KR20160118208A - Epoxy resin, curable resin composition, and cured product thereof - Google Patents

Abstract

(식 중, 복수 존재하는 A, B는 상기에 나타내는 바와 같고, *에서 결합된다. 또한, G는 글리시딜기를, m, n은 반복수의 평균값을 나타내고, 0∼5의 수를 나타낸다.)
식(2)

(식 중, G는 글리시딜기를 나타낸다.)It is an object of the present invention to provide a high heat resistant epoxy resin, a curable resin composition and a cured product thereof which have high heat resistance and excellent thermal stability. The epoxy resin of the present invention is represented by the following formula (1), wherein the total area of the chart measured by gel permeation chromatography ranges from 40 to 75% by area of the triglycidyl ether body and from 12 to 40% by number of the tetraglycidyl ether body And the total of the triglycidyl ether compound and the tetraglycidyl ether compound is 52 to 90% by area, and the tetraglycidyl ether compound has a structure represented by the following formula (2).
Equation (1)

(Wherein A and B are as defined above and are bonded at *). G represents a glycidyl group, and m and n represent an average value of the number of repeating units and represent a number of 0 to 5. )
Equation (2)

(Wherein G represents a glycidyl group).

Description

EPOXY RESIN, CURABLE RESIN COMPOSITION, AND CURED PRODUCT THEREOF}

TECHNICAL FIELD The present invention relates to an epoxy resin, a curable resin composition, and a cured product thereof that give a desired cured product for use in electrical and electronic materials, particularly, in heat resistant thermally decomposing and heat resistant cracking.

BACKGROUND ART Curable resin compositions are widely used in the fields of electric and electronic parts, structural materials, adhesives, paints and the like due to workability and excellent electrical properties, heat resistance, adhesiveness, moisture resistance (water resistance)

In recent years, however, in the field of electric and electronic fields, there has been a demand for a resin composition having high purity, moisture resistance, adhesiveness, dielectric properties, low viscosity for high filling of fillers (inorganic or organic fillers) And further improvement of various characteristics such as improvement of the characteristics of the liquid crystal display device. In addition, as a structural material, materials that are light in weight and excellent in mechanical properties are required for use in aerospace materials, leisure sports equipment, and the like. Particularly, in the field of semiconductor encapsulation and the substrate (substrate itself or peripheral materials thereof), it is complicated by thinning, stacking, systemization, and three-dimensionalization in accordance with the transition of the semiconductor, (Non-Patent Document 1). Particularly, in accordance with the expansion of use of plastic packages for in-vehicle use, the demand for improvement of heat resistance becomes more severe, and a resin having a high Tg and a low linear expansion coefficient is required (Non-Patent Document 2).

 "Seminar on Semiconductor Technology Roadmap 2008, JEITA Semiconductor Technology Roadmap Expert Committee, [March 2012]," Seminar on the 2008 Seminar on the Semiconductor Roadmap Seminar ", Chapter 8, p1-17, [online] Month 30 days search], Internet <URL: http://strj-jeita.elisasp.net/strj/nenjihoukoku-2008.cfm>  Takakura Nobuyuki et al., Matsushita Denko Kibo Tea Device technology High-temperature operation IC for vehicle, No. 74, Japan, May 31, 2001, pp. 35-40

Heat resistance is one of the most important characteristics in recent years. Conventionally, heat resistance has been regarded as important. However, in general, when heat resistance is improved, other properties are lowered. Therefore, even if the heat resistance is somewhat unsatisfied with the market demand, However, due to the increase in the amount of current due to the increase in the amount of information handled by electronic materials and the strictness of the environment in which the electronic material is used, heat resistance is indispensable. In addition, from the viewpoint of energy saving, the power device is required to have the heat resistance of the peripheral material in applications such as SiC that can be driven at a high temperature.

One of the characteristics in relation to heat resistance and trade-off is the property called thermal stability (here, heat resistance generally refers to glass transition point (Tg)). As a means for improving the heat resistance of an epoxy resin in general, a method of raising the concentration of the epoxy group (lowering the epoxy equivalent) and increasing the crosslinking density is employed.

In a cured product using this high heat resistant epoxy resin (for example, a trisphenol methane type epoxy resin or the like), since a large number of epoxy groups are contained in a molecule, when exposed to a high temperature, a structure derived from an epoxy- There is a tendency that the characteristics are improved in terms of heat resistance, but the properties are lowered in terms of thermal stability. Conversely, in the case of an epoxy resin having a small number of epoxy chains, for example, a phenol aralkyl type, thermal decomposition tends to be difficult to proceed, and the thermal stability tends to increase, while the heat resistance decreases.

It is an object of the present invention to provide a high heat resistant epoxy resin, a curable resin composition and a cured product thereof which have high heat resistance and excellent thermal stability.

In addition, in optical applications, particularly in a peripheral member of light having a high intensity such as an LED, it is required to have high color resistance from the requirement to transmit the light or to reflect the light effectively. In addition, especially when the light emitting intensity is high, the heat on the chip becomes very high, and therefore, a resin having heat resistance that can withstand the heat is required. As a cause of coloring, decomposition and deterioration due to heat and the like are caused, and similarly to the above, high heat resistance and thermal stability are demanded in optical applications.

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above-described facts and have completed the present invention.

That is, the present invention relates to the following [1] to [8].

[One]

As the epoxy resin represented by the following formula (1)

The total area of the chart measured by gel permeation chromatography is such that the triglycidyl ether body occupies 40-75 area%, the tetraglycidyl ether body occupies 12-40 area%, and the triglycidyl ether body and tetraglycidyl ether The total amount of the diallyl ether is 52 to 90%

And the tetraglycidyl ether derivative thereof has a structure represented by the following formula (2).

