resin of the present invention, the reaction between the epoxy resin (A) and the ester compound (B) is carried out at a reaction temperature such that the catalyst used is not decomposed. When the reaction temperature is too high, there is a fear that the catalyst decomposes, the reaction is stopped, or the resulting modified epoxy resin deteriorates. Conversely, if the temperature is too low, the reaction may not proceed sufficiently.

For this reason, the reaction temperature is preferably 50 to 200°C, more preferably 100 to 180°C, still more preferably 120°C to 160°C.

The reaction time is usually 1 to 12 hours, preferably 3 to 10 hours.

When using a low boiling point solvent such as acetone or methyl ethyl ketone, the reaction temperature can be secured by performing the reaction under high pressure using an autoclave.

[Epoxy Resin Composition]

The epoxy resin composition of this invention is an epoxy resin composition containing at least the modified|denatured epoxy resin of this invention mentioned above, and a hardening|curing agent. As for the epoxy resin composition of this invention, the epoxy resin composition containing the structure of Formula (4) mentioned above is preferable.

Moreover, various additives, such as other epoxy resins other than the modified epoxy resin of this invention, an inorganic filler, a coupling agent, and antioxidant, can be mix|blended with the epoxy resin composition of this invention suitably as needed. The epoxy resin composition of the present invention is excellent in heat resistance and low dielectric properties, and provides a cured product that sufficiently satisfies various physical properties required for various uses.

[hardener]

In this invention, a hardening|curing agent shows the substance which contributes to the crosslinking reaction and/or chain length extension reaction between the epoxy groups of an epoxy resin.

In this invention, even if it is what is normally called a "curing accelerator", if it is a substance which contributes to the crosslinking reaction and/or chain length extension reaction between the epoxy groups of an epoxy resin, it is regarded as a hardening|curing agent.

The content of the curing agent in the epoxy resin composition of the present invention is preferably 0.1 to 100 parts by weight by solid content, more preferably 90 parts by weight or less, still more preferably with respect to 100 parts by weight of the solid content of the modified epoxy resin of the present invention. 80 parts by weight or less.

When the epoxy resin composition of this invention contains the other epoxy resin mentioned later, the weight ratio of the solid content of the modified epoxy resin of this invention and another epoxy resin becomes like this. Preferably it is 99/1 - 1/99.

In this case, the content of the curing agent in the epoxy resin composition of the present invention is preferably 0.1 to 100 parts by weight in terms of solid content with respect to 100 parts by weight in total of the solid content of the modified epoxy resin of the present invention and the other epoxy resins, more preferably preferably 90 parts by weight or less, more preferably 80 parts by weight or less.

In the present invention, "solid content" means a component excluding a solvent, and includes not only a solid epoxy resin but also a semi-solid or viscous liquid.

"All epoxy resin components" means the sum total of the modified epoxy resin of this invention and other epoxy resins mentioned later.

There is no restriction|limiting in particular as a hardening|curing agent used for the epoxy resin composition of this invention, Any thing generally known as an epoxy resin hardening|curing agent can be used. A phenol-based curing agent, an amide-based curing agent, imidazoles, an active ester-based curing agent, and the like are preferred from the viewpoint of improving heat resistance. Hereinafter, examples of phenol-based curing agents, amide-based curing agents, imidazoles, active ester-based curing agents, and other usable curing agents are given.

[Phenolic Hardener]

It is preferable to use a phenol-type hardening|curing agent as a hardening|curing agent from a viewpoint of improving the handleability of the epoxy resin composition obtained, and the heat resistance after hardening.

