JP6240069B2 - Epoxy resin composition, cured product thereof, and curable resin composition - Google Patents

Description

  The present invention relates to an epoxy resin composition suitable for use in electrical and electronic materials, particularly for use in optical materials, and a cured product thereof. Furthermore, the present invention relates to a curable resin composition suitable for electrical and electronic material applications that require heat resistance and flame retardancy.

  Conventionally, epoxy resin compositions have been employed in the balance between performance and economy in applications such as LED products and transparent substrate materials. In particular, an epoxy resin composition using a bisphenol A type epoxy resin having an excellent balance of heat resistance, transparency, and mechanical properties has been widely used (Patent Documents 1 to 3).

  As mentioned above, bisphenol A type epoxy resins are versatile as optical resins, but they are generally liquid and have problems such as tackiness during sheeting and prepreg formation, and the molecular weight is increased. Some of them are solidified, but only extend in a straight line, so that the cured product is too soft and heat resistance is not easily produced.

On the other hand, development of a technique for producing an alternative to glass by impregnating glass cloth as one of transparent materials and then curing the glass cloth is progressing. It is known that various epoxy resin compositions can be used as substitutes for glass, and conventional epoxy resins have a large difference in refractive index from glass cloth or a high birefringence. In such a case, the visibility is lowered due to irregular reflection or the like, and it has been difficult to use as LCD or deflected light. In particular, a transparent base material such as a glass-substitute epoxy resin for LCD using deflection is strongly required to have a low birefringence.
Thus, development of an epoxy resin for optical materials that satisfies the above required characteristics has been strongly desired.

  In addition to the above, the curable resin composition can be used for electric / electronic parts, structural materials, and adhesives depending on workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. of the cured product. Widely used in the field of paints.

  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. In particular, with the expansion of plastic packages to in-vehicle applications, the demand for improved heat resistance is becoming more severe, and it is necessary to respond to solder reflow with high Tg and low linear expansion resin. At the same time, it is required to reduce or maintain the water absorption rate. Furthermore, in recent years, halogen-based epoxy resins and antimony trioxide are frequently used as flame retardants for electrical and electronic parts as flame retardants due to environmental problems. It has been pointed out that it contributes to the generation of toxic substances such as

Japanese Unexamined Patent Publication No. 07-157536 Japanese Unexamined Patent Publication No. 2005-082798 Japanese Unexamined Patent Publication No. 2007-284680

“2008 STRJ Report Semiconductor Roadmap Special Committee 2008 Report”, Chapter 8, p1-17, [online], March 2009, JEITA Japan Electronics and Information Technology Industries Association Semiconductor Technology Roadmap Specialist Association, [May 30, 2012 search], <http://strj-jeita.elisasp.net/strj/nenjihoukoku-2008.cfm> Nobuyuki Takakura et al., Matsushita Electric Engineering Technical Report Car-related device technology High-temperature operation IC for vehicles, 74, Japan, May 31, 2001, pp. 35-40

In order to solve the above-mentioned problems in optical materials, VG3105 manufactured by Printec, which is a trisphenol epoxy resin having a structure not having a benzylmethylene bond as in the case of bisphenol A type epoxy resin, is used. However, these have initial coloration, and one level of transparency is required for use as an optical material.
As a method for solving such problems, application of silsesquioxane structure epoxy resins and cycloaliphatic epoxy resins has also been studied, but silsesquioxane structure epoxy resins have high heat resistance but are brittle. However, the linear expansion coefficient tends to be high, and the refractive index is low. In addition, alicyclic epoxy resins also have improved heat resistance in the sense of glass transition point, but brittleness and low refractive index are issues, and aromatic glycidyl ether compounds with good optical properties and high toughness. Is desired.

  In addition, an epoxy resin having a phosphorus atom in the skeleton has been proposed as one of the methods for solving the problems in the applications in the electric / electronic field. In particular, since a normal phosphate ester type compound has low stability, a cyclic phosphate compound having good stability is used. Even if a phosphoric acid ester compound is not used, those having excellent flame retardancy compared to conventional epoxy resins have been developed by selecting a resin skeleton. However, at present, particularly in the field of semiconductor encapsulants, development of a system that can be made flame retardant without using phosphorus flame retardants is being studied, and flame retardant properties generally referred to as non-halogen, non-antimony, and non-phosphorus. Is required.

Therefore, the first aspect of the present invention is excellent in transparency and heat resistance, has a high refractive index, a low birefringence, and a low retardation, so that it can be applied to optical members that require high optical properties. It is an object to provide an epoxy resin composition.
The second object of the present invention is to provide a curable resin composition that can achieve both high heat resistance and flame retardancy and is advantageous for applications in the electric and electronic fields.

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 (11).
(1)
An epoxy resin composition comprising an epoxy resin obtained by a reaction between a phenol resin represented by the following formula (1) and epihalohydrin, and a carboxylic acid and / or a cationic polymerization catalyst, wherein the epoxy resin has a Gardner ratio An epoxy resin composition having a hue of 2 or less in a color method (40% MEK solution).

(In the formula, a plurality of R's each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.)
(2)
The epoxy resin composition according to item (1), wherein the amount of residual phenolphthalein derivative in the phenol resin to be reacted with epihalohydrin is 2% or less.
(3)
The epoxy resin composition according to the above item (1), wherein the residual iron content in the phenol resin to be reacted with epihalohydrin is 50 ppm or less.
(4)
The epoxy resin composition according to item (3), which contains a transition metal salt.
(5)
The epoxy resin composition according to item (3), which contains a quaternary phosphonium salt.
(6)
The epoxy resin composition according to item (3), which contains a cationic polymerization initiator.
(7)
A cured epoxy resin obtained by curing the epoxy resin composition according to any one of (4) to (6) above.
(8)
The epoxy resin composition for glass replacement according to any one of (1) to (6) above.

(9)
A curable resin composition containing an epoxy resin represented by the following formula (2), a phenol resin and / or a polymerization catalyst.

(In the formula, multiple Rs each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.)
(10)
The curable resin composition according to item (9), wherein the phenol resin is a phenol aralkyl resin (a resin having an aromatic alkylene structure).
(11)
The curable resin composition according to item (9), wherein the polymerization catalyst is a cationic polymerization catalyst.

The first epoxy resin composition of the present invention is excellent in transparency and heat resistance, has a high refractive index, and has a low birefringence, so that it can be applied to optical members that require high optical properties. .
Further, the curable resin composition according to the second aspect of the present invention exhibits flame retardancy without using a flame retardant and a phosphorus compound while ensuring sufficient curability, and the flame retardant in the composition An epoxy resin that contributes to the reduction of phosphorus compounds, and is useful for insulating materials for electrical and electronic parts, laminates (printed wiring boards, build-up boards, etc.), various composite materials including CFRP, adhesives, paints, etc. It is. In particular, it is extremely useful as a semiconductor sealing material or a substrate material for protecting a semiconductor element.

  The first of the present invention (hereinafter also referred to as “first invention”) is an epoxy resin obtained by the reaction of a phenol resin represented by the following formula (1) and epihalohydrin, a carboxylic acid and / or a cationic polymerization catalyst. The epoxy resin is an epoxy resin composition having a hue of 2 or less in a Gardner colorimetric method (40% MEK solution).

(In the formula, a plurality of R's each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.)

  The second of the present invention (hereinafter also referred to as “second invention”) is a curable resin composition containing an epoxy resin represented by the following formula (2), a phenol resin and / or a polymerization catalyst. It is.

(In the formula, multiple Rs each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.)