(Wherein A and B are as defined above and are bonded at *). G represents a glycidyl group, and m and n represent an average value of the number of repeating units and represent a number of 0 to 5. )

(Wherein G represents a glycidyl group).

[2]

The epoxy resin according to [1], which is obtained by the reaction of a compound represented by the following formula (3) with epihalohydrin.

[3]

The epoxy resin according to [1] or [2], wherein the epoxy resin has a softening point of 45 to 65 캜 and an epoxy equivalent of 165 to 180 g / eq.

[4]

The epoxy resin according to [2] or [3], which is obtained by reacting the compound of the formula (3) with epihalohydrin, and then treating the solution with toluene or a ketone compound having 4 to 7 carbon atoms and treating the resultant with a metal hydroxide aqueous solution .

[5]

A curable resin composition comprising the epoxy resin according to any one of [1] to [4] and a curing agent.

[6]

The curable resin composition according to [5], wherein the curing agent is a resin having a phenol resin structure.

[7]

The curable resin composition according to [5] or [6], which contains at least one of an acid anhydride and a polycarboxylic acid as a curing agent.

[8]

A cured product obtained by curing the curable resin composition according to any one of [5] to [7].

(Effects of the Invention)

The curable resin composition of the present invention containing the epoxy resin of the present invention can provide a cured product excellent in heat resistance, thermal stability and color resistance. Further, with the above properties, the cured product of the present invention can be applied to optical members requiring high optical characteristics.

1 is a graph showing an evaluation result of the embodiment.

The epoxy resin of the present invention has a structure represented by the following formula (1).

(Wherein A and B are as defined above and are bonded at *). G represents a glycidyl group, and m and n represent an average value of the number of repeating units and represent a number of 0 to 5. )

That is, the epoxy resin of the present invention is an epoxy resin based on a trisphenol skeleton having a relatively broad molecular weight distribution, and is composed of a small molecule having a trisphenol skeleton and a structure having a trisphenol skeleton based on epihalohydrin [1,3 -Deoxypropan-2-ol structure, the following formula (4)].

Specifically, the total area of the chart measured by gel permeation chromatography (GPC) is such that the triglycidyl ether content accounts for 40 to 75% by area, the tetraglycidyl ether content accounts for 12 to 40% And the total amount of the cydyl ether compound and the tetraglycidyl ether compound is 52 to 90% by area.

For example, the tetraglycidyl ether derivative can be specifically represented by the above formula (2). Further, as the higher molecular weight component, one of the glycidyl ether moieties is ring-opened and linked to the structure of the formula (4) similarly to the above formula (2). By such a combination, the epoxy resin of the present invention has a broad molecular weight distribution. Here, the preferable molecular weight distribution is Mw / Mn = 1.2 to 2.0.

In the present invention, when measured by gel permeation chromatography (GPC), when the triglycidyl ether body exceeds 75% by area and the tetraglycidyl ether body is below 12% by area, there arises a problem that heat resistance is difficult to exhibit do. When the triglycidyl ether is less than 40% by area and the tetraglycidylether exceeds 40% by area, the viscosity is too high to handle and the solubility in a solvent deteriorates. When the high molecular weight substance (the high molecular weight substance exceeding the tetraglycidyl ether substance and connected by the structure of the above formula (2)) exceeds 35% by area, there is a similar likelihood, and when considering viscosity and solubility, There is a case. In some cases, gelation may occur.

The amount of the triglycidyl ether compound in the epoxy resin is preferably from 40 to 75% by area, more preferably from 45 to 75% by area, even more preferably from 50 to 70% by area, and the tetraglycidyl ether compound is from 12 to 40% %, More preferably 15 to 35 area%, still more preferably 15 to 30 area%. At the same time, it is preferably 2 to 20% by area, and more preferably 5 to 20% by area, in terms of the higher polymer content. The total amount of the triglycidyl ether compound and the tetraglycidyl ether compound is from 52 to 90% by area, preferably from 60 to 87% by area, more preferably from 65 to 82% by area. The ratio of the area% of the tetraglycidyl ether compound and the triglycidyl compound is preferably from 1.1 to 3.7, more preferably from 1.1 to 3.5, and particularly preferably from 1.1 to 3.5, relative to the tetraglycidyl ether compound 1.5 to 3.2.

The epoxy equivalent of such an epoxy resin is preferably 165 to 190 g / eq., More preferably 165 to 185 g / eq., And still more preferably 165 g / eq. To 180 g / eq. Epoxy equivalent of 165 g / eq. , The heat resistance may be insufficient. If the amount is more than 190 g / eq, there may be a problem in workability.

The softening point is preferably 45 to 70 占 폚, more preferably 45 to 65 占 폚, particularly preferably 45 to 60 占 폚. The epoxy equivalent and the softening point tend to be effective for the heat resistance of the epoxy resin and the handling characteristics when the composition is used as the composition.

As the value of m and n in the above formula (1), the sum of m and n is preferably 0.01 to 1.0.

Further, when considering development for electronic materials, total chlorine becomes important because of its electrical characteristics. The total chlorine amount is preferably 1500 ppm or less, more preferably 1000 ppm or less, particularly preferably 900 ppm or less. From the halogen-free judgment value in the JPCA standard, it is preferable that the raw materials used are all halogen contents of 900 ppm or less, and in the present invention, particularly 900 ppm or less is preferable.

