WO2015119188A1

WO2015119188A1 - Epoxy resin, curable resin composition, and cured product thereof

Info

Publication number: WO2015119188A1
Application number: PCT/JP2015/053214
Authority: WO
Inventors: 政隆中西; 清二江原; 昌照木村
Original assignee: 日本化薬株式会社
Priority date: 2014-02-06
Filing date: 2015-02-05
Publication date: 2015-08-13
Also published as: TWI659974B; JP2015147854A; TW201536830A; JP6366052B2; CN105980440A; KR102226437B1; KR20160118208A

Abstract

The objective of the present invention is to provide: a highly heat-resistant epoxy resin having superior thermal stability and high heat resistance; a curable resin composition; and a cured product thereof. The epoxy resin is represented by formula (1), in the entire surface area of a chart measured by means of gel permeation chromatography, triglycidyl ether bodies account for 40-75 area% and tetraglycidyl ether bodies account for 12-40 area%, the total of the triglycidyl ether bodies and tetraglycidyl ether bodies is 52-90 area%, and the tetraglycidyl ether bodies have the structure represented by formula (2). (In formula 1, the plurality of A and B present are as indicated above, and are bonded by *. Also, G indicates a glycidyl group, and m and n indicate the average number of repeats and represent a number from 0 to 5. In formula 2, G represents a glycidyl group.)

Description

Epoxy resin, curable resin composition and cured product thereof

The present invention relates to an epoxy resin, a curable resin composition, and a cured product thereof, which gives a cured product suitable for use in electrical and electronic materials, particularly heat resistance and thermal decomposition.

Curable resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. It is used.

However, in recent years, with the development in the electric / electronic field, moisture resistance, adhesion, dielectric properties, low viscosity for high filling of filler (inorganic or organic filler) as well as high purity of resin composition, There is a need for further improvements in various properties such as increased reactivity to shorten the molding cycle. Further, as a structural material, there is a demand for a material that is lightweight and has excellent mechanical properties in applications such as aerospace materials and leisure / sports equipment. Especially in the field of semiconductor encapsulation and substrates (substrate itself or its peripheral materials), as the semiconductor transitions, it becomes increasingly complex with thinning, stacking, systematization, and three-dimensionalization. Required characteristics such as heat resistance and high fluidity are required (Non-Patent Document 1). In particular, with the expansion of plastic packages to in-vehicle applications, the demand for improvement in heat resistance has become more severe, and a resin having a high Tg and a low linear expansion coefficient is required (Non-patent Document 2).

In recent years, heat resistance is one of the characteristics that is particularly important. Conventionally, heat resistance has been regarded as important, but if heat resistance is generally cited, other characteristics will deteriorate, so even if heat resistance does not meet the market requirements, other characteristics will be prioritized and balanced. There was a history of taking. However, at present, applications that require heat resistance are expanding due to an increase in the amount of current accompanying an increase in the amount of information handled by electronic materials and the severe environment used. In addition, due to the problem of energy saving, the power device is required to have heat resistance of peripheral materials in applications where high temperature driving such as SiC is possible.
One of the characteristics that have a trade-off relationship with heat resistance is the characteristic of thermal stability (herein, heat resistance generally refers to the glass transition point (Tg)). Usually, as a means for improving the heat resistance of the epoxy resin, a technique of increasing the crosslinking density by increasing the concentration of the epoxy group (decreasing the epoxy equivalent) is employed.
The cured product using this highly heat-resistant epoxy resin (for example, trisphenolmethane type epoxy resin) has a large number of epoxy groups in the molecule, so that it is an aliphatic chain that is easily decomposed when exposed to high temperatures. Since the derived structure tends to be larger than usual, the thermal stability tends to decrease in spite of the improvement in characteristics in heat resistance. Conversely, for example, in the case of a phenol aralkyl type epoxy resin having a small number of epoxy chains, thermal decomposition does not proceed easily and thermal stability tends to increase, but heat resistance decreases.
An object of the present invention is to provide a highly heat-resistant epoxy resin, a curable resin composition and a cured product thereof having high heat resistance and excellent thermal stability.
Also in optical applications, particularly in the peripheral members with strong light such as LEDs, high color resistance is required because of the requirement to use the power more effectively by transmitting or reflecting the light. ing. In particular, in the case where the emission intensity is high, the heat on the chip becomes very high, and thus a resin having heat resistance that can withstand the heat is required. The cause of coloring is decomposition / deterioration due to heat or the like, and high heat resistance and thermal stability are also demanded in optical applications as in the above.