Specific examples of the phenolic curing agent include bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 1,4-bis(4-hydroxyphenoxy) C) benzene, 1,3-bis (4-hydroxyphenoxy) benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-di Hydroxydiphenylsulfone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phos Paphenanthrene-10-oxide, phenol novolac, bisphenol A novolac, o-cresol novolac, m-cresol novolac, p-cresol novolac, xylenol novolac, poly-p-hydroxystyrene, hydro Quinone, resorcinol, catechol, t-butylcatechol, t-butylhydroquinone, fluoroglycinol, pyrogallol, t-butylpyrogalol, allylated pyrogalol, polyallylated pyrogalol, 1,2, 4-Benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-di Hydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2 ,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allylated or polyallylated dihydroxynaphthalene Bisphenol A, allylated bisphenol F, allylated phenol novolac, allylated pyrogallol, etc. are illustrated.

The phenolic hardening|curing agent mentioned above may be used only by 1 type, and may mix and use 2 or more types by arbitrary combinations and ratios.

When the curing agent is a phenol-based curing agent, it is preferably used so that the equivalent ratio of the functional groups in the curing agent to the epoxy groups in all the epoxy resins in the epoxy resin composition is in the range of 0.8 to 1.5. If it is in this range, since it becomes difficult to remain unreacted epoxy group and the functional group of a hardening|curing agent, it is preferable.

[Amide-based curing agent]

It is preferable from a viewpoint of improving the heat resistance of the epoxy resin composition obtained to use an amide type hardening|curing agent as a hardening|curing agent.

Examples of the amide curing agent include dicyandiamide and its derivatives, and polyamide resins.

The above-mentioned amide type hardening|curing agent may be used only by 1 type, and may mix and use 2 or more types by arbitrary combinations and ratios.

It is preferable to use an amide-type hardening|curing agent in 0.1 to 20 weight% with respect to the sum total of all the epoxy resin components as solid content in an epoxy resin composition, and an amide-type hardening|curing agent.

[Imidazoles]

It is preferable to use imidazole as a hardening|curing agent from a viewpoint of fully advancing hardening reaction and improving heat resistance.

Examples of imidazoles include 2-phenylimidazole, 2-ethyl-4(5)-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole tri melitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-Diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-methyl Imidazolyl-(1')]-ethyl-s-triazineisocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole , 2-phenyl-4-methyl-5-hydroxymethylimidazole, and an adduct of an epoxy resin and the above imidazoles, and the like.

Since imidazoles have catalytic activity, they can generally be classified as curing accelerators described later, but in the present invention, they are classified as curing agents.

The number of imidazoles mentioned above may be one, and 2 or more types may be mixed and used by arbitrary combinations and ratios.

It is preferable to use imidazole in 0.1 to 20 weight% with respect to the sum total of all the epoxy resin components as solid content in an epoxy resin composition, and imidazole.

[Active Ester Hardener]

It is preferable to use an active ester-based curing agent as the curing agent from the viewpoint of exhibiting low water absorption and low dielectric properties of the resulting cured product.

As the active ester curing agent, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferable. And especially, the phenol ester which made the aromatic compound which has a carboxylic acid compound and phenolic hydroxyl group react are more preferable. Specific examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the aromatic compound having a phenolic hydroxyl group include catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzo phenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadienyldiphenol, phenol novolac, etc. are mentioned. As a similar curing agent, it is also possible to use polyarylates.

Commercially available products of the active ester curing agent include HPC-8000-65T (active ester curing agent containing a dicyclopentadiene structure), HPC-8150-60T (active ester curing agent containing a naphthalene structure in the main skeleton) (each, DIC (Co., Ltd.) is mentioned.

The number of active ester type hardening|curing agents mentioned above may be one, and 2 or more types may be mixed and used by arbitrary combinations and ratios.

The active ester curing agent is preferably used so that the equivalent ratio of the active ester groups in the curing agent to the epoxy groups in all the epoxy resins in the epoxy resin composition is in the range of 0.2 to 2.0.