Hereinafter, the production method of the epoxy resin of the present invention will be described.

The epoxy resin of the present invention is obtained by reacting a trisphenol compound represented by the following formula (3) with epihalohydrin.

A specific example of the production method of the epoxy resin of the present invention is shown below.

The trisphenol compound represented by the above formula (3) is a white crystalline phase and does not significantly undergo discoloration due to oxidation. However, there is a case where coloration is slightly caused by long-term storage. The purity of the trisphenol compound to be used is preferably 96% or more, more preferably 98% or more, and particularly preferably 99% or more.

One specific example of the production method of the epoxy resin of the present invention is obtained by condensation reaction of parahydroxyacetophenone with phenol. The by-products generated during the reaction are preferably removed and purified by recrystallization or the like.

In the reaction for obtaining the epoxy resin of the present invention, epihalohydrin is preferably epichlorohydrin which is industrially readily available. The amount of the epihalohydrin to be used is usually 1.5 to 4.0 mol, preferably 2.0 to 3.5 mol, more preferably 2.0 to 2.9 mol, per 1 mol of the hydroxyl group of the starting phenol mixture. If it is less than 1.5 moles, there is a fear of gelation at the time of the reaction, which may make the production difficult. In addition, the workability of the obtained epoxy resin is likely to deteriorate, which is not preferable. On the other hand, if it exceeds 4.0 moles, the molecular weight distribution may not be in the desired range, and there is a possibility that desired properties may not be obtained. The addition of 0.5 to 10 wt% of alkoxy glycidyl ether to the epihalohydrin is preferable because the resulting epoxy resin exhibits improved toughness. The alkyl glycidyl ether is preferably an alkyl glycidyl ether having 1 to 5 carbon atoms such as methyl glycidyl ether, ethyl glycidyl ether, and propyl glycidyl ether.

As the alkali metal hydroxide which can be used in the above reaction, sodium hydroxide, potassium hydroxide and the like can be enumerated, and a solid material or an aqueous solution thereof may be used. In the present invention, in particular, from the viewpoint of solubility and handling, Is preferred.

The amount of the alkali metal hydroxide to be used is generally 0.90 to 1.5 moles, preferably 0.95 to 1.25 moles, more preferably 0.99 to 1.15 moles, per 1 mole of the hydroxyl group of the raw material phenol mixture.

In order to promote the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, or trimethylbenzylammonium chloride may be added as a catalyst. The amount of the quaternary ammonium salt to be used is generally 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the hydroxyl group of the starting phenol mixture.

In this reaction, it is preferable to use a nonpolar proton solvent (dimethylsulfoxide, dioxane, dimethylimidazolidinone, etc.) or an alcohol having 1 to 5 carbon atoms in addition to the epihalohydrin. Examples of the alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol and isopropyl alcohol.

In the present invention, in particular, from the viewpoint of color sensitivity, the use of an alcohol having 1 to 5 carbon atoms is preferable, and an alcohol having a smaller number of carbon atoms is preferable from the viewpoint of solubility of an alkali metal hydroxide, and methanol is particularly preferable.

The amount of the nonpolar proton solvent or the alcohol having 1 to 5 carbon atoms is usually 2 to 50% by weight, preferably 4 to 25% by weight based on the amount of epihalohydrin used. Epoxidation may also be performed while controlling moisture in the system by a method such as azeotropic dehydration.

The reaction temperature is usually from 30 to 90 캜, preferably from 35 to 80 캜. Particularly, in the present invention, at least 60 DEG C is preferable for the epoxidation of higher purity, and the reaction is particularly preferable under the condition close to the reflux condition. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 3 hours. If the reaction time is short, there is a fear that the reaction will not proceed to the end. On the other hand, if the reaction time is prolonged, by-products may be generated, which is not preferable.

After the reaction product of these epoxidation reactions is washed with water or without water, epihalohydrin, a solvent and the like are removed under reduced pressure. Further, in order to obtain an epoxy resin having less hydrolyzable halogen, the recovered epoxy resin is dissolved in toluene or a ketone compound having 4 to 7 carbon atoms (e.g., methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, ) Can be dissolved as a solvent, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added to carry out the reaction so that the ring-closed state is ensured. In this case, the amount of the alkali metal hydroxide to be used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, per mol of the hydroxyl group of the starting phenol mixture used for the epoxidation. The reaction temperature is usually from 50 to 120 캜, and the reaction time is usually from 0.5 to 2 hours.

Further, in the reaction with epihalohydrin, it is preferable to blow in an inert gas such as nitrogen into the liquid or the liquid. If there is no blowing of the inert gas, coloration may occur in the obtained resin. Preferably, the reaction is carried out at an oxygen concentration of not more than 6%, particularly preferably not more than 5%, and the blowing amount of the inert gas differs depending on the volume of the kiln. For example, in the case of 1L to 5L scale, It is preferable to inject an inert gas in an amount capable of displacing the volume of the kiln to 10 hours. When the kiln capacity is large, it is preferable that the amount is such that it can be replaced by 0.5 to 20 hours. It is also possible to use a method in which the gas in the kiln is replaced with an inert gas to reduce the pressure to 5 to 20 hours.

After completion of the reaction, the resulting salt is removed by filtration, washing with water, and the solvent is further distilled off under reduced pressure and heating to obtain the epoxy resin of the present invention.

The epoxy resin thus obtained is a resin excellent in heat resistance, transparency, and heat resistance coloring property. The obtained epoxy resin usually has a softening point of 45 to 65 캜 and satisfies the above-mentioned characteristics.