As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention relates to the following [1] to [8].
[1]
An epoxy resin represented by the following formula (1),
Of the total area of the chart measured by gel permeation chromatography, triglycidyl ether forms 40 to 75 area%, tetraglycidyl ether forms 12 to 40 area%, and triglycidyl ether and tetraglycidyl ether forms. Is a total of 52 to 90 area%,
An epoxy resin in which the tetraglycidyl ether has a structure represented by the following formula (2).

(In the formula, a plurality of A and B are as described above, and bonded with *. G represents a glycidyl group, m and n represent an average number of repetitions, and represent a number of 0 to 5) .)

(In the formula, G represents a glycidyl group.)
[2]
The epoxy resin as described in [1] obtained by reaction of a compound represented by the following formula (3) and epihalohydrin.

[3]
The softening point is 45 to 65 ° C., and the epoxy equivalent is 165 to 180 g / eq. The epoxy resin according to [1] or [2].
[4]
[2] or [3] obtained by reacting the compound of the formula (3) with epihalohydrin and then treating with toluene or an aqueous metal hydroxide solution as a solution of a ketone compound having 4 to 7 carbon atoms. Epoxy resin.
[5]
[1] A curable resin composition comprising the epoxy resin according to any one of [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 polyvalent carboxylic acid as a curing agent.
[8]
[5] A cured product obtained by curing the curable resin composition according to any one of [7].

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 coloration resistance. Further, due to the characteristics, the cured product of the present invention can be applied to optical members that require high optical characteristics.

It is a graph which shows the evaluation result of an Example.

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

That is, the epoxy resin of the present invention is an epoxy resin based on a trisphenol skeleton having a relatively wide molecular weight distribution, and has a structure (1, 3) based on a low molecule having a trisphenol skeleton and an epihalohydrin based on the trisphenol skeleton. An epoxy resin containing a dioxypropan-2-ol structure and a molecule bonded via the following formula (4)).

Specifically, in the total area of the chart measured by gel permeation chromatography (GPC), the triglycidyl ether form accounts for 40 to 75 area%, the tetraglycidyl ether form accounts for 12 to 40 area%, and triglycidyl An epoxy resin characterized in that the total of the ether body and the tetraglycidyl ether body is 52 to 90 area%.
For example, specifically, the tetraglycidyl ether can be represented by the formula (2). Further, the higher molecular weight body is one in which one of the glycidyl ether moieties is ring-opened and linked by the structure of the formula (4), as in the formula (2). Due to such bonding, the epoxy resin of the present invention has a wide molecular weight distribution. Here, a 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 is more than 75 area% and the tetraglycidyl ether body is less than 12 area%, heat resistance is hardly obtained. Problems arise. Furthermore, when the triglycidyl ether form is less than 40 area% and the tetraglycidyl ether form exceeds 40 area%, not only the viscosity is high, but also the solubility in the solvent is deteriorated. When the high molecular weight body (high molecular weight body connected with the structure of the above formula (2) exceeding the tetraglycidyl ether body) exceeds 35 area%, the same problem may occur. It can be difficult. In some cases, it may gel.
Each amount in the epoxy resin is 40 to 75 area%, more preferably 45 to 75 area%, still more preferably 50 to 70 area% for the triglycidyl ether body, while 12 to 40 area for the tetraglycidyl ether body. %, More preferably 15 to 35 area%, still more preferably 15 to 30 area%. At the same time, the higher molecular weight is preferably 2 to 20 area%, more preferably 5 to 20 area%. The total of the triglycidyl ether and tetraglycidyl ether is 52 to 90 area%, preferably 60 to 87 area%, particularly preferably 65 to 82 area%. A suitable ratio of the area% of the tetraglycidyl ether body to the triglycidyl body is 1.1 to 3.7, more preferably 1.1 to 3.7, with respect to the tetraglycidyl ether body 1. 3.5, particularly preferably 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. More preferably, 165 g / eq. ~ 180 g / eq. It is. Epoxy equivalent was 165 g / eq. If it is less than 1, the heat resistance may be insufficient, and if it exceeds 190 g / eq, there may be a problem in workability.
The softening point is preferably 45 to 70 ° C, more preferably 45 to 65 ° C, particularly preferably 45 to 60 ° C. The epoxy equivalent and the softening point are preferable because they tend to be effective for the heat resistance of the epoxy resin and the handling characteristics when the composition is used.
In the above formula (1), as the values of m and n, the sum of m and n is preferably 0.01 to 1.0.