[Other curing agents]

Examples of other curing agents other than those described above that can be used in the epoxy resin composition of the present invention include amine curing agents (however, tertiary amines are excluded), acid anhydride curing agents, tertiary amines, and organic phosphors. Fins, phosphonium salts, tetraphenyl boron salts, organic acid dihydrazide, boron halide amine complexes, polymercaptan-based curing agents, isocyanate-based curing agents, block isocyanate-based curing agents, and the like can be mentioned.

The other hardening|curing agent mentioned above may be used only by 1 type, and may mix and use 2 or more types by arbitrary combinations and a ratio.

[Other Epoxy Resins]

The epoxy resin composition of the present invention may contain another epoxy resin in addition to the modified epoxy resin of the present invention. By using other epoxy resins, insufficient physical properties can be supplemented or various physical properties can be improved.

As another epoxy resin, what has two or more epoxy groups in a molecule|numerator is preferable. Examples of other epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, bisphenol Z epoxy resin, naphthalene epoxy resin, and phenol novolac epoxy resin. Various epoxy resins, such as resin, a cresol novolak-type epoxy resin, a phenol aralkyl-type epoxy resin, a biphenyl-type epoxy resin, a triphenylmethane-type epoxy resin, and a dicyclopentadiene-type epoxy resin, can be used.

These may be used alone or as a mixture of two or more.

In the epoxy resin composition of the present invention, when using an epoxy resin different from the modified epoxy resin of the present invention, the blending amount of the other epoxy resin is preferably 1% by weight or more among 100% by weight of the total epoxy resin component as a solid content. , More preferably, it is 5 weight% or more, More preferably, it is 10 weight% or more, Preferably it is 99 weight% or less, More preferably, it is 95 weight% or less, More preferably, it is 90 weight% or less. When the ratio of another epoxy resin is more than the said lower limit, the physical-property improvement effect by mix|blending another epoxy resin can fully be acquired. When the ratio of other epoxy resins is below the said upper limit, the effect of the modified epoxy resin of this invention is fully exhibited, and it is preferable from a viewpoint of acquiring the physical property improvement effect, such as low hygroscopicity.

[solvent]

In the epoxy resin composition containing the modified epoxy resin of this invention, in order to adjust the viscosity of an epoxy resin composition suitably at the time of handling at the time of coating film formation, you may mix|blend and dilute a solvent.

The epoxy resin composition of this invention WHEREIN: A solvent is used in order to ensure the handleability in the shaping|molding of an epoxy resin composition, and workability|operativity, and there is no restriction|limiting in particular in the usage-amount.

In this invention, although the word "solvent" and the word "solvent" mentioned above are used separately according to the usage form, respectively, the same thing may be used independently, and a different thing may be used.

As a solvent which the epoxy resin composition containing the modified epoxy resin of this invention can contain, For example, ketones, such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, Esters, such as ethyl acetate ethers such as ethylene glycol monomethyl ether, amides such as N,N-dimethylformamide and N,N-dimethylacetamide, alcohols such as methanol and ethanol, alkanes such as hexane and cyclohexane, toluene , and aromatics such as xylene.

The solvents mentioned above may be used only by 1 type, and may mix and use 2 or more types by arbitrary combinations and ratios.

[Other Ingredients]

In the epoxy resin composition containing the modified epoxy resin of the present invention, for the purpose of further improvement of its functionality, components other than those listed above (in the present invention, "other components" may be referred to). there may be Such other components include, but are not limited to, thermosetting resins or photocurable resins other than epoxy resins, curing accelerators (except those included in “curing agents”), ultraviolet inhibitors, antioxidants, coupling agents, plasticizers, fluxes, flame retardants, A colorant, a dispersing agent, an emulsifier, a low elasticity agent, a diluent, an antifoaming agent, an ion trapping agent, an inorganic filler, an organic filler, etc. are mentioned.

[Cured product]

The cured product obtained by curing the modified epoxy resin of the present invention with a curing agent is excellent in the balance between heat resistance and low dielectric properties, and exhibits good cured material properties. As for the hardened|cured material of this invention, the hardened|cured material containing the structure of Formula (4) mentioned above is preferable.