The obtained epoxy resin can be used as various resin raw materials. Examples thereof include epoxy acrylates and derivatives thereof, oxazolidin compounds, cyclic carbonate compounds and the like.

Hereinafter, the curable resin composition of the present invention comprising the epoxy resin of the present invention will be described.

The curable resin composition of the present invention contains the epoxy resin of the present invention as an essential component. In the curable resin composition of the present invention, two methods of thermosetting (curable resin composition A) using a curing agent and cation curing (curable resin composition B) using an acid as a curing catalyst can be adopted.

In the curable resin composition A and the curable resin composition B, the epoxy resin of the present invention can be used alone or in combination with another epoxy resin. When used in combination, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more. However, when the epoxy resin of the present invention is used as a modifier for the curable resin composition, it is added in a proportion of 1 to 30% by weight.

Examples of other epoxy resins which can be used in combination with the epoxy resin of the present invention include novolak type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins and phenol aralkyl type epoxy resins. Specific examples thereof include bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpenediphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl - [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (Phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene and the like) with formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o- Hydroxybenzophenone, dicycloheptene dihydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (Methoxymethyl) -1,1'-biphenyl, 1,4-bis (chloromethyl) benzene and 1,4-bis (methoxymethyl) benzene, and their modified products, tetrabromobisphenol Halogenated bisphenols such as A, There can be a glycidyl ether epoxy resin of a solid or liquid cargo, aliphatic epoxy resin, glycidyl amine type epoxy resin, glycidyl ester-type epoxy resins such as derived from acids, but is not limited to these. These may be used alone or in combination of two or more.

Hereinafter, each of the curable resin compositions will be referred to.

1. Thermal curing by curing agent (curable resin composition A)

Examples of the curing agent contained in the curable resin composition A of the present invention include an amine compound, an acid anhydride compound, an amide compound, a phenol compound, and a carboxylic acid compound. Specific examples of the curing agent that can be used include polyamides synthesized from dimers of diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, linolenic acid and ethylenediamine A resin selected from the group consisting of resin, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, Butane tetracarboxylic acid anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane- , 3,4-tricarboxylic acid-3,4-anhydride, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpendiphenol, 4,4'-biphenol, 2,2'-biphenol, 3 , 3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-di Tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl substituted phenol, naphthol, naphthalene diol, Alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene and the like) with formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o- Bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4 '- bis (chloromethyl) benzene, 1,4'-bis (methoxymethyl) benzene and their modified products, halogenated bisphenols such as tetrabromobisphenol A, imidazoles, trifluoroborane- Amine complexes, guanidine derivatives, condensates of terpenes and phenols, and the like, but are not limited thereto. These may be used alone or in combination of two or more.

The amount of the curing agent to be used in the curable resin composition (A) of the present invention is preferably 0.7 to 1.2 equivalents based on 1 equivalent of the epoxy group of the epoxy resin. When the equivalent of 0.7 equivalents or more than 1.2 equivalents based on one equivalent of the epoxy group is exceeded, the curing is incomplete in all cases, and good curing properties may not be obtained.

In the curable resin composition of the present invention, a curing accelerator (curing catalyst) may be used together with the curing agent. Specific examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) Tertiary amines such as 8-diaza-bicyclo [5.4.0] undecene-7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate. When a curing accelerator is used, 0.1 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin is used as needed.

In the case of an imidazole or amine compound, it may be used as a curing agent for anionic polymerization. When these curing agents are contained, the total amount of the curing agents may be cured using 0.1 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin.

The curable resin composition A of the present invention may contain a phosphorus-containing compound as a flame retardancy-imparting component. The phosphorus-containing compound may be a reaction-type compound or an addition-type compound. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tricresylenyl phosphate, cresyldiphenyl phosphate, cresyl-2,6-dicylenyl phosphate, Di-silylenyl phosphate), 1,4-phenylenebis (diksilylphosphate), and 4,4'-biphenyl (dicylanylphosphate); 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H- ; Containing epoxy compound obtained by reacting an epoxy resin with active hydrogens of the above-mentioned phosphates, and red phosphorus. Of these, phosphoric acid esters, phosphates or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylene bis (Dicylenyl phosphate), 4,4'-biphenyl (dicylanylphosphate) or a phosphorus-containing epoxy compound are particularly preferable. The content of the phosphorus-containing compound is preferably phosphorus-containing compound / epoxy resin = 0.1 to 0.6 (weight ratio). If it is 0.1 or less, flame retardancy may be insufficient, and when it is 0.6 or more, hygroscopicity and dielectric properties of the cured product may be adversely affected.

In the curable resin composition A of the present invention, a binder resin may be blended if necessary. As the binder resin, a butyral resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, an NBR-phenol resin, an epoxy-NBR resin, a polyamide resin, a polyimide resin, . The blending amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 20 parts by weight, based on 100 parts by weight of the resin component.

An inorganic filler may be added to the curable resin composition A of the present invention, if necessary. Examples of the inorganic filler include powders such as crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, stearate, spinel, titania, talc, Beads, and the like. However, the present invention is not limited to these. These may be used alone or in combination of two or more. The content of these inorganic fillers in the curable resin composition of the present invention is 0 to 95% by weight. The curable resin composition of the present invention may further contain various additives such as silane coupling agent, stearic acid, palmitic acid, zinc stearate, release agents such as calcium stearate, pigments, and various thermosetting resins.