In addition, when considering the development of electronic materials, total chlorine is important because of its electrical characteristics. The total amount of chlorine is preferably 1500 ppm or less, more preferably 1000 ppm or less, and particularly preferably 900 ppm or less. Further, from the halogen-free judgment value in the JPCA standard, it is preferable that all raw materials to be used have a halogen amount of 900 ppm or less, and in the present invention, 900 ppm or less is particularly preferable.

Hereafter, the manufacturing method of the epoxy resin of this invention is described.
The epoxy resin of the present invention is obtained by reacting a trisphenol compound represented by the following formula (3) with epihalohydrin.

An example of a specific method for producing the epoxy resin of the present invention is shown below.

The trisphenol compound represented by the formula (3) is in the form of white crystals and does not undergo much discoloration due to oxidation, but may be slightly colored 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.
A specific example of the method for producing an epoxy resin of the present invention is obtained by a condensation reaction of parahydroxyacetophenone and phenol. 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, the epihalohydrin is preferably epichlorohydrin which is easily available industrially. The amount of epihalohydrin 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 mol of hydroxyl group in the starting phenol mixture. Here, when the amount is less than 1.5 mol, there is a risk of gelation during the reaction, which may make the production difficult. Moreover, since the workability | operativity of the epoxy resin obtained becomes high, it is unpreferable. On the other hand, if it exceeds 4.0 moles, the molecular weight distribution may not fall within the desired range, and the intended characteristics may not be obtained.
In addition, it is preferable to add 0.5 to 10% by weight of alkoxy glycidyl ether to the epihalohydrin since the toughness of the resulting epoxy resin is improved. Here, the alkyl glycidyl ether is preferably an alkyl glycidyl ether having 1 to 5 carbon atoms such as methyl glycidyl ether, ethyl glycidyl ether, or propyl glycidyl ether.

Examples of the alkali metal hydroxide that can be used in the above reaction include sodium hydroxide, potassium hydroxide and the like, and a solid substance may be used, or an aqueous solution thereof may be used. From the viewpoint of solubility and handling, it is preferable to use a solid material molded into a flake shape.
The amount of the alkali metal hydroxide used is usually 0.90 to 1.5 mol, preferably 0.95 to 1.25 mol, more preferably 0.99 to 1 mol per mol of hydroxyl group in the raw material phenol mixture. .15 moles.

In order to accelerate 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 used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of hydroxyl group in the raw material phenol mixture.

In this reaction, in addition to the above epihalohydrin, it is preferable to use a nonpolar proton solvent (such as dimethyl sulfoxide, dioxane, dimethylimidazolidinone) or an alcohol having 1 to 5 carbon atoms. Examples of the alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol and isopropyl alcohol.
In the present invention, the use of alcohols having 1 to 5 carbon atoms is particularly preferred from the viewpoint of color, and alcohols having a smaller carbon number are preferred from the viewpoint of solubility of alkali metal hydroxides, and methanol is particularly preferred.
The amount of the nonpolar protic solvent or 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. Moreover, epoxidation may be performed while controlling the moisture in the system by a technique such as azeotropic dehydration.

The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. In particular, in the present invention, 60 ° C. or higher is preferable for higher-purity epoxidation, and reaction under conditions close to reflux conditions is particularly preferable. 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, the reaction may not proceed, and on the other hand, if the reaction time is long, a by-product may be formed.

After the reaction product of these epoxidation reactions is washed with water or without washing with water, the epihalohydrin, the solvent and the like are removed under heating and reduced pressure. Furthermore, in order to obtain an epoxy resin with less hydrolyzable halogen, the recovered epoxy resin may be toluene or a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.). ) As a solvent, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to carry out the reaction to ensure ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, relative to 1 mol of the hydroxyl group of the starting phenol mixture used for epoxidation. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.
In the reaction with epihalohydrin, it is preferable to blow an inert gas such as nitrogen into the air or liquid. If no inert gas is blown, the resulting resin may be colored. The reaction is preferably carried out at an oxygen concentration of 6% or less, particularly preferably 5% or less, and the amount of inert gas blown in varies depending on the volume of the kettle. For example, in the case of 1 L to 5 L scale, 0.5 to 10 Preference is given to blowing an inert gas in an amount that can replace the volume of the kettle over time. Further, when the capacity of the pot becomes large, it is preferable that the amount can be replaced in 0.5 to 20 hours. Further, a method of reducing the gas in the kettle to an inert gas by reducing the pressure so that the gas can be replaced in 5 to 20 hours can be used.

