JP6016647B2 - Epoxy resin and curable resin composition - Google Patents

Description

  The present invention relates to an epoxy resin, a curable resin composition, and a cured product thereof suitable for use in electrical and electronic materials, particularly in optical materials.

  Conventionally, in applications such as LED products and transparent substrate materials, curable resin compositions have been employed in terms of a balance between performance and economy. In particular, a curable resin composition using a bisphenol A type epoxy resin having an excellent balance of heat resistance, transparency, and mechanical properties has been widely used.

Japanese Patent Application Laid-Open No. 07-157536 JP 2007-284680 A Japanese Patent Application Laid-Open No. 2012-067156

As described above, the bisphenol A type epoxy resin is versatile as an optical resin, but these are generally in a liquid state and have a problem such that tackiness occurs when forming into a sheet or prepreg. In addition, there are some which are increased in molecular weight and solidified, but are only stretched in a straight line, so that the cured product is too soft and heat resistance is not easily produced.
In order to solve this problem, TRI3 phenolic epoxy resin VG3105, Nippon Kayaku NC-6000, etc., which have a structure not having a benzylmethylene bond like bisphenol A type epoxy resin, are used. Yes. However, this structure lacks heat resistance, and higher heat resistance is required. In such applications, dimensional stability is required from the viewpoint of stability as a sheet or substrate.
As a method for solving such problems, application of silsesquioxane structure epoxy resin or cycloaliphatic epoxy resin has been studied, but silsesquioxane structure epoxy resin has high heat resistance but is brittle. However, the linear expansion coefficient tends to be high, and the refractive index is low. In addition, although the alicyclic epoxy resin has improved heat resistance in the sense of a glass transition point, brittleness and low refractive index are problems, and an aromatic glycidyl ether compound having high toughness is desired.

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
(1)
Following formula (1)

Epoxy resin obtained by the reaction of glycine and epihalohydrin, the triglycidyl ether structure as measured by gel permeation chromatography is 40-75 area% epoxy resin, and the tetraglycidyl ether body is 12-40 area% Epoxy resin, characterized by
(2)
The softening point is 60 to 80 ° C. and the epoxy equivalent is 215 to 250 g / eq. The epoxy resin according to item (1), characterized in that
(3)
An epoxy resin obtained by a production method characterized in that after completion of the reaction with epihalohydrin in the preceding item (2), a solution of toluene or a ketone compound having 4 to 7 carbon atoms is post-treated with a metal hydroxide aqueous solution;
(4)
A curable resin composition comprising the epoxy resin according to any one of (1) to (3) and a curing agent,
(5)
A curable resin composition characterized by containing a transition metal salt in (4) above,
(6)
A curable resin composition comprising a quaternary phosphonium salt in the above item (4),
(7)
A curable resin composition characterized by containing a non-halogen quaternary ammonium salt in item (4);
(8)
A curable resin composition characterized by containing at least one of an acid anhydride and a polyvalent carboxylic acid as a curing agent in any one of the above items (4) to (7),
(9)
A curable resin composition, wherein the curable resin composition according to any one of (4) to (8) is cured;
About.

  The curable resin composition of the present invention can provide a cured product excellent in transparency, heat resistance, and mechanical strength. In addition, because of the characteristics, it can be applied to optical members that require advanced optical characteristics.

  The epoxy resin of the present invention is an epoxy resin based on a trisphenol skeleton having a relatively wide molecular weight distribution, and the distribution is a structure in which the trisphenol skeleton and the trisphenol skeleton are based on epihalohydrin (1,3-dioxy). Propan-2-ol structure An epoxy resin connected by the following formula 2).