The curable resin composition of the present invention is obtained by uniformly mixing each component. The curable resin composition A of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, the epoxy resin and the curing agent of the present invention and, if necessary, the curing catalyst, the phosphorus-containing compound, the binder resin, the inorganic filler and the compounding agent are thoroughly mixed by an extruder, a kneader, The cured product of the present invention can be obtained by obtaining a curable resin composition, molding the curable resin composition after melting, molding using a mold or a transfer molding machine, and further heating at 80 to 200 캜 for 2 to 10 hours.

The curable resin composition A of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl formamide, dimethylacetamide or N-methylpyrrolidone to prepare a curable resin composition varnish , A prepreg obtained by impregnating a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper with heat and drying is hot-pressed to obtain a cured product of the curable resin composition of the present invention have. The amount of the solvent used in the mixture of the curable resin composition of the present invention and the solvent is usually from 10 to 70% by weight, preferably from 15 to 70% by weight. Further, an epoxy resin cured product containing carbon fibers may be obtained by an RTM method in the state of being a liquid composition.

The curable resin composition A of the present invention can also be used as a modifier for film-like compositions. Concretely, it can be used for improving the flexibility in the B-stage. In order to obtain such a film-like resin composition, the varnish is applied onto a release film of the curable resin composition of the present invention, the solvent is removed under heating, and B-staged is performed to obtain a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

In addition, general applications in which a thermosetting resin such as an epoxy resin is used can be used. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP and the like), insulating materials (printed boards, , A cyanate resin composition for a sealing material and a substrate in addition to a sealing material, and an additive to other resins such as an acrylic ester resin as a curing agent for a resist.

Examples of the adhesive include adhesives for electronic materials, as well as adhesives for civil engineering, construction, automobile, general office, and medical applications. Among these, adhesives for electronic materials include interlayer adhesives for multilayer boards such as build-up substrates, adhesives for semiconductors such as die bonding agents and underfill, underfill for BGA reinforcement, anisotropic conductive films (ACF), anisotropic conductive pastes (ACP) , And the like.

Examples of encapsulants include potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light emitting diodes, ICs and LSIs, and underfill for QFPs, COFs and TABs for ICs and LSIs, , Sealing (including underfill for reinforcement) when mounting IC packages such as BGA and CSP, and the like.

2. Cation hardening as an acidic curing catalyst (curable resin composition B)

When the curable resin composition of the present invention is cured in an acidic curing catalyst, it contains a photopolymerization initiator or a thermal polymerization initiator. Further, it may contain various known compounds and materials such as a diluent, a polymerizable monomer, a polymerizable oligomer, a polymerization initiator, and a photosensitizer. In addition, various known additives such as an inorganic filler, a coloring pigment, an ultraviolet absorber, an antioxidant, and a stabilizer may be contained according to the desirability.

In the curable resin composition B, cationic polymerization is preferable, and photocatalytic polymerization is particularly preferable. Examples of the cationic catalyst (hereinafter referred to as a cationic polymerization initiator) include onium salts such as iodonium salts, sulfonium salts and diazonium salts, which may be used alone or in combination of two or more. The amount of the cationic polymerization initiator to be used is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the epoxy resin.

It is also possible to use at least one of these cationic polymerization initiators and known polymerization initiator aids (and, if necessary, photosensitizers) at the same time. Examples of the polymerization initiation auxiliary include benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinolpropan-1-one, N, N-dimethylaminoacetophenone, 2-methyl anthraquinone, 2- Ethyl anthraquinone, 2-tert-butyl anthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, , 2,4-diisopropylthioxanthone, acetophenone dimethyl ketal, benzophenone, 4-methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, And the like. The amount of the polymerization initiator such as a polymerization initiator to be used is usually 0.01 to 30 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the resin component.

Specific examples of the photosensitizer include anthracene, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, , Acridine yellow, phosphine R, benzoflavin, cetoflavin T, perylene, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, triethylamine . The amount of the photosensitizer is generally 0.01 to 30 parts by weight, preferably 0.1 to 10 parts by weight based on 100 parts by weight of the epoxy resin component.

If necessary, various additives such as an inorganic filler, a silane coupling agent, a release agent, a pigment, and various thermosetting resins may be added to the curable resin composition B of the present invention. Specific examples thereof are as described above.

The curable resin composition B of the present invention is obtained by uniformly mixing each component. It is also possible to dissolve them in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, and gamma -butyrolactone, make them uniform, and then remove the solvent by drying. The amount of the solvent used is usually 10 to 70% by weight, preferably 15 to 70% by weight, in the mixture of the curable resin composition B of the present invention and the solvent. The curable resin composition B of the present invention can be cured by thermal curing and / or irradiation with ultraviolet rays (for example, Reference: General Synthetic Epoxy Resin I, Volume I, p82-84) It is determined by the respective curing conditions since it varies depending on the resin composition. It is sufficient that the amount of heat and / or irradiation amount of the curable resin composition to be cured is sufficient, and that the curing condition satisfying the strength of the cured product in accordance with the purpose is satisfied. However, in the case of photo-curing, in particular, it is difficult to completely cure by light irradiation in these epoxy resin systems, and in applications where heat resistance is required, it is preferable to terminate the reaction completely by heating after light irradiation. It is required that the light penetrate to the detail at the time of curing, so that the epoxy compound of the present invention and the curable resin composition B are required to have high transparency.

The heating after the light irradiation is good for the curing temperature of the ordinary curable resin composition B. For example, it is preferable that the temperature is from room temperature to 150 DEG C for 30 minutes to 7 days. But the effect of accelerating the curing after the light irradiation and the effect of the heat treatment for a short period of time is more effective especially at a higher temperature range. Further, the lower the temperature, the longer the heat treatment is required. Such thermal after-curing also has an effect of aging moisture or deposited organic matter.