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

The epoxy resin obtained in this way is a resin that is extremely excellent in heat resistance, transparency, and heat resistance colorability. The obtained epoxy resin usually has a softening point of 45 to 65 ° C. and satisfies the above-mentioned characteristics.

The obtained epoxy resin can be used as various resin raw materials. For example, epoxy acrylate and its derivatives, oxazolidone compounds, cyclic carbonate compounds and the like can be mentioned.

Hereinafter, it describes about the curable resin composition of this invention containing the epoxy resin of this invention.
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 heat curing with a curing agent (curable resin composition A) and cationic curing with an acid as a curing catalyst (curable resin composition B) can be applied.

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 other epoxy resins. 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 of the curable resin composition, it is added in a proportion of 1 to 30% by weight.

Other epoxy resins that can be used in combination with the epoxy resin of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins and the like. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 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 (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetate Enone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols Solid or liquid epoxy resins such as chemical compounds, alicyclic epoxy resins, glycidyl amine epoxy resins, glycidyl ester epoxy resins and the like are not limited thereto. These may be used alone or in combination of two or more.

Hereinafter, each curable resin composition will be referred to.
1. Thermal curing with a curing agent (curable resin composition A)
Examples of the curing agent contained in the curable resin composition A of the present invention include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride Acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, Bicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid- 3, 4 Anhydride, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 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 (4-hydroxyphenyl) ethane, phenols (phenol Alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, -Hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4 ' -Condensation products with bis (chloromethyl) benzene, 1,4'-bis (methoxymethyl) benzene and their modified products, halogenated bisphenols such as tetrabromobisphenol A, imidazole, 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.

In the curable resin composition (A) of the present invention, the amount of the curing agent used is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

In the curable resin composition of the present invention, a curing accelerator (curing catalyst) may be used in combination with the curing agent. Specific examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza- And tertiary amines such as 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 is used as necessary with respect to 100 parts by weight of the epoxy resin.
In the case of imidazoles and amine compounds, they can also be used as a curing agent for anionic polymerization. When these curing agents are contained, the total amount of the curing agent is 0.1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin. It can be cured using 5.0 parts by weight.

The curable resin composition A of the present invention may contain a phosphorus-containing compound as a flame retardant imparting component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes Contains phosphorus obtained by reacting with Poxy compounds, red phosphorus and the like can be mentioned. Phosphate esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The phosphorus-containing compound content is preferably phosphorus-containing compound / epoxy resin = 0.1 to 0.6 (weight ratio). If it is 0.1 or less, the flame retardancy may be insufficient, and if it is 0.6 or more, there is a concern that it may adversely affect the hygroscopicity and dielectric properties of the cured product.

Furthermore, the curable resin composition A of the present invention can be blended with a binder resin as necessary. Examples of the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. However, it is not limited to these. 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 per 100 parts by weight of the resin component. Part by weight is used as needed.

An inorganic filler can be added to the curable resin composition A of the present invention as necessary. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, 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 is used in an amount of 0 to 95% by weight in the curable resin composition of the present invention. Furthermore, a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, various compounding agents such as pigments, and various thermosetting resins are added to the curable resin composition of the present invention. can do.

The curable resin composition of the present invention can be 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 of the present invention, a curing agent and, if necessary, a curing catalyst, a phosphorus-containing compound, a binder resin, an inorganic filler and a compounding agent are uniformly used using an extruder, a kneader, a roll or the like as necessary. Mix thoroughly until it is obtained to obtain a curable resin composition, melt the curable resin composition, mold using a casting or transfer molding machine, and then heat at 80 to 200 ° C. for 2 to 10 hours. Thus, the cured product of the present invention can be obtained.

Further, 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, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the curable resin composition varnish is obtained. A cured product of the curable resin composition of the present invention by hot press molding a prepreg obtained by impregnating a base material such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating. It can be. In this case, the solvent is used in an amount usually accounting for 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present invention and the solvent. Moreover, the epoxy resin hardened | cured material which contains a carbon fiber by a RTM system with a liquid composition can also be obtained.