The epoxy resin contained in the resin composition according to each of the first and second inventions is an epoxy resin having a phenolphthalimide skeleton. The basic skeleton of the epoxy resin is disclosed in British Patent No. 1158606 (Patent Document 4). According to Patent Document 4, epoxy equivalents per kg 3.4 (294 g / eq. In terms of the current epoxy equivalent), hue Gardner 8 (40% in methyl glycol), softening point 66 ° C. (kolfer heater), chlorine content 2 A result of 2% is disclosed. In addition, cured physical properties with DDS (diaminodiphenyl sulfone) are disclosed.
As it is, it is difficult to develop the optical material, and a resin with higher transparency is required.
Further, from the data of Patent Document 4, the present resin has a very large amount of chlorine and is unsuitable for use in electronic materials, and because it is very colored, it is difficult to use in applications that require tint. It is suggested that there is. The epoxy equivalent was 294 g / eq. And the theoretical value (252.7 g / eq.), And the amount of chlorine suggests that the epoxy contains a large amount of remaining epihalohydrin structure without ring closure. If such an epoxy ring structure is not completed, the cross-linking will not proceed well, and when the curing with a phenol resin, anionic polymerization with a basic catalyst such as imidazole, or cationic polymerization with an onium salt is performed, the machine Problems often occur in characteristics such as characteristics and water absorption. Particularly in the case of electronic materials, not only these curings but also amine-based curing is expected to cause corrosion of wiring due to the liberation of chlorine at the time of curing, resulting in a decrease in electrical reliability.
In recent years, in particular, copper wires are increasingly used for bonding a semiconductor chip and a substrate, and such a problem of electrocorrosion is becoming more important and a problem to be solved.
Moreover, in this patent document 4, there is no description about a flame retardance.

  The epoxy resin used in the epoxy resin composition according to the first invention is represented by the following formula (1):

(Wherein a plurality of R's independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms) by a reaction between a phenol resin represented by epihalohydrin and The resulting epoxy resin, specifically, the following formula (2)

(Wherein a plurality of R's each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms).

  Here, the epoxy resin used in the epoxy resin composition according to the first invention preferably contains the above epoxy compound in an amount of 70 to 95% (gel permeation chromatography area%), more preferably 70 to 93%. It is an epoxy resin. Here, in synthesizing an epoxy resin having a purity of more than 95%, the epoxy compound content may have a great deal of energy, and if the purity is too high, the crystallinity may increase, A reduction in toughness may be observed. If it is less than 70%, the epoxy ring is not completely closed, and many compounds having no functional group may be contained. In addition, many of these compounds that could not be ring-closed often contain chlorine, and as electronic materials, there is a concern about the release of chlorine ions under high-temperature and high-humidity conditions and the resulting corrosion of wiring. .

  In addition, when an epoxy resin having a phenolphthalein structure remains in the present epoxy resin, the electrical reliability is lowered and a large coloring is caused, so that the epoxy resin having a phenolphthalein structure is not preferable, preferably 2 % Or less, particularly preferably 1% or less. The epoxy resin having this phenolphthalein structure is greatly influenced by impurities derived from raw materials. If it exceeds 2%, coloring is particularly strong, which is not preferable.

In the formulas (1) and (2), R is most preferably a hydrogen atom. Examples of the alkyl group having 1 to 6 carbon atoms represented by R include alkyl groups having a linear, branched or cyclic structure such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Can be mentioned. Here, R is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
As a C1-C6 alkoxy group which R shows, the alkoxy group which has linear, branched chain, or cyclic structures, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, is mentioned, for example. Here, R is preferably a methoxy group, an ethoxy group, or a propoxy group, and particularly preferably a methoxy group.

As a preferable resin characteristic of the epoxy resin of the formula (2), the epoxy equivalent is 1.02 to 1.13 times the theoretical epoxy equivalent (252.7 g / eq.). More preferably, it is 1.03 to 1.10 times. When the ratio is less than 1.02, it takes a lot of cost to synthesize and purify the epoxy, which is not industrially preferable. When the ratio exceeds 1.13, the problem due to the amount of chlorine is concerned as described above.
The total chlorine remaining in the obtained epoxy resin is 5000 ppm or less, more preferably 3000 ppm or less, and particularly preferably 2000 ppm or less. The adverse effect of the chlorine amount is the same as described above. In addition, about chlorine ion and sodium ion, 5 ppm or less is preferable respectively, More preferably, it is 3 ppm or less. Chlorine ions are described above, and needless to say, cations such as sodium ions are also a very important factor, particularly in power device applications, and are members of failure modes when high voltages are applied.
Here, the theoretical epoxy equivalent is an epoxy equivalent calculated when the phenolic hydroxyl group of the phenol compound of the formula (1) is glycidylated without excess or deficiency.
Moreover, as a specific value of epoxy equivalent, when all R are hydrogen atoms, 257.8 g / eq. -285.6 g / eq. Is preferred, 260.3 g / eq. -278.0 g / eq. Is particularly preferred. When the epoxy equivalent is within the above range, an epoxy resin excellent in heat resistance and electrical reliability of the cured product can be obtained.

  The epoxy resin used for the resin composition of the present invention (also simply referred to as “the epoxy resin of the present invention”) has a resinous form having a softening point. Here, as a softening point, 70-130 degreeC is preferable, More preferably, it is 80-120 degreeC. When all the substituents R are hydrogen atoms, it is 70-120 degreeC especially, More preferably, it is 80-110 degreeC. If the softening point is too low, blocking during storage becomes a problem, and there are many problems such as handling at low temperatures. On the other hand, when the softening point is too high, problems such as poor handling occur during kneading with other resins. The melt viscosity is preferably 1 Pa · s (ICI melt viscosity 150 ° C. cone plate method) or less. When mixing and using an inorganic material (filler etc.), fluidity | liquidity may worsen, and the glass cloth etc. may have the finer mesh | network, and may be inferior to impregnation property.

The epoxy resin used in the first invention is excellent in transparency (hue). It is 2 or less, preferably 1.5 or less by Gardner colorimetric method (visually 40% methyl ethyl ketone solution). In particular, development on optical materials as well as ordinary PCB substrates and the like affect the color of the substrate, so that a material with less coloring is required.
The epoxy resin used in the second invention does not need to be excellent in transparency (hue) as described above, but is preferably excellent in the same manner.
The epoxy resin of the present invention has a high refractive index. Preferably it is 1.61 or more, More preferably, it is 1.62 or more, Most preferably, it is 1.62-1.65. Particularly in a field where refractive index adjustment is required, if the refractive index is high, the amount of aromatic rings of the composition used can be reduced, which can contribute to improvement of light resistance. In addition, in applications such as lenses, a lens having a smaller distortion can be produced as the refractive index is higher.

Hereafter, the manufacturing method of the epoxy resin of this invention is described.
The compound of the formula (2) is obtained by a reaction of a phenol compound (DPPI) synthesized with a phenolphthalein derivative and an aminobenzene derivative (for example, Japanese Patent Application Laid-Open No. 2005-290378) and an epihalohydrin. . The example of the specific manufacturing method of the epoxy resin of this invention is shown below.

It is known that phenolphthalein derivatives can be synthesized with phthalic acid and various corresponding phenols. If the phenols used are phenol, phenolphthalein is obtained, and if cresols, cresolphthalein is obtained. .
Here, examples of the various phenols include phenol, cresol, ethylphenol, propylphenol, xylenol, and methylbutylphenol.
Moreover, as a phenolphthalein derivative obtained by the said reaction, the following structure is mentioned, for example.

(Wherein R represents the same meaning as described above, and n represents an integer of 1 to 2)

  Examples of aminobenzene derivatives include the following structures.

(In the formula, R represents the same meaning as described above, and m represents an integer of 1 to 2).

The amount of residual phenolphthalein derivative in the phenol compound (DPPI) is preferably 2% or less, more preferably 1% or less, still more preferably 0.5% or less, particularly preferably 0.1% or less. (Measured by high performance liquid chromatography). When this phenolphthalein derivative remains, coloring tends to increase during the reaction. The same applies to aminobenzene derivatives. Further, the remaining iron content (ICP emission analysis) is one of the factors caused by coloring. The residual iron content is preferably 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 10 ppm or less. The phenol compound (DPPI) as the main body is desired to have a purity of 98% or more.
The amount of residual phenolphthalein derivative can be adjusted by purification of DPPI (washing, recrystallization, reprecipitation, etc.).

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 3.0 to 15 mol, preferably 3.0 to 10 mol, more preferably 3.5 to 8.5 mol, particularly preferably 1 mol per mol of the hydroxyl group of the phenol compound (DPPI). 5.5 to 8.5 mol.
When the amount is less than 3.0 mol, the epoxy equivalent may be increased, and the workability of the resulting epoxy resin may be deteriorated. If it exceeds 15 moles, the amount of solvent becomes large.