The shape of the cured product obtained by curing these curable resin composition B may be variously adopted depending on its use, and thus it is not particularly limited. However, it may be a film, a sheet, or a bulk. The molding method depends on each part and member. For example, a casting method, a casting method, a screen printing method, a spin coating method, a spraying method, a transferring method, a dispenser method and the like can be applied. However, It is not. The forming mold may be a polishing glass, a hard stainless steel abrasive plate, a polycarbonate plate, a polyethylene terephthalate plate, a polymethyl methacrylate plate, or the like. In order to improve the releasability from the mold, a polyethylene terephthalate film, a polycarbonate film, a polyvinyl chloride film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film and a polyimide film can be applied .

For example, when used in cationically curable resists, the photo cationically curable resin composition B of the present invention, which is dissolved in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone or? -Butyrolactone, is applied to a copper clad laminate, The composition of the present invention is applied on a substrate such as a substrate by a method such as screen printing or spin coating to a film thickness of 5 to 160 mu m and the coating film is preliminarily dried at 60 to 110 DEG C, (For example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon or the like, laser light or the like) is passed through the drawn negative film and then baked after exposure at 70 to 120 ° C. Thereafter, the unexposed portions are dissolved and removed (developed) with a solvent such as polyethylene glycol monoethyl ether, and then further irradiated with ultraviolet rays and / or heated (for example, at 100 to 200 ° C for 0.5 to 3 hours) Thereby obtaining a cured product. In this way, a printed wiring board can be obtained.

The cured product obtained in the present invention can be used for various applications including optical component materials. The optical material refers to a general material used for passing light such as visible light, infrared light, ultraviolet light, X-ray, and laser through the material. More specifically, in addition to LED sealing materials such as a lamp type and an SMD type, the following materials are listed. For example, it is a material around a liquid crystal display such as a substrate material in a liquid crystal display field, a light guide plate, a prism sheet, a deflection plate, a retardation plate, a viewing angle correcting film, an adhesive, and a polarizer protective film. In addition, the LEDs used for LED PDPs (Plasma Display) sealing materials, antireflection films, optical compensation films, housing materials, front glass protection films, front glass substitute materials, adhesives, and LED display devices expected as next generation flat panel displays A light guide plate, a prism sheet, a deflecting plate, a retardation plate, a viewing angle correcting film, an adhesive, and a substrate for a plasma addressed liquid crystal (PALC) display, a sealing material for an LED, a protective film for a front glass, An adhesive, a polarizer protective film, a protective film for the front glass in an organic EL (electroluminescence) display, a material for replacing the front glass, an adhesive, various film substrates in a field emission display (FED) Protective film, front glass replacement material, and adhesive. In the field of optical recording, a disk substrate material for a VD (video disk), a CD / CD-ROM, a CD-R / RW, a DVD-R / DVD-RAM, a MO / MD, a PD A lens, a protective film, a sealing material, and an adhesive.

In the field of optical instruments, it is a lens material for a still camera, a finder prism, a target prism, a finder cover, and a light receiving sensor part. It is also a photographing lens and a finder of a video camera. Further, projection lenses, protective films, sealing materials, adhesives and the like of projection televisions are used. Materials for lenses of optical sensing devices, sealing materials, adhesives, and films. In the field of optical components, fiber materials, lenses, waveguides, sealing materials of devices, adhesives, etc. around optical switches in optical communication systems. An optical fiber material around the optical connector, a ferrule, a sealing material, and an adhesive. Optical passive components, optical circuit components, lenses, waveguides, LED sealing materials, CCD sealing materials, and adhesives. A substrate material, a fiber material, a sealing material of an element, and an adhesive in the vicinity of an optoelectronic integrated circuit (OEIC). In the field of optical fiber, it is an optical fiber for connection to digital equipment such as illumination / light guide for decorative display, industrial use sensor, display / marking, communication infrastructure, and home digital appliance. In the semiconductor integrated circuit peripheral material, it is a resist material for microlithography for LSI and super LSI materials. In the field of automobiles and transportation vehicles, lamp reflector, bearing retainer, gear part, corrosion coat, switch part, head lamp, engine parts, electric parts, various internal and external parts, drive engine, brake oil tank, Panels, interior materials, wire nets for protection and bonding, fuel hoses, automobile lamps, and glass substitutes. Further, it is a multilayer glass for a railway car. Also, the toughness-imparting agent of the structural material of the aircraft, the members around the engine, the wire ness for protection and binding, and the corrosion-resistant coat. In the construction sector, it is used for interior and working materials, electric covers, sheets, glass interlayers, glass substitutes, and solar cell materials. For agricultural use, it is a house film. As a next-generation optoelectronic functional organic material, organic EL device peripheral materials, organic photoreflective devices, optical amplifiers as optical-to-optical conversion devices, optical computing devices, substrate materials around organic solar cells, fiber materials, , And adhesives.

Examples of encapsulants include potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light emitting diodes, ICs and LSIs, pot sealing for COB, COF and TAB for IC and LSI, underfill for BGA , And sealing (reinforcing underfill) when mounting IC packages such as CSP and the like.