Specifically, the epoxy resin is characterized in that the triglycidyl ether body is 40-75 area% and the tetraglycidyl ether body is 12-40 area% as measured by gel permeation chromatography.
As a tetraglycidyl ether body, for example, the following formula (3)

(In the formula, G represents a glycidyl group, and a plurality of Ars each independently represent formula (a) or formula (b). Formulas (a) and (b) are bonded at the position of *. And the ratio of the number of formulas (a) and (b) is 2: 1.)
Can be expressed as 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 (2), as in the formula (3). Such bonds result in a broad molecular weight distribution.
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%, it is difficult to handle in view of viscosity and solubility. In some cases, it may gel. More preferable amounts of the triglycidyl ether compound are 40 to 75 area%, more preferably 45 to 75 area%, still more preferably 50 to 70 area%, and the tetraglycidyl ether compound is 12 to 40 area%, More preferably, it is 15-35 area%, More preferably, it is 15-30 area%. Moreover, it is 2-20 area% about more high molecular weight body simultaneously, More preferably, it is 5-20 area%.
In addition, as a preferable molecular weight distribution range, a number average molecular weight (Mn) is 600-800 in polystyrene conversion, More preferably, it is 600-750. Moreover, about a preferable weight average molecular weight (Mw), it is 700-1200, More preferably, it is 800-1100.
The epoxy equivalent of such an epoxy resin is 210-260 g / eq. More preferably, 215 to 250 g / eq. More preferably, 215 g / eq. -245 g / eq. It is. Epoxy equivalent is 210 g / eq. If it is, the heat resistance is insufficient, and if it is 260 g / eq, there may be a problem in workability.
The softening point is preferably 60 to 90 ° C., more preferably 60 to 85 ° C., particularly preferably 60 to 80 ° C., and the softening point is effective for heat resistance and handling characteristics when the composition is used. It is.
The hue is preferably 1 or less, more preferably 0.5 or less in the case of a 40% by weight methyl ethyl ketone solution as a Gardner hue.
In addition, when considering the development for electronic materials, total chlorine is important because of its electrical characteristics. The preferable total chlorine amount is 2000 ppm or less, more preferably 1800 ppm or less, and particularly preferably 1500 ppm or less.

Hereafter, the manufacturing method of the epoxy resin of this invention is described.
The epoxy resin of the present invention has the following formula (1)
It is obtained by reacting the trisphenol compound described in 1 with epihalohydrin. The example of the specific manufacturing method of the epoxy resin of this invention is shown below.

The trisphenol compound described in the formula (1) is in the form of white crystals and does not undergo much discoloration due to oxidation, but produces a little color by long-term storage. The purity of the trisphenol compound used is preferably 96% or more, more preferably 98% or more, and particularly preferably 99% or more. Further, the transmittance is preferably 95% or more, more preferably 96% or more, particularly 97% or more in the transmittance at 400 nm (1 cm width) when dissolved in tetrahydrofuran at a concentration of 30% by weight. Is preferred. The coloring of the raw material also affects the subsequent epoxidation process and becomes a coloring factor.
In general, this structure can be obtained by techniques such as recrystallization of what is produced as a by-product during the production of bisphenol A, or purification of the resin obtained by the reaction of hydroxypropylacetophenone with phenol. It can be purified by repeated purification.