In the reaction of the above phenol resin and epihalohydrin, an alkali metal hydroxide can be used. Examples of the alkali metal hydroxide that can be used include sodium hydroxide and potassium hydroxide. The aqueous solution may be used, but in the present invention, it is particularly preferable to use a solid material formed into a flake shape from the viewpoint of solubility and handling.
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. 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.
When the amount of moisture in the system is large, it is not preferable because the electrical reliability of the obtained epoxy resin is deteriorated, and it is preferable to synthesize by controlling the moisture to 5% or less. Moreover, when an epoxy resin is obtained using a nonpolar proton solvent, an epoxy resin excellent in electrical reliability can be obtained, and therefore a nonpolar proton solvent can be suitably used.

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 cannot proceed, and 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. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the recovered epoxy resin is a solvent containing a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.). It can also be dissolved, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide can be added to react to ensure ring closure. In this case, the usage-amount of an alkali metal hydroxide is 0.01-0.3 mol normally with respect to 1 mol of hydroxyl groups of the raw material phenol mixture used for epoxidation, Preferably it is 0.05-0.2 mol. 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 preferably substituted with an inert gas such as nitrogen from the beginning of the reaction, and the oxygen concentration in the cavity is preferably 10% or less. Oxygen residue affects coloration. As a method, an inert gas such as nitrogen is blown before the phenol compound (DPPI) is charged (in the air or in the liquid), or after evacuating under reduced pressure and then replacing with an inert gas. If there is no substitution with an inert gas, the resulting resin may be colored. When the inert gas is blown, the amount varies depending on the volume of the kettle, but it is preferable to blow the inert gas in an amount that can replace 1 to 3 times the volume of the kettle in 0.5 to 10 hours. .

  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.

Hereinafter, the curable resin composition of the first invention and the second invention including the epoxy resin of the present invention will be described.
The epoxy resin composition of the first invention (hereinafter also referred to as “curable resin composition”) contains the epoxy resin of the present invention as an essential component.
In the curable resin composition of the first invention, heat curing (curable resin composition A) with a curing agent having carboxylic acids as essential components and cationic curing (curability) using a cationic polymerization catalyst such as an acid as a curing catalyst. Two methods of resin composition B) are applicable.

  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 mass or more, particularly preferably 40% by mass or more. However, when using the epoxy resin of this invention as a modifier of curable resin composition, you may add in the ratio of 1-30 mass%.

  Other epoxy resins that can be used in combination with the epoxy resin of the present invention include novolac type epoxy resins, bisphenol 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-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 or 1,4-bis (methoxymethyl) benzene and their modified products, halogenated bisphenols such as tetrabromobisphenol A, and alcohols , Cycloaliphatic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain structure, cyclic structure, ladder structure, or a mixed structure of at least two of these) Has glycidyl group and / or epoxycyclohexane structure Epoxy resin) solid or liquid epoxy resins and the like that, but not limited thereto.

In particular, when the curable resin composition of the present invention is used for optical applications, the epoxy resin of the present invention is preferably used in combination with an alicyclic epoxy resin or an epoxy resin having a silsesquioxane structure. Particularly in the case of an alicyclic epoxy resin, a compound having an epoxycyclohexane structure in the skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is particularly preferable.
As compounds having a cyclohexene structure, esterification reaction of cyclohexene carboxylic acid and alcohol or esterification reaction of cyclohexene methanol and carboxylic acid (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980) Or the Tyshenko reaction of cyclohexene aldehyde (method described in Japanese Patent Application Laid-Open No. 2003-170059, Japanese Patent Application Laid-Open No. 2004-262871, etc.), and further transesterification of cyclohexene carboxylic acid ester Examples thereof include compounds that can be produced by the method described in Japanese Patent Application Laid-Open No. 2006-052187.
The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentane. Diols, diols such as 1,6-hexanediol and cyclohexanedimethanol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, pentaerythritol, etc. And tetraols. Examples of carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.

Furthermore, as a compound having a cyclohexene structure other than the above, an acetal compound obtained by an acetal reaction between a cyclohexene aldehyde derivative and an alcohol is exemplified. As a reaction method, it can be produced by applying a general acetalization reaction. For example, a method of carrying out a reaction while azeotropically dehydrating using a solvent such as toluene or xylene as a reaction medium (US Pat. No. 2,945,008), A method in which polyhydric alcohol is dissolved in hydrochloric acid and then the reaction is carried out while gradually adding aldehydes (Japanese Unexamined Patent Publication No. 48-96590), a method in which water is used as a reaction medium (US Pat. No. 3,092,640) In addition, a method using an organic solvent as a reaction medium (Japanese Unexamined Patent Publication No. 7-215979), a method using a solid acid catalyst (Japanese Unexamined Patent Publication No. 2007-230992), and the like are disclosed. A cyclic acetal structure is preferable from the viewpoint of structural stability.
Specific examples of these epoxy resins include ERL-4221, UVR-6105, ERL-4299 (all trade names, all manufactured by Dow Chemical), Celoxide 2021P, Eporide GT401, EHPE3150, EHPE3150CE (all trade names, all Daicel). Chemical Industry) and dicyclopentadiene diepoxide, and the like, but are not limited to these (Reference: Review Epoxy Resin Basic Edition I p76-85).
These may be used alone or in combination of two or more.

Hereinafter, each curable resin composition will be referred to.
Curable resin composition A (thermal curing with curing agent)
As a curing agent contained in the curable resin composition A of the present invention, a resin having a carboxylic acid structure (hereinafter referred to as carboxylic acids) is an essential component. As the carboxylic acid, a di- to tetra-functional carboxylic acid is particularly preferable, and a polycarboxylic acid obtained by addition reaction of a 2- to 4-functional polyhydric alcohol and an acid anhydride is more preferable. A structure having an acid anhydride such as cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and a carboxylic acid is also preferable. In general, acid anhydrides are used for optical material applications. However, in the curable composition A of the present invention, carboxylic acid is an essential component from the viewpoint of suppressing volatility.
The 2- to 4-functional polyhydric alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol. 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1.3-propanediol, neopentyl glycol, tricyclodecanedi Diols such as methanol and norbornenediol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane and 2-hydroxymethyl-1,4-butanediol, and tet such as pentaerythritol and ditrimethylolpropane Such as ols, and the like.
Particularly preferably, branched or cyclic such as cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1.3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol It is a polyhydric alcohol.

Examples of acid anhydrides include 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 and the like are preferable. .
Particularly preferably, the following formula (5)

(Wherein Q represents at least one of a hydrogen atom, a methyl group, and a carboxyl group.) Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, cyclohexane-1,3,4-tricarboxylic acid- 3,4-anhydride is preferred.

  Examples of curing agents that can be used in combination with these carboxylic acids include amine compounds, acid anhydride compounds, amide compounds, and phenol compounds. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and nitrogen-containing compounds such as polyamide resins synthesized from linolenic acid and ethylenediamine (amine, Amide compounds); phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl hexahydro Phthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, Cyclohe Acid anhydrides such as sun-1,3,4-tricarboxylic acid-3,4-anhydride; carboxylic acid resins obtained by addition reaction of various alcohols, carbinol-modified silicones and the above-mentioned acid anhydrides; 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, dihydro Sinaphthalene etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1, Heavy weight with 1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1,4′-bis (chloromethyl) benzene, 1,4′-bis (methoxymethyl) benzene or the like Condensates and modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, polyphenols such as terpene and phenol condensates; imidazole, trifluoroborane-amine complexes, guanidine derivative compounds, etc. this It is not limited to that. These may be used alone or in combination of two or more.

  As for the usage-amount of the hardening | curing agent in the curable resin composition A of this invention, 0.7-1.2 equivalent is preferable with respect to 1 equivalent of epoxy groups of an 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 A 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 and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol and 1,8-diaza-bicyclo ( 5,4,0) Tertiary amines such as undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, hexadecyltrimethyl Quaternary ammonium salts such as ammonium hydroxide, quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, tetrabutylphosphonium salt (the counter ion of the quaternary salt is halogen) Organic acid ions, hydroxide ions and the like are not particularly specified, but organic acid ions and hydroxide ions are particularly preferable.) Tin octylate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, behen) Transition metal compounds (transition metal salts) such as zinc compounds such as zinc acid and zinc myristylate) and zinc phosphate ester (such as zinc octyl phosphate and zinc stearyl phosphate). The curing accelerator is used in an amount of 0.01 to 5.0 parts by weight with respect to the epoxy resin 100 as necessary.
In the present invention, in particular, a quaternary phosphonium salt or a transition metal compound (transition metal salt) is preferably used in order to maintain optical characteristics.