Examples of other uses of the optical material include general use in which the curable resin composition A is used, and examples thereof include adhesives, paints, coating agents, molding materials (including sheets, films, FRP, Wire coating, etc.), additives in other resins in addition to the sealant, and the like. Examples of the adhesive include adhesives for electronic materials, as well as adhesives for civil engineering, construction, automobile, general office, and medical applications. Among these, adhesives for electronic materials include interlayer adhesives for multilayer boards such as build-up substrates, adhesives for semiconductors such as die bonding agents and underfill, underfill for BGA reinforcement, anisotropic conductive films (ACF), anisotropic conductive pastes (ACP) , And the like.

Example

Next, the present invention will be described in more detail with reference to examples, but parts are parts by weight unless otherwise specified. Further, the present invention is not limited to these embodiments.

In the examples, the epoxy equivalent was measured according to JIS K-7236, and the viscosity was measured at 25 캜 using an E-type viscometer. The analysis conditions in the gas chromatography (hereinafter referred to as GC) were as follows: HP5-MS (0.25 mm ID x 15 m, film thickness 0.25 탆) was used as the separation column, the column oven temperature was set to the initial temperature 100 캜, The temperature was raised at a rate of 15 ° C and maintained at 300 ° C for 25 minutes. Further, helium was used as a carrier gas. The measurement of gel permeation chromatography (hereinafter referred to as GPC) is as follows. The column was a Shodex SYSTEM-21 column (KF-803L, KF-802.5 (x2), KF-802), the eluent was tetrahydrofuran and the flow rate was 1 ml / min. The column temperature was 40 캜 and the detection was conducted with UV (254 nm), and the calibration curve was standard polystyrene standardized by Shodex.

[Example 1]

A flask equipped with a stirrer, a reflux condenser, and a stirrer was evacuated once, purged with nitrogen, and purged with nitrogen to obtain a phenol compound (TPA1) (BisP-AP manufactured by Honshu Kagaku Kogyo Co., ), 185 parts of epichlorohydrin and 100 parts of methanol were added, and the water bath was heated to 75 占 폚. When the internal temperature exceeded 65 캜, 42 parts of sodium hydroxide on flakes was added in portions over 90 minutes, and further reaction was carried out at 70 캜 for 1 hour. After completion of the reaction, the reaction mixture was washed with water, and a solvent such as excess epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 占 폚 using a rotary evaporator. 400 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 占 폚. After 8 hours of 30% by weight aqueous sodium hydroxide solution was added under stirring, the reaction was carried out for 1 hour. The reaction mixture was washed with water until the wash water became neutral, and the obtained solution was treated with methyl isobutyl ketone And the like were distilled off to obtain 175 parts of an epoxy resin (EP1). The obtained epoxy resin had an epoxy equivalent of 229 g / eq., A softening point of 51 DEG C and a color of 0.2 or less (Gardner 40% MEK solution). Further, the triglycidyl ether structure was 57% by area, the tetraglycidyl ether was 23% by area, and the total was 80% by area. Further, the higher polymer content was 13 area% (GPC).

[Example 2]

A flask equipped with a stirrer, a reflux condenser, and a stirrer was evacuated once and purged with nitrogen. While nitrogen purge was carried out, 102 parts of a phenol compound (TPA1) (BisP-AP manufactured by Honshu Kagaku Kogyo Co., Ltd.) , And 150 parts of dimethyl sulfoxide were added, and the water bath was heated to 45 캜. When the internal temperature exceeded 45 캜, 42 parts of sodium hydroxide on the flakes was added in portions over 90 minutes, and then further reaction was carried out at 45 캜 for 2 hours and at 70 캜 for 1 hour. A solvent such as excess epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 占 폚 using a rotary evaporator. To the residue, 400 parts of methyl isobutyl ketone was added and dissolved. After completion of the reaction, washing with water was carried out, and the obtained organic layer was heated to 70 占 폚. After 8 hours of 30% by weight aqueous sodium hydroxide solution was added under stirring, the reaction was carried out for 1 hour. The reaction mixture was washed with water until the wash water became neutral, and the obtained solution was treated with methyl isobutyl ketone And the like were distilled off to obtain 171 parts of an epoxy resin (EP2). The obtained epoxy resin had an epoxy equivalent of 165 g / eq., A softening point of 53 캜, and a color of 0.2 or less (Gardner 40% MEK solution). Further, the triglycidyl ether structure was 58% by area, the tetraglycidyl ether was 25% by area, and the total was 83% by area. Further, the higher polymer content was 15 area% (GPC).

[Synthesis Example 1]

A flask equipped with a stirrer, a reflux condenser and a stirrer was purged with nitrogen, and 102 parts of a phenol compound (TPA1) (BisP-AP manufactured by Honshu Kagaku Kogyo Co., Ltd.), 370 parts of epichlorohydrin, and 37 And the water bath was heated to 75 캜. When the internal temperature exceeded 65 캜, 42 parts of sodium hydroxide on flakes was added in portions over 90 minutes, and further reaction was carried out at 70 캜 for 1 hour. After completion of the reaction, the reaction mixture was washed with water, and a solvent such as excess epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 占 폚 using a rotary evaporator. 400 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 占 폚. After 8 hours of 30% by weight aqueous sodium hydroxide solution was added under stirring, the reaction was carried out for 1 hour. The reaction mixture was washed with water until the wash water became neutral, and the obtained solution was treated with methyl isobutyl ketone And the like were distilled off to obtain 178 parts of comparative epoxy resin (EP3). The resulting epoxy resin had an epoxy equivalent of 164 g / eq., A softening point of semi-solid (<45 ° C), an ICI melt viscosity of 0.04 Pa · s (150 ° C) and a color of 0.2 or less (Gardner 40% MEK solution). The triglycidyl ether structure was 87% by area, the tetraglycidyl ether was 10% by area, and the total was 97% by area. Further, the higher polymer content was less than 1% by area (GPC).