The curable resin composition A of the present invention can also be used as a film type composition modifier. Specifically, it can be used to improve the flexibility of the B-stage. When obtaining such a film-type resin composition, the curable resin composition of the present invention is applied to the release film by applying the varnish, removing the solvent under heating, and performing a B-stage adhesion. Get the agent. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

Furthermore, general applications in which a thermosetting resin such as an epoxy resin is used are mentioned, for example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (printed boards, In addition to the encapsulating material, the encapsulating material, a cyanate resin composition for the substrate, and an additive to other resins such as an acrylate-based resin as the curing agent for the resist may be used.

Examples of adhesives include civil engineering, architectural, automotive, general office, and medical adhesives, as well as electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

As sealing agents, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip For example, underfill for sealing, etc., and sealing (including reinforcing underfill) when mounting IC packages such as QFP, BGA, and CSP.

2. Cationic curing as an acidic curing catalyst (curable resin composition B)
When the curable resin composition of the present invention is cured with an acidic curing catalyst, it contains a photopolymerization initiator or a thermal polymerization initiator. Furthermore, you may contain various well-known compounds, materials, such as a diluent, a polymerizable monomer, a polymerizable oligomer, a polymerization start adjuvant, a photosensitizer. Moreover, you may contain various well-known additives, such as an inorganic filler, a color pigment, a ultraviolet absorber, antioxidant, a stabilizer, as needed.

In the curable resin composition B, cationic polymerization is preferable, and photocationic polymerization is particularly preferable. Examples of cationic catalysts (hereinafter referred to as cationic polymerization initiators) include onium salts such as iodonium salts, sulfonium salts, and diazonium salts, and these can be used alone or in combination of two or more. The amount of the cationic polymerization initiator used is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin.

Furthermore, it is possible to simultaneously use one or more of these cationic polymerization initiators and known polymerization initiation assistants (and photosensitizers as necessary). Examples of polymerization initiators include, for example, benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinolpropan-1-one, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1- Chloroanthraquinone, 2-amylanthraquinone, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone di Chiruketaru, benzophenone, 4-methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis-diethylamino benzophenone, and a polymerization initiator such as Michler's ketone. The amount of the polymerization initiation assistant such as a polymerization initiator used is usually 0.01 to 30 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the resin component.

Specific examples of the photosensitizer include anthracene, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acridine orange, acridine yellow, phosphine R, benzo Examples include flavin, cetoflavin T, perylene, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, and triethylamine. The amount of the photosensitizer used is usually 0.01 to 30 parts by weight, preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin component.

Furthermore, various compounding agents such as inorganic fillers, silane coupling materials, mold release agents, pigments, and various thermosetting resins can be added to the curable resin composition B of the present invention as necessary. . Specific examples are as described above.

The curable resin composition B of the present invention can be obtained by uniformly mixing each component. It is also possible to dissolve in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or γ-butyrolactone and make it uniform, and then use it after removing the solvent by drying. In this case, the solvent is used in an amount of 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 ultraviolet irradiation (for example, Reference: Review Epoxy Resin Vol. 1, Fundamental Edition I, p82-84). Since it varies depending on the curable resin composition, it is determined by the respective curing conditions. The amount of heat and / or the amount of irradiation for curing the curable resin composition may be sufficient as long as the curing conditions satisfying the purpose are satisfactory. However, especially in the case of photocuring, it is difficult to completely cure by light irradiation alone in these epoxy resin-based photocuring, and in applications where heat resistance is required, it is preferable to complete the reaction by heating after light irradiation. . Since it is necessary for light to be transmitted through the details during the curing, the epoxy compound of the present invention and the curable resin composition B are desired to be highly transparent.

The heating after the light irradiation may be performed in the normal curing temperature range of the curable resin composition B. For example, the temperature is preferably from room temperature to 150 ° C. for 30 minutes to 7 days. Although it changes depending on the blending of the curable resin composition B, the higher the temperature range, the more effective the curing is after light irradiation, and the short heat treatment is effective. Further, the lower the temperature, the longer the heat treatment. By such heat after-curing, the effect of aging the moisture and the organic matter to be deposited is also obtained.

Moreover, since the shape of the cured product obtained by curing these curable resin compositions B can be variously selected depending on the application, it is not particularly limited. For example, it may be a film shape, a sheet shape, a bulk shape, or the like. . The molding method varies depending on each part and member. For example, a casting method, a casting method, a screen printing method, a spin coating method, a spray method, a transfer method, a dispenser method, etc. can be applied. It is not limited. As the mold, polishing glass, hard stainless steel polishing plate, polycarbonate plate, polyethylene terephthalate plate, polymethyl methacrylate plate, or the like can be applied. Moreover, in order to improve mold release properties, a polyethylene terephthalate film, a polycarbonate film, a polyvinyl chloride film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polyimide film, or the like can be applied.