  The curable resin composition A of the present invention can also 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 ( Phosphate esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate) and 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide and 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; active hydrogen of epoxy resin and said phosphanes Contains phosphorus obtained by reacting with An epoxy resin, red phosphorus, and the like can be mentioned. Phosphate 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. As for content of a phosphorus containing compound, 0.6 times or less is preferable with respect to the total amount of the epoxy resin component in the curable resin composition A of this invention. If it exceeds 0.6 times, it may adversely affect the hygroscopicity and dielectric properties of the cured product.

  Furthermore, you may add antioxidant to the curable resin composition A of this invention as needed. Antioxidants that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. Antioxidants can be used alone or in combination of two or more. The usage-amount of antioxidant is 0.008-1 weight part normally with respect to 100 weight part of resin components of A in the curable resin composition of this invention, Preferably it is 0.01-0.5 weight part. .

  Specific examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio)- Monophenols such as 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl] -o-cresol; 2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3- Til-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) ) Propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t) -Butyl-4-hydroxy-hydrocinnamamide), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,5-di-t -Butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5- Bisphenols such as (tilphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate) ethyl 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- Butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis- (4 '-Hydroxy-3'-tert-butylphenyl) butyric acid] glycol ester, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -iso Anureate, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol And the like.

  Specific examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like. .

  Specific examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4 -Di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, etc. 9,10-dihydro 9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxaphosphaphenanthrene oxides such as 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are exemplified.

  These antioxidants can be used alone, but two or more of them may be used in combination. In the present invention, a phosphorus-based antioxidant is particularly preferable.

Furthermore, you may add a light stabilizer to the curable resin composition A of this invention as needed.
As the light stabilizer, hindered amine-based light stabilizers, particularly HALS and the like are suitable. HALS is not particularly limited, but representative examples include dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4- Polycondensate of piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy succinate -2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], bis (1,2,2, 6,6-pentamethyl-4-pi Peridyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di -T-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), etc. Only one HALS is used. Two or more types may be used in combination.

  Furthermore, a binder resin can be added to the curable resin composition A of the present invention 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 in a range that does not impair the flame retardancy and heat resistance of the cured product, and the resin component (total amount of epoxy resin and binder resin) in the curable resin composition A of the present invention is 100 weight. Usually, 0.05 to 50 parts by weight, preferably 0.05 to 20 parts by weight, are used as required.

  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. As the content of these inorganic fillers, an amount occupying 95% by mass or less in A in the curable resin composition of the present invention is used. Further, the curable resin composition A of the present invention includes a silane coupling agent, stearic acid, palmitic acid, calcium stearate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate). And zinc compounds such as zinc phosphate phosphate (octyl zinc phosphate, zinc stearyl phosphate, etc.), various compounding agents such as surfactants, dyes, pigments, UV absorbers, and various thermosetting resins can be added. it can.

When using the curable resin composition A of this invention for an optical semiconductor sealing agent, a fluorescent substance can be added as needed. For example, the phosphor has a function of forming white light by absorbing part of blue light emitted from a blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in advance in the curable resin composition, the optical semiconductor is sealed. There is no restriction | limiting in particular as fluorescent substance, A conventionally well-known fluorescent substance can be used, For example, rare earth element aluminate, thio gallate, orthosilicate, etc. are illustrated. More specifically, phosphors such as a YAG phosphor, a TAG phosphor, an orthosilicate phosphor, a thiogallate phosphor, and a sulfide phosphor can be mentioned, and YAlO ₃ : Ce, Y ₃ Al ₅ O ₁₂ : Ce, Y ₄ Al ₂ O ₉ : Ce, Y ₂ O ₂ S: Eu, Sr ₅ (PO ₄ ) ₃ Cl: Eu, (SrEu) O.Al ₂ O _{3 and the} like are exemplified. As the particle size of the phosphor, those having a particle size known in this field are used, and the average particle size is preferably 1 to 250 μm, particularly preferably 2 to 50 μm. When these phosphors are used, the amount added is preferably 1 to 80 parts by weight, particularly preferably 5 to 60 parts by weight, based on 100 parts by weight of the resin component.

  The curable resin composition A of the present invention can be obtained by uniformly mixing the above components. 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, until the epoxy resin of the present invention, a curing agent, and if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent are uniform using an extruder, a kneader, a roll, or the like as necessary Mix well and obtain a curable resin composition. After potting and melting the curable resin composition (without melting in the case of liquid), it is molded using a casting or transfer molding machine, and further 80-200. The cured product of the present invention can be obtained by heating at a temperature of 2 to 10 hours.

  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, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone as necessary. The prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber and paper, and drying by heating is formed into a curable resin composition varnish by hot press molding. It can be set as the hardened | cured material of curable resin composition A of invention. In this case, the solvent occupies 10 to 70% by mass, preferably 15 to 70% by mass in the mixture of the curable resin composition A of the present invention and the solvent. Moreover, if it is a liquid composition, the epoxy resin hardened | cured material which contains a carbon fiber by the RTM system as it is can also be obtained as it is.

  Further, when the curable resin composition A of the present invention is used in the form of a film or a sheet, it has a characteristic that it is excellent in flexibility characteristics in the B stage. Such a film or sheet-shaped resin composition is applied to the release film using the curable resin composition A of the present invention as the curable resin composition varnish, and after removing the solvent under heating, it is made into a B-stage. Is obtained. This film or sheet-shaped resin composition can be used as an adhesive (interlayer insulating layer) in a multilayer substrate or the like.

Curable resin composition B (cationic curing with acidic curing catalyst)
The curable resin composition B of the present invention that is cured using an acidic curing catalyst (cationic polymerization catalyst) contains a photopolymerization initiator or a thermal polymerization initiator as an acidic curing catalyst. 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.

  As the acidic curing catalyst, a cationic polymerization initiator is preferable, and a light or thermal cationic polymerization initiator is particularly preferable. It can be used as the curable resin composition B by blending a cationic polymerization initiator activated by active energy rays and / or a cationic polymerization initiator activated by heat.

  Cationic polymerization initiators that initiate cationic polymerization of the curable resin composition B of the present invention by irradiation with active energy rays include diazonium salts, iodonium salts, sulfonium salts, selenium salts, pyridinium salts, ferrocenium salts, phosphonium salts. And iodonium salts and sulfonium salts, more preferably diaryl iodonium salts and dialkylphenacyl sulfonium salts, and diaryl iodonium salts can be preferably used.

When a photocationic polymerization initiator such as iodonium salt or sulfonium salt is used in the cationic curable resin composition B of the present invention, as anions, BF ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , PF ₆ ⁻ , and B ( C ₆ F _{5) 4} ^- and the like, preferably _SbF ⁶ -, PF ₆ ^-, or _{B (C 6} F _{5) 4} ^-, and particularly preferably SbF ₆ ^- or _{B (C 6} F _{5) 4} ^- .

  Specific examples of the cationic photopolymerization initiator include bis (dodecylphenyl) iodonium hexafluoroantimonate (manufactured by GE Toshiba Silicone, UV-9380C main component), tricumyliodonium tetrakis (pentafluorophenyl) borate (Rhodia) PHOTOINITIATOR 2074), bis (alkyl (C = 10-14) phenyliodonium) hexafluoroantimonate (Wcation Pure Chemicals photocationic polymerization initiator WPI-016), and the like.

  As the active energy rays for curing the curable resin composition B of the present invention, X-rays, electron beams, ultraviolet rays, visible light, and the like can be used, preferably ultraviolet rays or visible rays, particularly preferably. Is ultraviolet light. When ultraviolet rays are used, the wavelength range is not particularly limited, but is preferably 150 to 400 nm, and more preferably 200 to 380 nm. When ultraviolet rays are used, cationic polymerization can be efficiently started.