The term "curing" as used herein means intentionally curing the epoxy resin composition by heat and/or light, and the degree of curing may be controlled according to desired physical properties and applications. The degree of advancing may be complete hardening or a semi-hardened state may be sufficient, and it is not restrict|limited in particular. Usually, the reaction rate of the hardening reaction of an epoxy group and a hardening|curing agent is 5-95 %.

Although the hardening method of the epoxy resin composition at the time of hardening the epoxy resin composition of this invention and setting it as a hardened|cured material also changes with the compounding component and compounding quantity in an epoxy resin composition, Usually, at 80-280 degreeC, 60-360 minutes heating conditions are mentioned. It is preferable that this heating performs the two-stage process of the primary heating for 10-90 minutes at 80-160 degreeC, and the secondary heating for 60-150 minutes at 120-200 degreeC. In a compounding system in which a glass transition temperature (Tg) exceeds the temperature of secondary heating, it is further preferable to perform tertiary heating for 60-120 minutes at 150-280 degreeC. Thus, performing secondary heating and tertiary heating is preferable from a viewpoint of reducing hardening failure and residual of a solvent.

When producing a resin semi-cured material, it is preferable to advance the curing reaction of the epoxy resin composition to such an extent that the shape can be maintained by heating or the like. When the epoxy resin composition contains a solvent, most solvents are usually removed by methods, such as heating, reduced pressure, and air drying. You may make 5 weight% or less of solvent remain in resin semi-hardened|cured material.

〔purpose〕

The modified epoxy resin of this invention is excellent in film forming property. The epoxy resin composition containing the modified epoxy resin of this invention exhibits the effect of giving the hardened|cured material excellent in heat resistance and low dielectric characteristic. For this reason, the modified epoxy resin of the present invention and the epoxy resin composition containing the same can be applied to various fields such as adhesives, paints, materials for civil engineering and construction, and insulating materials for electrical and electronic components, and in particular, in the field of electrical and electronic components. It is useful as an insulating mold, a laminated material, a sealing material, etc. in

Examples of the use of the modified epoxy resin of the present invention and the epoxy resin composition containing the same include multilayer printed wiring boards, laminates for electrical and electronic circuits such as capacitors, adhesives such as film adhesives, liquid adhesives, semiconductor encapsulation materials, under A fill material, an interchip fill for 3D-LSI, an insulating sheet, a prepreg, a heat radiation board|substrate, etc. are mentioned. The use of the modified epoxy resin of this invention and the epoxy resin composition containing it is not limited to these at all.

[Laminate Board for Electric/Electronic Circuits]

As mentioned above, the epoxy resin composition of this invention can be used suitably for the use of the laminated board for electrical/electronic circuits. In the present invention, the "laminated board for electrical/electronic circuits" is a laminate of a layer containing the epoxy resin composition of the present invention and a conductive metal layer, and a layer containing the epoxy resin composition of the present invention and a conductive metal layer are laminated, Although it is not an electric/electronic circuit, it is used as a concept including a capacitor, for example.

The layer which consists of 2 or more types of epoxy resin compositions may be formed in the laminated board for electrical/electronic circuits, and the epoxy resin composition of this invention should just be used in at least 1 layer. Two or more types of conductive metal layers may be formed in the laminated board for electric/electronic circuits.

The thickness of the layer which consists of an epoxy resin composition in the laminated board for electric/electronic circuits is about 10-200 micrometers normally. The thickness of the conductive metal layer is usually about 0.2 to 70 µm.

[conductive metal]

As an electroconductive metal in the laminated board for electric/electronic circuits, metals, such as copper and aluminum, and the alloy containing these metals are mentioned. In the electroconductive metal layer of the laminated board for electric/electronic circuits, the metal foil of these metals, or the metal layer formed by plating or sputtering can be used.