For example, when used for a cation curable resist, the photocation curable resin composition B of the present invention dissolved in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, and γ-butyrolactone is used as a copper-clad laminate or a ceramic substrate. The composition of the present invention was applied to a substrate such as a glass substrate with a film thickness of 5 to 160 μm by a method such as screen printing or spin coating, and the coating film was pre-dried at 60 to 110 ° C. Ultraviolet light (for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a laser beam, etc.) is irradiated through a negative film having a desired pattern, followed by post-exposure baking at 70 to 120 ° C. Thereafter, the unexposed portion is dissolved and removed (developed) with a solvent such as polyethylene glycol monoethyl ether, and if necessary, sufficient by irradiation with ultraviolet rays and / or heating (for example, at 100 to 200 ° C. for 0.5 to 3 hours). Curing is performed to obtain a cured product. In this way, it is also possible to obtain a printed wiring board.

The cured product obtained in the present invention can be used for various applications including optical component materials. The optical material refers to general materials used for applications that allow light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material. More specifically, in addition to LED sealing materials such as lamp type and SMD type, the following may be mentioned. For example, it is a liquid crystal display peripheral material such as a substrate material, a light guide plate, a prism sheet, a deflector plate, a retardation plate, a viewing angle correction film, an adhesive, and a film for a liquid crystal such as a polarizer protective film in the liquid crystal display field. In addition, color PDP (plasma display) sealing materials, antireflection films, optical correction films, housing materials, front glass protective films, front glass replacement materials, adhesives, and LED displays that are expected as next-generation flat panel displays LED molding materials, LED sealing materials, front glass protective films, front glass substitute materials, adhesives, and substrate materials for plasma addressed liquid crystal (PALC) displays, light guide plates, prism sheets, deflection plates , Phase difference plate, viewing angle correction film, adhesive, polarizer protective film, front glass protective film in organic EL (electroluminescence) display, front glass substitute material, adhesive, and various in field emission display (FED) Film substrate Front glass protective films, front glass substitute material, an adhesive. In the field of optical recording, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate materials for optical cards, Pickup lenses, protective films, sealing materials, adhesives and the like.

In the field of optical equipment, they are steel camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor parts. It is also a photographic lens and viewfinder for video cameras. Projection lenses for projection televisions, protective films, sealing materials, adhesives, and the like. These include lens materials, sealing materials, adhesives, and films for optical sensing devices. In the field of optical components, they are fiber materials, lenses, waveguides, element sealing materials, adhesives and the like around optical switches in optical communication systems. Optical fiber materials, ferrules, sealing materials, adhesives, etc. around the optical connector. For optical passive components and optical circuit components, there are lenses, waveguides, LED sealing materials, CCD sealing materials, adhesives, and the like. These are substrate materials, fiber materials, device sealing materials, adhesives, etc. around an optoelectronic integrated circuit (OEIC). In the field of optical fiber, it is an optical fiber for lighting, light guides for decorative displays, sensors for industrial use, displays / signs, etc., and for communication infrastructure and home digital equipment connection. As the semiconductor integrated circuit peripheral material, it is a resist material for microlithography for LSI and VLSI material. In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Rusted steel plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, glass replacements. In addition, it is a multilayer glass for railway vehicles. Further, they are toughness imparting agents for aircraft structural materials, engine peripheral members, protective / bundling wireness, and corrosion-resistant coatings. In the construction field, it is interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house covering film. Next generation optical / electronic functional organic materials include peripheral materials for organic EL elements, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical computing elements, substrate materials around organic solar cells, fiber materials, elements Sealing material, adhesive and the like.

As sealing agents, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip Such as underfill for sealing, sealing (reinforcing underfill) when mounting IC packages such as BGA, CSP, and the like.

Other uses of the optical material include general uses in which the curable resin composition A is used. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), In addition to insulating materials (including printed circuit boards and wire coatings), sealants, additives to other resins and the like can be mentioned. Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples.
In the examples, the epoxy equivalent was measured according to JIS K-7236, and the viscosity was measured at 25 ° C. using an E-type viscometer. The analytical conditions in gas chromatography (hereinafter referred to as GC) were HP5-MS (0.25 mm ID × 15 m, film thickness 0.25 μm) for the separation column, and the column oven temperature was set to an initial temperature of 100 ° C. The temperature was raised at a rate of 15 ° C. per minute and held at 300 ° C. for 25 minutes. Helium was used as a carrier gas. Furthermore, in the measurement of gel permeation chromatography (hereinafter referred to as GPC), it is as follows. The column is a Shodex SYSTEM-21 column (KF-803L, KF-802.5 (× 2), KF-802), the coupled eluent is tetrahydrofuran, and the flow rate is 1 ml / min. The column temperature was 40 ° C., detection was performed at UV (254 nm), and a standard polystyrene manufactured by Shodex was used for the calibration curve.