  Further, in the curable resin composition B of the present invention, a sensitizer can be used in combination in order to further increase the activity of the photocationic polymerization initiator as necessary. As a sensitizer that can be used in the present invention, for example, a compound disclosed by Crivello in Advanced in Polymer Science (Adv. In Polymer Sci., 62, 1 (1984)) can be used. Specific examples include pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, and benzoflavine. In addition, compounds widely used as photo radical polymerization initiators can also be used, and specifically, thioxanthones such as benzophenone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2,4-dichlorothioxanthone. Benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2-hydroxy-2-methyl-1 Α-hydroxyalkylphenones such as phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, α such as camphorquinone -Dicarbo Nil compounds and the like. In the present invention, thioxanthones and α-hydroxyalkylphenones can be particularly preferably used.

  The compounding quantity of the photocationic polymerization initiator to the curable resin composition B of this invention can be suitably adjusted according to the kind and irradiation amount of an active energy ray. For example, in the case of ultraviolet rays, it is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts, and still more preferably 1 to 10 parts by mass with respect to 100 parts by mass in total of the cation curable resin composition B. 3 parts. When the amount of the cationic polymerization initiator is less than 0.1 part, the curability may be inferior. On the other hand, when it exceeds 10 parts by mass, the properties necessary for the cured product are reduced to reduce the physical properties of the cured product. May decrease or coloring of the cured product may become intense.

  The compounding amount in the case of adding a sensitizer to the curable resin composition B of the present invention can be appropriately adjusted according to the type of active energy ray and the irradiation amount. For example, in the case of ultraviolet rays, the amount is preferably 5 parts by mass or less, more preferably 0.2 to 2 parts with respect to 100 parts by mass in total of the curable resin composition B. When the blending amount of the sensitizer is more than 5 parts by mass, the components that are truly necessary for the cured product may be reduced to deteriorate the physical properties of the cured product, or the cured product may be intensely colored.

  When the active energy ray is ultraviolet light or visible light, the cationic curable resin composition is exposed to air. At this time, the humidity of the atmosphere is preferably low, and preferably 80% humidity. H. 70% R.V. H. More preferably, it is as follows. Here, when ultraviolet rays or visible light is installed in the production line, a method of sending dry air in front of the light irradiation device or a method of reducing the humidity by attaching a heating device can be employed.

  A compound that is activated by heat to initiate cationic polymerization, that is, a thermal cationic polymerization initiator, can also be used in the curable resin composition B of the present invention. Examples of this include various onium salts such as quaternary ammonium salts, phosphonium salts and sulfonium salts, combinations of alkoxysilanes and aluminum complexes, and the like. Available products include Adeka Opton CP-66 and Adeka Opton CP-77 (both trade names, manufactured by Asahi Denka Kogyo Co., Ltd.), Sun-Aid SI-60L, Sun-Aid SI-80L, and Sun-Aid SI-100L (both trade names) , Sanshin Chemical Industry Co., Ltd.), and CI series (Nihon Soda Co., Ltd.).

  The blending ratio of the thermal cationic polymerization initiator to the curable resin composition B of the present invention is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the cation curable resin composition, more preferably. Is 0.1 to 5 parts, more preferably 0.5 to 3 parts. When the blending ratio is less than 0.01 parts by mass, the ring-opening reaction of the ring-opening polymerizable group may not be allowed to proceed sufficiently even if it is activated by the action of heat. Moreover, even if it mixes exceeding 10 mass parts, since the effect | action which advances superposition | polymerization does not increase any more and the physical property of hardened | cured material may fall, it is unpreferable.

  Furthermore, the curable resin composition B of the present invention includes various compounding agents such as an inorganic filler, a silane coupling material, a release agent, and a pigment, and various compounding agents for various thermosetting resins as necessary. Can be added. 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 use the curable resin composition B of the present invention after uniformly dissolving it in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone or γ-butyrolactone, and then removing the solvent by drying. The solvent in this case is 10-70 mass% normally in the mixture of the curable resin composition B of this invention and this solvent, Preferably it is 15-70 mass%.
The curable resin composition B of the present invention can be cured by heating and / or ultraviolet irradiation (for example, Reference: Review Epoxy Resin Vol. 1 Basic Edition I p82-84). Since the amount varies depending on the composition of the curable resin composition B, the curing conditions are determined according to each composition. Basically, it is sufficient that the cured product has curing conditions that can express the strength required for the purpose of use. Usually, since these curable resin compositions are difficult to be completely cured only by light irradiation, it is necessary to completely complete the reaction by heating after light irradiation in applications requiring heat resistance. Moreover, since it is necessary to permeate | transmit the irradiation light in the case of photocuring to detail, the highly transparent compound and composition are desired in the epoxy resin and curable resin composition B of this invention.

  When heating is performed after light irradiation, the heating can be performed in a normal curing temperature range of the curable resin composition B. For example, the range of 30 minutes to 7 days at room 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 performing such heat after-curing, an effect of aging treatment is obtained.

  Moreover, since the shape of the cured product obtained by curing these curable resin compositions B can be various depending on the application, it is not particularly limited. For example, it can be a film shape, a sheet shape, a bulk shape, or the like. . Although the molding method varies depending on the applicable 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, and the like can be mentioned. An appropriate method may be employed to obtain the shape. As the mold, polishing glass, a hard stainless steel polishing plate, a polycarbonate plate, a polyethylene terephthalate plate, a polymethyl methacrylate plate, or the like can be used. Moreover, in order to improve the releasability between the mold and the curable resin composition B, 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 is used. Can do.

  For example, when used for a cationic curable resist, first, a curable resin composition B dissolved in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or γ-butyrolactone is used as a copper-clad laminate, a ceramic substrate, or a glass. The film is applied on a substrate such as a substrate with a film thickness of 5 to 160 μm by a method such as screen printing or spin coating, and the coating film is predried at 60 to 110 ° C. The curable resin composition B on the obtained substrate is irradiated with ultraviolet rays (for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a laser beam, etc.) through a negative film having a desired pattern drawn thereon, and then 70 A post-exposure bake treatment is performed at ˜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). A cured product is obtained by curing. In this way, it is also possible to obtain a printed wiring board. In addition, although the above-mentioned method is a case of a negative resist, the curable resin composition B of this invention can also be used as a positive resist.

  The cured product obtained by curing the curable resin composition A and the curable resin composition B of the present invention can be used for various applications including optical component materials. The optical material refers to general materials used for applications in which light such as visible light, infrared light, ultraviolet light, X-rays, and lasers passes through the material. More specifically, in addition to LED sealing materials such as lamp types and SMD types, in display-related fields, liquid crystal display substrate materials, light guide plates, prism sheets, deflection plates, retardation plates, viewing angle correction films Liquid crystal films including adhesives and polarizer protective films are expected to be used as next-generation flat panel displays for color PDP (plasma display) sealing materials, antireflection films, optical correction films, housing materials, front surfaces Glass protective film, front glass substitute material and adhesive, etc. are LED mold materials used in LED display devices, LED sealing material, front glass protective film, front glass substitute material and adhesive, etc. are plasma Substrate materials, light guide plates, prism sheets, deflector plates, etc. in address liquid crystal (PALC) displays Difference plates, viewing angle correction films, adhesives, polarizer protective films, etc., front glass protective films in organic EL (electroluminescence) displays, front glass substitute materials, adhesives, etc., are various in field emission displays (FED). Examples thereof include a film substrate, a front glass protective film, a front glass substitute material, and 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) and disc substrate materials for optical cards, A pickup lens, a protective film, a sealing material, an adhesive, and the like can be given.