[Method for manufacturing laminated board for electric/electronic circuits]

As a manufacturing method of the laminated board for electric/electronic circuits in this invention, the following method is mentioned, for example.

(1) Nonwoven fabric or cloth using inorganic and/or organic fiber materials such as glass fiber, polyester fiber, aramid fiber, cellulose, nanofiber cellulose, etc., impregnated with the epoxy resin composition of the present invention to obtain a prepreg, conductive After the conductive metal layer is formed by metal foil and/or plating, a circuit is formed using a photoresist or the like, and the necessary number of these layers are overlapped to obtain a laminate.

(2) The prepreg of the above (1) is used as a core material, and a layer made of an epoxy resin composition and a conductive metal layer are laminated on it (one side or both sides) (build-up method). The layer which consists of this epoxy resin composition may contain the organic and/or inorganic filler.

(3) Without using a core material, only a layer made of an epoxy resin composition and a conductive metal layer are alternately laminated to obtain a laminate for electric/electronic circuits.

Example

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited by the Examples below.

The values of various manufacturing conditions and evaluation results in the following examples have meanings as preferred values of the upper or lower limits in the embodiments of the present invention, and the preferred ranges are the values of the upper or lower limits described above; It may be the range defined by the combination of the value of the following Example or the value of each Example.

[Method for evaluating physical properties and properties]

In the following Examples and Comparative Examples, evaluation of physical properties and characteristics was performed by the methods described in 1) to 6) below.

1) Weight average molecular weight (Mw) and number average molecular weight (Mn)

TSK Standard Polystyrene: F-128 (Mw: 1,090,000, Mn: 1,030,000), F-10 (Mw: 106,000) as standard polystyrene using "HLC-8320 GPC apparatus" manufactured by Tosoh Corporation under the following measurement conditions , Mn: 103,000), F-4 (Mw: 43,000, Mn: 42,700), F-2 (Mw: 17,200, Mn: 16,900), A-5000 (Mw: 6,400, Mn: 6,100), A-2500 (Mw) : 2,800, Mn: 2,700) and A-300 (Mw: 453, Mn: 387) were prepared, and the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured as polystyrene conversion values.

Column: "TSKGEL SuperHM-H+H5000+H4000+H3000+H2000" manufactured by Tosoh Corporation

Eluent: tetrahydrofuran

Flow rate: 0.5 ml/min

Detection: UV (wavelength 254 nm)

Temperature: 40℃

Sample concentration: 0.1 wt%

Injection amount: 10 μl

2) The average number of epoxy groups in one molecule of the raw material epoxy resin

It computed as the value which divided the number average molecular weight obtained from GPC measurement by the epoxy equivalent.

3) Epoxy equivalent

It measured according to JISK7236, and in the case of a solution, it expressed as solid content conversion value.

4) softening point

The softening point of the solid epoxy resin was measured according to JIS K7234.

5) Heat resistance of cured product: glass transition temperature (Tg, DSC)

For an epoxy resin cured film having a thickness of about 50 µm in which a solution of an epoxy resin composition was dried and cured, "DSC7020" manufactured by SII Nanotechnology Co., Ltd. was used, and the temperature was raised to 30 to 250 °C at 10 °C/min to the glass transition temperature was measured.

The glass transition temperature here was measured based on "major glass transition temperature: Tmg" among those described in JIS K7121 "Method for measuring transition temperature of plastics".

The criterion for determining the glass transition temperature was as follows.

Tg above 120℃ : Judgment ◎

Tg 100℃ or more and less than 120℃ : Judgment ○

Tg less than 100℃ : Judgment ×

6) dielectric properties

The epoxy resin cured film or the prepared prepreg was cut into a test piece having a width of 2 mm and a length of 80 mm, and the test piece was measured by a cavity resonance perturbation method using a network analyzer at a measurement frequency of 10 GHz and a measurement temperature of 23 The dielectric loss tangent (tanδ) was measured at °C.