[Example 1]
A flask equipped with a stirrer, a reflux condenser, and a stirrer was once evacuated, purged with nitrogen, and then purged with nitrogen, then the phenol compound (TPA1) represented by the above formula (3) (BisP-AP manufactured by Honshu Chemical Industry Co., Ltd.) ) 102 parts, 185 parts epichlorohydrin, and 100 parts methanol were added, and the temperature of the water bath was raised to 75 ° C. When the internal temperature exceeded 65 ° C., 42 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 70 ° C. for 1 hour. After completion of the reaction, washing was performed, and excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 ° C. using a rotary evaporator. To the residue, 400 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 ° C. Under stirring, 8 parts of a 30% by weight aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour, followed by washing with water until the washing water became neutral, and the resulting solution was obtained at 180 ° C. using a rotary evaporator. 175 parts of epoxy resin (EP1) was obtained by distilling off methyl isobutyl ketone and the like under reduced pressure. The epoxy equivalent of the obtained epoxy resin was 229 g / eq. The softening point was 51 ° C. and the hue was 0.2 or less (Gardner 40% MEK solution). The triglycidyl ether structure was 57 area%, the tetraglycidyl ether body was 23 area%, and the total was 80 area%. Moreover, the higher molecular weight body was 13 area% (GPC).

[Example 2]
A flask equipped with a stirrer, a reflux condenser, and a stirrer was once evacuated and purged with nitrogen. Then, while purging with nitrogen, 102 parts of a phenol compound (TPA1) (BisP-AP manufactured by Honshu Chemical Industry), epichlorohydrin 185 And 150 parts of dimethyl sulfoxide were added, and the temperature of the water bath was raised to 45 ° C. When the internal temperature exceeded 45 ° C., 42 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. Excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 ° C. using a rotary evaporator. 400 parts of methyl isobutyl ketone was added to the residue to dissolve it, washed with water after completion of the reaction, and the resulting organic layer was heated to 70 ° C. Under stirring, 8 parts of a 30% by weight aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour, followed by washing with water until the washing water became neutral, and the resulting solution was obtained at 180 ° C. using a rotary evaporator. 171 parts of epoxy resin (EP2) was obtained by distilling off methyl isobutyl ketone and the like under reduced pressure. The epoxy equivalent of the obtained epoxy resin is 165 g / eq. The softening point was 53 ° C. and the hue was 0.2 or less (Gardner 40% MEK solution). The triglycidyl ether structure was 58 area%, the tetraglycidyl ether body was 25 area%, and the total was 83 area%. Moreover, the higher molecular weight body was 15 area% (GPC).

[Synthesis Example 1]
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen, and then purged with nitrogen, and 102 parts of phenol compound (TPA1) (BisP-AP manufactured by Honshu Chemical Industry), 370 parts of epichlorohydrin, methanol 37 And the water bath was heated to 75 ° C. When the internal temperature exceeded 65 ° C., 42 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 70 ° C. for 1 hour. After completion of the reaction, washing was performed, and excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 ° C. using a rotary evaporator. To the residue, 400 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 ° C. Under stirring, 8 parts of a 30% by weight aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour, followed by washing with water until the washing water became neutral, and the resulting solution was obtained at 180 ° C. using a rotary evaporator. By distilling off methyl isobutyl ketone and the like under reduced pressure, 178 parts of a comparative epoxy resin (EP3) was obtained. The epoxy equivalent of the obtained epoxy resin is 164 g / eq. The softening point was semi-solid (<45 ° C. or lower), ICI melt viscosity 0.04 Pa · s (150 ° C.), and hue 0.2 or lower (Gardner 40% MEK solution). The triglycidyl ether structure was 87 area%, the tetraglycidyl ether body was 10 area%, and the total was 97 area%. Moreover, the higher molecular weight body was less than 1 area% (GPC).