  In the optical equipment field, steel camera lens materials, finder prisms, target prisms, finder covers and light-receiving sensor parts, etc., video camera photographic lenses, finder, etc., projection TV projection lenses, protective films, sealing materials, etc. , And adhesives include materials for lenses of optical sensing devices, sealing materials, adhesives, and films. In the field of optical components, fiber materials, lenses, waveguides, element sealing materials and adhesives around optical switches in optical communication systems, optical fiber materials, ferrules, sealing materials and adhesives around optical connectors, etc. In optical passive components and optical circuit components, lenses, waveguides, LED sealing materials, CCD sealing materials and adhesives are used as substrate materials, fiber materials, and device sealing materials around optoelectronic integrated circuits (OEIC). And an adhesive. In the field of optical fibers, lighting for decorative displays, light guides, etc., sensors for industrial use and displays / signs, etc., optical fibers for communication infrastructure and for connecting digital devices in the home, etc. can be mentioned. Examples of peripheral materials for semiconductor integrated circuits include resist materials for microlithography for LSI and VLSI materials. 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 wire harnesses, fuel hoses, automotive lamps and glass replacements, multilayer glass for railway vehicles, etc., toughening agents for aircraft structural materials, engine peripheral members Protective / bundling wire harnesses and corrosion resistant coatings. In the construction field, interior and processing materials, electrical covers, sheets, glass interlayers, glass substitutes, solar cell peripheral materials, and the like can be mentioned. In agriculture, a film for house covering is exemplified. 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 And a sealing material and an adhesive.

  As sealing agents, potting used for capacitors, transistors, diodes, light emitting diodes, ICs and LSIs, dipping and transfer mold sealing, potting sealing used for ICs and LSIs such as COB, COF and TAB, flip An underfill used for a chip or the like, and sealing (reinforcing underfill) when mounting IC packages such as BGA and CSP can be given.

  Other uses of the optical material include general uses in which the curable resin composition A or the curable resin composition B is used. For example, adhesives, paints, coating agents, molding materials (sheets, films) , FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc.), sealants, additives to other resins, and the like. When using the curable resin composition A or curable resin composition B of the present invention as an additive to other resins, for example, when used as a curing agent to a sealant or a cyanate resin composition for a substrate, The case where it uses for acrylic ester-type resin etc. as a hardening agent for resists is mentioned. Examples of the adhesive include civil engineering, architectural use, automobile use, general office use, medical use, and electronic material use. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, semiconductor adhesives such as die bonding agents and underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

The curable resin composition of 2nd invention is demonstrated below.
In the curable resin composition of the second invention, a phenol resin or a polymerization catalyst is used as an essential component.

The phenol resin contained in the second invention includes 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, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1 ′ -Biphenyl, 1,4'-bis (chloromethyl) benzene, polycondensates with 1,4'-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, terpenes And polyphenols such as condensates of phenol and the like, but are not limited thereto. These may be used alone or in combination of two or more.
Preferable phenol resins include phenol aralkyl resins (resins having an aromatic alkylene structure), particularly preferably a structure having at least one selected from phenol, naphthol, and cresol, and the alkylene portion serving as the linker is benzene. A resin characterized by at least one selected from a structure, a biphenyl structure, and a naphthalene structure (specific examples include zylock, naphthol zylock, phenol biphenylene novolak resin, cresol-biphenylene novolak resin, phenol-naphthalene novolak resin, etc.) Is.)

  In the curable resin composition of the second invention, the amount of the curing agent including the phenol resin is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy groups of all epoxy resins. 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.

  The polymerization catalyst contained in the curable resin composition of the second invention can be used without limitation as long as it is a catalyst that initiates polymerization by heat or light, and specifically, a curing accelerator or an acidic curing catalyst is used. it can.

  Specific examples of the curing accelerator that can be used include the same ones that can be used in the curable resin composition A of the first invention described above. When using a hardening accelerator, it is the same as that of the curable resin composition A of the above-mentioned 1st invention also about the usage-amount.

  As the acidic curing catalyst, a cationic polymerization initiator is preferable, and a light or thermal cationic polymerization initiator is particularly preferable. By blending a cationic polymerization initiator activated by an active energy ray and / or a cationic polymerization initiator activated by heat, it can be used as the curable resin composition 2B described later.

  The cationic polymerization initiator for initiating cationic polymerization of the curable resin composition 2B of the present invention to be described later by irradiation with active energy rays is the same as that which can be used in the curable resin composition B of the first invention described above. Can be mentioned.

  A compound that is activated by heat to initiate cationic polymerization, that is, a thermal cationic polymerization initiator, can also be used in the curable resin composition 2B of the present invention. Also as this thing, the thing similar to what can be used in the curable resin composition B of the above-mentioned 1st invention is mentioned.

  In the curable resin composition of the second invention, those using a polymerization catalyst as an essential component are heat curing with a curing agent (curable resin composition 2A) and cationic curing with a curing catalyst as an acid (curable resin composition). Two methods of product 2B) are applicable.

  Similar to the curable resin composition of the first invention described above, in the curable resin composition 2A and the curable composite resin composition 2B, the epoxy resin of the present invention is used alone or in combination with other epoxy resins. I can do it. When using together, the usage-amount of the other epoxy resin which can be used together, a specific example is the same as that of the curable resin composition of the above-mentioned 1st invention.

Hereinafter, each curable resin composition will be referred to.
Thermal curing with a curing agent (curable resin composition 2A)
The curing agent contained in the curable resin composition 2A of the present invention is the same as the carboxylic acids that can be used in the curable resin composition A of the first invention described above and other curing agents that can be used in combination with the carboxylic acids. .
In the present invention, compounds having an acid anhydride structure and / or a carboxylic acid structure represented by the aforementioned acid anhydrides and carboxylic acid resins are particularly preferable.

  The amount of the curing agent used in the curable resin composition 2A of the present invention is also the same as that of the curable resin composition A of the first invention described above.

  In the curable resin composition 2A of the present invention, a curing accelerator may be used in combination with the curing agent. Specific examples of the curing accelerator that can be used include those described above. When a curing accelerator is used, the amount used is the same as that of the curable resin composition A of the first invention described above.

  In the curable resin composition 2A of the present invention, a phosphorus-containing compound can also be contained as a flame retardant imparting component, like the curable resin composition A of the first invention described above. Specific examples and usage amounts of the phosphorus-containing compound are the same as those of the curable resin composition A of the first invention.

  Furthermore, an antioxidant may be added to the curable resin composition 2A of the present invention as necessary, as with the curable resin composition A of the first invention described above. Specific examples and use amounts of the antioxidant that can be used are the same as those of the curable resin composition A of the first invention.

Further, a light stabilizer may be added to the curable resin composition 2A of the present invention as necessary, as in the case of the curable resin composition A of the first invention described above.
Specific examples of the light stabilizer are the same as those of the curable resin composition A of the first invention described above.

  Furthermore, in the curable resin composition 2A of the present invention, a binder resin can be blended as necessary, similarly to the curable resin composition A of the first invention described above. The specific examples and use amounts of the binder resin are also the same as those of the curable resin composition A of the first invention described above.

  In the curable resin composition 2A of the present invention, an inorganic filler can be added as necessary, similarly to the curable resin composition A of the first invention described above. Specific examples and usage amounts of the inorganic filler are also the same as those of the curable resin composition A of the first invention described above.

  When the curable resin composition 2A of the present invention is used for an optical semiconductor encapsulant, a phosphor can be added as necessary, similarly to the curable resin composition A of the first invention described above. . Specific examples and usage amounts of the phosphors are also the same as those of the curable resin composition A of the first invention described above.

  The curable resin composition 2A of the present invention is obtained by uniformly mixing the respective components as in the curable resin composition A of the first invention described above, and is a method similar to a conventionally known method. The cured product can be easily obtained.

  Moreover, the curable resin composition A of this invention can be made into hardened | cured material by the method similar to the curable resin composition A of the above-mentioned 1st invention.

Curable resin composition 2B (cationic curing with acidic curing catalyst)
The curable resin composition 2B of the present invention, which is cured using an acidic curing catalyst, has a photopolymerization initiator or a thermal polymerization initiator as an acidic curing catalyst in the same manner as the curable resin composition B of the first invention described above. Further, it may contain various known compounds and materials such as diluents, polymerizable monomers, polymerizable oligomers, polymerization initiation aids, photosensitizers, etc. You may contain various well-known additives, such as a material, a color pigment, a ultraviolet absorber, antioxidant, a stabilizer.

  Similar to the curable resin composition B of the first invention described above, the acidic curing catalyst is preferably a cationic polymerization initiator, and particularly preferably a light or thermal cationic polymerization initiator. It can be used as the curable resin composition 2B by blending a cationic polymerization initiator activated by active energy rays and / or a cationic polymerization initiator activated by heat.