The criteria for determining the dielectric properties were as follows.

tanδ ≤ 0.0075: : Judgment A

0.0075 < tanδ ≤ 0.0085 : Judgment B

0.0085 ＜ tanδ ＜ 0.010 : Judgment C

0.010 ≤ tanδ : Judgment ×

As described above, the smaller tan δ is better as a characteristic, and 0.010 or more is set to fail (x), and according to each value, it is set as A-C in order from favorable.

[Raw materials, etc.]

The raw material, catalyst, solvent, and solvent used in the following Examples and Comparative Examples are as follows.

[Epoxy Resin (A)]

(A-1): ortho-cresol novolak-type epoxy resin (epoxy equivalent: 197 g/equivalent, Mn: 416, average number of epoxy groups in one molecule: 2.1)

(A-2): ortho-cresol novolac-type epoxy resin (epoxy equivalent: 220 g/equivalent, Mn: 1018, average number of epoxy groups in one molecule: 4.7)

(A-3): ortho cresol novolac type epoxy resin (epoxy equivalent: 219 g/equivalent, Mn: 831, average number of epoxy groups in one molecule: 3.8)

(A-4): Mitsubishi Chemical Co., Ltd. product name "jER 157S70" (bisphenol A novolak type epoxy resin, epoxy equivalent: 209 g/equivalent, Mn: 500, average number of epoxy groups in one molecule: 2.4)

(A-5): Mitsubishi Chemical Co., Ltd. product name "jER 1031S" (tetraphenylethane type epoxy resin, epoxy equivalent: 196 g/equivalent, Mn: 666, average number of epoxy groups in one molecule: 3.4)

(A-6): Mitsubishi Chemical Co., Ltd. product name "jER 154" (phenol novolak type epoxy resin, epoxy equivalent: 178 g/equivalent, Mn: 480, average number of epoxy groups in one molecule: 2.7)

(A-7): Mitsubishi Chemical Co., Ltd. product name "jER YX7700" (novolak-type epoxy resin containing xylenol skeleton, epoxy equivalent: 271 g/equivalent, Mn: 660, average number of epoxy groups in one molecule: 2.4 )

(A-8): Mitsubishi Chemical Co., Ltd. product name "jER 828US" (bisphenol A epoxy resin, epoxy equivalent: 185 g/equivalent, Mn: 330, average number of epoxy groups in one molecule: 1.8)

[Ester compound (B)]

(B-1): benzoic acid-2-naphthyl (active equivalent: 248 g/equivalent)

(B-2): phenyl benzoate (active equivalent: 198 g/equivalent)

[diester compound]

(P-1): bisphenol A diacetate (active equivalent: 156 g/equivalent)

[Other ester compounds]

(P-2): terephthalic acid monomethyl ester

[catalyst]

(C-1): 4-(dimethylamino)pyridine

[Solvent, solvent]

(S-1): cyclohexanone

(S-2): methyl ethyl ketone (MEK)

[Production and evaluation of modified epoxy resin]

<Examples 1-1 to 1-16, Comparative Examples 1-1 to 1-3>

Epoxy resin, ester compound or diester compound, catalyst, and solvent for reaction in the formulation shown in Tables 1 and 2 are placed in a reaction vessel equipped with a stirrer, and in a nitrogen gas atmosphere, The reaction was carried out at the reaction time and reaction temperature. Then, the solvent for dilution was added and the solid content concentration was adjusted.

In Examples 1-14 to 16 and Comparative Example 1-1, the epoxy resin in a solid state was finally obtained, without using the solvent for reaction and dilution with a solvent, either.

In Comparative Example 1-3, gelation occurred during the reaction, and evaluation samples could not be obtained.

The analysis results of the obtained modified epoxy resin are shown in Table-1 and Table-2.