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 mol, preferably 1.7 to 3.5 mol, more preferably 1.7 to 2.9 mol, and particularly preferably 1. mol based on 1 mol of hydroxyl group of the raw material phenol mixture. 75-2.75 moles. If the amount of the raw material phenol mixture used is less than 1.5 mol, there is a risk of gelation during the reaction, which makes production difficult. Moreover, since the workability | operativity of the produced epoxy resin has high possibility, it is unpreferable. On the other hand, the molecular weight distribution exceeding 4.0 mol does not fall within the desired range, and the intended characteristics are not obtained.
In addition, it is preferable to add 0.5 to 10% by weight of alkoxy glycidyl ether to epihalohydrin since an improvement in toughness of the resulting epoxy resin is observed. 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 property and handling, it is preferable to use a solid material molded into a flake shape.
The amount of 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, it is preferable to use a nonpolar proton solvent (dimethyl sulfoxide, 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, the use of an alcohol having 1 to 5 carbon atoms is particularly preferred from the viewpoint of color, and an alcohol having a smaller carbon number is preferred from the viewpoint of solubility of alkali metal hydroxide, and methanol is particularly preferred.
The usage-amount of a nonpolar protic solvent or a C1-C5 alcohol is 2-50 weight% normally with respect to the usage-amount of an epihalohydrin, Preferably it is 4-25 weight%. 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 does not proceed. On the other hand, if the reaction time is long, a by-product is formed, which is not preferable.
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 is a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.). It can be dissolved as a solvent and reacted by adding an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to ensure ring closure. In this case, the amount of the 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 raw material phenol mixture used for the epoxidation. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.
Further, in the reaction with epihalohydrin, it is preferable to carry out the reaction while blowing 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 with an oxygen concentration of preferably 6% or less, particularly preferably 5% or less is preferred, and the amount of inert gas blown in varies depending on the volume of the kettle. Preference is given to blowing an inert gas in an amount that can replace the volume of the kettle over time. Moreover, when the capacity | capacitance capacity becomes large, it is preferable to make it the quantity which can be substituted in 0.5 to 20 hours. Moreover, the method of making it the quantity which can be substituted in 5 to 20 hours after substituting the gas in a kettle with an inert gas by pressure reduction can also 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 thus obtained is a resin that is extremely excellent in heat resistance, transparency, and heat resistance colorability. The obtained epoxy resin has a softening point of 55 to 90 ° C. and satisfies the above-described 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 using the epoxy resin of this invention as a modifier of a curable resin composition, it adds in the ratio of 1 to 30 weight%.

  Examples of 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, and phenol aralkyl type epoxy resins. 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-hydroxyacetaldehyde Non, 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.
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 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 using a hardening accelerator, 0.1-5.0 weight part is used as needed with respect to 100 weight part of epoxy resins.

  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 acid 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 A phosphorus-containing product obtained by reacting with Poxy resin, red phosphorus and the like can be mentioned, however, phosphoric esters, phosphanes or phosphorus-containing epoxy resins are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy resins 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 is 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, binder resin can also be mix | blended with the curable resin composition A of this invention as needed. 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 in 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 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 this invention is obtained by mixing each component uniformly. 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, etc. as necessary. Mix thoroughly until it is obtained to obtain a curable resin composition, melt the curable resin composition after molding using a casting or transfer molding machine, and further 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 to obtain a curable resin composition varnish, and glass fiber. 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, or paper and drying by heating. It can be. The solvent used here is usually 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.

  Moreover, the curable resin composition A of this invention can be used also as a modifier of a film type composition. 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 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).

  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 QFP, BGA, CSP, etc., and sealing (including reinforcing underfill) can be used.

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 and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin.

  Further, one or two or more of these cationic polymerization initiators and known polymerization initiation assistants (and photosensitizers if necessary) can be used at the same time. 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 usage-amount of polymerization start adjuvants, such as a polymerization initiator, is 0.01-30 weight part with respect to 100 weight part of resin components, Preferably it is 0.1-10 weight part.

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, triethylamine and the like. The usage-amount of a photosensitizer is 0.01-30 weight part with respect to 100 weight part of epoxy resin components, Preferably it is 0.1-10 weight part.

  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. The solvent used here 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 heat curing and / or ultraviolet irradiation (for example, Reference: Review Epoxy Resin Vol. 1 Basic 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 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 cure completely by light irradiation alone in these epoxy resin-based photocuring, and in applications where heat resistance is required, it is necessary 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 resin and the curable resin composition B of the present invention are 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 range of 30 minutes to 7 days at normal temperature to 150 ° C. is suitable. 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 hardened | cured material obtained by making these curable resin composition B harden | cure can take various according to a use, it is not specifically limited, For example, it can also be set as shapes, such as a film form, a sheet form, and a bulk form. Although the molding method varies depending on each part and member, for example, a molding method such as 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. However, it is not limited to these. As the mold, polishing glass, hard stainless steel polishing plate, polycarbonate plate, polyethylene terephthalate plate, polymethyl methacrylate plate, or the like can be applied. In addition, 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 in order to improve releasability from the mold.

  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. Then, on the substrate such as a glass substrate, the composition of the present invention is applied with a film thickness of 5 to 160 μm by a method such as screen printing and spin coating, and the coating film is 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, and then post-exposure baking is performed at 70 to 120 ° C. Thereafter, the unexposed part 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. It is a peripheral material for liquid crystal display devices such as a substrate material, a light guide plate, a prism sheet, a deflection 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 optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Pickup lenses, protective films, sealing materials, adhesives and the like.