[Examples 3, 4 and 5 and Comparative Examples 1 and 2]

Phenol novolak and phenol aralkyl resin as a curing agent and triphenylphosphine (TPP) as a curing accelerator were mixed with the epoxy resin (EP1, EP2) and the epoxy resin (EP3) Were mixed and kneaded uniformly to obtain a curable resin composition for sealing comprising each epoxy resin.

This curable resin composition was pulverized with a mixer, and tableted by a tablet machine. The tableted curable resin composition was transferred (175 DEG C for 60 seconds) and further demolded and cured under conditions of 160 DEG C x 2 hours + 180 DEG C x 6 hours to obtain test pieces for evaluation of each epoxy resin.

The physical properties of the cured product were measured in the following manner. The results are shown in Table 1 below.

&Lt; TMA measurement condition >

Thermomechanical measuring device TM-7000 manufactured by Shinkuriko Co., Ltd. Heating rate: 2 ° C / min

Comparing the results of the Example using the same curing agent and the Comparative Example (Examples 3, 4 and Comparative Example 1 and Example 5 and Comparative Example 2), it is clear that the epoxy resin of the present invention is excellent in heat resistance.

[Examples 6 and 7 and Comparative Examples 3 to 13]

The epoxy resin (EP1, 2) obtained above and the epoxy resin (EP3 to EP13) for comparison were used. The details of each of the epoxy resins EP4 to EP13 (all manufactured by Nippon Kayaku Co., Ltd.) are shown in Table 2 below.

Phenol novolak was used as a curing agent in an amount equivalent to that of the epoxy resin. Tritolylphosphine (TPTP) was added as a curing accelerator in an amount of 1 wt% based on the epoxy resin. The mixture was uniformly mixed and kneaded using a mixing roll, To obtain a curable resin composition for sealing. This curable resin composition was pulverized with a mixer, and tableted by a tablet machine. The tableted curable resin composition was transferred (175 DEG C x 40 seconds) and further demolded and cured under the conditions of 160 DEG C x 2 hours + 180 DEG C x 6 hours to obtain test pieces for evaluation of each epoxy resin.

The physical properties of the cured product were measured in the following manner. The results are shown in Table 3 below.

&Lt; TMA measurement condition >

Thermomechanical measuring device TM-7000 manufactured by Shinkuriko Co., Ltd. Heating rate: 2 ° C / min

&Lt; Td5: 5% thermogravimetric reduction temperature >

The obtained cured product was pulverized to obtain a powdery product, which was passed through a 100-mesh wire netting and a 200-mesh wire netting sample was used, and the thermal decomposition temperature was measured by TG-DTA. The amount of sample used is about 10 mg, and the rate of temperature increase is 10 ° C / min. The measurement was carried out while flowing in air at 200 ml / hr, and the temperature at which the weight reduction of 5% occurred was evaluated.

Further, the above results are shown in a graph on a graph (see the drawing).

From the above results, it is clear that the epoxy resin of the present invention and its composition impart not only heat resistance but also a cured product excellent in thermal decomposition resistance.

This indicates that the stability of the resin skeleton is good, and it is also excellent in properties such as heat resistance coloring property.

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

The present application is based on Japanese Patent Application (Japanese Patent Application No. 2014-020897) filed on Feb. 6, 2014, which is incorporated by reference in its entirety. Also, all references cited herein are incorporated by reference in their entirety.

(Industrial availability)

Since the epoxy resin of the present invention has high heat resistance and excellent thermal stability, the resin composition containing the epoxy resin of the present invention can be widely used in the fields of electric and electronic parts, structural materials, adhesives, paints and the like. Further, even in optical applications requiring high intrinsic coloring resistance, since they have heat resistance capable of withstanding heat in peripheral members of light having high light emission intensity, decomposition and deterioration due to heat, which is a cause of coloring, can be avoided .

Claims (8)

As the epoxy resin represented by the following formula (1)
The total area of the chart measured by gel permeation chromatography was such that the triglycidyl ether body occupied from 40 to 75 area%, the tetraglycidyl ether body occupied from 12 to 40 area%, the triglycidyl ether body and the tetraglycidyl ether The total amount of the diallyl ether is 52 to 90%
And the tetraglycidyl ether derivative thereof has a structure represented by the following formula (2).

(Wherein A and B are as defined above and are bonded at *). G represents a glycidyl group, and m and n represent an average value of the number of repeating units and represent a number of 0 to 5. )

(Wherein G represents a glycidyl group). The method according to claim 1,
An epoxy resin obtained by the reaction of a compound represented by the following formula (3) with epihalohydrin.
3. The method according to claim 1 or 2,
Epoxy resin having a softening point of 45 to 65 占 폚 and an epoxy equivalent of 165 to 180 g / eq. The method according to claim 2 or 3,
An epoxy resin obtained by reacting a compound represented by the formula (3) with epihalohydrin, and then treating with toluene or a ketone compound having 4 to 7 carbon atoms as a solution and then treating with a metal hydroxide aqueous solution. A curable resin composition comprising the epoxy resin according to any one of claims 1 to 4 and a curing agent. 6. The method of claim 5,
Wherein the curing agent is a resin having a phenol resin structure. The method according to claim 5 or 6,
A curable resin composition comprising at least one of an acid anhydride and a polyvalent carboxylic acid as a curing agent. A cured product obtained by curing the curable resin composition according to any one of claims 5 to 7.

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