[Table 1]

[Table 2]

[Production and evaluation of epoxy resin composition/cured product]

<Examples 2-1 to 2-13, Comparative Examples 2-1 to 2-2>

60 wt% cyclohexanone of the modified epoxy resin obtained in Examples 1-1 to 1-13 and Comparative Examples 1-1 to 1-2 and a commercially available polyarylate resin (polyarylate having a bisphenol skeleton) as a curing agent A solution, a 5 wt% toluene solution of 4-(dimethylamino)pyridine (abbreviated as “DMAP”) as a curing accelerator, and a polymer epoxy resin (manufactured by Mitsubishi Chemical, trade name “YL7891T30” as another epoxy resin serving as a film-forming agent; Mn: 10,000, Mw: 30,000, epoxy equivalent: 6,000 g/equivalent) in the weight ratio shown in Tables-3A and 3B (epoxy equivalent of all epoxy resin: active equivalent of curing agent = 1:1), An epoxy resin composition was obtained. A solution of the obtained epoxy resin composition was applied to a separator (silicone-treated polyethylene terephthalate film) with an applicator, dried at 160°C for 1.5 hours and then at 200°C for 1.5 hours to obtain a film of a cured epoxy resin product.

About these, heat resistance was evaluated according to the method mentioned above. The results are shown in Tables-3A and 3B.

In Examples 2-1 to 8 and 11 and Comparative Examples 1-1 and 2, dielectric properties were further evaluated. The results are shown in Tables 4A and 4B.

[Table 3A]

[Table 3B]

[Table 4A]

[Table 4B]

From the results of Tables 3A and 3B, it is understood that the cured epoxy resin film made of the epoxy resin composition using the modified epoxy resin of the present invention is excellent in heat resistance.

From the results of Tables 4A and 4B, it is understood that the cured epoxy resin film made of the epoxy resin composition using the modified epoxy resin of the present invention is excellent in low dielectric properties.

From these results, it turns out that the film of the epoxy resin hardened|cured material which consists of the epoxy resin composition using the epoxy resin of this invention is excellent in the balance of heat resistance and low dielectric characteristic.

On the other hand, the film of the cured epoxy resin using the modified epoxy resin of Comparative Example 1-1 is inferior in heat resistance and low dielectric properties. Moreover, the film of the epoxy resin cured product using the modified epoxy resin of Comparative Example 1-2 is inferior in low dielectric properties.

[Production and evaluation of prepregs and laminates]

The modified epoxy resin synthesized in Example 1-14 was dissolved in methylethylketone so that the resin content was 70% by weight. The prepared epoxy resin solution (solution amount 120 g, solid content 84 g) and a 50 wt% methyl ethyl ketone solution (solution amount 75 g, solid content 38) of a commercially available polyarylate resin (polyarylate having a bisphenol skeleton) as a curing agent g) and a 5 wt% toluene solution of 4-(dimethylamino)pyridine (a solution amount of 2.4 g, a solid content of 0.12 g) as a curing accelerator were mixed to obtain an epoxy resin composition (varnish solution). After impregnating the following base material with the obtained varnish solution, it dried at 160 degreeC for 5 minutes, and obtained the prepreg. The laminated board was obtained by laminating|stacking 6 sheets of obtained prepreg, and hardening it on the following conditions using a hot press machine.

Material: Glass cloth (「#2116」manufactured by Nitto Spinning Co., Ltd.)

Number of plies: 6

Prepreg condition: 160 ℃

Curing conditions: 1.5 hours at 200 °C, 2 MPa

Plate thickness after forming: 0.8 m

The thermal properties of the obtained laminate were measured using DMS (manufactured by Hitachi High-Technologies) under conditions of 1 GHz and 30 to 280°C (temperature increase rate of 5°C/min). As a result, from the tan δ (E''/E') of the elastic modulus, the glass transition temperature was measured to be 162°C.