  In the optical equipment field, they are still camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor sections. 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 organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical arithmetic 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 For example, underfill for sealing, and sealing (reinforcing underfill) when mounting IC packages such as BGA and CSP.

  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 using an E-type viscometer at JIS K-7236 and the viscosity at 25 ° C. The analytical conditions in gas chromatography (hereinafter GC) are HP5-MS (0.25 mm IDx) in the separation column.
Column oven temperature was set to an initial temperature of 100 ° C., and 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 linking 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 and purged with nitrogen, and then a phenol compound (TPA1) (TrisP-PA Honshu Chemical Co., Ltd.) was applied while purging with nitrogen (2 times the volume of kiln capacity / hr). 142 parts, 185 parts epichlorohydrin, and 90 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 70 ° C., the ICI melt viscosity was 0.27 Pa · s (150 ° C.), and the hue was 0.2 or less (Gardner 40% methyl ethyl ketone (MEK) solution). Further, the triglycidyl ether structure is 64 area%, the tetraglycidyl ether body is 23 area%, the higher molecular weight body is 13 area% (GPC), Mn is 686, Mw is 981, Mw / Mn is 1.43. (Polystyrene conversion).

Example 2
A flask equipped with a stirrer, a reflux condenser, and a stirrer was once evacuated and purged with nitrogen, and then a phenol compound (TPA1) (TrisP-PA Honshu Chemical Co., Ltd.) was applied while purging with nitrogen (twice the volume of the kettle volume / hr). 142 parts, 185 parts epichlorohydrin and 90 parts dimethyl sulfoxide were added, and the temperature of the water bath was raised to 45 ° C. When the internal temperature exceeded 40 ° C., 42 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and 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, 177 parts of an epoxy resin (EP2) was obtained. The epoxy equivalent of the obtained epoxy resin is 221 g / eq. The softening point was 70 ° C., the ICI melt viscosity was 0.25 Pa · s (150 ° C.), and the hue was 0.5 (Gardner 40% MEK solution). The triglycidyl ether structure is 67 area%, the tetraglycidyl ether body is 22 area%, the higher molecular weight body is 11 area% (GPC), Mn is 670, Mw is 968, and Mw / Mn is 1.44. (Polystyrene conversion).

Example 3
A flask equipped with a stirrer, a reflux condenser, and a stirrer was once evacuated and purged with nitrogen, and then a phenol compound (TPA1) (TrisP-PA Honshu Chemical Industry Co., Ltd.) was applied while purging with nitrogen (twice volume / hr of volume). 142 parts, epichlorohydrin 185 parts, methyl glycidyl ether 15 parts and methanol 90 parts 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. 178 parts of epoxy resin (EP3) was obtained by distilling off methyl isobutyl ketone and the like under reduced pressure. The epoxy equivalent of the obtained epoxy resin is 220 g / eq. The softening point was 69.8 ° C., the ICI melt viscosity was 0.29 Pa · s (150 ° C.), and the hue was 0.2 or less (Gardner 40% MEK solution). The triglycidyl ether structure is 60 area%, the tetraglycidyl ether body is 23 area%, the higher molecular weight body is 12 area% (GPC), Mn is 690, Mw is 982, Mw / Mn is 1.42. (Polystyrene conversion).

Example 4
A flask equipped with a stirrer, a reflux condenser, and a stirrer was once evacuated and purged with nitrogen, and then a phenol compound (TPA1) (TrisP-PA Honshu Chemical Co., Ltd.) was applied while purging with nitrogen (twice the volume of the kettle volume / hr). 142 parts, 185 parts epichlorohydrin, 15 parts methyl glycidyl ether and 90 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. 178 parts of epoxy resin (EP4) was obtained by distilling off methyl isobutyl ketone and the like under reduced pressure. The epoxy equivalent of the obtained epoxy resin is 219 g / eq. The softening point was 69.8 ° C., the ICI melt viscosity was 0.29 Pa · s (150 ° C.), and the hue was 0.2 or less (Gardner 40% MEK solution). The triglycidyl ether structure is 60 area%, the tetraglycidyl ether body is 23 area%, the higher molecular weight body is 12 area% (GPC), Mn is 690, Mw is 982, Mw / Mn is 1.42. (Polystyrene conversion).