[Examples 3, 4, and 5 and Comparative Examples 1 and 2]
About the epoxy resin (EP1, EP2) obtained above and the epoxy resin for comparison (EP3), phenol novolak and phenol aralkyl resin are blended as a curing agent, and triphenylphosphine (TPP) is blended as a curing accelerator. Using a roll, the mixture was uniformly mixed and kneaded to obtain a curable resin composition for sealing containing each epoxy resin.
The curable resin composition was pulverized with a mixer and further tableted with a tablet machine. This tableted curable resin composition was transfer molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours. I got a piece.
In addition, the physical property of hardened | cured material was measured in the following ways. The results are shown in Table 1 below.
<TMA measurement conditions>
Thermo-mechanical measuring device TM-7000, manufactured by Vacuum Riko Co., Ltd.

By comparing the results of Examples and Comparative Examples (Examples 3 and 4 and Comparative Example 1 and Examples 5 and 2) using the same curing agent, the epoxy resin of the present invention has improved heat resistance. It became clear that it was excellent.

[Examples 6 and 7 and Comparative Examples 3 to 13]
The epoxy resins (EP1 and EP2) obtained above and comparative epoxy resins (EP3 to EP13) were used. Details of each of the epoxy resins EP4 to EP13 (all products of Nippon Kayaku Co., Ltd.) are as shown in Table 2 below.

Phenol novolac as the curing agent is equivalent to the epoxy resin, and 1% by weight of tritoluylphosphine (TPTP) as the curing accelerator is mixed with the epoxy resin, and mixed and kneaded uniformly using a mixing roll. A curable resin composition for sealing was obtained. The curable resin composition was pulverized with a mixer and further tableted with a tablet machine. This tableted curable resin composition is transfer molded (175 ° C. × 40 seconds), further demolded and cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours, and each epoxy resin evaluation test I got a piece.
In addition, the physical property of hardened | cured material was measured in the following ways. The results are shown in Table 3 below.

<TMA measurement conditions>
Thermomechanical measuring device TM-7000, manufactured by Vacuum Riko Co., Ltd.
The obtained cured product was pulverized and powdered, passed through a 100-mesh wire mesh, and a sample with the same particle size remaining in a 200-mesh wire mesh was used to measure the thermal decomposition temperature by TG-DTA. Sample usage amount of about 10 mg, temperature increase rate: 10 ° C./min. Measurement was performed in a state where the air flowed at 200 mL / hr, and the temperature at which the weight loss was 5% was evaluated.

Also, the above results were graphed and shown in the graph (see figure).

From the above results, it has been clarified that the epoxy resin of the present invention and the composition thereof give a cured product excellent in not only heat resistance but also heat decomposition resistance.
This indicates that the stability of the resin skeleton is good, and it is understood that the properties such as heat-resistant coloration are also excellent.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on February 6, 2014 (Japanese Patent Application No. 2014-020897), which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

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 is widely used in the fields of electric / electronic parts, structural materials, adhesives, paints and the like. be able to. Also in optical applications where high color resistance is required, it has heat resistance that can withstand the heat of peripheral members with high light emission intensity, so it can be useful to avoid decomposition and deterioration due to heat that causes coloration. It is.

Claims

An epoxy resin represented by the following formula (1),
Of the total area of the chart measured by gel permeation chromatography, triglycidyl ether forms 40 to 75 area%, tetraglycidyl ether forms 12 to 40 area%, and triglycidyl ether and tetraglycidyl ether forms. Is a total of 52 to 90 area%,
An epoxy resin in which the tetraglycidyl ether has a structure represented by the following formula (2).

(In the formula, a plurality of A and B are as described above, and bonded with *. G represents a glycidyl group, m and n represent an average number of repetitions, and represent a number of 0 to 5) .)

(In the formula, G represents a glycidyl group.)
The epoxy resin of Claim 1 obtained by reaction of the compound and epihalohydrin which are represented by following formula (3).
Softening point is 45 to 65 ° C. and epoxy equivalent is 165 to 180 g / eq. The epoxy resin according to claim 1 or 2.
The epoxy according to claim 2 or 3, obtained by reacting a compound of formula (3) with epihalohydrin, followed by post-treatment with toluene or an aqueous metal hydroxide solution as a solution of a ketone compound having 4 to 7 carbon atoms. resin.
A curable resin composition comprising the epoxy resin according to any one of claims 1 to 4 and a curing agent.
The curable resin composition according to claim 5, wherein the curing agent is a resin having a phenol resin structure.
The curable resin composition according to claim 5 or 6, 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.