  As the cationic polymerization initiator for initiating cationic polymerization of the curable resin composition 2B of the present invention by irradiation with active energy rays, the same ones that can be used in the curable resin composition B of the first invention described above are used. Can be mentioned.

  The active energy rays for curing the curable resin composition 2B of the present invention are the same as those of the curable resin composition B of the first invention described above.

  Further, in the curable resin composition 2B of the present invention, as in the case of the curable resin composition B of the first invention described above, a sensitizer is used to further increase the activity of the photocationic polymerization initiator as necessary. Can also be used together. Examples of the sensitizer that can be used in the present invention include the same sensitizers that can be used in the curable resin composition B of the first invention described above. This is the same as the curable resin composition B of the first invention.

  The blending amount when adding a sensitizer to the curable resin composition 2B of the present invention, the irradiation conditions of active energy rays, and the like are the same as those of the curable resin composition B of the first invention described above.

  A compound that is activated by heat and initiates cationic polymerization, that is, a thermal cationic polymerization initiator, can also be used in the curable resin composition 2B of the present invention. This is the same as the curable resin composition B of the first invention.

  Further, in the curable resin composition 2B of the present invention, as in the case of the curable resin composition B of the first invention described above, the inorganic filler, the silane coupling material, and the release agent as described above are used as necessary. Various compounding agents such as agents and pigments and various thermosetting resins can be added.

  The curable resin composition 2B of the present invention can be obtained, used, and cured by uniformly mixing each component, like the curable resin composition A of the first invention described above.

  The cured product obtained by curing the curable resin composition 2A and the curable resin composition 2B of the second invention can be used for various applications.

  Examples include general applications in which the curable resin composition 2A or the curable resin composition 2B is used. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials ( In addition to the sealing agent, the additive to other resins, etc. are 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).

  As sealing agent and substrate, potting sealing for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., dipping, transfer mold sealing, ICs, LSIs for COB, COF, TAB, etc. Examples include underfill for flip chip, sealing (including reinforcing underfill) and package substrate when mounting IC packages such as QFP, BGA, and CSP. Moreover, it is suitable also for the board | substrate use with which functionality, such as a network board | substrate and a module board, is calculated | required.

Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples. The present invention is not limited to these synthesis examples and examples. In addition, each physical property value in an Example was measured with the following method.
The various analysis methods used in the examples are described below.
Epoxy equivalent: Conforms to JIS K 7236 (ISO 3001)
ICI melt viscosity: compliant with JIS K 7117-2 (ISO 3219) Softening point: compliant with JIS K 7234 Total chlorine: compliant with JIS K 7243-3 (ISO 21672-3) Chlorine ion: JIS K 7243-1 (ISO 21672) -1) in accordance with sodium ion: measured by ion chromatography Iron content: ICP emission spectroscopic analysis refractive index: in accordance with ISO 5661 Gardner color number: in accordance with ISO 4630-1 GPC:
Column (Shodex KF-603, KF-602x2, KF-601x2)
The coupled eluent has a tetrahydrofuran flow rate of 0.5 ml / min.
Column temperature is 40 ° C
Detection: RI (differential refraction detector)

Synthesis example 1
A flask equipped with a stirrer, a reflux condenser, and a stirrer is once evacuated and purged with nitrogen, and then subjected to a nitrogen purge (2 L / hr) while phenol compound (DPPI1) (all the substituents R in Formula (1) are Compound of hydrogen atom (SABIC PPPBP ) 255 parts, 842 parts of epichlorohydrin, and 168 parts of methanol were added, and the temperature of the water bath was raised to 75 ° C. When the internal temperature exceeded 65 ° C, 21 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, 200 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 ° C. Under stirring, 26 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, 301 parts of an epoxy resin (EP1) was obtained. The epoxy equivalent of the obtained epoxy resin is 266 g / eq. The softening point was 88 ° C., the ICI melt viscosity was 0.44 Pa · s (150 ° C.), the chlorine ion was 2 ppm, the sodium ion was 0.5 ppm, and the hue was 0.2 or less (Gardner 40% THF solution). The structure of the formula (1) was 93 area% (GPC). The refractive index was 1.63. (A normal epoxy or cresol novolac type epoxy resin has a very high refractive index since it is 1.59.)

Synthesis example 2
A phenol compound (DPPI1) (a compound in which the substituents R are all hydrogen atoms in the above formula (1) SABIC PPPB P while nitrogen purge (2 L / hr) is applied to a 1 L flask equipped with a stirrer, a reflux condenser, and a stirrer ) 255 parts, 601 parts of epichlorohydrin, and 180 parts of methanol were added, and the temperature of the water bath was raised to 75 ° C. After 1.5 hours from the start of nitrogen purge (blowing with about 3 times the amount of nitrogen in the flask) and after confirming that the internal temperature exceeded 65 ° C, 21 parts of flaky sodium hydroxide was added over 90 minutes. Added in portions. Thereafter, 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, 200 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 ° C. Under stirring, 5 parts of a 30% by weight sodium hydroxide aqueous 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. 300 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 270 g / eq. The softening point was 90 ° C., the ICI melt viscosity was 0.46 Pa · s (150 ° C.), the chlorine ion was 2 ppm, the sodium ion was 0.5 ppm, and the hue was 0.2 or less (Gardner 40% THF solution). The structure of the formula (1) was 93 area% (GPC). The refractive index was 1.63.

Synthesis example 3
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, phenolic compound (DPPI1) (a compound in which the substituents R are all hydrogen atoms in the formula (1) SABIC PPPB P) 256 parts, 661 parts epichlorohydrin, benzyl 3 parts of trimethylammonium chloride was added and the water bath was heated to 70 ° C. To this, 100 parts of a 49% aqueous sodium hydroxide solution was added dropwise over 90 minutes, followed by further reaction at 70 ° C. for 4 hours. After completion of the reaction, washing with water was performed, and a solvent such as excess epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 ° C. using a rotary evaporator to obtain 290 parts of an epoxy resin (EP3). The epoxy equivalent of the obtained epoxy resin was 297 g / eq. , Softening point 95 ° C., ICI melt viscosity 0.70 Pa · s (150 ° C.), total chlorine amount 10450 ppm, hydrolyzable chlorine 9700 ppm, chlorine ion 0.5 ppm, sodium ion 0.5 ppm, hue 3 (Gardner 40% THF Solution). The structure of the formula (1) was 65 area% (GPC).

Synthesis example 4
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen, while 15 parts of tricyclodecane dimethanol, 70 parts of methylcyclohexanedicarboxylic anhydride (Rikacid MH manufactured by Shin Nippon Rika), cyclohexane-1,2 , 4-tricarboxylic acid-1,2-anhydride (Mitsubishi Gas Chemical Co., Ltd., H-TMAn) (15 parts) was added, reacted at 40 ° C. for 3 hours, and then heated and stirred at 70 ° C. for 1 hour (tricyclodehydride by GPC The disappearance of candimethanol (1 area% or less) was confirmed.) 100 parts of a curing agent composition (H-1) containing carboxylic acids and acid anhydrides was obtained. The resulting curing agent composition (H-1) is a colorless liquid resin, and the purity by GPC is 37% by area of carboxylic acids (formula 6 below), acid anhydride (cyclohexane-1,2,4-tricarboxylic acid). -1,2-anhydride) was 11 area%, and acid anhydride (methylcyclohexanecarboxylic acid anhydride) was 52 area%. The functional group equivalent was 171 g / eq. Met.

Example 1 and Comparative Example 1
An epoxy resin (EP1) obtained in Synthesis Example 1 as an example and a bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical) as a comparative example, respectively, and an alicyclic epoxy resin (Celoxide 3150, manufactured by Daicel Industries, Ltd.) A cationic curing catalyst (SI-150L manufactured by Sanshin Chemical Industry Co., Ltd.) was blended at a ratio of 53: 47: 2 to prepare a 55% solution of methyl ethyl ketone. The resulting solution was impregnated with a 40 micron thick E glass glass cloth (manufactured by Unitika), and the solvent was evaporated at 150 ° C. for 4 minutes to prepare a prepreg. Then, after preheating at 150 ° C. for 1 minute, pressure pressing was performed at 150 ° C. and 30 kg / cm ² for 15 minutes, and finally curing was performed at 150 ° C. for 3 hours. The obtained film was cut into a size of 10 × 40 mm, and the retardation, which is an index of birefringence, was measured. The film thickness was 56 μm.

The retardation was measured under the following conditions.
Measuring instrument: Ellipso M-220 (manufactured by JASCO)
Incident angle: 90 degrees Bandwidth: 1.0 nm
Measurement range: 0.1-0.4kgf
Measurement wavelength: 550 nm

As a result, those using epoxy resin EP1 showed retardation of 0.4 to 0.8 μm, and those using bisphenol A type epoxy resin for comparison showed retardation in the range of 0.7 to 1.6 μm. .
In addition, retardation is a phase difference, and it is so preferable that it is small, and from this result, it was confirmed that the epoxy resin composition of the present invention has low retardation, that is, low birefringence.

Examples 2, 3, 4 and Comparative Example 2
As an example, the epoxy resins (EP1) and (EP2) obtained in Synthesis Examples 1 and 2 were used, and the epoxy resin (EP3) obtained in Synthesis Example 3 was used as a comparative example. Formulation was performed in a ratio. The obtained curable resin composition was a film obtained by volatilizing the solvent at 80 ° C. for 20 minutes on a Teflon (registered trademark) plate for Examples 2 and 3 and Comparative Example 2, and for Example 4. The solvent was volatilized at 150 ° C. for 3 minutes, the resulting film was cut out, and 0.9 g was stacked on a test piece mold having a width of 7 mm and a length of 5 cm, and then pressed at 150 ° C. and 30 kg / cm ² for 15 minutes. It was obtained by performing pressure pressing and finally curing at 160 ° C. for 3 hours. All were molded to a thickness of 0.7 to 0.8 mm. The obtained plate was evaluated for transparency. In addition, about the evaluation of transparency, Nippon Denshoku color and turbidity simultaneous measuring device COH400 was used, and it compared by the measured value of YI. The results are shown in Table 1.

Synthesis Example 2-1
A 1 L four-necked flask equipped with a stirrer, a reflux condenser and a stirrer was once evacuated and purged with nitrogen (oxygen concentration: 4.9%), and then subjected to a nitrogen purge (2 L / hr) and a phenol compound (DPPI1 ) (Compound with all substituents R in the formula (1) SABIC PPPBP ) 256 parts, 842 parts of epichlorohydrin and 180 parts of methanol were added, and the temperature of the water bath was raised to 75 ° C. When the internal temperature exceeded 65 ° C., 21 parts of flaky sodium hydroxide was added in 90 divided portions, followed by further reaction 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, 600 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 ° C. Under stirring, 26 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, 305 parts of epoxy resin (EP2-1) was obtained. The epoxy equivalent of the obtained epoxy resin is 266 g / eq. , Softening point 89 ° C, ICI melt viscosity 0.42 Pa · s (150 ° C), total chlorine amount 1600 ppm, hydrolyzable chlorine 1540 ppm, chlorine ion 2 ppm, sodium ion 0.5 ppm, hue 0.2 or less (Gardner 40% MEK (methyl ethyl ketone) solution). The structure of the formula (1) was 93 area% (GPC).

Synthesis Example 22
A 1 L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer was once evacuated, purged with nitrogen (oxygen concentration 5.3%), and then subjected to a nitrogen purge (2 L / hr) with a phenol compound (DPPI2 (The reaction was performed in the same manner as in Synthesis Example 2-1 except that the compound SABIC PPPB P in which the substituents R were all hydrogen atoms in the formula (1) was used ) . The epoxy equivalent of the obtained epoxy resin (EP2-2) was 266 g / eq. , Softening point 90 ° C., ICI melt viscosity 0.44 Pa · s (150 ° C.), total chlorine amount 2000 ppm, hydrolyzable chlorine 1950 ppm, chlorine ion 1 ppm, sodium ion 0.3 ppm, hue 0.2 (Gardner 40% MEK Solution). The structure of the formula (1) was 93 area% (GPC).

Synthesis Example 2-3
A 1 L four-necked flask equipped with a stirrer, reflux condenser, and stirrer was purged with nitrogen at 4 L / h for 30 minutes (oxygen concentration 6.5%), and then subjected to a nitrogen purge (2 L / hr) and a phenol compound. (DPPI1) (compound SABIC PPPB P in which substituent R is all hydrogen atoms in formula (1) ) 256 parts, 661 parts of epichlorohydrin, and 165 parts of methanol were added, and the temperature of the water bath was raised to 75 ° C. When the internal temperature exceeded 65 ° C, 57 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, 600 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 ° C. Under stirring, 5 parts of a 30% by weight sodium hydroxide aqueous 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. 297 parts of epoxy resin (EP2-3) was obtained by distilling off methyl isobutyl ketone and the like under reduced pressure. The epoxy equivalent of the obtained epoxy resin was 277 g / eq. , Softening point 96 ° C., ICI melt viscosity 0.62 Pa · s (150 ° C.), total chlorine amount 2230 ppm, hydrolyzable chlorine 2100 ppm, chlorine ion 0.5 ppm, sodium ion 0.5 ppm, hue 0.2 or less (Gardner 40% MEK solution). The structure of the formula (1) was 82 area% (GPC).

Synthesis Example 2-4
A 1 L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer was once evacuated, purged with nitrogen (oxygen concentration 5.2%), and then subjected to a nitrogen purge (2 L / hr) with a phenol compound (DPPI1 ) (Compound with all substituents R in formula (1) SABIC PPPB P) 256 parts, 661 parts epichlorohydrin, 200 parts dimethyl sulfoxide were added, and the temperature of the water bath was raised to 45 ° C. When the internal temperature exceeded 40 ° C, 57 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, 600 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 ° C. Under stirring, 16 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 heated at 180 ° C. using a rotary evaporator. 300 parts of epoxy resin (EP2-4) was obtained by distilling off methyl isobutyl ketone and the like under reduced pressure. The epoxy equivalent of the obtained epoxy resin is 270 g / eq. , Softening point 92 ° C., ICI melt viscosity 0.48 Pa · s (150 ° C.), total chlorine amount 1050 ppm, hydrolyzable chlorine 960 ppm, chlorine ion 0.3 ppm, sodium ion 0.1 ppm, hue 0.6 (Gardner 40 % MEK solution). The structure of the formula (1) was 90 area% (GPC).

Examples 2-1, 2-2, 2-3 and Comparative Example 2-1
Using the epoxy resin obtained above, it was blended according to the formulation shown in Table 2 below, cured at 120 ° C. for 2 hours, 160 ° C. for 2 hours, and 180 ° C. for 4 hours, and tested for flame retardancy. The flame retardant test method is shown below.
Determination of flame retardancy and flame retardancy: Performed according to UL94. However, the test was conducted with a sample size of 12.5 mm wide × 150 mm long and a thickness of 0.8 mm.

  From the above results, it became clear that the curable resin composition of the present invention can achieve both high heat resistance and flame retardancy.

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.
In addition, this application is based on the Japanese patent application (Japanese Patent Application No. 2012-129406 and Japanese Patent Application No. 2012-129408) for which it applied on June 7, 2012, The whole is used by reference. Also, all references cited herein are incorporated as a whole.

  The epoxy resin composition of the first invention can be used for various applications including optical component materials. Further, the curable resin composition of the second invention includes an adhesive, a paint, a coating agent, a molding material (including a sheet, a film, FRP, etc.), an insulating material (including a printed board, a wire coating, etc.), a sealing agent. In addition, it can be used as an additive to other resins.

Claims (3)

A curable resin composition comprising an epoxy resin represented by the following formula (2) and having a softening point of 80 to 110 ° C., a phenol resin and / or a polymerization catalyst.

(In the formula, multiple Rs each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.) The curable resin composition according to claim 1 , wherein the phenol resin is a phenol aralkyl resin (a resin having an aromatic alkylene structure). The curable resin composition according to claim 1 , wherein the polymerization catalyst is a cationic polymerization catalyst.