Synthesis example 1
A flask equipped with a stirrer, a reflux condenser, and a stirrer was once evacuated and purged with nitrogen, and then a phenol compound (TPA1) (TrisP-PA Honshu Chemical Co., Ltd.) was applied with a nitrogen purge (twice the volume of the kettle volume / hr). 142 parts, 370 parts of epichlorohydrin and 37 parts of 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. 178 parts of epoxy resin (EP6) was obtained by distilling off methyl isobutyl ketone and the like under reduced pressure. The epoxy equivalent of the obtained epoxy resin is 205 g / eq. The softening point was 59.0 ° C., the ICI melt viscosity was 0.10 Pa · s (150 ° C.), and the hue was 0.2 or less (Gardner 40% MEK solution). The triglycidyl ether structure is 87 area%, the tetraglycidyl ether body is 12 area%, the higher molecular weight body is less than 1 area% (GPC), Mn is 566, Mw is 655, and Mw / Mn is 1. 16 (polystyrene conversion).

Examples 4, 5, 6 and Comparative Example 1
Epoxy resins (EP1, EP2, EP3, EP4) obtained above and comparative epoxy resins (EP5; trisphenol methane type epoxy resin, NC-6000 manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 208 g / eq., Softening point 60 .2 ° C., 82% by area of triglycidyl ether structure, 10% by area of tetraglycidyl ether (GPC) Mn574 Mw677, Mw / Mn is 1.18 (polystyrene conversion) Gardner hue 1, EP6) phenol resin as curing agent ( Meiwa Kasei Kogyo Co., Ltd. phenol novolak H-1 hereafter referred to as PN1), triphenylphosphine (TPP) as a curing accelerator, fused silica as an inorganic filler (MSR-2122 manufactured by Kashimori), and additive Coupling agent (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) and carnauba wax (Sera Rica NODA Co.) was used and blended in the proportions (parts by weight) shown in Table 1, and mixed and kneaded using a mixing roll to obtain a curable resin composition for sealing. 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 to obtain a test piece for evaluation.
In addition, the physical property of hardened | cured material was measured in the following ways.
<TMA measurement conditions>
Thermomechanical measuring device TM-7000, manufactured by Vacuum Riko Co., Ltd. Temperature rising rate: 2 ° C./min <IZOD impact test conditions>
Measurement in accordance with JIS K-6911 <Peel strength measurement conditions>
Measured according to JIS K-6911 <HDT measurement conditions>
Measured according to JIS K7191

  From the above results, it was confirmed that the curable resin composition using the epoxy resin of the present invention was particularly excellent in heat resistance, toughness and adhesion.

Claims (7)

An epoxy resin obtained by the reaction of a compound of the following formula (1) with epihalohydrin, the triglycidyl ether body being 40-75 area% and the tetraglycidyl ether body being 12-40 as measured by gel permeation chromatography A thermosetting resin composition containing an epoxy resin characterized by area% and a curing agent.
The epoxy resin has a softening point of 60 to 80 ° C. and an epoxy equivalent of 215 to 250 g / eq. The thermosetting resin composition according to claim 1, wherein Claim 1 or thermosetting resin composition according to claim 2, characterized in that it contains a transition metal salt. Claim 1 or thermosetting resin composition according to claim 2, characterized in that it contains a quaternary phosphonium salt. The non-halogen quaternary ammonium salt is contained, The thermosetting resin composition of Claim 1 or Claim 2 characterized by the above-mentioned. The acid anhydride as the curing agent, a thermosetting resin composition according to claim 1 or claim 2, characterized in that it contains at least one of a polycarboxylic acid. A cured product obtained by curing the thermosetting resin composition according to any one of claims 1 to 6.