About the obtained laminated board, the value of 0.0074 was shown as a result of measuring the dielectric loss tangent (tanδ) of the obtained laminated board using the cavity resonance perturbation method at the measurement frequency of 10 GHz, and the measurement temperature of 23 degreeC by the cavity resonance perturbation method.

From this measurement result, it turns out that the outstanding heat resistance and low dielectric characteristic are expressed also when a laminated board is produced by using the modified epoxy resin of this invention.

Although the present invention has been described in detail using specific embodiments, it is apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the present invention.

This application is based on Japanese Patent Application No. 2019-002733 for which it applied on January 10, 2019, The whole is used by reference.

Industrial Applicability

ADVANTAGE OF THE INVENTION According to this invention, the modified epoxy resin excellent in the balance of heat resistance and low dielectric characteristic, the epoxy resin composition containing the modified epoxy resin, and a hardening|curing agent, and its hardened|cured material can be provided. For this reason, the epoxy resin composition of this invention and its hardened|cured material can be applied to various fields, such as an adhesive agent, a paint, a material for civil engineering construction, and the insulating material of an electric/electronic component, In particular, the insulation in the electric/electronic field. It is useful as a mold, a laminate material, a sealing material, etc.

Examples of the use of the modified epoxy resin of the present invention and the epoxy resin composition containing the same include multilayer printed wiring boards, laminates for electrical and electronic circuits such as capacitors, adhesives such as film adhesives, liquid adhesives, semiconductor encapsulation materials, under A fill material, an interchip fill for 3D-LSI, an insulating sheet, a prepreg, a heat radiation board|substrate, etc. are mentioned. However, it is not limited to these at all.

Claims (11)

A modified epoxy resin obtained by reacting an epoxy resin (A) having an average of two or more epoxy groups in one molecule and an ester compound (B) represented by the following formula (1) having one ester structure in one molecule.

In Formula (1), R<^1> is the alkyl group which may have a substituent, or the aryl group which may have a substituent. R ² is an aryl group which may have a substituent. The substituent is a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms. The method of claim 1,
The modified epoxy resin whose reaction equivalent ratio of the said epoxy resin (A) and the ester compound (B) is 1.6-6.0 by ratio of the number of moles of the number of moles of the epoxy group of this epoxy resin (A), and the number of moles of the ester group of this ester compound (B). 3. The method according to claim 1 or 2,
^{The modified epoxy resin in which R<1>} , R<^2> in said Formula (1) is a phenyl group which may have a substituent, or a naphthyl group which may have a substituent each independently. An epoxy resin composition containing the modified epoxy resin according to any one of claims 1 to 3 and a curing agent. 5. The method of claim 4,
An epoxy resin composition comprising 0.1 to 100 parts by weight of the curing agent as a solid content, based on 100 parts by weight of the solid content of the modified epoxy resin. 6. The method according to claim 4 or 5,
The epoxy resin composition containing the said modified|denatured epoxy resin and another epoxy resin, and weight ratio of the modified|denatured epoxy resin and the solid content of this other epoxy resin is 99/1 - 1/99. 7. The method of claim 6,
The epoxy resin composition which contains 0.1-100 weight part of said hardening|curing agents by solid content with respect to a total of 100 weight part of the said modified|denatured epoxy resin and solid content of another epoxy resin. 8. The method according to any one of claims 4 to 7,
The epoxy resin composition, wherein the curing agent is at least one selected from the group consisting of a phenol-based curing agent, an amide-based curing agent, imidazoles, and an active ester-based curing agent. Hardened|cured material formed by hardening|curing the epoxy resin composition in any one of Claims 4-8. The laminated board for electric/electronic circuits formed using the epoxy resin composition in any one of Claims 4-8. A modified epoxy resin including a structure represented by the following formula (4).

In Formula (4), R<^1> is the alkyl group which may have a substituent, or the aryl group which may have a substituent. R ² is an aryl group which may have a substituent. The substituent is a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms.